# Patent

## Title
ZnO vapor deposition material, process for producing the same, and ZnO film

## Abstract

A ZnO vapor deposition material for formation of a transparent conductive film or the like consists mainly of a porous ZnO sintered body containing one or more first additive elements selected from Ce, La, Y, Pr, Nd, Pm, and Sm, and second additive elements selected from Al, Ga, Sc, and B. The content of the first additive elements is higher than the content of the second additive elements. The content of the first additive elements is in a range of 0.1 to 14.9% by mass, and the content of the second additive elements is in a range of 0.1 to 10% by mass. The sintered body has a porosity of 3 to 50%.

## Background
This application is a divisional application of U.S. application Ser. No. 12/733,897, filed Mar. 26, 2010 which claims the right of priority under 35 U.S.C. §119 based on Japanese Patent Application Nos. 2007-252759 filed Sep. 27, 2007; 2007-252760 filed Sep. 27, 2007; 2007-252761 filed Sep. 27, 2007; 2007-252762 filed Sep. 27, 2007; 2007-252763 filed Sep. 27, 2007; 2007-252764 filed Sep. 27, 2007; 2007-252765 filed Sep. 27, 2007; 2007-252766 filed Sep. 27, 2007; 2008-245299 filed Sep. 25, 2008; 2008-245300 filed Sep. 25, 2008; 2008-245301 filed Sep. 25, 2008; 2008-245302 filed Sep. 25, 2008; 2008-245303 filed Sep. 25, 2008; 2008-245304 filed Sep. 25, 2008; 2008-245305 filed Sep. 25, 2008 and 2008-245306 filed Sep. 25, 2008.


TECHNICAL FIELD
The present invention relates to a ZnO vapor deposition material for formation of, for example, a transparent conductive film used for solar cells; a gas and vapor-resistant film; a transparent electrode of a transparent piezoelectric sensor or a gas or vapor-resistant film in liquid crystal displays, electroluminescence display devices, and touch panel devices; and various films used in active matrix drivers constituting display devices, antistatic conductive coatings, gas sensors, electromagnetic shielding panels, piezoelectric devices, photoelectric converters, luminescence devices, thin film type secondary cells, and the like, a process for producing a ZnO vapor deposition material, a ZnO film formed of the ZnO vapor deposition material, and a process for producing a ZnO film.
This application claims priority based on Japanese Patent Application Nos. 2007-252759, 2007-252760, 2007-252761, 2007-252762, 2007-252763, 2007-252764, 2007-252765, and 2007-252766 filed on Sep. 27, 2007, and Japanese Patent Application Nos. 2008-245299, 2008-245300, 2008-245301, 2008-245302, 2008-245303, 2008-245304, 2008-245305, and 2008-245306 filed on Sep. 25, 2008, the enclosures of which are incorporated herein by reference.
BACKGROUND ART
In recent years, transparent conductive films have been indispensable when manufacturing photoelectric converters, such as solar cells and the like. As a known transparent conductive film, an ITO film (a tin-doped indium oxide film) is known. The ITO film has the advantages of excellent transparency and low resistance.
Meanwhile, there has been a need for cost reduction in solar cells or liquid crystal displays. However, since indium is expensive, when the ITO film is used as a transparent conductive film, there is a disadvantage in that the solar cell also inevitably becomes expensive. In the case of manufacturing solar cells or the like, an amorphous silicon film is formed on a transparent conductive film by a plasma CVD method or the like. At this time, if the transparent conductive film is an ITO film, there is a problem in that hydrogen plasma at the time of plasma CVD leads to deterioration of the ITO film.
In order to solve such problems, it has been proposed that a zinc oxide-based film doped with a conductive active element, such as Al, B, Si, Ga, or Sc, which can be prepared at low cost is used as a transparent conductive film for solar cells or the like, and a zinc oxide-based sputtering target is used to form the zinc oxide-based film by sputtering (for example, Patent Document 1). According to this zinc oxide-based sputtering target, an extremely low resistance zinc oxide-based sintered body is obtained by containing a predetermined amount of the conductive active element in zinc. Sintering density and conductivity of the sintered body are improved if the raw powder is fine and has high dispersibility.
[Patent Document 1] Japanese Unexamined Patent Application Publication No.
DISCLOSURE OF INVENTION
Technical Problem
However, if sputtering is performed to form a film at high speed using the conventional zinc oxide-based sputtering target while applying high voltage, there are disadvantages in that abnormal discharge is likely to occur, the target is inhomogeneously consumed because of an unstable discharge state, compositional shift occurs in the resultant film, and it is difficult to obtain a low resistance film. On the other hand, if the voltage is decreased by decreasing power to be applied, there are disadvantages in that the speed of film formation is lowered and the efficiency of zinc oxide-based film formation is significantly reduced.
Further, since the conventional target material has low evaporation efficiency and film formation efficiency, the lifespan of the target material replacement cycle is shortened, and there is a need for a target material having good evaporation efficiency and film formation efficiency so as to increase productivity. If the speed of film formation increases, film density is lowered, so the refractive index and sputtering resistance may be lowered, and discharge characteristics and insulation characteristics are deteriorated.
The present invention has been completed in order to solve the above-described problems, and an object of the present invention is to provide a ZnO vapor deposition material capable of forming a film having high conductivity like an ITO film at high speed and forming a conductive film having excellent transparency and denseness, and a ZnO film using the ZnO vapor deposition material. Another object of the present invention is to provide a ZnO vapor deposition material capable of improving the speed of film formation with a large amount of evaporation per unit energy, and a ZnO film using the ZnO vapor deposition material.
Technical Solution
A first aspect of the present invention has the following configuration.
[A1] A ZnO vapor deposition material for formation of a transparent conductive film which is composed of a porous ZnO sintered body containing Ce and Al, wherein the Ce content is higher than the Al content, the Ce content is in a range of 0.1 to 14.9% by mass, the Al content is in a range of 0.1 to 10% by mass, and the sintered body has a porosity of 3 to 50%.
[A2] The ZnO vapor deposition material described in [A1], wherein the total content of Ce and Al is in a range of 0.2 to 15% by mass.
[A3] The ZnO vapor deposition material described in [A1] or [A2], wherein the porous ZnO sintered body has pores having an average pore diameter of 0.1 to 500 μm.
[A4] The ZnO vapor deposition material described in any one of [A1] to [A3], wherein the porous ZnO sintered body is a sintered body of grains having an average crystal grain size of 1 to 500 μm.
[A5] The ZnO vapor deposition material described in any one of [A1] to [A4], wherein the porous ZnO sintered body is polycrystal or monocrystal.
In the ZnO vapor deposition material of this aspect, since the porous ZnO sintered body contains a predetermined amount of the two elements Ce and Al at a specific ratio, a ZnO film having high conductivity like an ITO film can be obtained by using the ZnO vapor deposition material. Preferably, the total content of Ce and Al is in a range of 0.2 to 15% by mass, so excellent effects in terms of conduction properties and spectroscopic properties are obtained.
In the ZnO vapor deposition material of this aspect, since the porous ZnO sintered body has a porosity of 3 to 50%, the specific surface area inside the vapor deposition material is large, and the evaporation speed of the vapor deposition material can be increased. Specifically, the evaporation speed can be 1.1 to 2 times higher than the conventional ZnO vapor deposition material.
In the ZnO vapor deposition material of this aspect, since the porous ZnO sintered body has pores having an average pore diameter of 0.1 to 500 μm, the evaporation speed can be increased. The porous ZnO sintered body is a sintered body of grains having an average crystal grain size of 1 to 500 μm, so the specific surface area inside the vapor deposition material increases, thereby increasing the evaporation speed of the vapor deposition material. The formed ZnO film has excellent film characteristics.
In the ZnO vapor deposition material of this aspect, the porous ZnO sintered body is polycrystal or monocrystal, and contains a predetermined amount of the two elements Ce and Al at a specific ratio, so a ZnO film having high conductivity like an ITO film can be obtained.
Another aspect of the present invention provides a process for producing a ZnO vapor deposition material having the following configuration.
[A6] A process for producing a ZnO vapor deposition material, the process including the steps of (I) mixing ZnO powder having a purity equal to or greater than 98%, CeO2 powder in such an amount that the Ce content in the ZnO vapor deposition material is in a range of 0.1 to 14.9% by mass, Al2O3 powder in such an amount that the Al content in the ZnO vapor deposition material is in a range of 0.1 to 10% by mass, a binder, and an organic solvent to prepare a slurry with a concentration of 30 to 75% by mass, (II) blowing gas into the slurry to obtain a gas-containing slurry, (III) spray-drying the gas-containing slurry to obtain a porous granulation powder having an average grain size of 50 to 300 μm, (IV) molding the porous granulation powder to obtain a porous molded body, and (V) sintering the porous molded body at a predetermined temperature to obtain a porous ZnO sintered body.
[A7] The process for producing a ZnO vapor deposition material of [A6] including, instead of the steps (II) and (III), the steps of (II-2) mixing a foaming agent in raw powder or slurry to obtain a foaming agent-containing slurry, and (III-2) foaming the foaming agent-containing slurry while spray-drying the foaming agent-containing slurry to obtain a porous granulation powder having an average grain size of 50 to 300 μm.
[A8] The process for producing a ZnO vapor deposition material of [A6] including, instead of the steps (II) to (V), the steps of (II-3) mixing an additive, which will be volatized and dissolved at the time of calcination, in raw powder or slurry to obtain an additive-containing slurry, (III-3) spray-drying the additive-containing slurry to obtain a granulation powder having an average grain size of 50 to 300 μm, (IV-3) molding the granulation powder to obtain a molded body, and (V-3) sintering the molded body while volatizing and dissolving the additive to obtain a porous ZnO sintered body.
[A9] The processes for producing a ZnO vapor deposition material of any one of [A6] to [A8], wherein in the step (I), ZnO powder having a purity equal to or greater than 98%, an average grain size of 10 to 500 μm, and a grain size distribution within a range of ±10% of the average grain size, CeO2 powder, and Al2O3 powder are used, and the powders, a binder, and an organic solvent are mixed to prepare a slurry with a concentration of 30 to 75% by mass.
In the process of this aspect, by the steps (I) to (V), a ZnO vapor deposition material having a large amount of evaporation, and having excellent film formation properties and denseness can be relatively easily produced. In particular, by the step (II) blowing gas into the slurry to obtain a gas-containing slurry, or (II-2) mixing a foaming agent in raw powder or slurry to obtain a foaming agent-containing slurry, a ZnO vapor deposition material having pores with predetermined porosity and average pore diameter, and an average crystal grain size can be relatively easily produced.
In the process of this aspect, since the powder having an average grain size of 10 to 500 μm and a grain size distribution within a range of ±10% of the average grain size is used, fine grains do not substantially enter between grains, and thus a porous molded body having a porosity of 3 to 50% can be easily obtained.
The present invention provides the following ZnO film and production of the same.
[A10] A ZnO film which is formed using the ZnO vapor deposition material described in any one of [A1] to [A5], or a ZnO vapor deposition material produced by the process described in any one of [A6] to [A9].
[A11] A ZnO film which is formed by an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method with the ZnO vapor deposition material described in any one of [A 1] to [A5], or a ZnO vapor deposition material produced by the process described in any one of [A6] to [A9] as a target material.
[A12] A process for forming a ZnO film by an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method with the ZnO vapor deposition material described in any one of [A1] to [A5], or a ZnO vapor deposition material produced by the process described in any one of [A6] to [A9] as a target material.
The ZnO vapor deposition material of this aspect can be widely used in a vacuum deposition method, such as an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method. By using the ZnO vapor deposition material of this aspect, for example, when a film is formed at the same speed of film formation as the related art by an electron beam deposition method, the filament replacement frequency can be reduced, and the speed of film formation can be increased, thereby shortening the production time.
The ZnO vapor deposition material of this aspect contains Ce and Al as additive elements, so crystals distorted by Ce having an ion radius greater than Zn are recovered and aligned by adding Al having a small ion radius. Thus, a ZnO film having high permeability is formed, such that a ZnO film having excellent denseness and high durability can be formed. A film having excellent moisture resistance and gas and vapor barrier properties can be obtained.
The ZnO vapor deposition material of this aspect has porosity within a predetermined range, and preferably, pores have an average pore diameter within a specific range, and grains have an average crystal grain size within a predetermined range, so the specific surface area inside the vapor deposition material increases, thereby increasing the evaporation speed. Thus, a ZnO film having good film formation efficiency can be formed. A ZnO film formed of the ZnO vapor deposition material of this aspect is dense, and has high conductivity and excellent durability.
Another aspect of the present invention has the following configuration.
[B1] A ZnO vapor deposition material for formation of a transparent conductive film which is composed of a porous ZnO sintered body containing Ce and Ga, wherein the Ce content is higher than the Ga content, the Ce content is in a range of 0.1 to 14.9% by mass, the Ga content is in a range of 0.1 to 10% by mass, and the sintered body has a porosity of 3 to 50%.
[B2] The ZnO vapor deposition material described in [B1], wherein the total content of Ce and Ga is in a range of 0.2 to 15% by mass.
[B3] The ZnO vapor deposition material described in [B1] or [B2], wherein the porous ZnO sintered body has pores having an average pore diameter of 0.1 to 500 μm.
[B4] The ZnO vapor deposition material described in any one of [B1] to [B3], wherein the porous ZnO sintered body is a sintered body of grains having an average crystal grain size of 1 to 500 μm.
[B5] The ZnO vapor deposition material described in any one of [B1] to [B4], wherein the porous ZnO sintered body is polycrystal or monocrystal.
In the ZnO vapor deposition material of this aspect, the porous ZnO sintered body contains a predetermined amount of the two elements Ce and Ga at a specific ratio, so a ZnO film having high conductivity like an ITO film can be obtained by using the ZnO vapor deposition material. Preferably, the total content of Ce and Ga is in a range of 0.2 to 15% by mass, so excellent effects in terms of conduction properties and spectroscopic properties are obtained.
In the ZnO vapor deposition material of this aspect, since the porous ZnO sintered body has a porosity of 3 to 50%, the specific surface area inside the vapor deposition material is large, and the evaporation speed of the vapor deposition material can be increased. Specifically, the evaporation speed can be 1.1 to 2 times higher than the conventional ZnO vapor deposition material.
In the ZnO vapor deposition material of this aspect, since the porous ZnO sintered body has pores having an average pore diameter of 0.1 to 500 μm, the evaporation speed can be increased. The porous ZnO sintered body is a sintered body of grains having an average crystal grain size of 1 to 500 μm, so the specific surface area inside the vapor deposition material increases, thereby increasing the evaporation speed of the vapor deposition material. The formed ZnO film has excellent film characteristics.
In the ZnO vapor deposition material of this aspect, the porous ZnO sintered body is polycrystal or monocrystal, and contains a predetermined amount of the two elements Ce and Ga at a specific ratio, so a ZnO film having high conductivity like an ITO film can be obtained.
Another aspect of the present invention provides a process for producing a ZnO vapor deposition material having the following configuration.
[B6] A process for producing a ZnO vapor deposition material, the process including the steps of (I) mixing ZnO powder having a purity equal to or greater than 98%, CeO2 powder in such an amount that the Ce content in the ZnO vapor deposition material is in a range of 0.1 to 14.9% by mass, Ga2O3 powder in such an amount that the Ga content in the ZnO vapor deposition material is in a range of 0.1 to 10% by mass, a binder, and an organic solvent to prepare a slurry with a concentration of 30 to 75% by mass, (II) blowing gas into the slurry to obtain a gas-containing slurry, (III) spray-drying the gas-containing slurry to obtain a porous granulation powder having an average grain size of 50 to 300 μm, (IV) molding the porous granulation powder to obtain a porous molded body, and (V) sintering the porous molded body at a predetermined temperature to obtain a porous ZnO sintered body.
[B7] The process for producing a ZnO vapor deposition material of [B6] including, instead of the steps (II) and (III), the steps of (II-2) mixing a foaming agent in raw powder or slurry to obtain a foaming agent-containing slurry, and (III-2) foaming the foaming agent-containing slurry while spray-drying the foaming agent-containing slurry to obtain a porous granulation powder having an average grain size of 50 to 300 μm.
[B8] The process for producing a ZnO vapor deposition material of [B6] including, instead of the steps (II) to (V), the steps of (II-3) mixing an additive, which will be volatized and dissolved at the time of calcination, in raw powder or slurry to obtain an additive-containing slurry, (III-3) spray-drying the additive-containing slurry to obtain a granulation powder having an average grain size of 50 to 300 μm, (IV-3) molding the granulation powder to obtain a molded body, and (V-3) sintering the molded body while volatizing and dissolving the additive to obtain a porous ZnO sintered body.
[B9] The processes for producing a ZnO vapor deposition material of any one of [B6] to [B8], wherein in the step (I), ZnO powder having a purity equal to or greater than 98%, an average grain size of 10 to 500 μm, and a grain size distribution within a range of ±10% of the average grain size, CeO2 powder, and Ga2O3 powder are used, and the powders, a binder, and an organic solvent are mixed to prepare a slurry with a concentration of 30 to 75% by mass.
In the process of this aspect, by the steps (I) to (V), a ZnO vapor deposition material having a large amount of evaporation, and having excellent film formation properties and denseness can be relatively easily produced. In particular, by the step (II) blowing gas into the slurry to obtain a gas-containing slurry, or (II-2) mixing a foaming agent in raw powder or slurry to obtain a foaming agent-containing slurry, a ZnO vapor deposition material having pores with predetermined porosity and average pore diameter, and an average crystal grain size can be relatively easily produced.
In the process of this aspect, since the powder having an average grain size of 10 to 500 μm and a grain size distribution within a range of ±10% of the average grain size is used, fine grains do not substantially enter between grains, and thus a porous molded body having a porosity of 3 to 50% can be easily obtained.
The present invention provides the following ZnO film and production of the same.
[B10] A ZnO film which is formed using the ZnO vapor deposition material described in any one of [B1] to [B5], or a ZnO vapor deposition material produced by the process described in any one of [B6] to [B9].
[B11] A ZnO film which is formed by an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method with the ZnO vapor deposition material described in any one of [B1] to [B5], or a ZnO vapor deposition material produced by the process described in any one of [B6] to [B9] as a target material.
[B12] A process for forming a ZnO film by an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method with the ZnO vapor deposition material described in any one of [B1] to [B5], or a ZnO vapor deposition material produced by the process described in any one of [B6] to [B9] as a target material.
The ZnO vapor deposition material of this aspect can be widely used in a vacuum deposition method, such as an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method. By using the ZnO vapor deposition material of this aspect, for example, when a film is formed at the same speed of film formation as the related art by an electron beam deposition method, the filament replacement frequency can be reduced, and the speed of film formation can be increased, thereby shortening the production time.
The ZnO vapor deposition material of this aspect contains Ce and Ga as additive elements, so crystals distorted by Ce having an ion radius greater than Zn are recovered and aligned by adding Ga having a small ion radius. Thus, a ZnO film having high permeability is formed, such that a ZnO film having excellent denseness and high durability can be formed. A film having excellent moisture resistance and gas and vapor barrier properties can be obtained.
The ZnO vapor deposition material of this aspect has porosity within a predetermined range, and preferably, pores have an average pore diameter within a specific range, and grains have an average crystal grain size within a predetermined range, so the specific surface area inside the vapor deposition material increases, thereby increasing the evaporation speed. Thus, a ZnO film having good film formation efficiency can be formed. A ZnO film formed of the ZnO vapor deposition material of this aspect is dense, and has high conductivity and excellent durability.
Another aspect of the present invention has the following configuration.
[C1] A ZnO vapor deposition material for formation of a transparent conductive film which is composed of a porous ZnO sintered body containing Ce and Sc, wherein the Ce content is higher than the Sc content, the Ce content is in a range of 0.1 to 14.9% by mass, the Sc content is in a range of 0.1 to 10% by mass, and the sintered body has a porosity of 3 to 50%.
[C2] The ZnO vapor deposition material described in [C1], wherein the total content of Ce and Sc is in a range of 0.2 to 15% by mass.
[C3] The ZnO vapor deposition material described in [C1] or [C2], wherein the porous ZnO sintered body has pores having an average pore diameter of 0.1 to 500 μm.
[C4] The ZnO vapor deposition material described in any one of [C1] to [C3], wherein the porous ZnO sintered body is a sintered body of grains having an average crystal grain size of 1 to 500 μm.
[C5] The ZnO vapor deposition material described in any one of [C1] to [C4], wherein the porous ZnO sintered body is polycrystal or monocrystal.
In the ZnO vapor deposition material of this aspect, the porous ZnO sintered body contains a predetermined amount of the two elements Ce and Sc at a specific ratio, so a ZnO film having high conductivity like an ITO film can be obtained by using the ZnO vapor deposition material. Preferably, the total content of Ce and Sc is in a range of 0.2 to 15% by mass, so excellent effects in terms of conduction properties and spectroscopic properties are obtained.
In the ZnO vapor deposition material of this aspect, since the porous ZnO sintered body has a porosity of 3 to 50%, the specific surface area inside the vapor deposition material is large, and the evaporation speed of the vapor deposition material can be increased. Specifically, the evaporation speed can be 1.1 to 2 times higher than the conventional ZnO vapor deposition material.
In the ZnO vapor deposition material of this aspect, since the porous ZnO sintered body has pores having an average pore diameter of 0.1 to 500 μm, the evaporation speed can be increased. The porous ZnO sintered body is a sintered body of grains having an average crystal grain size of 1 to 500 μm, so the specific surface area inside the vapor deposition material increases, thereby increasing the evaporation speed of the vapor deposition material. The formed ZnO film has excellent film characteristics.
In the ZnO vapor deposition material of this aspect, the porous ZnO sintered body is polycrystal or monocrystal, and contains a predetermined amount of the two elements Ce and Sc at a specific ratio, so a ZnO film having high conductivity like an ITO film can be obtained.
Another aspect of the present invention provides a process for producing a ZnO vapor deposition material having the following configuration.
[C6] A process for producing a ZnO vapor deposition material, the process including the steps of (I) mixing ZnO powder having a purity equal to or greater than 98%, CeO2 powder in such an amount that the Ce content in the ZnO vapor deposition material is in a range of 0.1 to 14.9% by mass, Sc2O3 powder in such an amount that the Sc content in the ZnO vapor deposition material is in a range of 0.1 to 10% by mass, a binder, and an organic solvent to prepare a slurry with a concentration of 30 to 75% by mass, (II) blowing gas into the slurry to obtain a gas-containing slurry, (III) spray-drying the gas-containing slurry to obtain a porous granulation powder having an average grain size of 50 to 300 μm, (IV) molding the porous granulation powder to obtain a porous molded body, and (V) sintering the porous molded body at a predetermined temperature to obtain a porous ZnO sintered body.
[C7] The process for producing a ZnO vapor deposition material of [C6] including, instead of the steps (II) and (III), the steps of (II-2) mixing a foaming agent in raw powder or slurry to obtain a foaming agent-containing slurry, and (III-2) foaming the foaming agent-containing slurry while spray-drying the foaming agent-containing slurry to obtain a porous granulation powder having an average grain size of 50 to 300 μm.
[C8] The process for producing a ZnO vapor deposition material of [C6] including, instead of the steps (II) to (V), the steps of (II-3) mixing an additive, which will be volatized and dissolved at the time of calcination, in raw powder or slurry to obtain an additive-containing slurry, (III-3) spray-drying the additive-containing slurry to obtain a granulation powder having an average grain size of 50 to 300 (IV-3) molding the granulation powder to obtain a molded body, and (V-3) sintering the molded body while volatizing and dissolving the additive to obtain a porous ZnO sintered body.
[C9] The process for producing a ZnO vapor deposition material of any one of [C6] to [C8], wherein in the step (I), ZnO powder having a purity equal to or greater than 98%, an average grain size of 10 to 500 μm, and a grain size distribution within a range of ±10% of the average grain size, CeO2 powder, and Sc2O3 powder are used, and the powders, a binder, and an organic solvent are mixed to prepare a slurry with a concentration of 30 to 75% by mass.
In the process of this aspect, by the steps (I) to (V), a ZnO vapor deposition material having a large amount of evaporation, and having excellent film formation properties and denseness can be relatively easily produced. In particular, by the step (II) blowing gas into the slurry to obtain a gas-containing slurry, or (II-2) mixing a foaming agent in raw powder or slurry to obtain a foaming agent-containing slurry, a ZnO vapor deposition material having pores with predetermined porosity and average pore diameter, and an average crystal grain size can be relatively easily produced.
In the process of this aspect, since the powder having an average grain size of 10 to 500 μm and a grain size distribution within a range of ±10% of the average grain size is used, fine grains do not substantially enter between grains, and thus a porous molded body having a porosity of 3 to 50% can be easily obtained.
The present invention provides the following ZnO film and production of the same.
[C10] A ZnO film which is formed using the ZnO vapor deposition material described in any one of [C1] to [C5], or a ZnO vapor deposition material produced by the process described in any one of [C6] to [C9].
[C11] A ZnO film which is formed by an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method with the ZnO vapor deposition material described in any one of [C1] to [C5], or a ZnO vapor deposition material produced by the process described in any one of [C6] to [C9] as a target material.
[C12] A process for forming a ZnO film by an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method with the ZnO vapor deposition material described in any one of [C1] to [C5], or a ZnO vapor deposition material produced by the process described in any one of [C6] to [C9] as a target material.
The ZnO vapor deposition material of this aspect can be widely used in a vacuum deposition method, such as an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method. By using the ZnO vapor deposition material of this aspect, for example, when a film is formed at the same speed of film formation as the related art by an electron beam deposition method, the filament replacement frequency can be reduced, and the speed of film formation can be increased, thereby shortening the production time.
The ZnO vapor deposition material of this aspect contains Ce and Sc as additive elements, so crystals distorted by Ce having an ion radius greater than Zn are recovered and aligned by adding Sc having a small ion radius. Thus, a ZnO film having high permeability is formed, such that a ZnO film having excellent denseness and high durability can be formed. A film having excellent moisture resistance and gas and vapor barrier properties can be obtained.
The ZnO vapor deposition material of this aspect has porosity within a predetermined range, and preferably, pores have an average pore diameter within a specific range, and grains have an average crystal grain size within a predetermined range, so the specific surface area inside the vapor deposition material increases, thereby increasing the evaporation speed. Thus, a ZnO film having good film formation efficiency can be formed. A ZnO film formed of the ZnO vapor deposition material of this aspect is dense, and has high conductivity and excellent durability.
Another aspect of the present invention has the following configuration.
[D1] A ZnO vapor deposition material for formation of a transparent conductive film which is composed of a porous ZnO sintered body containing Ce and B, wherein the Ce content is higher than the B content, the Ce content is in a range of 0.1 to 14.9% by mass, the B content is in a range of 0.1 to 10% by mass, and the sintered body has a porosity of 3 to 50%.
[D2] The ZnO vapor deposition material described in [D1], wherein the total content of Ce and B is in a range of 0.2 to 15% by mass.
[D3] The ZnO vapor deposition material described in [D1] or [D2], wherein the porous ZnO sintered body has pores having an average pore diameter of 0.1 to 500 μm.
[D4] The ZnO vapor deposition material described in any one of [D1] to [D3], wherein the porous ZnO sintered body is a sintered body of grains having an average crystal grain size of 1 to 500 μm.
[D5] The ZnO vapor deposition material described in any one of [D1] to [D4], wherein the porous ZnO sintered body is polycrystal or monocrystal.
In the ZnO vapor deposition material of this aspect, the porous ZnO sintered body contains a predetermined amount of the two elements Ce and B at a specific ratio, so a ZnO film having high conductivity like an ITO film can be obtained by using the ZnO vapor deposition material. Preferably, the total content of Ce and B is in a range of 0.2 to 15% by mass, so excellent effects in terms of conduction properties and spectroscopic properties are obtained.
In the ZnO vapor deposition material of this aspect, since the porous ZnO sintered body has a porosity of 3 to 50%, the specific surface area inside the vapor deposition material is large, and the evaporation speed of the vapor deposition material can be increased. Specifically, the evaporation speed can be 1.1 to 2 times higher than the conventional ZnO vapor deposition material.
In the ZnO vapor deposition material of this aspect, since the porous ZnO sintered body has pores having an average pore diameter of 0.1 to 500 μm, the evaporation speed can be increased. The porous ZnO sintered body is a sintered body of grains having an average crystal grain size of 1 to 500 μm, so the specific surface area inside the vapor deposition material increases, thereby increasing the evaporation speed of the vapor deposition material. The formed ZnO film has excellent film characteristics.
In the ZnO vapor deposition material of this aspect, the porous ZnO sintered body is polycrystal or monocrystal, and contains a predetermined amount of the two elements Ce and B at a specific ratio, so a ZnO film having high conductivity like an ITO film can be obtained.
Another aspect of the present invention provides a process for producing a ZnO vapor deposition material having the following configuration.
[D6] A process for producing a ZnO vapor deposition material, the process including the steps of (I) mixing ZnO powder having a purity equal to or greater than 98%, CeO2 powder in such an amount that the Ce content in the ZnO vapor deposition material is in a range of 0.1 to 14.9% by mass, B2O3 powder in such an amount that the B content in the ZnO vapor deposition material is in a range of 0.1 to 10% by mass, a binder, and an organic solvent to prepare a slurry with a concentration of 30 to 75% by mass, (II) blowing gas into the slurry to obtain a gas-containing slurry, (III) spray-drying the gas-containing slurry to obtain a porous granulation powder having an average grain size of 50 to 300 μm, (IV) molding the porous granulation powder to obtain a porous molded body, and (V) sintering the porous molded body at a predetermined temperature to obtain a porous ZnO sintered body.
[D7] The process for producing a ZnO vapor deposition material of [D6] including, instead of the steps (II) and (III), the steps of (II-2) mixing a foaming agent in raw powder or slurry to obtain a foaming agent-containing slurry, and (III-2) foaming the foaming agent-containing slurry while spray-drying the foaming agent-containing slurry to obtain a porous granulation powder having an average grain size of 50 to 300 μm.
[D8] The process for producing a ZnO vapor deposition material of [D6] including, instead of the steps (II) to (V), the steps of (II-3) mixing an additive, which will be volatized and dissolved at the time of calcination, in raw powder or slurry to obtain an additive-containing slurry, (III-3) spray-drying the additive-containing slurry to obtain a granulation powder having an average grain size of 50 to 300 μm, (IV-3) molding the granulation powder to obtain a molded body, and (V-3) sintering the molded body while volatizing and dissolving the additive to obtain a porous ZnO sintered body.
[D9] The process for producing a ZnO vapor deposition material of any one of [D6] to [D8], wherein in the step (I), ZnO powder having a purity equal to or greater than 98%, an average grain size of 10 to 500 μm, and a grain size distribution within a range of ±10% of the average grain size, CeO2 powder, and B2O3 powder are used, and the powders, a binder, and an organic solvent are mixed to prepare a slurry with a concentration of 30 to 75% by mass.
In the process of this aspect, by the steps (I) to (V), a ZnO vapor deposition material having a large amount of evaporation, and having excellent film formation properties and denseness can be relatively easily produced. In particular, by the step (II) blowing gas into the slurry to obtain a gas-containing slurry, or (II-2) mixing a foaming agent in raw powder or slurry to obtain a foaming agent-containing slurry, a ZnO vapor deposition material having pores with predetermined porosity and average pore diameter, and an average crystal grain size can be relatively easily produced.
In the process of this aspect, since the powder having an average grain size of 10 to 500 μm and a grain size distribution within a range of ±10% of the average grain size is used, fine grains do not substantially enter between grains, and thus a porous molded body having a porosity of 3 to 50% can be easily obtained.
The present invention provides the following ZnO film and production of the same.
[D10] A ZnO film which is formed using the ZnO vapor deposition material described in any one of [D1] to [D5], or a ZnO vapor deposition material produced by the process described in any one of [D6] to [D9].
[D11] A ZnO film which is formed by an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method with the ZnO vapor deposition material described in any one of [D1] to [D5], or a ZnO vapor deposition material produced by the process described in any one of [D6] to [D9] as a target material.
[D12] A process for forming a ZnO film by an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method with the ZnO vapor deposition material described in any one of [D1] to [D5], or a ZnO vapor deposition material produced by the process described in any one of [D6] to [D9] as a target material.
The ZnO vapor deposition material of this aspect can be widely used in a vacuum deposition method, such as an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method. By using the ZnO vapor deposition material of this aspect, for example, when a film is formed at the same speed of film formation as the related art by an electron beam deposition method, the filament replacement frequency can be reduced, and the speed of film formation can be increased, thereby shortening the production time.
The ZnO vapor deposition material of this aspect contains Ce and B as additive elements, so crystals distorted by Ce having an ion radius greater than Zn are recovered and aligned by adding B having a small ion radius. Thus, a ZnO film having high permeability is formed, such that a ZnO film having excellent denseness and high durability can be formed. A film having excellent moisture resistance and gas and vapor barrier properties can be obtained.
The ZnO vapor deposition material of this aspect has porosity within a predetermined range, and preferably, pores have an average pore diameter within a specific range, and grains have an average crystal grain size within a predetermined range, so the specific surface area inside the vapor deposition material increases, thereby increasing the evaporation speed. Thus, a ZnO film having good film formation efficiency can be formed. A ZnO film formed of the ZnO vapor deposition material of this aspect is dense, and has high conductivity and excellent durability.
Another aspect of the present invention has the following configuration.
[E1] A ZnO vapor deposition material for formation of a transparent conductive film which is composed of a sintered body containing ZnO as a major component, wherein the sintered body contains La as a first additive element and a second additive element, the second additive element is one or more elements selected from the group consisting of B, Al, Ga, and Sc, the La content is in a range of 0.1 to 14.9% by mass, the content of the second additive element is in a range of 0.1 to 10% by mass, the La content is higher than the content of the second additive element, and the sintered body is a porous sintered body having a porosity of 3 to 50%.
[E2] The ZnO vapor deposition material described in [E1], wherein the total content of La as a first additive element and the second additive element is in a range of 0.2 to 15% by mass.
[E3] The ZnO vapor deposition material described in [E1] or [E2], wherein the porous ZnO sintered body has pores having an average pore diameter of 0.1 to 500 μm.
[E4] The ZnO vapor deposition material described in any one of [E1] to [E3], wherein the porous ZnO sintered body is a sintered body of grains having an average crystal grain size of 1 to 500 μm.
[E5] The ZnO vapor deposition material described in any one of [E1] to [E4], wherein the porous ZnO sintered body is polycrystal or monocrystal.
In the ZnO vapor deposition material of this aspect, the porous sintered body containing ZnO as a major component (hereinafter, simply referred to as porous ZnO sintered body) contains La as a first additive element and the second additive element at a specific ratio, so a ZnO film having high conductivity like an ITO film can be obtained by using the ZnO vapor deposition material. Specifically, the porous sintered body contains one or more elements selected from the group consisting of B, Al, Ga, and Sc as the second additive element, and the total content of La as a first additive element and the second additive element is in a range of 0.2 to 15% by mass, so excellent effects in terms of conduction properties and spectroscopic properties are obtained.
In the ZnO vapor deposition material of this aspect, since the porous ZnO sintered body has a porosity of 3 to 50%, the specific surface area inside the vapor deposition material is large, and the evaporation speed of the vapor deposition material can be increased. Specifically, the evaporation speed can be 1.1 to 2 times higher than the conventional ZnO vapor deposition material.
In the ZnO vapor deposition material of this aspect, since the porous ZnO sintered body has pores having an average pore diameter of 0.1 to 500 μm, the evaporation speed can be increased. The porous ZnO sintered body is a sintered body of grains having an average crystal grain size of 1 to 500 μm, so the specific surface area inside the vapor deposition material increases, thereby increasing the evaporation speed of the vapor deposition material. The formed ZnO film has excellent film characteristics.
In the ZnO vapor deposition material of this aspect, the porous ZnO sintered body is polycrystal or monocrystal, and contains a predetermined amount of the two elements La and Al at a specific ratio, so a ZnO film having high conductivity like an ITO film can be obtained.
Another aspect of the present invention provides a process for producing a ZnO vapor deposition material having the following configuration.
[E6] A process for producing a ZnO vapor deposition material, the process including the steps of (I) mixing ZnO powder having a purity equal to or greater than 98%, La2O3 powder in such an amount that the La content in the ZnO vapor deposition material is in a range of 0.1 to 14.9% by mass, an oxide powder of a second additive element in such an amount that the content of the second additive element in the ZnO vapor deposition material is in a range of 0.1 to 10% by mass, a binder, and an organic solvent to prepare a slurry with a concentration of 30 to 75% by mass, (II) blowing gas into the slurry to obtain a gas-containing slurry, (III) spray-drying the gas-containing slurry to obtain a porous granulation powder having an average grain size of 50 to 300 μm, (IV) molding the porous granulation powder to obtain a porous molded body, and (V) sintering the porous molded body at a predetermined temperature to obtain a porous ZnO sintered body.
[E7] The process for producing a ZnO vapor deposition material of [E6] including, instead of the steps (II) and (III), the steps of (II-2) mixing a foaming agent in raw powder or slurry to obtain a foaming agent-containing slurry, and (III-2) foaming the foaming agent-containing slurry while spray-drying the foaming agent-containing slurry to obtain a porous granulation powder having an average grain size of 50 to 300 μm.
[E8] The process for producing a ZnO vapor deposition material of [E6] including, instead of the steps (II) to (V), the steps of (II-3) mixing an additive, which will be volatized and dissolved at the time of calcination, in raw powder or slurry to obtain an additive-containing slurry, (III-3) spray-drying the additive-containing slurry to obtain a granulation powder having an average grain size of 50 to 300 μm, (IV-3) molding the granulation powder to obtain a molded body, and (V-3) sintering the molded body while volatizing and dissolving the additive to obtain a porous ZnO sintered body.
[E9] The process for producing a ZnO vapor deposition material of any one of [E6] to [E8], wherein in the step (I), ZnO powder having a purity equal to or greater than 98%, an average grain size of 10 to 500 μm, and a grain size distribution within a range of ±10% of the average grain size, La2O3 powder, and oxide powder of the second additive element are used, and the powders, a binder, and an organic solvent are mixed to prepare a slurry with a concentration of 30 to 75% by mass.
In the process of this aspect, by the steps (I) to (V), a ZnO vapor deposition material having a large amount of evaporation, and having excellent film formation properties and denseness can be relatively easily produced. In particular, by the step (II) blowing gas into the slurry to obtain a gas-containing slurry, or (II-2) mixing a foaming agent in raw powder or slurry to obtain a foaming agent-containing slurry, a ZnO vapor deposition material having pores with predetermined porosity and average pore diameter, and an average crystal grain size can be relatively easily produced.
In the process of this aspect, since the powder having an average grain size of 10 to 500 μm and a grain size distribution within a range of ±10% of the average grain size is used, fine grains do not substantially enter between grains, and thus a porous molded body having a porosity of 3 to 50% can be easily obtained.
The present invention provides the following ZnO film and production of the same.
[E10] A ZnO film which is formed using the ZnO vapor deposition material described in any one of [E1] to [E5], or a ZnO vapor deposition material produced by the process described in any one of [E6] to [E9].
[E11] A ZnO film which is formed by an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method with the ZnO vapor deposition material described in any one of [E1] to [E5], or a ZnO vapor deposition material produced by the process described in any one of [E6] to [E9] as a target material.
[E12] A process for forming a ZnO film by an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method with the ZnO vapor deposition material described in any one of [E1] to [E5], or a ZnO vapor deposition material produced by the process described in any one of [E6] to [E9] as a target material.
The ZnO vapor deposition material of this aspect can be widely used in a vacuum deposition method, such as an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method. By using the ZnO vapor deposition material of this aspect, for example, when a film is formed at the same speed of film formation as the related art by an electron beam deposition method, the filament replacement frequency can be reduced, and the speed of film formation can be increased, thereby shortening the production time.
The ZnO vapor deposition material of this aspect contains La as a first additive element and the second additive element, and the second additive element is one or more elements selected from the group consisting of B, Al, Ga, and Sc, so crystals distorted by La having an ion radius greater than Zn are recovered and aligned by adding B, Al, or Ga having an ion radius smaller than La, or Sc having high reactivity is added to form a film having a regulated crystal structure. Thus, a ZnO film having high permeability is formed, such that a ZnO film having excellent denseness and high durability can be formed. A film having excellent moisture resistance and gas and vapor barrier properties can be obtained.
The ZnO vapor deposition material of this aspect has porosity within a predetermined range, and preferably, pores have an average pore diameter within a specific range, and grains have an average crystal grain size within a predetermined range, so the specific surface area inside the vapor deposition material increases, thereby increasing the evaporation speed. Thus, a ZnO film having good film formation efficiency can be formed. A ZnO film formed of the ZnO vapor deposition material of this aspect is dense, and has high conductivity and excellent durability.
Another aspect of the present invention has the following configuration.
[F1] A ZnO vapor deposition material for formation of a transparent conductive film which is composed of a sintered body containing ZnO as a major component, wherein the sintered body contains Y as a first additive element and a second additive element, the second additive element is one or more elements selected from the group consisting of B, Al, Ga, and Sc, the Y content is in a range of 0.1 to 14.9% by mass, the content of the second additive element is in a range of 0.1 to 10% by mass, the Y content is higher than the content of the second additive element, and the sintered body is a porous sintered body having a porosity of 3 to 50%.
[F2] The ZnO vapor deposition material described in [F1], wherein the total content of Y as a first additive element and the second additive element is in a range of 0.2 to 15% by mass.
[F3] The ZnO vapor deposition material described in [F1] or [F2], wherein the porous ZnO sintered body has pores having an average pore diameter of 0.1 to 500 μm.
[F4] The ZnO vapor deposition material described in any one of [F1] to [F3], wherein the porous ZnO sintered body is a sintered body of grains having an average crystal grain size of 1 to 500 μm.
[F5] The ZnO vapor deposition material described in any one of [F1] to [F4], wherein the porous ZnO sintered body is polycrystal or monocrystal.
In the ZnO vapor deposition material of this aspect, the porous sintered body containing ZnO as a major component (hereinafter, simply referred to as porous ZnO sintered body) contains Y as a first additive element and the second additive element at a specific ratio, so a ZnO film having high conductivity like an ITO film can be obtained by using the ZnO vapor deposition material. Specifically, the porous sintered body contains one or more elements selected from the group consisting of B, Al, Ga, and Sc as the second additive element, and the total content of Y as a first additive element and the second additive element is in a range of 0.2 to 15% by mass, so excellent effects in terms of conduction properties and spectroscopic properties are obtained.
In the ZnO vapor deposition material of this aspect, since the porous ZnO sintered body has a porosity of 3 to 50%, the specific surface area inside the vapor deposition material is large, and the evaporation speed of the vapor deposition material can be increased. Specifically, the evaporation speed can be 1.1 to 2 times higher than the conventional ZnO vapor deposition material.
In the ZnO vapor deposition material of this aspect, since the porous ZnO sintered body has pores having an average pore diameter of 0.1 to 500 μm, the evaporation speed can be increased. The porous ZnO sintered body is a sintered body of grains having an average crystal grain size of 1 to 500 μm, so the specific surface area inside the vapor deposition material increases, thereby increasing the evaporation speed of the vapor deposition material. The formed ZnO film has excellent film characteristics.
In the ZnO vapor deposition material of this aspect, the porous ZnO sintered body is polycrystal or monocrystal, and contains a predetermined amount of the two elements Y and Al at a specific ratio, so a ZnO film having high conductivity like an ITO film can be obtained.
Another aspect of the present invention provides a process for producing a ZnO vapor deposition material having the following configuration.
[F6] A process for producing a ZnO vapor deposition material, the process including the steps of (I) mixing ZnO powder having a purity equal to or greater than 98%, Y2O3 powder in such an amount that the Y content in the ZnO vapor deposition material is in a range of 0.1 to 14.9% by mass, an oxide powder of a second additive element in such an amount that the content of the second additive element in the ZnO vapor deposition material is in a range of 0.1 to 10% by mass, a binder, and an organic solvent to prepare a slurry with a concentration of 30 to 75% by mass, (II) blowing gas into the slurry to obtain a gas-containing slurry, (III) spray-drying the gas-containing slurry to obtain a porous granulation powder having an average grain size of 50 to 300 μm, (IV) molding the porous granulation powder to obtain a porous molded body, and (V) sintering the porous molded body at a predetermined temperature to obtain a porous ZnO sintered body.
[F7] The process for producing a ZnO vapor deposition material of [F6] including, instead of the steps (II) and (III), the steps of (II-2) mixing a foaming agent in raw powder or slurry to obtain a foaming agent-containing slurry, and (III-2) foaming the foaming agent-containing slurry while spray-drying the foaming agent-containing slurry to obtain a porous granulation powder having an average grain size of 50 to 300 μm.
[F8] The process for producing a ZnO vapor deposition material of [F6] including, instead of the steps (II) to (V), the steps of (II-3) mixing an additive, which will be volatized and dissolved at the time of calcination, in raw powder or slurry to obtain an additive-containing slurry, (III-3) spray-drying the additive-containing slurry to obtain a granulation powder having an average grain size of 50 to 300 μm, (IV-3) molding the granulation powder to obtain a molded body, and (V-3) sintering the molded body while volatizing and dissolving the additive to obtain a porous ZnO sintered body.
[F9] The process for producing a ZnO vapor deposition material of any one of [F6] to [F8], wherein in the step (I), ZnO powder having a purity equal to or greater than 98%, an average grain size of 10 to 500 μm, and a grain size distribution within a range of ±10% of the average grain size, Y2O3 powder, and oxide powder of the second additive element are used, and the powders, a binder, and an organic solvent are mixed to prepare a slurry with a concentration of 30 to 75% by mass.
In the process of this aspect, by the steps (I) to (V), a ZnO vapor deposition material having a large amount of evaporation, and having excellent film formation properties and denseness can be relatively easily produced. In particular, by the step (II) blowing gas into the slurry to obtain a gas-containing slurry, or (II-2) mixing a foaming agent in raw powder or slurry to obtain a foaming agent-containing slurry, a ZnO vapor deposition material having pores with predetermined porosity and average pore diameter, and an average crystal grain size can be relatively easily produced.
In the process of this aspect, since the powder having an average grain size of 10 to 500 μm and a grain size distribution within a range of ±10% of the average grain size is used, fine grains do not substantially enter between grains, and thus a porous molded body having a porosity of 3 to 50% can be easily obtained.
The present invention provides the following ZnO film and production of the same.
[F10] A ZnO film which is formed using the ZnO vapor deposition material described in any one of [F1] to [F5], or a ZnO vapor deposition material produced by the process described in any one of [F6] to [F9].
[F11] A ZnO film which is formed by an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method with the ZnO vapor deposition material described in any one of [F1] to [F5], or a ZnO vapor deposition material produced by the process described in any one of [F6] to [F9] as a target material.
[F12] A process for forming a ZnO film by an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method with the ZnO vapor deposition material described in any one of [F1] to [F5], or a ZnO vapor deposition material produced by the process described in any one of [F6] to [F9] as a target material.
The ZnO vapor deposition material of this aspect can be widely used in a vacuum deposition method, such as an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method. By using the ZnO vapor deposition material of this aspect, for example, when a film is formed at the same speed of film formation as the related art by an electron beam deposition method, the filament replacement frequency can be reduced, and the speed of film formation can be increased, thereby shortening the production time.
The ZnO vapor deposition material of this aspect contains Y as a first additive element and the second additive element, and the second additive element is one or more elements selected from the group consisting of B, Al, Ga, and Sc, so crystals distorted by Y having an ion radius greater than Zn are recovered and aligned by adding B, Al, or Ga having an ion radius smaller than Y, or Sc having high reactivity is added to form a film having a regulated crystal structure. Thus, a ZnO film having high permeability is formed, such that a ZnO film having excellent denseness and high durability can be formed. A film having excellent moisture resistance and gas and vapor barrier properties can be obtained.
The ZnO vapor deposition material of this aspect has porosity within a predetermined range, and preferably, pores have an average pore diameter within a specific range, and grains have an average crystal grain size within a predetermined range, so the specific surface area inside the vapor deposition material increases, thereby increasing the evaporation speed. Thus, a ZnO film having good film formation efficiency can be formed. A ZnO film formed of the ZnO vapor deposition material of this aspect is dense, and has high conductivity and excellent durability.
Another aspect of the present invention has the following configuration.
[G1] A ZnO vapor deposition material for formation of a transparent conductive film which is composed of a sintered body containing ZnO as a major component, wherein the sintered body contains a first additive element and a second additive element, the first additive element is one or more elements selected from the group consisting of Pr, Nd, Pm, and Sm, the second additive element is one or more elements selected from the group consisting of B, Al, Ga, and Sc, the content of the first additive element is in a range of 0.1 to 14.9% by mass, the content of the second additive element is in a range of 0.1 to 10% by mass, the content of the first additive element is higher than the content of the second additive element, and the sintered body is a porous sintered body having a porosity of 3 to 50%.
[G2] The ZnO vapor deposition material described in [G1], wherein the total content of the first additive element and the second additive element is in a range of 0.2 to 15% by mass.
[G3] The ZnO vapor deposition material described in [G1] or [G2], wherein the porous ZnO sintered body has pores having an average pore diameter of 0.1 to 500 μm.
[G4] The ZnO vapor deposition material described in any one of [G1] to [G3], wherein the porous ZnO sintered body is a sintered body of grains having an average crystal grain size of 1 to 500 μm.
[G5] The ZnO vapor deposition material described in any one of [G1] to [G4], wherein the porous ZnO sintered body is polycrystal or monocrystal.
In the ZnO vapor deposition material of this aspect, the porous sintered body containing ZnO as a major component (hereinafter, simply referred to as porous ZnO sintered body) contains the first additive element and the second additive element at a specific ratio, so a ZnO film having high conductivity like an ITO film can be obtained by using the ZnO vapor deposition material. Specifically, the first additive element is one or more elements selected from the group consisting of Pr, Nd, Pm, and Sm, and the total content of the first additive element and the second additive element is in a range of 0.2 to 15% by mass, so excellent effects in terms of conduction properties and spectroscopic properties are obtained.
In the ZnO vapor deposition material of this aspect, since the porous ZnO sintered body has a porosity of 3 to 50%, the specific surface area inside the vapor deposition material is large, and the evaporation speed of the vapor deposition material can be increased. Specifically, the evaporation speed can be 1.1 to 2 times higher than the conventional ZnO vapor deposition material.
In the ZnO vapor deposition material of this aspect, since the porous ZnO sintered body has pores having an average pore diameter of 0.1 to 500 μm, the evaporation speed can be increased. The porous ZnO sintered body is a sintered body of grains having an average crystal grain size of 1 to 500 μm, so the specific surface area inside the vapor deposition material increases, thereby increasing the evaporation speed of the vapor deposition material. The formed ZnO film has excellent film characteristics.
In the ZnO vapor deposition material of this aspect, the porous ZnO sintered body is polycrystal or monocrystal, and contains a predetermined amount of the two elements the first additive element and Al at a specific ratio, so a ZnO film having high conductivity like an ITO film can be obtained.
Another aspect of the present invention provides a process for producing a ZnO vapor deposition material having the following configuration.
[G6] A process for producing a ZnO vapor deposition material, the process including the steps of (I) mixing ZnO powder having a purity equal to or greater than 98%, an oxide powder of a first additive element in such an amount that the content of the first additive element in the ZnO vapor deposition material is in a range of 0.1 to 14.9% by mass, an oxide powder of a second additive element in such an amount that the content of the second additive element in the ZnO vapor deposition material is in a range of 0.1 to 10% by mass, a binder, and an organic solvent to prepare a slurry with a concentration of 30 to 75% by mass, (II) blowing gas into the slurry to obtain a gas-containing slurry, (III) spray-drying the gas-containing slurry to obtain a porous granulation powder having an average grain size of 50 to 300 μm, (IV) molding the porous granulation powder to obtain a porous molded body, and (V) sintering the porous molded body at a predetermined temperature to obtain a porous ZnO sintered body.
[G7] The process for producing a ZnO vapor deposition material of [G6] including, instead of the steps (II) and (III), the steps of (II-2) mixing a foaming agent in raw powder or slurry to obtain a foaming agent-containing slurry, and (III-2) foaming the foaming agent-containing slurry while spray-drying the foaming agent-containing slurry to obtain a porous granulation powder having an average grain size of 50 to 300 μm.
[G8] The process for producing a ZnO vapor deposition material of [G6] including, instead of the steps (II) to (V), the steps of (II-3) mixing an additive, which will be volatized and dissolved at the time of calcination, in raw powder or slurry to obtain an additive-containing slurry, (III-3) spray-drying the additive-containing slurry to obtain a granulation powder having an average grain size of 50 to 300 μm, (IV-3) molding the granulation powder to obtain a molded body, and (V-3) sintering the molded body while volatizing and dissolving the additive to obtain a porous ZnO sintered body.
[G9] The process for producing a ZnO vapor deposition material of any one of [G6] to [G8], wherein in the step (I), ZnO powder having a purity equal to or greater than 98%, an average grain size of 10 to 500 μm, and a grain size distribution within a range of ±10% of the average grain size, and oxide powder of the first additive element and the second additive element are used, and the powders, a binder, and an organic solvent are mixed to prepare a slurry with a concentration of 30 to 75% by mass.
In the process of this aspect, by the steps (I) to (V), a ZnO vapor deposition material having a large amount of evaporation, and having excellent film formation properties and denseness can be relatively easily produced. In particular, by the step (II) blowing gas into the slurry to obtain a gas-containing slurry, or (II-2) mixing a foaming agent in raw powder or slurry to obtain a foaming agent-containing slurry, a ZnO vapor deposition material having pores with predetermined porosity and average pore diameter, and an average crystal grain size can be relatively easily produced.
In the process of this aspect, since the powder having an average grain size of 10 to 500 μm and a grain size distribution within a range of ±10% of the average grain size is used, fine grains do not substantially enter between grains, and thus a porous molded body having a porosity of 3 to 50% can be easily obtained.
The present invention provides the following ZnO film and production of the same.
[G10] A ZnO film which is formed using the ZnO vapor deposition material described in any one of [G1] to [G5], or a ZnO vapor deposition material produced by the process described in any one of [G6] to [G9].
[G11] A ZnO film which is formed by an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method with the ZnO vapor deposition material described in any one of [G1] to [G5], or a ZnO vapor deposition material produced by the process described in any one of [G6] to [G9] as a target material.
[G12] A process for forming a ZnO film by an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method with the ZnO vapor deposition material described in any one of [G1] to [G5], or a ZnO vapor deposition material produced by the process described in any one of [G6] to [G9] as a target material.
The ZnO vapor deposition material of this aspect can be widely used in a vacuum deposition method, such as an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method. By using the ZnO vapor deposition material of this aspect, for example, when a film is formed at the same speed of film formation as the related art by an electron beam deposition method, the filament replacement frequency can be reduced, and the speed of film formation can be increased, thereby shortening the production time.
The ZnO vapor deposition material of this aspect contains the first additive element and the second additive element, the first additive element is one or more elements selected from the group consisting of Pr, Nd, Pm, and Sm, and the second additive element is one or more elements selected from the group consisting of B, Al, Ga, and Sc, so crystals distorted by the first additive element having an ion radius greater than Zn are recovered and aligned by adding B, Al, or Ga, which is the second additive element having an ion radius smaller than the first additive element, or Sc having high reactivity is added to form a film having a regulated crystal structure. Thus, a ZnO film having high permeability is formed, such that a ZnO film having excellent denseness and high durability can be formed. A film having excellent moisture resistance and gas and vapor barrier properties can be obtained.
The ZnO vapor deposition material of this aspect has porosity within a predetermined range, and preferably, pores have an average pore diameter within a specific range, and grains have an average crystal grain size within a predetermined range, so the specific surface area inside the vapor deposition material increases, thereby increasing the evaporation speed. Thus, a ZnO film having good film formation efficiency can be formed. A ZnO film formed of the ZnO vapor deposition material of this aspect is dense, and has high conductivity and excellent durability.
Another aspect of the present invention has the following configuration.
[H1] A ZnO vapor deposition material for formation of a transparent conductive film which is composed of a ZnO sintered body having a ZnO purity equal to or greater than 98%, wherein the sintered body contains one or more additive elements selected from the group consisting of Y, La, Sc, Ce, Pr, Nd, Pm, and Sm, and the sintered body is a porous sintered body having a porosity of 3 to 50%.
[H2] The ZnO vapor deposition material described in [H1], wherein the content of the additive elements in the ZnO sintered body is in a range of 2 to 20% by mass.
[H3] The ZnO vapor deposition material described in [H1] or [H2], wherein the porous ZnO sintered body has pores having an average pore diameter of 0.1 to 500 μm.
[H4] The ZnO vapor deposition material described in any one of [H1] to [H3], wherein the porous ZnO sintered body is a sintered body of grains having an average crystal grain size of 1 to 500 μm.
[H5] The ZnO vapor deposition material described in any one of [H1] to [H4], wherein the porous ZnO sintered body is polycrystal or monocrystal.
The ZnO vapor deposition material of this aspect is composed of a ZnO sintered body having a ZnO purity equal to or greater than 98%, and the sintered body contains one or more additive elements selected from the group consisting of Y, La, Sc, Ce, Pr, Nd, Pm, and Sm, so a ZnO film having good conductivity over a wide temperature range can be obtained by using the ZnO vapor deposition material.
In the ZnO vapor deposition material of this aspect, since the porous ZnO sintered body has a porosity of 3 to 50%, the specific surface area inside the vapor deposition material is large, and the evaporation speed of the vapor deposition material can be increased. Specifically, the evaporation speed can be 1.1 to 2 times higher than the conventional ZnO vapor deposition material.
In the ZnO vapor deposition material of this aspect, since the porous ZnO sintered body has pores having an average pore diameter of 0.1 to 500 μm, the evaporation speed can be increased. The porous ZnO sintered body is a sintered body of grains having an average crystal grain size of 1 to 500 μm, so the specific surface area inside the vapor deposition material increases, thereby increasing the evaporation speed of the vapor deposition material. The formed ZnO film has excellent film characteristics.
In the ZnO vapor deposition material of this aspect, the porous ZnO sintered body is polycrystal or monocrystal, and contains a predetermined amount of the two elements the first additive element and Al at a specific ratio, so a ZnO film having high conductivity like an ITO film can be obtained.
Another aspect of the present invention provides a process for producing a ZnO vapor deposition material having the following configuration.
[H6] A process for producing a ZnO vapor deposition material, the process including the steps of (I) mixing ZnO powder having a purity equal to or greater than 98%, an oxide powder of additive elements, a binder, and an organic solvent to prepare a slurry with a concentration of 30 to 75% by mass, (II) blowing gas into the slurry to obtain a gas-containing slurry, (III) spray-drying the gas-containing slurry to obtain a porous granulation powder having an average grain size of 50 to 300 μm, (IV) molding the porous granulation powder to obtain a porous molded body, and (V) sintering the porous molded body at a predetermined temperature to obtain a porous ZnO sintered body.
[H7] The process for producing a ZnO vapor deposition material of [H6] including, instead of the steps (II) and (III), the steps of (II-2) mixing a foaming agent in raw powder or slurry to obtain a foaming agent-containing slurry, and (III-2) foaming the foaming agent-containing slurry while spray-drying the foaming agent-containing slurry to obtain a porous granulation powder having an average grain size of 50 to 300 μm.
[H8] The process for producing a ZnO vapor deposition material of [H6] including, instead of the steps (II) to (V), the steps of (II-3) mixing an additive, which will be volatized and dissolved at the time of calcination, in raw powder or slurry to obtain an additive-containing slurry, (III-3) spray-drying the additive-containing slurry to obtain a granulation powder having an average grain size of 50 to 300 μm, (IV-3) molding the granulation powder to obtain a molded body, and (V-3) sintering the molded body while volatizing and dissolving the additive to obtain a porous ZnO sintered body.
[H9] The process for producing a ZnO vapor deposition material of any one of [H6] to [H8], wherein in the step (I), ZnO powder having a purity equal to or greater than 98%, an average grain size of 10 to 500 μm, and a grain size distribution within a range of ±10% of the average grain size, and oxide powder of the additive element are used, and the powders, a binder, and an organic solvent are mixed to prepare a slurry with a concentration of 30 to 75% by mass.
In the process of this aspect, by the steps (I) to (V), a ZnO vapor deposition material having a large amount of evaporation, and having excellent film formation properties and denseness can be relatively easily produced. In particular, by the step (II) blowing gas into the slurry to obtain a gas-containing slurry, or (II-2) mixing a foaming agent in raw powder or slurry to obtain a foaming agent-containing slurry, a ZnO vapor deposition material having pores with predetermined porosity and average pore diameter, and an average crystal grain size can be relatively easily produced.
In the process of this aspect, since the powder having an average grain size of 10 to 500 μm and a grain size distribution within a range of ±10% of the average grain size is used, fine grains do not substantially enter between grains, and thus a porous molded body having a porosity of 3 to 50% can be easily obtained.
The present invention provides the following ZnO film and production of the same.
[H10] A ZnO film which is formed using the ZnO vapor deposition material described in any one of [H1] to [H5], or a ZnO vapor deposition material produced by the process described in any one of [H6] to [H9].
[H11] A ZnO film which is formed by an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method with the ZnO vapor deposition material described in any one of [H1] to [H5], or a ZnO vapor deposition material produced by the process described in any one of [H6] to [H9] as a target material.
[H12] A process for forming a ZnO film by an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method with the ZnO vapor deposition material described in any one of [H1] to [H5], or a ZnO vapor deposition material produced by the process described in any one of [H6] to [H9] as a target material.
The ZnO vapor deposition material of this aspect can be widely used in a vacuum deposition method, such as an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method. By using the ZnO vapor deposition material of this aspect, for example, when a film is formed at the same speed of film formation as the related art by an electron beam deposition method, the filament replacement frequency can be reduced, and the speed of film formation can be increased, thereby shortening the production time.
The ZnO vapor deposition material of this aspect is composed of the ZnO sintered body having a ZnO purity equal to or greater than 98%, and the sintered body contains one or more additive elements selected from the group consisting of Y, La, Sc, Ce, Pr, Nd, Pm, and Sm, so a ZnO film having good conductivity over a wide temperature range can be obtained by using the ZnO vapor deposition material.
In the ZnO vapor deposition material of this aspect, since the ZnO sintered body contains the additive element(s), regardless of polycrystal or monocrystal, a ZnO film having good conductivity over a wide temperature range can be obtained. Further, a film having excellent moisture resistance, and gas and vapor barrier properties can be obtained.
The ZnO vapor deposition material of this aspect has porosity within a predetermined range, and preferably, pores have an average pore diameter within a specific range, and grains have an average crystal grain size within a predetermined range, so the specific surface area inside the vapor deposition material increases, thereby increasing the evaporation speed. Thus, a ZnO film having good film formation efficiency can be formed. A ZnO film formed of the ZnO vapor deposition material of this aspect is dense, and has high conductivity and excellent durability.
Advantageous Effects
According to the present invention, a ZnO film having high permeability, excellent denseness, and high durability can be formed. Further, a film having excellent moisture resistance, and gas and vapor barrier properties can be obtained.


BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, an aspect of the present invention will be described specifically.
[ZnO Vapor Deposition Material]
A ZnO vapor deposition material of this aspect is a ZnO vapor deposition material for formation of a transparent conductive film which is composed mainly of a porous ZnO sintered body containing Ce and Al, wherein the Ce content is higher than the Al content, the Ce content is in a range of 0.1 to 14.9% by mass, the Al content is in a range of 0.1 to 10% by mass, and the sintered body has a porosity of 3 to 50%.
The inventors have investigated in detail the effect on conductivity due to additive species and its content in a ZnO vapor deposition material and a ZnO film formed by using the vapor deposition material, and have found that there is a significant level of influence due to the content ratio of the two elements of Ce and Al as the additive elements in the porous ZnO sintered body. Based on the above-described knowledge, the ZnO vapor deposition material according to this aspect contains ZnO as a major component, and also contains both elements of Ce and Al, such that excess electrons contributing to conduction are developed in large amounts and maintained, thereby forming a ZnO film having high conductivity.
As the ratio of the two elements of Ce and Al in the porous ZnO sintered body increases within a predetermined range, the conductivity of the ZnO film becomes better, and if the ratio is outside the range, the conductivity adversely deteriorates. Specifically, the Ce content in the ZnO vapor deposition material is appropriately in a range of 0.1 to 14.9% by mass, and preferably, in a range of 3 to 6% by mass. If the Ce content is lower than the lower limit value, 0.1% by mass, the conductivity is significantly lowered. If the Ce content exceeds the upper limit value, 14.9% by mass, the permeability is significantly lowered.
The Al content in the ZnO vapor deposition material is appropriately in a range of 0.1 to 10% by mass, and preferably, in a range of 1 to 3% by mass. If the Al content is lower than the lower limit value, 0.1% by mass, the conductivity is significantly lowered. If the Al content exceeds the upper limit value, 10% by mass, compositional shift at the time of deposition occurs.
The ZnO vapor deposition material of this aspect contains a larger amount of Ce than Al, such that a dense crystal structure is maintained. If the Ce content is lower than the Al content, the conductivity and permeability are lowered. The total content of Ce and Al is preferably in a range of 0.2 to 15% by mass. If the total content of Ce and Al exceeds this range, the specific resistance and permeability of the ZnO vapor deposition material are significantly lowered.
When a very small amount of Ce and Al is contained in the ZnO vapor deposition material, Ce and Al do not exist as granular precipitates in grain boundaries or grains in the ZnO matrix but are uniformly dispersed in the ZnO vapor deposition material. It is considered that, in the ZnO vapor deposition material, Ce is present as an oxide, such as CeO2 or Ce2O3, and Al is present as Al2O3.
The ZnO vapor deposition material of this aspect contains Ce, which is a trivalent or quadrivalent rare earth element, as an additive element, and Ce causes excess carrier electrons to be generated with respect to divalent Zn, such that high conductivity can be ensured. When a rare earth element is added to the ZnO vapor deposition material, compositional shift at the time of deposition is unlikely to occur, and a desired composition ratio can be maintained when a film is formed.
According to the ZnO vapor deposition material of this aspect, the conductivity is obtained by oxygen defect as well as compulsive injection of carrier electrons. Usually, oxygen gas is introduced in a vapor deposition method, but generally oxygen in the film composition is insufficient. At the time of transparent conductive film formation, a technique is conventionally used in which resistance is lowered by generating oxygen defect. However, in the case of adding a rare earth element, it is easy to control because the element is excellent in evaporation performance. In addition to this advantage, since the ZnO vapor deposition material of this aspect contains Al as an additive element, high conductivity like ITO can be obtained.
The ZnO vapor deposition material of this aspect is composed of a porous ZnO sintered body having a porosity of 3 to 50%. The porosity of the sintered body is appropriately in a range of 3 to 50%, preferably in a range of 5 to 30%, more preferably in a range of 10 to 30%, and still more preferably in a range of 20 to 30%. If the porosity is smaller than 3%, it is not preferable since, at the time of film formation by an electron beam deposition method or an ion plating method, the evaporation speed of the vapor deposition material does not increase, and as a result, the speed of film formation decreases, which results in an increase in manufacturing costs. If the porosity exceeds 50%, the strength of the porous sintered body is lowered, and it is difficult to obtain sufficient mechanical strength. If the porosity is equal to or greater than 10%, the evaporation speed can be improved. Further, if the porosity is equal to or greater than 20%, a vapor deposition material having an evaporation speed about 2.0 times higher than the conventional ZnO vapor deposition material can be obtained.
In the porous ZnO sintered body of this aspect, the pores preferably have an average pore diameter of 0.1 to 500 μm. If the average pore diameter of the pores is within the above-described range, the evaporation speed can be further increased. If the pore diameter is smaller than 0.1 μm, there is no merit in the pores. If the pore diameter exceeds 500 μm, it is not preferable because the strength of the sintered body is lowered, which causes damages due to EB (electron beam) irradiation, that is, splash.
The term “pore diameter” (the inner diameter of the pore) refers to, for example, the maximum value of the internal dimensions in the pores when the sectional portion of the vapor deposition material is observed by observation means, such as SEM or the like. As the evaluation method of the pores, measurement of porosity by a substitution method, measurement of porosity by microscopy, measurement of surface area and micropore distribution by gas absorption, measurement of surface area and micropore distribution by a mercury intrusion method, measurement of surface area by a gas permeation method, or measurement of micropore distribution by an X-ray small-angle scattering method may be used.
The pores are preferably rounded, and in terms of improvement in the evaporation speed, micropores are preferably formed at the surface of the pores. For the evaluation method of the pores, the surface area is preferably in a range of 5 to 40 m2/g, and at least one peak of the micropore distribution is present within a range of 1 to 100 μm. Portions (frame portion) other than the pores are preferably substantially sintered. For example, the frame portion of the porous sintered body preferably has a density equal to or greater than 98%.
In the porous ZnO sintered body of this aspect, it is preferable that grains preferably have an average crystal grain size of 1 to 500 μm, and rounded pores of about 0.1 to 500 μm are provided in the sintered body. The porous ZnO sintered body has a fine crystal structure in which the average crystal grain size is within the above-described range, and the occurrence of defects in the boundary of crystal grains can be reduced. Thus, the formed ZnO film has excellent film characteristics, such as ZnO film density, thickness distribution, refractive index, sputtering resistance, discharge characteristics (discharge voltage, discharge responsiveness, and the like), insulation characteristics, and the like. If the average crystal grain size is smaller than 1 μm, the speed of film formation is lowered. If the average crystal grain size exceeds 500 μm, the deposition rate of the additive element is not uniform. The average crystal grain size is preferably in a range of 5 to 40 μm, and more preferably, in a range of 10 to 30 μm.
The ZnO vapor deposition material of this aspect is preferably molded in the form of disc-like or circular pellets. When the vapor deposition material has a circular shape, the diameter of the vapor deposition material is appropriately in a range of 5 to 30 mm, and preferably, in a range of 5 to 15 mm. This is because, if the diameter is excessively small and smaller than 5 mm, splash occurs, and if the diameter exceeds 30 mm, it is difficult to handle the vapor deposition material in an actual production process. When the vapor deposition material is disc-like, the diameter of the vapor deposition material is appropriately in a range of 5 to 20 mm, and preferably, in a range of 5 to 10 mm. The height of the vapor deposition material is in a range of 1 to 10 mm, and preferably, in a range of 2 to 5 mm. This is because, if the diameter is excessively small and smaller than 5 mm or the height is excessively small and smaller than 1 mm, splash occurs, and if the diameter exceeds 30 mm or the height exceeds 10 mm, it is difficult to handle the vapor deposition material in an actual production process.
Hereinafter, a process for producing a ZnO vapor deposition material according to this aspect will be described.
[Production Process]
The ZnO vapor deposition material according to this aspect can be produced by mixing ZnO powder having a purity equal to or greater than 98%, CeO2 powder in such an amount that the Ce content in the ZnO vapor deposition material is in a range of 0.1 to 14.9% by mass, Al2O3 powder in such an amount that the Al content in the ZnO vapor deposition material is in a range of 0.1 to 10% by mass, a binder, and an organic solvent to prepare a slurry with a concentration of 30 to 75% by mass, spray-drying the slurry to obtain a granulation powder having an average grain size of 50 to 300 μm, molding the granulation powder to obtain a porous molded body, and sintering the molded body at a predetermined temperature to obtain a porous ZnO sintered body.
The ZnO powder preferably has purity equal to or greater than 98%, and more preferably, equal to or greater than 98.4%. If the ZnO powder has purity equal to or greater than 98%, reduction of conductivity by the effect of impurities can be suppressed. The average grain size of the ZnO powder is in a range of 0.1 to 10 μm. When the average grain size of the ZnO powder is smaller than 0.1 μm, the powder is excessively fine and aggregated, so there is a tendency that the handling of the powder becomes worse, and it is difficult to prepare a high-concentration slurry. When the average grain size exceeds 10 μm, there is a tendency that it is difficult to control the micro-structure, and a dense pellet is hard to obtain. If the average grain size of the ZnO powder is adjusted to the above-described range, a desired sintered body is also obtained without using a sintering auxiliary agent.
With regard to the CeO2 powder, considering the prevention of maldistribution of the Ce powder, reactivity with the ZnO matrix, and the purity of the Ce compound, it is preferable to add cerium oxide grains whose primary grain size is of a nanometer scale. The Al2O3 powder preferably has an average grain size of 0.01 to 1 μm, and still more preferably, the average grain size is in a range of 0.05 to 0.5 μm. If the Al2O3 powder having this average grain size is used, it is beneficial in terms of the uniform dispersion of the CeO2 powder.
For a binder, polyethylene glycol, polyvinyl butyral, or the like may be used. It is preferable to add the binder at 0.2 to 2.5% by mass. For an organic solvent, ethanol, propanol, or the like may be used.
The raw powder, the binder, and the organic solvent are mixed to prepare a slurry with a concentration of 30 to 75% by mass, and preferably, 40 to 65% by mass. If the slurry concentration exceeds 75% by mass, since the slurry is a non-aqueous system, stable granulation is difficult. If the slurry concentration is less than 30% by mass, it is difficult to obtain a dense ZnO sintered body having a uniform composition. If the slurry concentration is adjusted within the above-described range, the viscosity of the slurry is in a range of 200 to 1000 cps. Therefore, powder granulation using a spray drier can be performed stably. Further, the density of a molded body increases, such that a dense sintered body can be obtained.
Wet blending of raw powder, a binder, and an organic solvent, and in particular, wet blending of raw powder and an organic solvent as a dispersion medium is preferably performed by a wet ball mill or a stirring mill. In the case of using a ZrO2 ball in the wet ball mill, wet blending is preferably performed using a large number of ZrO2 balls having a diameter of 5 to 10 mm for 8 to 24 hours, and preferably, for 20 to 24 hours. If the diameter of the ZrO2 ball is smaller than 5 mm, blending may be insufficient. If the diameter of the ZrO2 ball exceeds 10 mm, impurities are increased. Even though the blending time is long, up to 24 hours, impurities are hardly generated due to milling. On the other hand, when a resin ball with a metal support is used in the wet ball mill, a ball having a diameter of 10 to 15 mm is preferably used.
In the stirring mill, wet blending is preferably performed using a ZrO2 ball having a diameter of 1 to 3 mm for 0.5 to 1 hour. If the diameter of the ZrO2 ball is smaller than 1 mm, blending is insufficient. If the diameter exceeds 3 mm, impurities are increased. If the blending time exceeds 1 hour, while raw materials are mixed, milling leads to the generation of impurities. Sufficient blending can be done within 1 hour. Blending/granulation of powder and additives may be performed by a general tumbling granulation method. In this case, it is not necessary to perform a separation operation from the balls or the like after the process, and thus the process is simplified.
In the production process of this aspect, as a first step for obtaining a porous sintered body, gas is blown and mixed into the slurry to prepare a gas-containing slurry. Gas blowing and mixing is preferably performed by blowing using a mechanical pump, gas pressure, or the like. As the gas, air, an insoluble gas, a non-aqueous gas, or the like may be used.
The gas-containing slurry is spray-dried. The spray drying is preferably performed at 150 to 250° C. for 3 hours by using a spray drier. Since gas is blown into the slurry, the granulation powder obtained by spray-drying the slurry is porous. Through the spray drying, a porous granulation powder having an average grain size of 50 to 300 μm can be obtained.
In the production process of this aspect, as a second step for obtaining a porous sintered body, a slurry is prepared in which a foaming agent is mixed. For the foaming agent, an organic foaming agent or an inorganic foaming agent may be used. For the organic foaming agent, azodicarboxylamide, dinitrosobenta methylene tetramine, or the like is used, and for the inorganic foaming agent, carbonate or the like is used. The foaming agent may be mixed with ZnO powder, CeO2 powder, and Al2O3 powder, or may be added upon slurry preparation.
The foaming agent-containing slurry is spray-dried. The spray drying is preferably performed at 150 to 250° C. for 3 hours by using a spray drier. The foaming agent contained in the slurry is foamed and dissolved upon this spray drying, such that resultant granulation powder is made porous. Through the spray drying, a porous granulation powder having an average grain size of 50 to 300 μm can be obtained.
In the production process of this aspect, as a third step for obtaining a porous sintered body, a slurry is prepared in which an additive, which will be volatized and dissolved upon sintering, is mixed. Examples of the additive include butyral capable of being dissolved in a solvent, and a cellulose-based additive, a polyvinyl-based additive, a polyester-based additive, a polyethylene-based additive, and the like capable of being dissolved in an alcohol-based solvent. Examples of the additive which will not be dissolved in the alcohol-based solvent include a starch-based additive and a polystyrene-based additive having an average grain size of about several μm to 500 μm. It is preferable that butyral is mixed in the slurry at about 20% by mass, or starch is mixed in the slurry at about 20% by mass.
If the slurry contains the additive, the additive is volatized and dissolved upon sintering to form pores, thereby obtaining a porous sintered body. The diameter and shape of the pores can be controlled by adjusting the kind and amount of the additive. For example, when a butyral-based additive is used, pores having a pore diameter of 0.1 μm to 10 μm order can be formed. When starch is used, pores having the same pore diameter as the grain size of starch and the same shape as starch can be formed. Thus, when starch is used, the pore diameter and shape of the pores can be more easily controlled.
Specifically, in the case of the ZnO vapor deposition material of this aspect, a vapor deposition material using a butyral-based additive can obtain a deposition speed about 1.3 times higher than the evaporation speed of the conventional ZnO vapor deposition material having relative density equal to or greater than about 98%, and a vapor deposition material using starch having an average grain size of 0.1 to 500 μm can obtain an evaporation speed about two times higher than the evaporation speed of the conventional ZnO vapor deposition material having relative density equal to or greater than about 98%. Therefore, a high speed of film formation can be obtained.
In the production process of this aspect, as a fourth step for obtaining a porous sintered body, a slurry using ZnO powder having a grain size distribution within a predetermined range is prepared. Specifically, ZnO powder having an average grain size of 10 to 500 μm and a grain size distribution within a range of ±10% of the average grain size is used. If the grain size distribution of ZnO powder is outside the range of ±10% of the average grain size, the porosity is lowered. More preferably, the grain size distribution is within a range of ±5% of the average grain size. The preferred grain size of CeO2 powder and Al2O3 powder is significantly smaller than that of ZnO powder, and the usage is smaller than that of ZnO powder, so CeO2 powder and Al2O3 powder may be outside the limitation of the grain size distribution.
The slurry using ZnO powder with a controlled grain size distribution is spray-dried. The spray drying is preferably performed at 150 to 250° C. for 3 hours by using a spray drier. In the slurry to be spray-dried, ZnO powder having an average grain size of 10 to 500 μm and a grain size distribution within a range of ±10% of the average grain size is used, and no fine ZnO powder is substantially contained. Thus, there are no cases where fine ZnO grains fill the gaps between ZnO grains, so the gaps between ZnO grains remain as pores, and granulation powder becomes porous. Through the spray drying, a porous granulation powder having an average grain size of 50 to 300 μm can be obtained.
After the slurry is spray-dried to obtain a granulation powder having an average grain size of 50 to 300 the granulation powder is molded under a predetermined pressure. If the average grain size of the granulation powder is smaller than 50 μm, moldability deteriorates, and if the average grain size is larger than 300 μm, the density of the molded body is lowered, and the strength is likely to be insufficient.
For a pressing molding device, a uniaxial press device, a cold isostatic press (CIP) molding device, or other devices may be used. The molding pressure is appropriately in a range of 100 to 2000 kgf/cm2 (9.8 to 196 MPa), and preferably, 100 to 1000 kgf/cm2 (9.8 to 98 MPa). Molding is performed under pressure within the above-described range, such that the density of the molded body can be increased, deformation after sintering can be suppressed, and postprocessing is not required.
Next, the molded body is sintered. Before sintering, the molded body is preferably degreased at a temperature of 350 to 620° C. Through this degreasing, spots on the molded body after sintering can be suppressed. The degreasing is preferably performed for a sufficient time.
Sintering is performed in an atmosphere of air, an inactive gas, a vacuum, or a reductive gas at a temperature equal to or higher than 1000° C., and preferably, at a temperature of 1200 to 1400° C. for 1 to 10 hours, and preferably, for 2 to 5 hours. The sintering is performed under air pressure, but in the case of pressure sintering, such as hot press (HP) sintering or hot isostatic press (HIP) sintering, the sintering is preferably performed in an atmosphere of inactive gas, vacuum, or reductive gas at a temperature equal to or higher than 1000° C. for 1 to 5 hours.
A ZnO film is formed on the surface of the substrate by a vacuum film formation method with a ZnO vapor deposition material composed of the resultant porous sintered body as a target material. As the vacuum film formation method suitable for forming a film using the ZnO vapor deposition material of this aspect, an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method may be used. A ZnO film of this aspect formed by the film formation method uses the ZnO vapor deposition material of this aspect, so the ZnO film has high conductivity with specific resistance of 3 to 5×10−4 Ω·cm and high permeability with visible light permeability equal to or greater than 90%, like ITO. Crystals distorted by Ce having an ion radius larger than Zn are recovered and aligned by adding Al having a small ion radius, such that the durability of the film is improved.
According to the production process of this aspect, in any of the first step of mixing gas in the slurry, the second step of preparing the foaming agent-containing slurry, the third step of preparing the slurry containing the additive which will be volatized and dissolved upon sintering, and the fourth step of preparing the slurry using ZnO powder having a grain size distribution within a predetermined range, the porosity, pore diameter, and pore shape can be easily controlled. Therefore, a vapor deposition material having optimum pores can be produced. As a result, even when a large number of pore states are required by the production conditions or the like, an optimum vapor deposition material can be provided to cope with the requirements.
The ZnO vapor deposition material of this aspect is composed mainly of a porous sintered body having a porosity of 5 to 30% and a pore diameter of 0.1 to 500 μm, so when a ZnO transparent conductive film is formed by an electron beam deposition method or an ion plating method using the ZnO vapor deposition material, the evaporation speed can be improved. That is, when film formation is performed with the same electron beam energy, the speed of film formation increases, and the operation time is shortened, thereby increasing the number of products for a predetermined time. Further, when film formation is performed at the same film formation speed, electron beam energy is reduced, and the replacement timing of a filament of an electron gun or the like is delayed, such that the number of times of maintenance is reduced and productivity is improved. As a result, manufacturing costs can be reduced.
Next, another aspect of the present invention will be described.
[ZnO Vapor Deposition Material]
A ZnO vapor deposition material of this aspect is a ZnO vapor deposition material for formation of a transparent conductive film which is composed mainly of a porous ZnO sintered body containing Ce and Ga, wherein the Ce content is higher than the Ga content, the Ce content is in a range of 0.1 to 14.9% by mass, the Ga content is in a range of 0.1 to 10% by mass, and the sintered body has a porosity of 3 to 50%.
The inventors have investigated in detail the effect on conductivity due to additive species and its content in a ZnO vapor deposition material and a ZnO film formed by using the vapor deposition material, and have found that there is a significant level of influence due to the content ratio of the two elements of Ce and Ga as the additive elements in the porous ZnO sintered body. Based on the above-described knowledge, the ZnO vapor deposition material according to this aspect contains ZnO as a major component, and also contains both elements of Ce and Ga, such that excess electrons contributing to conduction are developed in large amounts and maintained, thereby forming a ZnO film having high conductivity.
As the ratio of the two elements of Ce and Ga in the porous ZnO sintered body increases within a predetermined range, the conductivity of the ZnO film becomes better, and if the ratio is outside the range, the conductivity adversely deteriorates. Specifically, the Ce content in the ZnO vapor deposition material is appropriately in a range of 0.1 to 14.9% by mass, and preferably, in a range of 3 to 6% by mass. If the Ce content is lower than the lower limit value, 0.1% by mass, the conductivity is significantly lowered. If the Ce content exceeds the upper limit value, 14.9% by mass, the permeability is significantly lowered.
The Ga content in the ZnO vapor deposition material is appropriately in a range of 0.1 to 10% by mass, and preferably, in a range of 1 to 3% by mass. If the Ga content is lower than the lower limit value, 0.1% by mass, the conductivity is significantly lowered. If the Ga content exceeds the upper limit value, 10% by mass, compositional shift at the time of deposition occurs.
The ZnO vapor deposition material of this aspect contains a larger amount of Ce than Ga, such that a dense crystal structure is maintained. If the Ce content is lower than the Ga content, the conductivity and permeability are lowered. The total content of Ce and Ga is preferably in a range of 0.2 to 15% by mass. If the total content of Ce and Ga exceeds this range, the specific resistance and permeability of the ZnO vapor deposition material are significantly lowered.
When a very small amount of Ce and Ga is contained in the ZnO vapor deposition material, Ce and Ga do not exist as granular precipitates in grain boundaries or grains in the ZnO matrix but are uniformly dispersed in the ZnO vapor deposition material. It is considered that, in the ZnO vapor deposition material, Ce is present as an oxide, such as CeO2 or Ce2O3, and Ga is present as Ga2O3.
The ZnO vapor deposition material of this aspect contains Ce, which is a trivalent or quadrivalent rare earth element, as an additive element, and Ce causes excess carrier electrons to be generated with respect to divalent Zn, such that high conductivity can be ensured. When a rare earth element is added to the ZnO vapor deposition material, compositional shift at the time of deposition is unlikely to occur, and a desired composition ratio can be maintained when a film is formed.
According to the ZnO vapor deposition material of this aspect, the conductivity is obtained by oxygen defect as well as compulsive injection of carrier electrons. Usually, oxygen gas is introduced in a vapor deposition method, but generally oxygen in the film composition is insufficient. At the time of transparent conductive film formation, a technique is conventionally used in which resistance is lowered by generating oxygen defect. However, in the case of adding a rare earth element, it is easy to control because the element is excellent in evaporation performance. In addition to this advantage, since the ZnO vapor deposition material of this aspect contains Ga as an additive element, high conductivity like ITO can be obtained.
The ZnO vapor deposition material of this aspect is composed of a porous ZnO sintered body having a porosity of 3 to 50%. The porosity of the sintered body is appropriately in a range of 3 to 50%, preferably in a range of 5 to 30%, more preferably in a range of 10 to 30%, and still more preferably in a range of 20 to 30%. If the porosity is smaller than 3%, it is not preferable since, at the time of film formation by an electron beam deposition method or an ion plating method, the evaporation speed of the vapor deposition material does not increase, and as a result, the speed of film formation decreases, which results in an increase in manufacturing costs. If the porosity exceeds 50%, the strength of the porous sintered body is lowered, and it is difficult to obtain sufficient mechanical strength. If the porosity is equal to or greater than 10%, the evaporation speed can be improved. Further, if the porosity is equal to or greater than 20%, a vapor deposition material having an evaporation speed about two times higher than the conventional ZnO vapor deposition material can be obtained.
In the porous ZnO sintered body of this aspect, the pores preferably have an average pore diameter of 0.1 to 500 μm. If the average pore diameter of the pores is within the above-described range, the evaporation speed can be further increased. If the pore diameter is smaller than 0.1 μm, there is no merit in the pores. If the pore diameter exceeds 500 μm, it is not preferable because the strength of the sintered body is lowered, which causes damages due to EB (electron beam) irradiation, that is, splash.
The term “pore diameter” (the inner diameter of the pore) refers to, for example, the maximum value of the internal dimensions in the pores when the sectional portion of the vapor deposition material is observed by observation means, such as SEM or the like. As the evaluation method of the pores, measurement of porosity by a substitution method, measurement of porosity by microscopy, measurement of surface area and micropore distribution by gas absorption, measurement of surface area and micropore distribution by a mercury intrusion method, measurement of surface area by a gas permeation method, or measurement of micropore distribution by an X-ray small-angle scattering method may be used.
The pores are preferably rounded, and in terms of improvement in the evaporation speed, micropores are preferably formed at the surface of the pores. For the evaluation method of the pores, the surface area is preferably in a range of 5 to 40 m2/g, and at least one peak of the micropore distribution is present within a range of 1 to 100 μm. Portions (frame portion) other than the pores are preferably substantially sintered. For example, the frame portion of the porous sintered body preferably has a density equal to or greater than 98%.
In the porous ZnO sintered body of this aspect, it is preferable that grains preferably have an average crystal grain size of 1 to 500 μm, and rounded pores of about 0.1 to 500 μm are provided in the sintered body. The porous ZnO sintered body has a fine crystal structure in which the average crystal grain size is within the above-described range, and the occurrence of defects in the boundary of crystal grains can be reduced. Thus, the formed ZnO film has excellent film characteristics, such as ZnO film density, thickness distribution, refractive index, sputtering resistance, discharge characteristics (discharge voltage, discharge responsiveness, and the like), insulation characteristics, and the like. If the average crystal grain size is smaller than 1 μm, the speed of film formation is lowered. If the average crystal grain size exceeds 500 μm, the deposition rate of the additive element is not uniform. The average crystal grain size is preferably in a range of 5 to 40 μm, and more preferably, in a range of 10 to 30 μm.
The ZnO vapor deposition material of this aspect is preferably molded in the form of disc-like or circular pellets. When the vapor deposition material has a circular shape, the diameter of the vapor deposition material is appropriately in a range of 5 to 30 mm, and preferably, in a range of 5 to 15 mm. This is because, if the diameter is excessively small and smaller than 5 mm, splash occurs, and if the diameter exceeds 30 mm, it is difficult to handle the vapor deposition material in an actual production process. When the vapor deposition material is disc-like, the diameter of the vapor deposition material is appropriately in a range of 5 to 20 mm, and preferably, in a range of 5 to 10 mm. The height of the vapor deposition material is in a range of 1 to 10 mm, and preferably, in a range of 2 to 5 mm. This is because, if the diameter is excessively small and smaller than 5 mm or the height is excessively small and smaller than 1 mm, splash occurs, and if the diameter exceeds 30 mm or the height exceeds 10 mm, it is difficult to handle the vapor deposition material in an actual production process.
Hereinafter, a process for producing a ZnO vapor deposition material according to this aspect will be described.
[Production Process]
The ZnO vapor deposition material according to this aspect can be produced by mixing ZnO powder having a purity equal to or greater than 98%, CeO2 powder in such an amount that the Ce content in the ZnO vapor deposition material is in a range of 0.1 to 14.9% by mass, Ga2O3 powder in such an amount that the Ga content in the ZnO vapor deposition material is in a range of 0.1 to 10% by mass, a binder, and an organic solvent to prepare a slurry with a concentration of 30 to 75% by mass, spray-drying the slurry to obtain a granulation powder having an average grain size of 50 to 300 μm, molding the granulation powder to obtain a porous molded body, and sintering the molded body at a predetermined temperature to obtain a porous ZnO sintered body.
The ZnO powder preferably has purity equal to or greater than 98%, more preferably, equal to or greater than 98.4%, and still more preferably, equal to or greater than 99%. If the ZnO powder has purity equal to or greater than 98%, reduction of conductivity by the effect of impurities can be suppressed. The average grain size of the ZnO powder is in a range of 0.1 to 10 μm. When the average grain size of the ZnO powder is smaller than 0.1 μm, the powder is excessively fine and aggregated, so there is a tendency that the handling of the powder becomes worse, and it is difficult to prepare a high-concentration slurry. When the average grain size exceeds 10 μm, there is a tendency that it is difficult to control the micro-structure, and a dense pellet is hard to obtain. If the average grain size of the ZnO powder is adjusted to the above-described range, a desired sintered body is also obtained without using a sintering auxiliary agent.
With regard to the CeO2 powder, considering the prevention of maldistribution of the Ce powder, reactivity with the ZnO matrix, and the purity of the Ce compound, it is preferable to add cerium oxide grains whose primary grain size is of a nanometer scale. The Ga2O3 powder preferably has an average grain size of 0.01 to 1 μm, and still more preferably, the average grain size is in a range of 0.05 to 0.5 μm. If the Ga2O3 powder having this average grain size is used, it is beneficial in terms of the uniform dispersion of the CeO2 powder.
For a binder, polyethylene glycol, polyvinyl butyral, or the like may be used. It is preferable to add the binder at 0.2 to 2.5% by mass. For an organic solvent, ethanol, propanol, or the like may be used.
The raw powder, the binder, and the organic solvent are mixed to prepare a slurry with a concentration of 30 to 75% by mass, and preferably, 40 to 65% by mass. If the slurry concentration exceeds 75% by mass, since the slurry is a non-aqueous system, stable granulation is difficult. If the slurry concentration is less than 30% by mass, it is difficult to obtain a dense ZnO sintered body having a uniform composition. If the slurry concentration is adjusted within the above-described range, the viscosity of the slurry is in a range of 200 to 1000 cps. Therefore, powder granulation using a spray drier can be performed stably. Further, the density of a molded body increases, such that a dense sintered body can be obtained.
Wet blending of raw powder, a binder, and an organic solvent, and in particular, wet blending of raw powder and an organic solvent as a dispersion medium is preferably performed by a wet ball mill or a stirring mill. In the case of using a ZrO2 ball in the wet ball mill, wet blending is preferably performed using a large number of ZrO2 balls having a diameter of 5 to 10 mm for 8 to 24 hours, and preferably, for 20 to 24 hours. If the diameter of the ZrO2 ball is smaller than 5 mm, blending may be insufficient. If the diameter of the ZrO2 ball exceeds 10 mm, impurities are increased. Even though the blending time is long, up to 24 hours, impurities are hardly generated due to milling. On the other hand, when a resin ball with a metal support is used in the wet ball mill, a ball having a diameter of 10 to 15 mm is preferably used.
In the stirring mill, wet blending is preferably performed using a ZrO2 ball having a diameter of 1 to 3 mm for 0.5 to 1 hour. If the diameter of the ZrO2 ball is smaller than 1 mm, blending is insufficient. If the diameter exceeds 3 mm, impurities are increased. If the blending time exceeds 1 hour, while raw materials are mixed, milling leads to the generation of impurities. Sufficient blending can be done within 1 hour. Blending/granulation of powder and additives may be performed by a general tumbling granulation method. In this case, it is not necessary to perform a separation operation from the balls or the like after the process, and thus the process is simplified.
In the production process of this aspect, as a first step for obtaining a porous sintered body, gas is blown and mixed into the slurry to prepare a gas-containing slurry. Gas blowing and mixing is preferably performed by blowing using a mechanical pump, gas pressure, or the like. As the gas, air, an insoluble gas, a non-aqueous gas, or the like may be used.
The gas-containing slurry is spray-dried. The spray drying is preferably performed at 150 to 250° C. for 3 hours by using a spray drier. Since gas is blown into the slurry, the granulation powder obtained by spray-drying the slurry is porous. Through the spray drying, a porous granulation powder having an average grain size of 50 to 300 μm can be obtained.
In the production process of this aspect, as a second step for obtaining a porous sintered body, a slurry is prepared in which a foaming agent is mixed. For the foaming agent, an organic foaming agent or an inorganic foaming agent may be used. For the organic foaming agent, azodicarboxylamide, dinitrosobenta methylene tetramine, or the like is used, and for the inorganic foaming agent, carbonate or the like is used. The foaming agent may be mixed with ZnO powder, CeO2 powder, and Ga2O3 powder, or may be added upon slurry preparation.
The foaming agent-containing slurry is spray-dried. The spray drying is preferably performed at 150 to 250° C. for 3 hours by using a spray drier. The foaming agent contained in the slurry is foamed and dissolved upon this spray drying, such that resultant granulation powder is made porous. Through the spray drying, a porous granulation powder having an average grain size of 50 to 300 μm can be obtained.
In the production process of this aspect, as a third step for obtaining a porous sintered body, a slurry is prepared in which an additive, which will be volatized and dissolved upon sintering, is mixed. Examples of the additive include butyral capable of being dissolved in a solvent, and a cellulose-based additive, a polyvinyl-based additive, a polyester-based additive, a polyethylene-based additive, and the like capable of being dissolved in an alcohol-based solvent. Examples of the additive which will not be dissolved in the alcohol-based solvent include a starch-based additive and a polystyrene-based additive having an average grain size of about several μm to 500 μm. It is preferable that butyral is mixed in the slurry at about 20% by mass, or starch is mixed in the slurry at about 20% by mass.
If the slurry contains the additive, the additive is volatized and dissolved upon sintering to form pores, thereby obtaining a porous sintered body. The diameter and shape of the pores can be controlled by adjusting the kind and amount of the additive. For example, when a butyral-based additive is used, pores having a pore diameter of 0.1 μm to 10 μm order can be formed. When starch is used, pores having the same pore diameter as the grain size of starch and the same shape as starch can be formed. Thus, when starch is used, the pore diameter and shape of the pores can be more easily controlled.
Specifically, in the case of the ZnO vapor deposition material of this aspect, a vapor deposition material using a butyral-based additive can obtain a deposition speed about 1.3 times higher than the evaporation speed of the conventional ZnO vapor deposition material having relative density equal to or greater than about 98%, and a vapor deposition material using starch having an average grain size of 0.1 to 500 μm can obtain an evaporation speed about two times higher than the evaporation speed of the conventional ZnO vapor deposition material having relative density equal to or greater than about 98%. Therefore, a high speed of film formation can be obtained.
In the production process of this aspect, as a fourth step for obtaining a porous sintered body, a slurry using ZnO powder having a grain size distribution within a predetermined range is prepared. Specifically, ZnO powder having an average grain size of 10 to 500 μm and a grain size distribution within a range of ±10% of the average grain size is used. If the grain size distribution of ZnO powder is outside the range of ±10% of the average grain size, the porosity is lowered. More preferably, the grain size distribution is within a range of ±5% of the average grain size. The preferred grain size of CeO2 powder and Ga2O3 powder is significantly smaller than that of ZnO powder, and the usage is smaller than that of ZnO powder, so CeO2 powder and Ga2O3 powder may be outside the limitation of the grain size distribution.
The slurry using ZnO powder with a controlled grain size distribution is spray-dried. The spray drying is preferably performed at 150 to 250° C. for 3 hours by using a spray drier. In the slurry to be spray-dried, ZnO powder having an average grain size of 10 to 500 μm and a grain size distribution within a range of ±10% of the average grain size is used, and no fine ZnO powder is substantially contained. Thus, there are no cases where fine ZnO grains fill the gaps between ZnO grains, so the gaps between ZnO grains remain as pores, and granulation powder becomes porous. Through the spray drying, a porous granulation powder having an average grain size of 50 to 300 μm can be obtained.
After the slurry is spray-dried to obtain a granulation powder having an average grain size of 50 to 300 μm, the granulation powder is molded under a predetermined pressure. If the average grain size of the granulation powder is smaller than 50 μm, moldability deteriorates, and if the average grain size is larger than 300 μm, the density of the molded body is lowered, and the strength is likely to be insufficient.
For a pressing molding device, a uniaxial press device, a cold isostatic press (CIP) molding device, or other devices may be used. The molding pressure is appropriately in a range of 100 to 2000 kgf/cm2 (9.8 to 196 MPa), and preferably, 100 to 1000 kgf/cm2 (9.8 to 98 MPa). Molding is performed under pressure within the above-described range, such that the density of the molded body can be increased, deformation after sintering can be suppressed, and postprocessing is not required.
Next, the molded body is sintered. Before sintering, the molded body is preferably degreased at a temperature of 350 to 620° C. Through this degreasing, spots on the molded body after sintering can be suppressed. The degreasing is preferably performed for a sufficient time.
Sintering is performed in an atmosphere of air, an inactive gas, a vacuum, or a reductive gas at a temperature equal to or higher than 1000° C., and preferably, at a temperature of 1200 to 1400° C. for 1 to 10 hours, and preferably, for 2 to 5 hours. The sintering is performed under air pressure, but in the case of pressure sintering, such as hot press (HP) sintering or hot isostatic press (HIP) sintering, the sintering is preferably performed in an atmosphere of inactive gas, vacuum, or reductive gas at a temperature equal to or higher than 1000° C. for 1 to 5 hours.
A ZnO film is formed on the surface of the substrate by a vacuum film formation method with a ZnO vapor deposition material composed of the resultant porous sintered body as a target material. As the vacuum film formation method suitable for forming a film using the ZnO vapor deposition material of this aspect, an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method may be used. A ZnO film of this aspect formed by the film formation method uses the ZnO vapor deposition material of this aspect, so the ZnO film has high conductivity with specific resistance of 3 to 5×10−4 Ω·cm and high permeability with visible light permeability equal to or greater than 90%, like ITO. Crystals distorted by Ce having an ion radius larger than Zn are recovered and aligned by adding Ga having a small ion radius, such that the durability of the film is improved.
According to the production process of this aspect, in any of the first step of mixing gas in the slurry, the second step of preparing the foaming agent-containing slurry, the third step of preparing the slurry containing the additive which will be volatized and dissolved upon sintering, and the fourth step of preparing the slurry using ZnO powder having a grain size distribution within a predetermined range, the porosity, pore diameter, and pore shape can be easily controlled. Therefore, a vapor deposition material having optimum pores can be produced. As a result, even when a large number of pore states are required by the production conditions or the like, an optimum vapor deposition material can be provided to cope with the requirements.
The ZnO vapor deposition material of this aspect is composed mainly of a porous sintered body having a porosity of 5 to 30% and a pore diameter of 0.1 to 500 μm, so when a ZnO transparent conductive film is formed by an electron beam deposition method or an ion plating method using the ZnO vapor deposition material, the evaporation speed can be improved. That is, when film formation is performed with the same electron beam energy, the speed of film formation increases, and the operation time is shortened, thereby increasing the number of products for a predetermined time. Further, when film formation is performed at the same film formation speed, electron beam energy is reduced, and the replacement timing of a filament of an electron gun or the like is delayed, such that the number of times of maintenance is reduced and productivity is improved. As a result, manufacturing costs can be reduced.
Next, another aspect of the present invention will be described.
[ZnO Vapor Deposition Material]
A ZnO vapor deposition material of this aspect is a ZnO vapor deposition material for formation of a transparent conductive film which is composed mainly of a porous ZnO sintered body containing Ce and Sc, wherein the Ce content is higher than the Sc content, the Ce content is in a range of 0.1 to 14.9% by mass, the Sc content is in a range of 0.1 to 10% by mass, and the sintered body has a porosity of 3 to 50%.
The inventors have investigated in detail the effect on conductivity due to additive species and its content in a ZnO vapor deposition material and a ZnO film formed by using the vapor deposition material, and have found that there is a significant level of influence due to the content ratio of the two elements of Ce and Sc as the additive elements in the porous ZnO sintered body. Based on the above-described knowledge, the ZnO vapor deposition material according to this aspect contains ZnO as a major component, and also contains both elements of Ce and Sc, such that excess electrons contributing to conduction are developed in large amounts and maintained, thereby forming a ZnO film having high conductivity.
As the ratio of the two elements of Ce and Sc in the porous ZnO sintered body increases within a predetermined range, the conductivity of the ZnO film becomes better, and if the ratio is outside the range, the conductivity adversely deteriorates. Specifically, the Ce content in the ZnO vapor deposition material is appropriately in a range of 0.1 to 14.9% by mass, and preferably, in a range of 3 to 6% by mass. If the Ce content is lower than the lower limit value, 0.1% by mass, the conductivity is significantly lowered. If the Ce content exceeds the upper limit value, 14.9% by mass, the permeability is significantly lowered.
The Sc content in the ZnO vapor deposition material is appropriately in a range of 0.1 to 10% by mass, and preferably, in a range of 1 to 3% by mass. If the Sc content is lower than the lower limit value, 0.1% by mass, the conductivity is significantly lowered. If the Sc content exceeds the upper limit value, 10% by mass, compositional shift at the time of deposition occurs.
The ZnO vapor deposition material of this aspect contains a larger amount of Ce than Sc, such that a dense crystal structure is maintained. If the Ce content is lower than the Sc content, the conductivity and permeability are lowered. The total content of Ce and Sc is preferably in a range of 0.2 to 15% by mass. If the total content of Ce and Sc exceeds this range, the specific resistance and permeability of the ZnO vapor deposition material are significantly lowered.
When a very small amount of Ce and Sc is contained in the ZnO vapor deposition material, Ce and Sc do not exist as granular precipitates in grain boundaries or grains in the ZnO matrix but are uniformly dispersed in the ZnO vapor deposition material. It is considered that, in the ZnO vapor deposition material, Ce is present as an oxide, such as CeO2 or Ce2O3, and Sc is present as Sc2O3.
The ZnO vapor deposition material of this aspect contains Ce, which is a trivalent or quadrivalent rare earth element, as an additive element, and Ce causes excess carrier electrons to be generated with respect to divalent Zn, such that high conductivity can be ensured. When a rare earth element is added to the ZnO vapor deposition material, compositional shift at the time of deposition is unlikely to occur, and a desired composition ratio can be maintained when a film is formed.
According to the ZnO vapor deposition material of this aspect, the conductivity is obtained by oxygen defect as well as compulsive injection of carrier electrons. Usually, oxygen gas is introduced in a vapor deposition method, but generally oxygen in the film composition is insufficient. At the time of transparent conductive film formation, a technique is conventionally used in which resistance is lowered by generating oxygen defect. However, in the case of adding a rare earth element, it is easy to control because the element is excellent in evaporation performance. In addition to this advantage, since the ZnO vapor deposition material of this aspect contains Sc as an additive element, high conductivity like ITO can be obtained.
The ZnO vapor deposition material of this aspect is composed of a porous ZnO sintered body having a porosity of 3 to 50%. The porosity of the sintered body is appropriately in a range of 3 to 50%, preferably in a range of 5 to 30%, more preferably in a range of 10 to 30%, and still more preferably in a range of 20 to 30%. If the porosity is smaller than 3%, it is not preferable since, at the time of film formation by an electron beam deposition method or an ion plating method, the evaporation speed of the vapor deposition material does not increase, and as a result, the speed of film formation decreases, which results in an increase in manufacturing costs. If the porosity exceeds 50%, the strength of the porous sintered body is lowered, and it is difficult to obtain sufficient mechanical strength. If the porosity is equal to or greater than 10%, the evaporation speed can be improved. Further, if the porosity is equal to or greater than 20%, a vapor deposition material having an evaporation speed about two times higher than the conventional ZnO vapor deposition material can be obtained.
In the porous ZnO sintered body of this aspect, the pores preferably have an average pore diameter of 0.1 to 500 μm. If the average pore diameter of the pores is within the above-described range, the evaporation speed can be further increased. If the pore diameter is smaller than 0.1 μm, there is no merit in the pores. If the pore diameter exceeds 500 μm, it is not preferable because the strength of the sintered body is lowered, which causes damages due to EB (electron beam) irradiation, that is, splash.
The term “pore diameter” (the inner diameter of the pore) refers to, for example, the maximum value of the internal dimensions in the pores when the sectional portion of the vapor deposition material is observed by observation means, such as SEM or the like. As the evaluation method of the pores, measurement of porosity by a substitution method, measurement of porosity by microscopy, measurement of surface area and micropore distribution by gas absorption, measurement of surface area and micropore distribution by a mercury intrusion method, measurement of surface area by a gas permeation method, or measurement of micropore distribution by an X-ray small-angle scattering method may be used.
The pores are preferably rounded, and in terms of improvement in the evaporation speed, micropores are preferably formed at the surface of the pores. For the evaluation method of the pores, the surface area is preferably in a range of 5 to 40 m2/g, and at least one peak of the micropore distribution is present within a range of 1 to 100 μm. Portions (frame portion) other than the pores are preferably substantially sintered. For example, the frame portion of the porous sintered body preferably has a density equal to or greater than 98%.
In the porous ZnO sintered body of this aspect, it is preferable that grains preferably have an average crystal grain size of 1 to 500 and rounded pores of about 0.1 to 500 μm are provided in the sintered body. The porous ZnO sintered body has a fine crystal structure in which the average crystal grain size is within the above-described range, and the occurrence of defects in the boundary of crystal grains can be reduced. Thus, the formed ZnO film has excellent film characteristics, such as ZnO film density, thickness distribution, refractive index, sputtering resistance, discharge characteristics (discharge voltage, discharge responsiveness, and the like), insulation characteristics, and the like. If the average crystal grain size is smaller than 1 μm, the speed of film formation is lowered. If the average crystal grain size exceeds 500 μm, the deposition rate of the additive element is not uniform. The average crystal grain size is preferably in a range of 5 to 40 μm, and more preferably, in a range of 10 to 30 μm.
The ZnO vapor deposition material of this aspect is preferably molded in the form of disc-like or circular pellets. When the vapor deposition material has a circular shape, the diameter of the vapor deposition material is appropriately in a range of 5 to 30 mm, and preferably, in a range of 5 to 15 mm. This is because, if the diameter is excessively small and smaller than 5 mm, splash occurs, and if the diameter exceeds 30 mm, it is difficult to handle the vapor deposition material in an actual production process. When the vapor deposition material is disc-like, the diameter of the vapor deposition material is appropriately in a range of 5 to 20 mm, and preferably, in a range of 5 to 10 mm. The height of the vapor deposition material is in a range of 1 to 10 mm, and preferably, in a range of 2 to 5 mm. This is because, if the diameter is excessively small and smaller than 5 mm or the height is excessively small and smaller than 1 mm, splash occurs, and if the diameter exceeds 30 mm or the height exceeds 10 mm, it is difficult to handle the vapor deposition material in an actual production process.
Hereinafter, a process for producing a ZnO vapor deposition material according to this aspect will be described.
[Production Process]
The ZnO vapor deposition material according to this aspect can be produced by mixing ZnO powder having a purity equal to or greater than 98%, CeO2 powder in such an amount that the Ce content in the ZnO vapor deposition material is in a range of 0.1 to 14.9% by mass, Sc2O3 powder in such an amount that the Sc content in the ZnO vapor deposition material is in a range of 0.1 to 10% by mass, a binder, and an organic solvent to prepare a slurry with a concentration of 30 to 75% by mass, spray-drying the slurry to obtain a granulation powder having an average grain size of 50 to 300 μm, molding the granulation powder to obtain a porous molded body, and sintering the molded body at a predetermined temperature to obtain a porous ZnO sintered body.
The ZnO powder preferably has purity equal to or greater than 98%, more preferably, equal to or greater than 98.4%, and still more preferably, equal to or greater than 99%. If the ZnO powder has purity equal to or greater than 98%, reduction of conductivity by the effect of impurities can be suppressed. The average grain size of the ZnO powder is in a range of 0.1 to 10 μm. When the average grain size of the ZnO powder is smaller than 0.1 μm, the powder is excessively fine and aggregated, so there is a tendency that the handling of the powder becomes worse, and it is difficult to prepare a high-concentration slurry. When the average grain size exceeds 10 μm, there is a tendency that it is difficult to control the micro-structure, and a dense pellet is hard to obtain. If the average grain size of the ZnO powder is adjusted to the above-described range, a desired sintered body is also obtained without using a sintering auxiliary agent.
With regard to the CeO2 powder, considering the prevention of maldistribution of the Ce powder, reactivity with the ZnO matrix, and the purity of the Ce compound, it is preferable to add cerium oxide grains whose primary grain size is of a nanometer scale. The Sc2O3 powder preferably has an average grain size of 0.01 to 1 μm, and still more preferably, the average grain size is in a range of 0.05 to 0.5 μm. If the Sc2O3 powder having this average grain size is used, it is beneficial in terms of the uniform dispersion of the CeO2 powder.
For a binder, polyethylene glycol, polyvinyl butyral, or the like may be used. It is preferable to add the binder at 0.2 to 2.5% by mass. For an organic solvent, ethanol, propanol, or the like may be used.
The raw powder, the binder, and the organic solvent are mixed to prepare a slurry with a concentration of 30 to 75% by mass, and preferably, 40 to 65% by mass. If the slurry concentration exceeds 75% by mass, since the slurry is a non-aqueous system, stable granulation is difficult. If the slurry concentration is less than 30% by mass, it is difficult to obtain a dense ZnO sintered body having a uniform composition. If the slurry concentration is adjusted within the above-described range, the viscosity of the slurry is in a range of 200 to 1000 cps. Therefore, powder granulation using a spray drier can be performed stably. Further, the density of a molded body increases, such that a dense sintered body can be obtained.
Wet blending of raw powder, a binder, and an organic solvent, and in particular, wet blending of raw powder and an organic solvent as a dispersion medium is preferably performed by a wet ball mill or a stirring mill. In the case of using a ZrO2 ball in the wet ball mill, wet blending is preferably performed using a large number of ZrO2 balls having a diameter of 5 to 10 mm for 8 to 24 hours, and preferably, for 20 to 24 hours. If the diameter of the ZrO2 ball is smaller than 5 mm, blending may be insufficient. If the diameter of the ZrO2 ball exceeds 10 mm, impurities are increased. Even though the blending time is long, up to 24 hours, impurities are hardly generated due to milling. On the other hand, when a resin ball with a metal support is used in the wet ball mill, a ball having a diameter of 10 to 15 mm is preferably used.
In the stirring mill, wet blending is preferably performed using a ZrO2 ball having a diameter of 1 to 3 mm for 0.5 to 1 hour. If the diameter of the ZrO2 ball is smaller than 1 mm, blending is insufficient. If the diameter exceeds 3 mm, impurities are increased. If the blending time exceeds 1 hour, while raw materials are mixed, milling leads to the generation of impurities. Sufficient blending can be done within 1 hour. Blending/granulation of powder and additives may be performed by a general tumbling granulation method. In this case, it is not necessary to perform a separation operation from the balls or the like after the process, and thus the process is simplified.
In the production process of this aspect, as a first step for obtaining a porous sintered body, gas is blown and mixed into the slurry to prepare a gas-containing slurry. Gas blowing and mixing is preferably performed by blowing using a mechanical pump, gas pressure, or the like. As the gas, air, an insoluble gas, a non-aqueous gas, or the like may be used.
The gas-containing slurry is spray-dried. The spray drying is preferably performed at 150 to 250° C. for 3 hours by using a spray drier. Since gas is blown into the slurry, the granulation powder obtained by spray-drying the slurry is porous. Through the spray drying, a porous granulation powder having an average grain size of 50 to 300 μm can be obtained.
In the production process of this aspect, as a second step for obtaining a porous sintered body, a slurry is prepared in which a foaming agent is mixed. For the foaming agent, an organic foaming agent or an inorganic foaming agent may be used. For the organic foaming agent, azodicarboxylamide, dinitrosobenta methylene tetramine, or the like is used, and for the inorganic foaming agent, carbonate or the like is used. The foaming agent may be mixed with ZnO powder, CeO2 powder, and Sc2O3 powder, or may be added upon slurry preparation.
The foaming agent-containing slurry is spray-dried. The spray drying is preferably performed at 150 to 250° C. for 3 hours by using a spray drier. The foaming agent contained in the slurry is foamed and dissolved upon this spray drying, such that resultant granulation powder is made porous. Through the spray drying, a porous granulation powder having an average grain size of 50 to 300 μm can be obtained.
In the production process of this aspect, as a third step for obtaining a porous sintered body, a slurry is prepared in which an additive, which will be volatized and dissolved upon sintering, is mixed. Examples of the additive include butyral capable of being dissolved in a solvent, and a cellulose-based additive, a polyvinyl-based additive, a polyester-based additive, a polyethylene-based additive, and the like capable of being dissolved in an alcohol-based solvent. Examples of the additive which will not be dissolved in the alcohol-based solvent include a starch-based additive and a polystyrene-based additive having an average grain size of about several μm to 500 μm. It is preferable that butyral is mixed in the slurry at about 20% by mass, or starch is mixed in the slurry at about 20% by mass.
If the slurry contains the additive, the additive is volatized and dissolved upon sintering to form pores, thereby obtaining a porous sintered body. The diameter and shape of the pores can be controlled by adjusting the kind and amount of the additive. For example, when a butyral-based additive is used, pores having a pore diameter of 0.1 μm to 10 μm order can be formed. When starch is used, pores having the same pore diameter as the grain size of starch and the same shape as starch can be formed. Thus, when starch is used, the pore diameter and shape of the pores can be more easily controlled.
Specifically, in the case of the ZnO vapor deposition material of this aspect, a vapor deposition material using a butyral-based additive can obtain a deposition speed about 1.3 times higher than the evaporation speed of the conventional ZnO vapor deposition material having relative density equal to or greater than about 98%, and a vapor deposition material using starch having an average grain size of 0.1 to 500 μm can obtain an evaporation speed about two times higher than the evaporation speed of the conventional ZnO vapor deposition material having relative density equal to or greater than about 98%. Therefore, a high speed of film formation can be obtained.
In the production process of this aspect, as a fourth step for obtaining a porous sintered body, a slurry using ZnO powder having a grain size distribution within a predetermined range is prepared. Specifically, ZnO powder having an average grain size of 10 to 500 μm and a grain size distribution within a range of ±10% of the average grain size is used. If the grain size distribution of ZnO powder is outside the range of ±10% of the average grain size, the porosity is lowered. More preferably, the grain size distribution is within a range of ±5% of the average grain size. The preferred grain size of CeO2 powder and Sc2O3 powder is significantly smaller than that of ZnO powder, and the usage is smaller than that of ZnO powder, so CeO2 powder and Sc2O3 powder may be outside the limitation of the grain size distribution.
The slurry using ZnO powder with a controlled grain size distribution is spray-dried. The spray drying is preferably performed at 150 to 250° C. for 3 hours by using a spray drier. In the slurry to be spray-dried, ZnO powder having an average grain size of 10 to 500 μm and a grain size distribution within a range of ±10% of the average grain size is used, and no fine ZnO powder is substantially contained. Thus, there are no cases where fine ZnO grains fill the gaps between ZnO grains, so the gaps between ZnO grains remain as pores, and granulation powder becomes porous. Through the spray drying, a porous granulation powder having an average grain size of 50 to 300 μm can be obtained.
After the slurry is spray-dried to obtain a granulation powder having an average grain size of 50 to 300 μm, the granulation powder is molded under a predetermined pressure. If the average grain size of the granulation powder is smaller than 50 μm, moldability deteriorates, and if the average grain size is larger than 300 μm, the density of the molded body is lowered, and the strength is likely to be insufficient.
For a pressing molding device, a uniaxial press device, a cold isostatic press (CIP) molding device, or other devices may be used. The molding pressure is appropriately in a range of 100 to 2000 kgf/cm2 (9.8 to 196 MPa), and preferably, 100 to 1000 kgf/cm2 (9.8 to 98 MPa). Molding is performed under pressure within the above-described range, such that the density of the molded body can be increased, deformation after sintering can be suppressed, and postprocessing is not required.
Next, the molded body is sintered. Before sintering, the molded body is preferably degreased at a temperature of 350 to 620° C. Through this degreasing, spots on the molded body after sintering can be suppressed. The degreasing is preferably performed for a sufficient time.
Sintering is performed in an atmosphere of air, an inactive gas, a vacuum, or a reductive gas at a temperature equal to or higher than 1000° C., and preferably, at a temperature of 1200 to 1400° C. for 1 to 10 hours, and preferably, for 2 to 5 hours. The sintering is performed under air pressure, but in the case of pressure sintering, such as hot press (HP) sintering or hot isostatic press (HIP) sintering, the sintering is preferably performed in an atmosphere of inactive gas, vacuum, or reductive gas at a temperature equal to or higher than 1000° C. for 1 to 5 hours.
A ZnO film is formed on the surface of the substrate by a vacuum film formation method with a ZnO vapor deposition material composed of the resultant porous sintered body as a target material. As the vacuum film formation method suitable for forming a film using the ZnO vapor deposition material of this aspect, an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method may be used. A ZnO film of this aspect formed by the film formation method uses the ZnO vapor deposition material of this aspect, so the ZnO film has high conductivity with specific resistance of 3 to 5×10−4 Ω·cm and high permeability with visible light permeability equal to or greater than 90%, like ITO. Crystals distorted by Ce having an ion radius larger than Zn are recovered and aligned by adding Sc having a small ion radius, such that the durability of the film is improved.
According to the production process of this aspect, in any of the first step of mixing gas in the slurry, the second step of preparing the foaming agent-containing slurry, the third step of preparing the slurry containing the additive which will be volatized and dissolved upon sintering, and the fourth step of preparing the slurry using ZnO powder having a grain size distribution within a predetermined range, the porosity, pore diameter, and pore shape can be easily controlled. Therefore, a vapor deposition material having optimum pores can be produced. As a result, even when a large number of pore states are required by the production conditions or the like, an optimum vapor deposition material can be provided to cope with the requirements.
The ZnO vapor deposition material of this aspect is composed mainly of a porous sintered body having a porosity of 5 to 30% and a pore diameter of 0.1 to 500 μm, so when a ZnO transparent conductive film is formed by an electron beam deposition method or an ion plating method using the ZnO vapor deposition material, the evaporation speed can be improved. That is, when film formation is performed with the same electron beam energy, the speed of film formation increases, and the operation time is shortened, thereby increasing the number of products for a predetermined time. Further, when film formation is performed at the same film formation speed, electron beam energy is reduced, and the replacement timing of a filament of an electron gun or the like is delayed, such that the number of times of maintenance is reduced and productivity is improved. As a result, production costs can be reduced.
Next, another aspect of the present invention will be described.
[ZnO Vapor Deposition Material]
A ZnO vapor deposition material of this aspect is a ZnO vapor deposition material for formation of a transparent conductive film which is composed mainly of a porous ZnO sintered body containing Ce and B, wherein the Ce content is higher than the B content, the Ce content is in a range of 0.1 to 14.9% by mass, the B content is in a range of 0.1 to 10% by mass, and the sintered body has a porosity of 3 to 50%.
The inventors have investigated in detail the effect on conductivity due to additive species and its content in a ZnO vapor deposition material and a ZnO film formed by using the vapor deposition material, and have found that there is a significant level of influence due to the content ratio of the two elements of Ce and B as the additive elements in the porous ZnO sintered body. Based on the above-described knowledge, the ZnO vapor deposition material according to this aspect contains ZnO as a major component, and also contains both elements of Ce and B, such that excess electrons contributing to conduction are developed in large amounts and maintained, thereby forming a ZnO film having high conductivity.
As the ratio of the two elements of Ce and B in the porous ZnO sintered body increases within a predetermined range, the conductivity of the ZnO film becomes better, and if the ratio is outside the range, the conductivity adversely deteriorates. Specifically, the Ce content in the ZnO vapor deposition material is appropriately in a range of 0.1 to 14.9% by mass, and preferably, in a range of 3 to 6% by mass. If the Ce content is lower than the lower limit value, 0.1% by mass, the conductivity is significantly lowered. If the Ce content exceeds the upper limit value, 14.9% by mass, the permeability is significantly lowered.
The B content in the ZnO vapor deposition material is appropriately in a range of 0.1 to 10% by mass, and preferably, in a range of 1 to 3% by mass. If the B content is lower than the lower limit value, 0.1% by mass, the conductivity is significantly lowered. If the B content exceeds the upper limit value, 10% by mass, compositional shift at the time of deposition occurs.
The ZnO vapor deposition material of this aspect contains a larger amount of Ce than B, such that a dense crystal structure is maintained. If the Ce content is lower than the B content, the conductivity and permeability are lowered. The total content of Ce and B is preferably in a range of 0.2 to 15% by mass. If the total content of Ce and B exceeds this range, the specific resistance and permeability of the ZnO vapor deposition material are significantly lowered.
When a very small amount of Ce and B is contained in the ZnO vapor deposition material, Ce and B do not exist as granular precipitates in grain boundaries or grains in the ZnO matrix but are uniformly dispersed in the ZnO vapor deposition material. It is considered that, in the ZnO vapor deposition material, Ce is present as an oxide, such as CeO2 or Ce2O3, and B is present as B2O3.
The ZnO vapor deposition material of this aspect contains Ce, which is a trivalent or quadrivalent rare earth element, as an additive element, and Ce causes excess carrier electrons to be generated with respect to divalent Zn, such that high conductivity can be ensured. When a rare earth element is added to the ZnO vapor deposition material, compositional shift at the time of deposition is unlikely to occur, and a desired composition ratio can be maintained when a film is formed.
According to the ZnO vapor deposition material of this aspect, the conductivity is obtained by oxygen defect as well as compulsive injection of carrier electrons. Usually, oxygen gas is introduced in a vapor deposition method, but generally oxygen in the film composition is insufficient. At the time of transparent conductive film formation, a technique is conventionally used in which resistance is lowered by generating oxygen defect. However, in the case of adding a rare earth element, it is easy to control because the element is excellent in evaporation performance. In addition to this advantage, since the ZnO vapor deposition material of this aspect contains B as an additive element, high conductivity like ITO can be obtained.
The ZnO vapor deposition material of this aspect is composed of a porous ZnO sintered body having a porosity of 3 to 50%. The porosity of the sintered body is appropriately in a range of 3 to 50%, preferably in a range of 5 to 30%, more preferably in a range of 10 to 30%, and still more preferably in a range of 20 to 30%. If the porosity is smaller than 3%, it is not preferable since, at the time of film formation by an electron beam deposition method or an ion plating method, the evaporation speed of the vapor deposition material does not increase, and as a result, the speed of film formation decreases, which results in an increase in production costs. If the porosity exceeds 50%, the strength of the porous sintered body is lowered, and it is difficult to obtain sufficient mechanical strength. If the porosity is equal to or greater than 10%, the evaporation speed can be improved. Further, if the porosity is equal to or greater than 20%, a vapor deposition material having an evaporation speed about two times higher than the conventional ZnO vapor deposition material can be obtained.
In the porous ZnO sintered body of this aspect, the pores preferably have an average pore diameter of 0.1 to 500 μm. If the average pore diameter of the pores is within the above-described range, the evaporation speed can be further increased. If the pore diameter is smaller than 0.1 μm, there is no merit in the pores. If the pore diameter exceeds 500 μm, it is not preferable because the strength of the sintered body is lowered, which causes damages due to EB (electron beam) irradiation, that is, splash.
The term “pore diameter” (the inner diameter of the pore) refers to, for example, the maximum value of the internal dimensions in the pores when the sectional portion of the vapor deposition material is observed by observation means, such as SEM or the like. As the evaluation method of the pores, measurement of porosity by a substitution method, measurement of porosity by microscopy, measurement of surface area and micropore distribution by gas absorption, measurement of surface area and micropore distribution by a mercury intrusion method, measurement of surface area by a gas permeation method, or measurement of micropore distribution by an X-ray small-angle scattering method may be used.
The pores are preferably rounded, and in terms of improvement in the evaporation speed, micropores are preferably formed at the surface of the pores. For the evaluation method of the pores, the surface area is preferably in a range of 5 to 40 m2/g, and at least one peak of the micropore distribution is present within a range of 1 to 100 μm. Portions (frame portion) other than the pores are preferably substantially sintered. For example, the frame portion of the porous sintered body preferably has a density equal to or greater than 98%.
In the porous ZnO sintered body of this aspect, it is preferable that grains preferably have an average crystal grain size of 1 to 500 μm, and rounded pores of about 0.1 to 500 μm are provided in the sintered body. The porous ZnO sintered body has a fine crystal structure in which the average crystal grain size is within the above-described range, and the occurrence of defects in the boundary of crystal grains can be reduced. Thus, the formed ZnO film has excellent film characteristics, such as ZnO film density, thickness distribution, refractive index, sputtering resistance, discharge characteristics (discharge voltage, discharge responsiveness, and the like), insulation characteristics, and the like. If the average crystal grain size is smaller than 1 μm, the speed of film formation is lowered. If the average crystal grain size exceeds 500 μm, the deposition rate of the additive element is not uniform. The average crystal grain size is preferably in a range of 5 to 40 μm, and more preferably, in a range of 10 to 30 μm.
The ZnO vapor deposition material of this aspect is preferably molded in the form of disc-like or circular pellets. When the vapor deposition material has a circular shape, the diameter of the vapor deposition material is appropriately in a range of 5 to 30 mm, and preferably, in a range of 5 to 15 mm. This is because, if the diameter is excessively small and smaller than 5 mm, splash occurs, and if the diameter exceeds 30 mm, it is difficult to handle the vapor deposition material in an actual production process. When the vapor deposition material is disc-like, the diameter of the vapor deposition material is appropriately in a range of 5 to 20 mm, and preferably, in a range of 5 to 10 mm. The height of the vapor deposition material is in a range of 1 to 10 mm, and preferably, in a range of 2 to 5 mm. This is because, if the diameter is excessively small and smaller than 5 mm or the height is excessively small and smaller than 1 mm, splash occurs, and if the diameter exceeds 30 mm or the height exceeds 10 mm, it is difficult to handle the vapor deposition material in an actual production process.
Hereinafter, a process for producing a ZnO vapor deposition material according to this aspect will be described.
[Production Process]
The ZnO vapor deposition material according to this aspect can be produced by mixing ZnO powder having a purity equal to or greater than 98%, CeO2 powder in such an amount that the Ce content in the ZnO vapor deposition material is in a range of 0.1 to 14.9% by mass, B2O3 powder in such an amount that the B content in the ZnO vapor deposition material is in a range of 0.1 to 10% by mass, a binder, and an organic solvent to prepare a slurry with a concentration of 30 to 75% by mass, spray-drying the slurry to obtain a granulation powder having an average grain size of 50 to 300 μm, molding the granulation powder to obtain a porous molded body, and sintering the molded body at a predetermined temperature to obtain a porous ZnO sintered body.
The ZnO powder preferably has purity equal to or greater than 98%, more preferably, equal to or greater than 98.4%, and still more preferably, equal to or greater than 99%. If the ZnO powder has purity equal to or greater than 98%, reduction of conductivity by the effect of impurities can be suppressed. The average grain size of the ZnO powder is in a range of 0.1 to 10 μm. When the average grain size of the ZnO powder is smaller than 0.1 μm, the powder is excessively fine and aggregated, so there is a tendency that the handling of the powder becomes worse, and it is difficult to prepare a high-concentration slurry. When the average grain size exceeds 10 μm, there is a tendency that it is difficult to control the micro-structure, and a dense pellet is hard to obtain. If the average grain size of the ZnO powder is adjusted to the above-described range, a desired sintered body is also obtained without using a sintering auxiliary agent.
With regard to the CeO2 powder, considering the prevention of maldistribution of the Ce powder, reactivity with the ZnO matrix, and the purity of the Ce compound, it is preferable to add cerium oxide grains whose primary grain size is of a nanometer scale. The B2O3 powder preferably has an average grain size of 0.01 to 1 μm, and still more preferably, the average grain size is in a range of 0.05 to 0.5 μm. If the B2O3 powder having this average grain size is used, it is beneficial in terms of the uniform dispersion of the CeO2 powder.
For a binder, polyethylene glycol, polyvinyl butyral, or the like may be used. It is preferable to add the binder at 0.2 to 2.5% by mass. For an organic solvent, ethanol, propanol, or the like may be used.
The raw powder, the binder, and the organic solvent are mixed to prepare a slurry with a concentration of 30 to 75% by mass, and preferably, 40 to 65% by mass. If the slurry concentration exceeds 75% by mass, since the slurry is a non-aqueous system, stable granulation is difficult. If the slurry concentration is less than 30% by mass, it is difficult to obtain a dense ZnO sintered body having a uniform composition. If the slurry concentration is adjusted within the above-described range, the viscosity of the slurry is in a range of 200 to 1000 cps. Therefore, powder granulation using a spray drier can be performed stably. Further, the density of a molded body increases, such that a dense sintered body can be obtained.
Wet blending of raw powder, a binder, and an organic solvent, and in particular, wet blending of raw powder and an organic solvent as a dispersion medium is preferably performed by a wet ball mill or a stirring mill. In the case of using a ZrO2 ball in the wet ball mill, wet blending is preferably performed using a large number of ZrO2 balls having a diameter of 5 to 10 mm for 8 to 24 hours, and preferably, for 20 to 24 hours. If the diameter of the ZrO2 ball is smaller than 5 mm, blending may be insufficient. If the diameter of the ZrO2 ball exceeds 10 mm, impurities are increased. Even though the blending time is long, up to 24 hours, impurities are hardly generated due to milling. On the other hand, when a resin ball with a metal support is used in the wet ball mill, a ball having a diameter of 10 to 15 mm is preferably used.
In the stirring mill, wet blending is preferably performed using a ZrO2 ball having a diameter of 1 to 3 mm for 0.5 to 1 hour. If the diameter of the ZrO2 ball is smaller than 1 mm, blending is insufficient. If the diameter exceeds 3 mm, impurities are increased. If the blending time exceeds 1 hour, while raw materials are mixed, milling leads to the generation of impurities. Sufficient blending can be done within 1 hour. Blending/granulation of powder and additives may be performed by a general tumbling granulation method. In this case, it is not necessary to perform a separation operation from the balls or the like after the process, and thus the process is simplified.
In the production process of this aspect, as a first step for obtaining a porous sintered body, gas is blown and mixed into the slurry to prepare a gas-containing slurry. Gas blowing and mixing is preferably performed by blowing using a mechanical pump, gas pressure, or the like. As the gas, air, an insoluble gas, a non-aqueous gas, or the like may be used.
The gas-containing slurry is spray-dried. The spray drying is preferably performed at 150 to 250° C. for 3 hours by using a spray drier. Since gas is blown into the slurry, the granulation powder obtained by spray-drying the slurry is porous. Through the spray drying, a porous granulation powder having an average grain size of 50 to 300 μm can be obtained.
In the production process of this aspect, as a second step for obtaining a porous sintered body, a slurry is prepared in which a foaming agent is mixed. For the foaming agent, an organic foaming agent or an inorganic foaming agent may be used. For the organic foaming agent, azodicarboxylamide, dinitrosobenta methylene tetramine, or the like is used, and for the inorganic foaming agent, carbonate or the like is used. The foaming agent may be mixed with ZnO powder, CeO2 powder, and B2O3 powder, or may be added upon slurry preparation.
The foaming agent-containing slurry is spray-dried. The spray drying is preferably performed at 150 to 250° C. for 3 hours by using a spray drier. The foaming agent contained in the slurry is foamed and dissolved upon this spray drying, such that resultant granulation powder is made porous. Through the spray drying, a porous granulation powder having an average grain size of 50 to 300 μm can be obtained.
In the production process of this aspect, as a third step for obtaining a porous sintered body, a slurry is prepared in which an additive, which will be volatized and dissolved upon sintering, is mixed. Examples of the additive include butyral capable of being dissolved in a solvent, and a cellulose-based additive, a polyvinyl-based additive, a polyester-based additive, a polyethylene-based additive, and the like capable of being dissolved in an alcohol-based solvent. Examples of the additive which will not be dissolved in the alcohol-based solvent include a starch-based additive and a polystyrene-based additive having an average grain size of about several μm to 500 μm. It is preferable that butyral is mixed in the slurry at about 20% by mass, or starch is mixed in the slurry at about 20% by mass.
If the slurry contains the additive, the additive is volatized and dissolved upon sintering to form pores, thereby obtaining a porous sintered body. The diameter and shape of the pores can be controlled by adjusting the kind and amount of the additive. For example, when a butyral-based additive is used, pores having a pore diameter of 0.1 μm to 10 μm order can be formed. When starch is used, pores having the same pore diameter as the grain size of starch and the same shape as starch can be formed. Thus, when starch is used, the pore diameter and shape of the pores can be more easily controlled.
Specifically, in the case of the ZnO vapor deposition material of this aspect, a vapor deposition material using a butyral-based additive can obtain a deposition speed about 1.3 times higher than the evaporation speed of the conventional ZnO vapor deposition material having relative density equal to or greater than about 98%, and a vapor deposition material using starch having an average grain size of 0.1 to 500 μm can obtain an evaporation speed about two times higher than the evaporation speed of the conventional ZnO vapor deposition material having relative density equal to or greater than about 98%. Therefore, a high speed of film formation can be obtained.
In the production process of this aspect, as a fourth step for obtaining a porous sintered body, a slurry using ZnO powder having a grain size distribution within a predetermined range is prepared. Specifically, ZnO powder having an average grain size of 10 to 500 μm and a grain size distribution within a range of ±10% of the average grain size is used. If the grain size distribution of ZnO powder is outside the range of ±10% of the average grain size, the porosity is lowered. More preferably, the grain size distribution is within a range of ±5% of the average grain size. The preferred grain size of CeO2 powder and B2O3 powder is significantly smaller than that of ZnO powder, and the usage is smaller than that of ZnO powder, so CeO2 powder and B2O3 powder may be outside the limitation of the grain size distribution.
The slurry using ZnO powder with a controlled grain size distribution is spray-dried. The spray drying is preferably performed at 150 to 250° C. for 3 hours by using a spray drier. In the slurry to be spray-dried, ZnO powder having an average grain size of 10 to 500 μm and a grain size distribution within a range of ±10% of the average grain size is used, and no fine ZnO powder is substantially contained. Thus, there are no cases where fine ZnO grains fill the gaps between ZnO grains, so the gaps between ZnO grains remain as pores, and granulation powder becomes porous. Through the spray drying, a porous granulation powder having an average grain size of 50 to 300 μm can be obtained.
After the slurry is spray-dried to obtain a granulation powder having an average grain size of 50 to 300 μm, the granulation powder is molded under a predetermined pressure. If the average grain size of the granulation powder is smaller than 50 μm, moldability deteriorates, and if the average grain size is larger than 300 μm, the density of the molded body is lowered, and the strength is likely to be insufficient.
For a pressing molding device, a uniaxial press device, a cold isostatic press (CIP) molding device, or other devices may be used. The molding pressure is appropriately in a range of 100 to 2000 kgf/cm2 (9.8 to 196 MPa), and preferably, 100 to 1000 kgf/cm2 (9.8 to 98 MPa). Molding is performed under pressure within the above-described range, such that the density of the molded body can be increased, deformation after sintering can be suppressed, and postprocessing is not required.
Next, the molded body is sintered. Before sintering, the molded body is preferably degreased at a temperature of 350 to 620° C. Through this degreasing, spots on the molded body after sintering can be suppressed. The degreasing is preferably performed for a sufficient time.
Sintering is performed in an atmosphere of air, an inactive gas, a vacuum, or a reductive gas at a temperature equal to or higher than 1000° C., and preferably, at a temperature of 1200 to 1400° C. for 1 to 10 hours, and preferably, for 2 to 5 hours. The sintering is performed under air pressure, but in the case of pressure sintering, such as hot press (HP) sintering or hot isostatic press (HIP) sintering, the sintering is preferably performed in an atmosphere of inactive gas, vacuum, or reductive gas at a temperature equal to or higher than 1000° C. for 1 to 5 hours.
A ZnO film is formed on the surface of the substrate by a vacuum film formation method with a ZnO vapor deposition material composed of the resultant porous sintered body as a target material. As the vacuum film formation method suitable for forming a film using the ZnO vapor deposition material of this aspect, an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method may be used. A ZnO film of this aspect formed by the film formation method uses the ZnO vapor deposition material of this aspect, so the ZnO film has high conductivity with specific resistance of 3 to 5×10−4 Ω·cm and high permeability with visible light permeability equal to or greater than 90%, like ITO. Crystals distorted by Ce having an ion radius larger than Zn are recovered and aligned by adding B having a small ion radius, such that the durability of the film is improved.
According to the production process of this aspect, in any of the first step of mixing gas in the slurry, the second step of preparing the foaming agent-containing slurry, the third step of preparing the slurry containing the additive which will be volatized and dissolved upon sintering, and the fourth step of preparing the slurry using ZnO powder having a grain size distribution within a predetermined range, the porosity, pore diameter, and pore shape can be easily controlled. Therefore, a vapor deposition material having optimum pores can be produced. As a result, even when a large number of pore states are required by the production conditions or the like, an optimum vapor deposition material can be provided to cope with the requirements.
The ZnO vapor deposition material of this aspect is composed mainly of a porous sintered body having a porosity of 5 to 30% and a pore diameter of 0.1 to 500 μm, so when a ZnO transparent conductive film is formed by an electron beam deposition method or an ion plating method using the ZnO vapor deposition material, the evaporation speed can be improved. That is, when film formation is performed with the same electron beam energy, the speed of film formation increases, and the operation time is shortened, thereby increasing the number of products for a predetermined time. Further, when film formation is performed at the same film formation speed, electron beam energy is reduced, and the replacement timing of a filament of an electron gun or the like is delayed, such that the number of times of maintenance is reduced and productivity is improved. As a result, production costs can be reduced.
Next, another aspect of the present invention will be described.
[ZnO Vapor Deposition Material]
A ZnO vapor deposition material of this aspect is a ZnO vapor deposition material for formation of a transparent conductive film which is composed of a sintered body containing ZnO as a major component, wherein the sintered body contains La as a first additive element and a second additive element, the second additive element is one or more elements selected from the group consisting of B, Al, Ga, and Sc, the La content is in a range of 0.1 to 14.9% by mass, the content of the second additive element is in a range of 0.1 to 10% by mass, the La content is higher than the content of the second additive element, and the sintered body is a porous sintered body having a porosity of 3 to 50%.
The inventors have investigated in detail the effect on conductivity due to additive species and its content in a ZnO vapor deposition material and a ZnO film formed by using the vapor deposition material, and have found that there is a significant level of influence on conductivity due to the species and content of La as an additive element and B, Al, Ga, or Sc in the porous ZnO sintered body. Based on the above-described knowledge, the ZnO vapor deposition material according to this aspect contains ZnO as a major component, and also contains La as a first additive element and the second additive element, such that excess electrons contributing to conduction are developed in large amounts and maintained, thereby forming a ZnO film having high conductivity.
The ZnO vapor deposition material of this aspect contains La as a first additive element and the second additive element together, and the second additive element is one or more elements selected from B, Al, Ga, and Sc. Of the second additive elements, B, Al, and Ga have an ion radius smaller than La as a first additive element, so crystals distorted by the addition of La having an ion radius larger than Zn are recovered and aligned by adding B, Al, or Ga, or the crystal structure distorted by the addition of La is recovered and aligned by adding Sc having high reactivity as the second additive element. For this reason, a ZnO film having high permeability, excellent denseness, high conductivity, and excellent durability can be formed.
As the ratio of La as a first additive element and the second additive element in the porous ZnO sintered body increases within a predetermined range, the conductivity of the ZnO film becomes better, and if the ratio is outside the range, the conductivity adversely deteriorates. Specifically, the La content in the ZnO vapor deposition material is appropriately in a range of 0.1 to 14.9% by mass, and preferably, in a range of 3 to 6% by mass. If the La content is lower than the lower limit value, 0.1% by mass, the conductivity is significantly lowered. If the La content exceeds the upper limit value, 14.9% by mass, the permeability is significantly lowered.
The content of the second additive element in the ZnO vapor deposition material is appropriately in a range of 0.1 to 10% by mass, and preferably, in a range of 1 to 3% by mass. If the content of the second additive element is lower than the lower limit value, 0.1% by mass, the conductivity is significantly lowered. If the content of the second additive element exceeds the upper limit value, 10% by mass, compositional shift at the time of deposition occurs.
The ZnO vapor deposition material of this aspect contains a larger amount of La as a first additive element than the second additive element, such that a dense crystal structure is maintained. If the La content is lower than that of the second additive element, the conductivity and permeability are lowered. The total content of Ce as a first additive element and the second additive element is preferably in a range of 0.2 to 15% by mass. If the total content of La and the second additive element exceeds this range, the specific resistance and permeability of the ZnO vapor deposition material are significantly lowered.
When a very small amount of La as a first additive element and the second additive element is contained in the ZnO vapor deposition material, La as a first additive element and the second additive element do not exist as granular precipitates in grain boundaries or grains in the ZnO matrix but are uniformly dispersed in the ZnO vapor deposition material. It is considered that, in the ZnO vapor deposition material, the first additive element and the second additive element are present as oxides.
The ZnO vapor deposition material of this aspect contains La, which is a trivalent rare earth element, as a first additive element, and La causes excess carrier electrons to be generated with respect to divalent Zn, such that high conductivity can be ensured. When a rare earth element is added to the ZnO vapor deposition material, compositional shift at the time of deposition is unlikely to occur, and a desired composition ratio can be maintained when a film is formed.
According to the ZnO vapor deposition material of this aspect, the conductivity is obtained by oxygen defect as well as compulsive injection of carrier electrons. Usually, oxygen gas is introduced in a vapor deposition method, but generally oxygen in the film composition is insufficient. At the time of transparent conductive film formation, a technique is conventionally used in which resistance is lowered by generating oxygen defect. However, in the case of adding a rare earth element, it is easy to control because the element is excellent in evaporation performance. In addition to this advantage by the addition of La which is a rare earth element, since the ZnO vapor deposition material of this aspect contains the second additive element, high conductivity like ITO can be obtained.
The ZnO vapor deposition material of this aspect is composed of a porous ZnO sintered body having a porosity of 3 to 50%. The porosity of the sintered body is appropriately in a range of 3 to 50%, preferably in a range of 5 to 30%, more preferably in a range of 10 to 30%, and still more preferably in a range of 20 to 30%. If the porosity is smaller than 3%, it is not preferable since, at the time of film formation by an electron beam deposition method or an ion plating method, the evaporation speed of the vapor deposition material does not increase, and as a result, the speed of film formation decreases, which results in an increase in production costs. If the porosity exceeds 50%, the strength of the porous sintered body is lowered, and it is difficult to obtain sufficient mechanical strength. If the porosity is equal to or greater than 10%, the evaporation speed can be improved. Further, if the porosity is equal to or greater than 20%, a vapor deposition material having an evaporation speed about two times higher than the conventional ZnO vapor deposition material can be obtained.
In the porous ZnO sintered body of this aspect, the pores preferably have an average pore diameter of 0.1 to 500 μm. If the average pore diameter of the pores is within the above-described range, the evaporation speed can be further increased. If the pore diameter is smaller than 0.1 μm, there is no merit in the pores. If the pore diameter exceeds 500 μm, it is not preferable because the strength of the sintered body is lowered, which causes damages due to EB (electron beam) irradiation, that is, splash.
The term “pore diameter” (the inner diameter of the pore) refers to, for example, the maximum value of the internal dimensions in the pores when the sectional portion of the vapor deposition material is observed by observation means, such as SEM or the like. As the evaluation method of the pores, measurement of porosity by a substitution method, measurement of porosity by microscopy, measurement of surface area and micropore distribution by gas absorption, measurement of surface area and micropore distribution by a mercury intrusion method, measurement of surface area by a gas permeation method, or measurement of micropore distribution by an X-ray small-angle scattering method may be used.
The pores are preferably rounded, and in terms of improvement in the evaporation speed, micropores are preferably formed at the surface of the pores. For the evaluation method of the pores, the surface area is preferably in a range of 5 to 40 m2/g, and at least one peak of the micropore distribution is present within a range of 1 to 100 μm. Portions (frame portion) other than the pores are preferably substantially sintered. For example, the frame portion of the porous sintered body preferably has a density equal to or greater than 98%.
In the porous ZnO sintered body of this aspect, it is preferable that grains preferably have an average crystal grain size of 1 to 500 μm, and rounded pores of about 0.1 to 500 μm are provided in the sintered body. The porous ZnO sintered body has a fine crystal structure in which the average crystal grain size is within the above-described range, and the occurrence of defects in the boundary of crystal grains can be reduced. Thus, the formed ZnO film has excellent film characteristics, such as ZnO film density, thickness distribution, refractive index, sputtering resistance, discharge characteristics (discharge voltage, discharge responsiveness, and the like), insulation characteristics, and the like. If the average crystal grain size is smaller than 1 μm, the speed of film formation is lowered. If the average crystal grain size exceeds 500 μm, the deposition rate of the additive element is not uniform. The average crystal grain size is preferably in a range of 5 to 40 μm, and more preferably, in a range of 10 to 30 μm.
The ZnO vapor deposition material of this aspect is preferably molded in the form of disc-like or circular pellets. When the vapor deposition material has a circular shape, the diameter of the vapor deposition material is appropriately in a range of 5 to 30 mm, and preferably, in a range of 5 to 15 mm. This is because, if the diameter is excessively small and smaller than 5 mm, splash occurs, and if the diameter exceeds 30 mm, it is difficult to handle the vapor deposition material in an actual production process. When the vapor deposition material is disc-like, the diameter of the vapor deposition material is appropriately in a range of 5 to 20 mm, and preferably, in a range of 5 to 10 mm. The height of the vapor deposition material is in a range of 1 to 10 mm, and preferably, in a range of 2 to 5 mm. This is because, if the diameter is excessively small and smaller than 5 mm or the height is excessively small and smaller than 1 mm, splash occurs, and if the diameter exceeds 30 mm or the height exceeds 10 mm, it is difficult to handle the vapor deposition material in an actual production process.
Hereinafter, a process for producing a ZnO vapor deposition material according to this aspect will be described.
[Production Process]
The ZnO vapor deposition material according to this aspect can be produced by mixing ZnO powder having a purity equal to or greater than 98%, La2O3 powder in such an amount that the La content in the ZnO vapor deposition material is in a range of 0.1 to 14.9% by mass, an oxide powder of a second additive element in such an amount that the content of the second additive element in the ZnO vapor deposition material is in a range of 0.1 to 10% by mass, a binder, and an organic solvent to prepare a slurry with a concentration of 30 to 75% by mass, blowing gas into the slurry to obtain a gas-containing slurry, spray-drying the gas-containing slurry to obtain a porous granulation powder having an average grain size of 50 to 300 μm, molding the porous granulation powder to obtain a porous molded body, and sintering the porous molded body at a predetermined temperature to obtain a porous ZnO sintered body.
The ZnO powder preferably has purity equal to or greater than 98%, more preferably, equal to or greater than 98.4%, and still more preferably, equal to or greater than 99%. If the ZnO powder has purity equal to or greater than 98%, reduction of conductivity by the effect of impurities can be suppressed. The average grain size of the ZnO powder is in a range of 0.1 to 10 μm. When the average grain size of the ZnO powder is smaller than 0.1 μm, the powder is excessively fine and aggregated, so there is a tendency that the handling of the powder becomes worse, and it is difficult to prepare a high-concentration slurry. When the average grain size exceeds 10 μm, there is a tendency that it is difficult to control the micro-structure, and a dense pellet is hard to obtain. If the average grain size of the ZnO powder is adjusted to the above-described range, a desired sintered body is also obtained without using a sintering auxiliary agent.
With regard to the La2O3 powder, considering the prevention of maldistribution of the La powder, reactivity with a ZnO matrix, and the purity of a La compound, it is preferable to add La oxide grains whose primary grain size is of a nanometer scale. The oxide powder of the second additive element preferably has an average grain size of 0.01 to 1 μm, and still more preferably, the average grain size is in a range of 0.05 to 0.5 μm. If the oxide powder of the second additive element having this average grain size is used, it is beneficial in terms of the uniform dispersion of the oxide powder of the second additive element.
For a binder, polyethylene glycol, polyvinyl butyral, or the like may be used. It is preferable to add the binder at 0.2 to 2.5% by mass. For an organic solvent, ethanol, propanol, or the like may be used.
The raw powder, the binder, and the organic solvent are mixed to prepare a slurry with a concentration of 30 to 75% by mass, and preferably, 40 to 65% by mass. If the slurry concentration exceeds 75% by mass, since the slurry is a non-aqueous system, stable granulation is difficult. If the slurry concentration is less than 30% by mass, it is difficult to obtain a dense ZnO sintered body having a uniform composition. If the slurry concentration is adjusted within the above-described range, the viscosity of the slurry is in a range of 200 to 1000 cps. Therefore, powder granulation using a spray drier can be performed stably. Further, the density of a molded body increases, such that a dense sintered body can be obtained.
Wet blending of raw powder, a binder, and an organic solvent, and in particular, wet blending of raw powder and an organic solvent as a dispersion medium is preferably performed by a wet ball mill or a stirring mill. In the case of using a ZrO2 ball in the wet ball mill, wet blending is preferably performed using a large number of ZrO2 balls having a diameter of 5 to 10 mm for 8 to 24 hours, and preferably, for 20 to 24 hours. If the diameter of the ZrO2 ball is smaller than 5 mm, blending may be insufficient. If the diameter of the ZrO2 ball exceeds 10 mm, impurities are increased. Even though the blending time is long, up to 24 hours, impurities are hardly generated due to milling. On the other hand, when a resin ball with a metal support is used in the wet ball mill, a ball having a diameter of 10 to 15 mm is preferably used.
In the stirring mill, wet blending is preferably performed using a ZrO2 ball having a diameter of 1 to 3 mm for 0.5 to 1 hour. If the diameter of the ZrO2 ball is smaller than 1 mm, blending is insufficient. If the diameter exceeds 3 mm, impurities are increased. If the blending time exceeds 1 hour, while raw materials are mixed, milling leads to the generation of impurities. Sufficient blending can be done within 1 hour. Blending/granulation of powder and additives may be performed by a general tumbling granulation method. In this case, it is not necessary to perform a separation operation from the balls or the like after the process, and thus the process is simplified.
In the production process of this aspect, as a first step for obtaining a porous sintered body, gas is blown and mixed into the slurry to prepare a gas-containing slurry. Gas blowing and mixing is preferably performed by blowing using a mechanical pump, gas pressure, or the like. As the gas, air, an insoluble gas, a non-aqueous gas, or the like may be used.
The gas-containing slurry is spray-dried. The spray drying is preferably performed at 150 to 250° C. for 3 hours by using a spray drier. Since gas is blown into the slurry, the granulation powder obtained by spray-drying the slurry is porous. Through the spray drying, a porous granulation powder having an average grain size of 50 to 300 μm can be obtained.
In the production process of this aspect, as a second step for obtaining a porous sintered body, a slurry is prepared in which a foaming agent is mixed. For the foaming agent, an organic foaming agent or an inorganic foaming agent may be used. For the organic foaming agent, azodicarboxylamide, dinitrosobenta methylene tetramine, or the like is used, and for the inorganic foaming agent, carbonate or the like is used. The foaming agent may be mixed with ZnO powder, LaO2 powder, and Al2O3 powder, or may be added upon slurry preparation.
The foaming agent-containing slurry is spray-dried. The spray drying is preferably performed at 150 to 250° C. for 3 hours by using a spray drier. The foaming agent contained in the slurry is foamed and dissolved upon this spray drying, such that resultant granulation powder is made porous. Through the spray drying, a porous granulation powder having an average grain size of 50 to 300 μm can be obtained.
In the production process of this aspect, as a third step for obtaining a porous sintered body, a slurry is prepared in which an additive, which will be volatized and dissolved upon sintering, is mixed. Examples of the additive include butyral capable of being dissolved in a solvent, and a cellulose-based additive, a polyvinyl-based additive, a polyester-based additive, a polyethylene-based additive, and the like capable of being dissolved in an alcohol-based solvent. Examples of the additive which will not be dissolved in the alcohol-based solvent include a starch-based additive and a polystyrene-based additive having an average grain size of about several μm to 500 μm. It is preferable that butyral is mixed in the slurry at about 20% by mass, or starch is mixed in the slurry at about 20% by mass.
If the slurry contains the additive, the additive is volatized and dissolved upon sintering to form pores, thereby obtaining a porous sintered body. The diameter and shape of the pores can be controlled by adjusting the kind and amount of the additive. For example, when a butyral-based additive is used, pores having a pore diameter of 0.1 μm to 10 μm order can be formed. When starch is used, pores having the same pore diameter as the grain size of starch and the same shape as starch can be formed. Thus, when starch is used, the pore diameter and shape of the pores can be more easily controlled.
Specifically, in the case of the ZnO vapor deposition material of this aspect, a vapor deposition material using a butyral-based additive can obtain a deposition speed about 1.3 times higher than the evaporation speed of the conventional ZnO vapor deposition material having relative density equal to or greater than about 98%, and a vapor deposition material using starch having an average grain size of 0.1 to 500 μm can obtain an evaporation speed about two times. Therefore, a high speed of film formation can be obtained.
In the production process of this aspect, as a fourth step for obtaining a porous sintered body, a slurry using ZnO powder having a grain size distribution within a predetermined range is prepared. Specifically, ZnO powder having an average grain size of 10 to 500 μm and a grain size distribution within a range of ±10% of the average grain size is used. If the grain size distribution of ZnO powder is outside the range of ±10% of the average grain size, the porosity is lowered. More preferably, the grain size distribution is within a range of ±5% of the average grain size. The preferred grain size of oxide powder of the first additive element and the second additive element is significantly smaller than that of ZnO powder, and the usage is smaller than that of ZnO powder, so oxide powder of the first additive element and the second additive element may be outside the limitation of the grain size distribution.
The slurry using ZnO powder with a controlled grain size distribution is spray-dried. The spray drying is preferably performed at 150 to 250° C. for 3 hours by using a spray drier. In the slurry to be spray-dried, ZnO powder having an average grain size of 10 to 500 μm and a grain size distribution within a range of ±10% of the average grain size is used, and no fine ZnO powder is substantially contained. Thus, there are no cases where fine ZnO grains fill the gaps between ZnO grains, so the gaps between ZnO grains remain as pores, and granulation powder becomes porous. Through the spray drying, a porous granulation powder having an average grain size of 50 to 300 μm can be obtained.
After the slurry is spray-dried to obtain a granulation powder having an average grain size of 50 to 300 μm, the granulation powder is molded under a predetermined pressure. If the average grain size of the granulation powder is smaller than 50 μm, moldability deteriorates, and if the average grain size is larger than 300 μm, the density of the molded body is lowered, and the strength is likely to be insufficient.
For a pressing molding device, a uniaxial press device, a cold isostatic press (CIP) molding device, or other devices may be used. The molding pressure is appropriately in a range of 100 to 2000 kgf/cm2 (9.8 to 196 MPa), and preferably, 100 to 1000 kgf/cm2 (9.8 to 98 MPa). Molding is performed under pressure within the above-described range, such that the density of the molded body can be increased, deformation after sintering can be suppressed, and postprocessing is not required.
Next, the molded body is sintered. Before sintering, the molded body is preferably degreased at a temperature of 350 to 620° C. Through this degreasing, spots on the molded body after sintering can be suppressed. The degreasing is preferably performed for a sufficient time.
Sintering is performed in an atmosphere of air, an inactive gas, a vacuum, or a reductive gas at a temperature equal to or higher than 1000° C., and preferably, at a temperature of 1200 to 1400° C. for 1 to 10 hours, and preferably, for 2 to 5 hours. The sintering is performed under air pressure, but in the case of pressure sintering, such as hot press (HP) sintering or hot isostatic press (HIP) sintering, the sintering is preferably performed in an atmosphere of inactive gas, vacuum, or reductive gas at a temperature equal to or higher than 1000° C. for 1 to 5 hours.
A ZnO film is formed on the surface of the substrate by a vacuum film formation method with a ZnO vapor deposition material composed of the resultant porous sintered body as a target material. As the vacuum film formation method suitable for forming a film using the ZnO vapor deposition material of this aspect, an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method may be used. A ZnO film of this aspect formed by the film formation method uses the ZnO vapor deposition material of this aspect, so the ZnO film has high conductivity with specific resistance of 3 to 5×10−4 Ω·cm and high permeability with visible light permeability equal to or greater than 90%, like ITO.
In the ZnO vapor deposition material of this aspect, the crystal structure distorted by the addition of La having an ion radius larger than Zn is recovered and aligned by addition of the second additive element having a small ion radius, such as B, Al, or Ga, or Sc having high reactivity is added to recover a film having a regulated crystal structure. Therefore, a dense film can be formed, and the durability of the film can also be improved.
According to the production process of this aspect, in any of the first step of mixing gas in the slurry, the second step of preparing the foaming agent-containing slurry, the third step of preparing the slurry containing the additive which will be volatized and dissolved upon sintering, and the fourth step of preparing the slurry using ZnO powder having a grain size distribution within a predetermined range, the porosity, pore diameter, and pore shape can be easily controlled. Therefore, a vapor deposition material having optimum pores can be produced. As a result, even when a large number of pore states are required by the production conditions or the like, an optimum vapor deposition material can be provided to cope with the requirements.
The ZnO vapor deposition material of this aspect is composed mainly of a porous sintered body having a porosity of 5 to 30% and a pore diameter of 0.1 to 500 μm, so when a ZnO transparent conductive film is formed by an electron beam deposition method or an ion plating method using the ZnO vapor deposition material, the evaporation speed can be improved. That is, when film formation is performed with the same electron beam energy, the speed of film formation increases, and the operation time is shortened, thereby increasing the number of products for a predetermined time. Further, when film formation is performed at the same film formation speed, electron beam energy is reduced, and the replacement timing of a filament of an electron gun or the like is delayed, such that the number of times of maintenance is reduced and productivity is improved. As a result, production costs can be reduced.
Next, another aspect of the present invention will be described.
[ZnO Vapor Deposition Material]
A ZnO vapor deposition material of this aspect is a ZnO vapor deposition material for formation of a transparent conductive film which is composed of a sintered body containing ZnO as a major component, wherein the sintered body contains Y as a first additive element and a second additive element, the second additive element is one or more elements selected from the group consisting of B, Al, Ga, and Sc, the Y content is in a range of 0.1 to 14.9% by mass, the content of the second additive element is in a range of 0.1 to 10% by mass, the Y content is higher than the content of the second additive element, and the sintered body is a porous sintered body having a porosity of 3 to 50%.
The inventors have investigated in detail the effect on conductivity due to additive species and the content in a ZnO vapor deposition material and a ZnO film formed by using the vapor deposition material, and have found that there is a significant level of influence on conductivity due to the species and content of Y as a first additive element and the second additive element, such as B, Al, Ga, or Sc, in the porous ZnO sintered body. Based on the above-described knowledge, the ZnO vapor deposition material according to this aspect contains ZnO as a major component, and also contains Y as a first additive element and the second additive element, such that excess electrons contributing to conduction are developed in large amounts and maintained, thereby forming a ZnO film having high conductivity.
The ZnO vapor deposition material of this aspect contains Y as a first additive element and the second additive element together, and the second additive element is one or more elements selected from B, Al, Ga, and Sc. Of the second additive elements, B, Al, and Ga have an ion radius smaller than Y as a first additive element, so crystals distorted by the addition of Y having an ion radius larger than Zn are recovered and aligned by adding B, Al, or Ga, or the crystal structure distorted by the addition of Y is recovered and aligned by adding Sc having high reactivity as the second additive element. For this reason, a ZnO film having high permeability, excellent denseness, high conductivity, and excellent durability can be formed.
As the ratio of Y as a first additive element and the second additive element in the porous ZnO sintered body increases within a predetermined range, the conductivity of the ZnO film becomes better, and if the ratio is outside the range, the conductivity adversely deteriorates. Specifically, the Y content in the ZnO vapor deposition material is appropriately in a range of 0.1 to 14.9% by mass, and preferably, in a range of 3 to 6% by mass. If the Y content is lower than the lower limit value, 0.1% by mass, the conductivity is significantly lowered. If the Y content exceeds the upper limit value, 14.9% by mass, the permeability is significantly lowered.
The content of the second additive element in the ZnO vapor deposition material is appropriately in a range of 0.1 to 10% by mass, and preferably, in a range of 1 to 3% by mass. If the content of the second additive element is lower than the lower limit value, 0.1% by mass, the conductivity is significantly lowered. If the content of the second additive element exceeds the upper limit value, 10% by mass, compositional shift at the time of deposition occurs.
The ZnO vapor deposition material of this aspect contains a larger amount of Y as a first additive element than the second additive element, such that a dense crystal structure is maintained. If the Y content is lower than that of the second additive element, the conductivity and permeability are lowered. The total content of Y as a first additive element and the second additive element is preferably in a range of 0.2 to 15% by mass. If the total content of Y and the second additive element exceeds this range, the specific resistance and permeability of the ZnO vapor deposition material are significantly lowered.
When a very small amount of Y as a first additive element and the second additive element is contained in the ZnO vapor deposition material, Y as a first additive element and the second additive element do not exist as granular precipitates in grain boundaries or grains in the ZnO matrix but are uniformly dispersed in the ZnO vapor deposition material. It is considered that, in the ZnO vapor deposition material, the first additive element and the second additive element are present as oxides.
The ZnO vapor deposition material of this aspect contains Y, which is a trivalent rare earth element, as a first additive element, and Y causes excess carrier electrons to be generated with respect to divalent Zn, such that high conductivity can be ensured. When a rare earth element is added to the ZnO vapor deposition material, compositional shift at the time of deposition is unlikely to occur, and a desired composition ratio can be maintained when a film is formed.
According to the ZnO vapor deposition material of this aspect, the conductivity is obtained by oxygen defect as well as compulsive injection of carrier electrons. Usually, oxygen gas is introduced in a vapor deposition method, but generally oxygen in the film composition is insufficient. At the time of transparent conductive film formation, a technique is conventionally used in which resistance is lowered by generating oxygen defect. However, in the case of adding a rare earth element, it is easy to control because the element is excellent in evaporation performance. In addition to this advantage by the addition of Y which is a rare earth element, since the ZnO vapor deposition material of this aspect contains the second additive element, high conductivity like ITO can be obtained.
The ZnO vapor deposition material of this aspect is composed of a porous ZnO sintered body having a porosity of 3 to 50%. The porosity of the sintered body is appropriately in a range of 3 to 50%, preferably in a range of 5 to 30%, more preferably in a range of 10 to 30%, and still more preferably in a range of 20 to 30%. If the porosity is smaller than 3%, it is not preferable since, at the time of film formation by an electron beam deposition method or an ion plating method, the evaporation speed of the vapor deposition material does not increase, and as a result, the speed of film formation decreases, which results in an increase in production costs. If the porosity exceeds 50%, the strength of the porous sintered body is lowered, and it is difficult to obtain sufficient mechanical strength. If the porosity is equal to or greater than 10%, the evaporation speed can be improved. Further, if the porosity is equal to or greater than 20%, a vapor deposition material having an evaporation speed about two times higher than the conventional ZnO vapor deposition material can be obtained.
In the porous ZnO sintered body of this aspect, the pores preferably have an average pore diameter of 0.1 to 500 μm. If the average pore diameter of the pores is within the above-described range, the evaporation speed can be further increased. If the pore diameter is smaller than 0.1 μm, there is no merit in the pores. If the pore diameter exceeds 500 μm, it is not preferable because the strength of the sintered body is lowered, which causes damages due to EB (electron beam) irradiation, that is, splash.
The term “pore diameter” (the inner diameter of the pore) refers to, for example, the maximum value of the internal dimensions in the pores when the sectional portion of the vapor deposition material is observed by observation means, such as SEM or the like. As the evaluation method of the pores, measurement of porosity by a substitution method, measurement of porosity by microscopy, measurement of surface area and micropore distribution by gas absorption, measurement of surface area and micropore distribution by a mercury intrusion method, measurement of surface area by a gas permeation method, or measurement of micropore distribution by an X-ray small-angle scattering method may be used.
The pores are preferably rounded, and in terms of improvement in the evaporation speed, micropores are preferably formed at the surface of the pores. For the evaluation method of the pores, the surface area is preferably in a range of 5 to 40 m2/g, and at least one peak of the micropore distribution is present within a range of 1 to 100 μm. Portions (frame portion) other than the pores are preferably substantially sintered. For example, the frame portion of the porous sintered body preferably has a density equal to or greater than 98%.
In the porous ZnO sintered body of this aspect, it is preferable that grains preferably have an average crystal grain size of 1 to 500 μm and rounded pores of about 0.1 to 500 μm are provided in the sintered body. The porous ZnO sintered body has a fine crystal structure in which the average crystal grain size is within the above-described range, and the occurrence of defects in the boundary of crystal grains can be reduced. Thus, the formed ZnO film has excellent film characteristics, such as ZnO film density, thickness distribution, refractive index, sputtering resistance, discharge characteristics (discharge voltage, discharge responsiveness, and the like), insulation characteristics, and the like. If the average crystal grain size is smaller than 1 μm, the speed of film formation is lowered. If the average crystal grain size exceeds 500 μm, the deposition rate of the additive element is not uniform. The average crystal grain size is preferably in a range of 5 to 40 μm, and more preferably, in a range of 10 to 30 μm.
The ZnO vapor deposition material of this aspect is preferably molded in the form of disc-like or circular pellets. When the vapor deposition material has a circular shape, the diameter of the vapor deposition material is appropriately in a range of 5 to 30 mm, and preferably, in a range of 5 to 15 mm. This is because, if the diameter is excessively small and smaller than 5 mm, splash occurs, and if the diameter exceeds 30 mm, it is difficult to handle the vapor deposition material in an actual production process. When the vapor deposition material is disc-like, the diameter of the vapor deposition material is appropriately in a range of 5 to 20 mm, and preferably, in a range of 5 to 10 mm. The height of the vapor deposition material is in a range of 1 to 10 mm, and preferably, in a range of 2 to 5 mm. This is because, if the diameter is excessively small and smaller than 5 mm or the height is excessively small and smaller than 1 mm, splash occurs, and if the diameter exceeds 30 mm or the height exceeds 10 mm, it is difficult to handle the vapor deposition material in an actual production process.
Hereinafter, a process for producing a ZnO vapor deposition material according to this aspect will be described.
[Production Process]
The ZnO vapor deposition material according to this aspect can be produced by mixing ZnO powder having a purity equal to or greater than 98%, Y2O3 powder in such an amount that the Y content in the ZnO vapor deposition material is in a range of 0.1 to 14.9% by mass, an oxide powder of a second additive element in such an amount that the content of the second additive element in the ZnO vapor deposition material is in a range of 0.1 to 10% by mass, a binder, and an organic solvent to prepare a slurry with a concentration of 30 to 75% by mass, blowing gas into the slurry to obtain a gas-containing slurry, spray-drying the gas-containing slurry to obtain a porous granulation powder having an average grain size of 50 to 300 μm, molding the porous granulation powder to obtain a porous molded body, and sintering the porous molded body at a predetermined temperature to obtain a porous ZnO sintered body.
The ZnO powder preferably has purity equal to or greater than 98%, more preferably, equal to or greater than 98.4%, and still more preferably, equal to or greater than 99%. If the ZnO powder has purity equal to or greater than 98%, reduction of conductivity by the effect of impurities can be suppressed. The average grain size of the ZnO powder is in a range of 0.1 to 10 μm. When the average grain size of the ZnO powder is smaller than 0.1 μm, the powder is excessively fine and aggregated, so there is a tendency that the handling of the powder becomes worse, and it is difficult to prepare a high-concentration slurry. When the average grain size exceeds 10 μm, there is a tendency that it is difficult to control the micro-structure, and a dense pellet is hard to obtain. If the average grain size of the ZnO powder is adjusted to the above-described range, a desired sintered body is also obtained without using a sintering auxiliary agent.
With regard to the Y2O3 powder, considering the prevention of maldistribution of the Y powder, reactivity with a ZnO matrix, and the purity of a Y compound, it is preferable to add Y oxide grains whose primary grain size is of a nanometer scale. The oxide powder of the second additive element preferably has an average grain size of 0.01 to 1 μm, and still more preferably, the average grain size is in a range of 0.05 to 0.5 μm. If the oxide powder of the second additive element having this average grain size is used, it is beneficial in terms of the uniform dispersion of the oxide powder of the second additive element.
For a binder, polyethylene glycol, polyvinyl butyral, or the like may be used. It is preferable to add the binder at 0.2 to 2.5% by mass. For an organic solvent, ethanol, propanol, or the like may be used.
The raw powder, the binder, and the organic solvent are mixed to prepare a slurry with a concentration of 30 to 75% by mass, and preferably, 40 to 65% by mass. If the slurry concentration exceeds 75% by mass, since the slurry is a non-aqueous system, stable granulation is difficult. If the slurry concentration is less than 30% by mass, it is difficult to obtain a dense ZnO sintered body having a uniform composition. If the slurry concentration is adjusted within the above-described range, the viscosity of the slurry is in a range of 200 to 1000 cps. Therefore, powder granulation using a spray drier can be performed stably. Further, the density of a molded body increases, such that a dense sintered body can be obtained.
Wet blending of raw powder, a binder, and an organic solvent, and in particular, wet blending of raw powder and an organic solvent as a dispersion medium is preferably performed by a wet ball mill or a stirring mill. In the case of using a ZrO2 ball in the wet ball mill, wet blending is preferably performed using a large number of ZrO2 balls having a diameter of 5 to 10 mm for 8 to 24 hours, and preferably, for 20 to 24 hours. If the diameter of the ZrO2 ball is smaller than 5 mm, blending may be insufficient. If the diameter of the ZrO2 ball exceeds 10 mm, impurities are increased. Even though the blending time is long, up to 24 hours, impurities are hardly generated due to milling. On the other hand, when a resin ball with a metal support is used in the wet ball mill, a ball having a diameter of 10 to 15 mm is preferably used.
In the stirring mill, wet blending is preferably performed using a ZrO2 ball having a diameter of 1 to 3 mm for 0.5 to 1 hour. If the diameter of the ZrO2 ball is smaller than 1 mm, blending is insufficient. If the diameter exceeds 3 mm, impurities are increased. If the blending time exceeds 1 hour, while raw materials are mixed, milling leads to the generation of impurities. Sufficient blending can be done within 1 hour. Blending/granulation of powder and additives may be performed by a general tumbling granulation method. In this case, it is not necessary to perform a separation operation from the balls or the like after the process, and thus the process is simplified.
In the production process of this aspect, as a first step for obtaining a porous sintered body, gas is blown and mixed into the slurry to prepare a gas-containing slurry. Gas blowing and mixing is preferably performed by blowing using a mechanical pump, gas pressure, or the like. As the gas, air, an insoluble gas, a non-aqueous gas, or the like may be used.
The gas-containing slurry is spray-dried. The spray drying is preferably performed at 150 to 250° C. for 3 hours by using a spray drier. Since gas is blown into the slurry, the granulation powder obtained by spray-drying the slurry is porous. Through the spray drying, a porous granulation powder having an average grain size of 50 to 300 μm can be obtained.
In the production process of this aspect, as a second step for obtaining a porous sintered body, a slurry is prepared in which a foaming agent is mixed. For the foaming agent, an organic foaming agent or an inorganic foaming agent may be used. For the organic foaming agent, azodicarboxylamide, dinitrosobenta methylene tetramine, or the like is used, and for the inorganic foaming agent, carbonate or the like is used. The foaming agent may be mixed with ZnO powder, YO2 powder, and Al2O3 powder, or may be added upon slurry preparation.
The foaming agent-containing slurry is spray-dried. The spray drying is preferably performed at 150 to 250° C. for 3 hours by using a spray drier. The foaming agent contained in the slurry is foamed and dissolved upon this spray drying, such that resultant granulation powder is made porous. Through the spray drying, a porous granulation powder having an average grain size of 50 to 300 μm can be obtained.
In the production process of this aspect, as a third step for obtaining a porous sintered body, a slurry is prepared in which an additive, which will be volatized and dissolved upon sintering, is mixed. Examples of the additive include butyral capable of being dissolved in a solvent, and a cellulose-based additive, a polyvinyl-based additive, a polyester-based additive, a polyethylene-based additive, and the like capable of being dissolved in an alcohol-based solvent. Examples of the additive which will not be dissolved in the alcohol-based solvent include a starch-based additive and a polystyrene-based additive having an average grain size of about several μm to 500 μm. It is preferable that butyral is mixed in the slurry at about 20% by mass, or starch is mixed in the slurry at about 20% by mass.
If the slurry contains the additive, the additive is volatized and dissolved upon sintering to form pores, thereby obtaining a porous sintered body. The diameter and shape of the pores can be controlled by adjusting the kind and amount of the additive. For example, when a butyral-based additive is used, pores having a pore diameter of 0.1 μm to 10 μm order can be formed. When starch is used, pores having the same pore diameter as the grain size of starch and the same shape as starch can be formed. Thus, when starch is used, the pore diameter and shape of the pores can be more easily controlled.
Specifically, in the case of the ZnO vapor deposition material of this aspect, a vapor deposition material using a butyral-based additive can obtain a deposition speed about 1.3 times higher than the evaporation speed of the conventional ZnO vapor deposition material having relative density equal to or greater than about 98%, and a vapor deposition material using starch having an average grain size of 0.1 to 500 μm can obtain an evaporation speed about two times. Therefore, a high speed of film formation can be obtained.
In the production process of this aspect, as a fourth step for obtaining a porous sintered body, a slurry using ZnO powder having a grain size distribution within a predetermined range is prepared. Specifically, ZnO powder having an average grain size of 10 to 500 μm and a grain size distribution within a range of ±10% of the average grain size is used. If the grain size distribution of ZnO powder is outside the range of ±10% of the average grain size, the porosity is lowered. More preferably, the grain size distribution is within a range of ±5% of the average grain size. The preferred grain size of oxide powder of the first additive element and the second additive element is significantly smaller than that of ZnO powder, and the usage is smaller than that of ZnO powder, so oxide powder of the first additive element and the second additive element may be outside the limitation of the grain size distribution.
The slurry using ZnO powder with a controlled grain size distribution is spray-dried. The spray drying is preferably performed at 150 to 250° C. for 3 hours by using a spray drier. In the slurry to be spray-dried, ZnO powder having an average grain size of 10 to 500 μm and a grain size distribution within a range of ±10% of the average grain size is used, and no fine ZnO powder is substantially contained. Thus, there are no cases where fine ZnO grains fill the gaps between ZnO grains, so the gaps between ZnO grains remain as pores, and granulation powder becomes porous. Through the spray drying, a porous granulation powder having an average grain size of 50 to 300 μm can be obtained.
After the slurry is spray-dried to obtain a granulation powder having an average grain size of 50 to 300 μm, the granulation powder is molded under a predetermined pressure. If the average grain size of the granulation powder is smaller than 50 μm, moldability deteriorates, and if the average grain size is larger than 300 μm, the density of the molded body is lowered, and the strength is likely to be insufficient.
For a pressing molding device, a uniaxial press device, a cold isostatic press (CIP) molding device, or other devices may be used. The molding pressure is appropriately in a range of 100 to 2000 kgf/cm2 (9.8 to 196 MPa), and preferably, 100 to 1000 kgf/cm2 (9.8 to 98 MPa). Molding is performed under pressure within the above-described range, such that the density of the molded body can be increased, deformation after sintering can be suppressed, and postprocessing is not required.
Next, the molded body is sintered. Before sintering, the molded body is preferably degreased at a temperature of 350 to 620° C. Through this degreasing, spots on the molded body after sintering can be suppressed. The degreasing is preferably performed for a sufficient time.
Sintering is performed in an atmosphere of air, an inactive gas, a vacuum, or a reductive gas at a temperature equal to or higher than 1000° C., and preferably, at a temperature of 1200 to 1400° C. for 1 to 10 hours, and preferably, for 2 to 5 hours. The sintering is performed under air pressure, but in the case of pressure sintering, such as hot press (HP) sintering or hot isostatic press (HIP) sintering, the sintering is preferably performed in an atmosphere of inactive gas, vacuum, or reductive gas at a temperature equal to or higher than 1000° C. for 1 to 5 hours.
A ZnO film is formed on the surface of the substrate by a vacuum film formation method with a ZnO vapor deposition material composed of the resultant porous sintered body as a target material. As the vacuum film formation method suitable for forming a film using the ZnO vapor deposition material of this aspect, an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method may be used. A ZnO film of this aspect formed by the film formation method uses the ZnO vapor deposition material of this aspect, so the ZnO film has high conductivity with specific resistance of 3 to 5×10−4 Ω·cm and high permeability with visible light permeability equal to or greater than 90%, like ITO.
In the ZnO vapor deposition material of this aspect, the crystal structure distorted by the addition of Y having an ion radius larger than Zn is recovered and aligned by addition of the second additive element having a small ion radius, such as B, Al, or Ga, or Sc having high reactivity is added to recover a film having a regulated crystal structure. Therefore, a dense film can be formed, and the durability of the film can also be improved.
According to the production process of this aspect, in any of the first step of mixing gas in the slurry, the second step of preparing the foaming agent-containing slurry, the third step of preparing the slurry containing the additive which will be volatized and dissolved upon sintering, and the fourth step of preparing the slurry using ZnO powder having a grain size distribution within a predetermined range, the porosity, pore diameter, and pore shape can be easily controlled. Therefore, a vapor deposition material having optimum pores can be produced. As a result, even when a large number of pore states are required by the production conditions or the like, an optimum vapor deposition material can be provided to cope with the requirements.
The ZnO vapor deposition material of this aspect is composed mainly of a porous sintered body having a porosity of 5 to 30% and a pore diameter of 0.1 to 500 μm, so when a ZnO transparent conductive film is formed by an electron beam deposition method or an ion plating method using the ZnO vapor deposition material, the evaporation speed can be improved. That is, when film formation is performed with the same electron beam energy, the speed of film formation increases, and the operation time is shortened, thereby increasing the number of products for a predetermined time. Further, when film formation is performed at the same film formation speed, electron beam energy is reduced, and the replacement timing of a filament of an electron gun or the like is delayed, such that the number of times of maintenance is reduced and productivity is improved. As a result, production costs can be reduced.
Next, another aspect of the present invention will be described.
[ZnO Vapor Deposition Material]
A ZnO vapor deposition material of this aspect is a ZnO vapor deposition material for formation of a transparent conductive film which is composed of a sintered body containing ZnO as a major component, wherein the sintered body contains a first additive element and a second additive element, the first additive element is one or more elements selected from the group consisting of Pr, Nd, Pm, and Sm, the second additive element is one or more elements selected from the group consisting of B, Al, Ga, and Sc, the content of the first additive element is in a range of 0.1 to 14.9% by mass, the content of the second additive element is in a range of 0.1 to 10% by mass, the content of the first additive element is higher than the content of the second additive element, and the sintered body is a porous sintered body having a porosity of 3 to 50%.
The inventors have investigated in detail the effect on conductivity due to additive species and the content in a ZnO vapor deposition material and a ZnO film formed by using the vapor deposition material, and have found that there is a significant level of influence on conductivity due to the species and content of one or more first additive elements selected from the group consisting of Pr, Nd, Pm, and Sm and one or more second additive elements selected from the group consisting of B, Al, Ga, and Sc in the porous ZnO sintered body. Based on the above-described knowledge, the ZnO vapor deposition material according to this aspect contains ZnO as a major component, and also contains the first additive elements and the second additive elements, such that excess electrons contributing to conduction are developed in large amounts and maintained, thereby forming a ZnO film having high conductivity.
The ZnO vapor deposition material of this aspect contains the first additive element and the second additive element together, the first additive element is one or more rare earth elements selected from the group consisting of Pr, Nd, Pm, and Sm, and the second additive element is one or more elements selected from B, Al, Ga, and Sc. Of the second additive elements, B, Al, and Ga have an ion radius smaller than the first additive element (rare earth element), so crystals distorted by the addition of the first additive element having an ion radius larger than Zn are recovered and aligned by adding the second additive element, such as B, Al, or Ga, or the crystal structure distorted by the addition of the first additive element is recovered and aligned by adding Sc having high reactivity as the second additive element. For this reason, a ZnO film having high permeability, excellent denseness, high conductivity, and excellent durability can be formed.
As the ratio of the first additive element and the second additive element in the porous ZnO sintered body increases within a predetermined range, the conductivity of the ZnO film becomes better, and if the ratio is outside the range, the conductivity adversely deteriorates. Specifically, the content of the first additive element in the ZnO vapor deposition material is appropriately in a range of 0.1 to 14.9% by mass, and preferably, in a range of 3 to 6% by mass. If the content of the first additive element is lower than the lower limit value, 0.1% by mass, the conductivity is significantly lowered. If the content of the first additive element exceeds the upper limit value, 14.9% by mass, the permeability is significantly lowered.
The content of the second additive element in the ZnO vapor deposition material is appropriately in a range of 0.1 to 10% by mass, and preferably, in a range of 1 to 3% by mass. If the content of the second additive element is lower than the lower limit value, 0.1% by mass, the conductivity is significantly lowered. If the content of the second additive element exceeds the upper limit value, 10% by mass, compositional shift at the time of deposition occurs.
The ZnO vapor deposition material of this aspect contains a larger amount of the first additive element than the second additive element, such that a dense crystal structure is maintained. If the content of the first additive element is lower than that of the second additive element, the conductivity and permeability are lowered. The total content of the first additive element and the second additive element is preferably in a range of 0.2 to 15% by mass. If the total content of the first additive element and the second additive element exceeds this range, the specific resistance and permeability of the ZnO vapor deposition material are significantly lowered.
When a very small amount of the first additive element and the second additive element is contained in the ZnO vapor deposition material, the first additive element and the second additive element do not exist as granular precipitates in grain boundaries or grains in the ZnO matrix but are uniformly dispersed in the ZnO vapor deposition material. It is considered that, in the ZnO vapor deposition material, the first additive element and the second additive element are present as oxides.
The ZnO vapor deposition material of this aspect contains the first additive element, which is a trivalent or quadrivalent rare earth element, and the first additive element causes excess carrier electrons to be generated with respect to divalent Zn, such that high conductivity can be ensured. When a rare earth element is added to the ZnO vapor deposition material, compositional shift at the time of deposition is unlikely to occur, and a desired composition ratio can be maintained when a film is formed.
According to the ZnO vapor deposition material of this aspect, the conductivity is obtained by oxygen defect as well as compulsive injection of carrier electrons. Usually, oxygen gas is introduced in a vapor deposition method, but generally oxygen in the film composition is insufficient. At the time of transparent conductive film formation, a technique is conventionally used in which resistance is lowered by generating oxygen defect. However, in the case of adding a rare earth element, it is easy to control because the element is excellent in evaporation performance. In addition to this advantage by the addition of the first additive element which is a rare earth element, since the ZnO vapor deposition material of this aspect contains the second additive element, high conductivity like ITO can be obtained.
The ZnO vapor deposition material of this aspect is composed of a porous ZnO sintered body having a porosity of 3 to 50%. The porosity of the sintered body is appropriately in a range of 3 to 50%, preferably in a range of 5 to 30%, more preferably in a range of 10 to 30%, and still more preferably in a range of 20 to 30%. If the porosity is smaller than 3%, it is not preferable since, at the time of film formation by an electron beam deposition method or an ion plating method, the evaporation speed of the vapor deposition material does not increase, and as a result, the speed of film formation decreases, which results in an increase in production costs. If the porosity exceeds 50%, the strength of the porous sintered body is lowered, and it is difficult to obtain sufficient mechanical strength. If the porosity is equal to or greater than 10%, the evaporation speed can be improved. Further, if the porosity is equal to or greater than 20%, a vapor deposition material having an evaporation speed about two times higher than the conventional ZnO vapor deposition material can be obtained.
In the porous ZnO sintered body of this aspect, the pores preferably have an average pore diameter of 0.1 to 500 μm. If the average pore diameter of the pores is within the above-described range, the evaporation speed can be further increased. If the pore diameter is smaller than 0.1 μm, there is no merit in the pores. If the pore diameter exceeds 500 μm, it is not preferable because the strength of the sintered body is lowered, which causes damages due to EB (electron beam) irradiation, that is, splash.
The term “pore diameter” (the inner diameter of the pore) refers to, for example, the maximum value of the internal dimensions in the pores when the sectional portion of the vapor deposition material is observed by observation means, such as SEM or the like. As the evaluation method of the pores, measurement of porosity by a substitution method, measurement of porosity by microscopy, measurement of surface area and micropore distribution by gas absorption, measurement of surface area and micropore distribution by a mercury intrusion method, measurement of surface area by a gas permeation method, or measurement of micropore distribution by an X-ray small-angle scattering method may be used.
The pores are preferably rounded, and in terms of improvement in the evaporation speed, micropores are preferably formed at the surface of the pores. For the evaluation method of the pores, the surface area is preferably in a range of 5 to 40 m2/g, and at least one peak of the micropore distribution is present within a range of 1 to 100 μm. Portions (frame portion) other than the pores are preferably substantially sintered. For example, the frame portion of the porous sintered body preferably has a density equal to or greater than 98%.
In the porous ZnO sintered body of this aspect, it is preferable that grains preferably have an average crystal grain size of 1 to 500 μm, and rounded pores of about 0.1 to 500 μm are provided in the sintered body. The porous ZnO sintered body has a fine crystal structure in which the average crystal grain size is within the above-described range, and the occurrence of defects in the boundary of crystal grains can be reduced. Thus, the formed ZnO film has excellent film characteristics, such as ZnO film density, thickness distribution, refractive index, sputtering resistance, discharge characteristics (discharge voltage, discharge responsiveness, and the like), insulation characteristics, and the like. If the average crystal grain size is smaller than 1 μm, the speed of film formation is lowered. If the average crystal grain size exceeds 500 μm, the deposition rate of the additive element is not uniform. The average crystal grain size is preferably in a range of 5 to 40 μm, and more preferably, in a range of 10 to 30 μm.
The ZnO vapor deposition material of this aspect is preferably molded in the form of disc-like or circular pellets. When the vapor deposition material has a circular shape, the diameter of the vapor deposition material is appropriately in a range of 5 to 30 mm, and preferably, in a range of 5 to 15 mm. This is because, if the diameter is excessively small and smaller than 5 mm, splash occurs, and if the diameter exceeds 30 mm, it is difficult to handle the vapor deposition material in an actual production process. When the vapor deposition material is disc-like, the diameter of the vapor deposition material is appropriately in a range of 5 to 20 mm, and preferably, in a range of 5 to 10 mm. The height of the vapor deposition material is in a range of 1 to 10 mm, and preferably, in a range of 2 to 5 mm. This is because, if the diameter is excessively small and smaller than 5 mm or the height is excessively small and smaller than 1 mm, splash occurs, and if the diameter exceeds 30 mm or the height exceeds 10 mm, it is difficult to handle the vapor deposition material in an actual production process.
Hereinafter, a process for producing a ZnO vapor deposition material according to this aspect will be described.
[Production Process]
The ZnO vapor deposition material according to this aspect can be produced by mixing ZnO powder having a purity equal to or greater than 98%, an oxide powder of a first additive element in such an amount that the content of the first additive element in the ZnO vapor deposition material is in a range of 0.1 to 14.9% by mass, an oxide powder of a second additive element in such an amount that the content of the second additive element in the ZnO vapor deposition material is in a range of 0.1 to 10% by mass, a binder, and an organic solvent to prepare a slurry with a concentration of 30 to 75% by mass, blowing gas into the slurry to obtain a gas-containing slurry, spray-drying the gas-containing slurry to obtain a porous granulation powder having an average grain size of 50 to 300 μm, molding the porous granulation powder to obtain a porous molded body, and sintering the porous molded body at a predetermined temperature to obtain a porous ZnO sintered body.
The ZnO powder preferably has purity equal to or greater than 98%, more preferably, equal to or greater than 98.4%, and still more preferably, equal to or greater than 99%. If the ZnO powder has purity equal to or greater than 98%, reduction of conductivity by the effect of impurities can be suppressed. The average grain size of the ZnO powder is in a range of 0.1 to 10 μm. When the average grain size of the ZnO powder is smaller than 0.1 μm, the powder is excessively fine and aggregated, so there is a tendency that the handling of the powder becomes worse, and it is difficult to prepare a high-concentration slurry. When the average grain size exceeds 10 μm, there is a tendency that it is difficult to control the micro-structure, and a dense pellet is hard to obtain. If the average grain size of the ZnO powder is adjusted to the above-described range, a desired sintered body is also obtained without using a sintering auxiliary agent.
With regard to the oxide powder of the first additive element, considering the prevention of maldistribution of powder of the first additive element, reactivity with a ZnO matrix, and the purity of a compound of the first additive element, it is preferable to add oxide grains whose primary grain size is of a nanometer scale. The oxide powder of the second additive element preferably has an average grain size of 0.01 to 1 μm, and still more preferably, the average grain size is in a range of 0.05 to 0.5 μm. If the oxide powder of the second additive element having this average grain size is used, it is beneficial in terms of the uniform dispersion of the oxide powder of the second additive element.
For a binder, polyethylene glycol, polyvinyl butyral, or the like may be used. It is preferable to add the binder at 0.2 to 2.5% by mass. For an organic solvent, ethanol, propanol, or the like may be used.
The raw powder, the binder, and the organic solvent are mixed to prepare a slurry with a concentration of 30 to 75% by mass, and preferably, 40 to 65% by mass. If the slurry concentration exceeds 75% by mass, since the slurry is a non-aqueous system, stable granulation is difficult. If the slurry concentration is less than 30% by mass, it is difficult to obtain a dense ZnO sintered body having a uniform composition. If the slurry concentration is adjusted within the above-described range, the viscosity of the slurry is in a range of 200 to 1000 cps. Therefore, powder granulation using a spray drier can be performed stably. Further, the density of a molded body increases, such that a dense sintered body can be obtained.
Wet blending of raw powder, a binder, and an organic solvent, and in particular, wet blending of raw powder and an organic solvent as a dispersion medium is preferably performed by a wet ball mill or a stirring mill. In the case of using a ZrO2 ball in the wet ball mill, wet blending is preferably performed using a large number of ZrO2 balls having a diameter of 5 to 10 mm for 8 to 24 hours, and preferably, for 20 to 24 hours. If the diameter of the ZrO2 ball is smaller than 5 mm, blending may be insufficient. If the diameter of the ZrO2 ball exceeds 10 mm, impurities are increased. Even though the blending time is long, up to 24 hours, impurities are hardly generated due to milling. On the other hand, when a resin ball with a metal support is used in the wet ball mill, a ball having a diameter of 10 to 15 mm is preferably used.
In the stirring mill, wet blending is preferably performed using a ZrO2 ball having a diameter of 1 to 3 mm for 0.5 to 1 hour. If the diameter of the ZrO2 ball is smaller than 1 mm, blending is insufficient. If the diameter exceeds 3 mm, impurities are increased. If the blending time exceeds 1 hour, while raw materials are mixed, milling leads to the generation of impurities. Sufficient blending can be done within 1 hour. Blending/granulation of powder and additives may be performed by a general tumbling granulation method. In this case, it is not necessary to perform a separation operation from the balls or the like after the process, and thus the process is simplified.
In the production process of this aspect, as a first step for obtaining a porous sintered body, gas is blown and mixed into the slurry to prepare a gas-containing slurry. Gas blowing and mixing is preferably performed by blowing using a mechanical pump, gas pressure, or the like. As the gas, air, an insoluble gas, a non-aqueous gas, or the like may be used.
The gas-containing slurry is spray-dried. The spray drying is preferably performed at 150 to 250° C. for 3 hours by using a spray drier. Since gas is blown into the slurry, the granulation powder obtained by spray-drying the slurry is porous. Through the spray drying, a porous granulation powder having an average grain size of 50 to 300 μm can be obtained.
In the production process of this aspect, as a second step for obtaining a porous sintered body, a slurry is prepared in which a foaming agent is mixed. For the foaming agent, an organic foaming agent or an inorganic foaming agent may be used. For the organic foaming agent, azodicarboxylamide, dinitrosobenta methylene tetramine, or the like is used, and for the inorganic foaming agent, carbonate or the like is used. The foaming agent may be mixed with ZnO powder, oxide powder of the first additive element, and Al2O3 powder, or may be added upon slurry preparation.
The foaming agent-containing slurry is spray-dried. The spray drying is preferably performed at 150 to 250° C. for 3 hours by using a spray drier. The foaming agent contained in the slurry is foamed and dissolved upon this spray drying, such that resultant granulation powder is made porous. Through the spray drying, a porous granulation powder having an average grain size of 50 to 300 μm can be obtained.
In the production process of this aspect, as a third step for obtaining a porous sintered body, a slurry is prepared in which an additive, which will be volatized and dissolved upon sintering, is mixed. Examples of the additive include butyral capable of being dissolved in a solvent, and a cellulose-based additive, a polyvinyl-based additive, a polyester-based additive, a polyethylene-based additive, and the like capable of being dissolved in an alcohol-based solvent. Examples of the additive which will not be dissolved in the alcohol-based solvent include a starch-based additive and a polystyrene-based additive having an average grain size of about several μm to 500 μm. It is preferable that butyral is mixed in the slurry at about 20% by mass, or starch is mixed in the slurry at about 20% by mass.
If the slurry contains the additive, the additive is volatized and dissolved upon sintering to form pores, thereby obtaining a porous sintered body. The diameter and shape of the pores can be controlled by adjusting the kind and amount of the additive. For example, when a butyral-based additive is used, pores having a pore diameter of 0.1 μm to 10 μm order can be formed. When starch is used, pores having the same pore diameter as the grain size of starch and the same shape as starch can be formed. Thus, when starch is used, the pore diameter and shape of the pores can be more easily controlled.
Specifically, in the case of the ZnO vapor deposition material of this aspect, a vapor deposition material using a butyral-based additive can obtain a deposition speed about 1.3 times higher than the evaporation speed of the conventional ZnO vapor deposition material having relative density equal to or greater than about 98%, and a vapor deposition material using starch having an average grain size of 0.1 to 500 μm can obtain an evaporation speed about 2.5 times higher than the evaporation speed of the conventional ZnO vapor deposition material having relative density equal to or greater than about 98%. Therefore, a high speed of film formation can be obtained.
In the production process of this aspect, as a fourth step for obtaining a porous sintered body, a slurry using ZnO powder having a grain size distribution within a predetermined range is prepared. Specifically, ZnO powder having an average grain size of 10 to 500 μm and a grain size distribution within a range of ±10% of the average grain size is used. If the grain size distribution of ZnO powder is outside the range of ±10% of the average grain size, the porosity is lowered. More preferably, the grain size distribution is within a range of ±5% of the average grain size. The preferred grain size of oxide powder of the first additive element and Al2O3 powder is significantly smaller than that of ZnO powder, and the usage is smaller than that of ZnO powder, so oxide powder of the first additive element and Al2O3 powder may be outside the limitation of the grain size distribution.
The slurry using ZnO powder with a controlled grain size distribution is spray-dried. The spray drying is preferably performed at 150 to 250° C. for 3 hours by using a spray drier. In the slurry to be spray-dried, ZnO powder having an average grain size of 10 to 500 μm and a grain size distribution within a range of ±10% of the average grain size is used, and no fine ZnO powder is substantially contained. Thus, there are no cases where fine ZnO grains fill the gaps between ZnO grains, so the gaps between ZnO grains remain as pores, and granulation powder becomes porous. Through the spray drying, a porous granulation powder having an average grain size of 50 to 300 μm can be obtained.
After the slurry is spray-dried to obtain a granulation powder having an average grain size of 50 to 300 μm, the granulation powder is molded under a predetermined pressure. If the average grain size of the granulation powder is smaller than 50 μm, moldability deteriorates, and if the average grain size is larger than 300 μm, the density of the molded body is lowered, and the strength is likely to be insufficient.
For a pressing molding device, a uniaxial press device, a cold isostatic press (CIP) molding device, or other devices may be used. The molding pressure is appropriately in a range of 100 to 2000 kgf/cm2 (9.8 to 196 MPa), and preferably, 100 to 1000 kgf/cm2 (9.8 to 98 MPa). Molding is performed under pressure within the above-described range, such that the density of the molded body can be increased, deformation after sintering can be suppressed, and postprocessing is not required.
Next, the molded body is sintered. Before sintering, the molded body is preferably degreased at a temperature of 350 to 620° C. Through this degreasing, spots on the molded body after sintering can be suppressed. The degreasing is preferably performed for a sufficient time.
Sintering is performed in an atmosphere of air, an inactive gas, a vacuum, or a reductive gas at a temperature equal to or higher than 1000° C., and preferably, at a temperature of 1200 to 1400° C. for 1 to 10 hours, and preferably, for 2 to 5 hours. The sintering is performed under air pressure, but in the case of pressure sintering, such as hot press (HP) sintering or hot isostatic press (HIP) sintering, the sintering is preferably performed in an atmosphere of inactive gas, vacuum, or reductive gas at a temperature equal to or higher than 1000° C. for 1 to 5 hours.
A ZnO film is formed on the surface of the substrate by a vacuum film formation method with a ZnO vapor deposition material composed of the resultant porous sintered body as a target material. As the vacuum film formation method suitable for forming a film using the ZnO vapor deposition material of this aspect, an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method may be used. A ZnO film of this aspect formed by the film formation method uses the ZnO vapor deposition material of this aspect, so the ZnO film has high conductivity with specific resistance of 3 to 5×10−4 Ω·cm and high permeability with visible light permeability equal to or greater than 90%, like ITO.
In the ZnO vapor deposition material of this aspect, the crystal structure distorted by the addition of the first additive element (rare earth element) having an ion radius larger than Zn is recovered and aligned by addition of the second additive element having a small ion radius, such as B, Al, or Ga, or Sc having high reactivity is added to recover a film having a regulated crystal structure. Therefore, a dense film can be formed, and the durability of the film can also be improved.
According to the production process of this aspect, in any of the first step of mixing gas in the slurry, the second step of preparing the foaming agent-containing slurry, the third step of preparing the slurry containing the additive which will be volatized and dissolved upon sintering, and the fourth step of preparing the slurry using ZnO powder having a grain size distribution within a predetermined range, the porosity, pore diameter, and pore shape can be easily controlled. Therefore, a vapor deposition material having optimum pores can be produced. As a result, even when a large number of pore states are required by the production conditions or the like, an optimum vapor deposition material can be provided to cope with the requirements.
The ZnO vapor deposition material of this aspect is composed mainly of a porous sintered body having a porosity of 5 to 30% and a pore diameter of 0.1 to 500 μm, so when a ZnO transparent conductive film is formed by an electron beam deposition method or an ion plating method using the ZnO vapor deposition material, the evaporation speed can be improved. That is, when film formation is performed with the same electron beam energy, the speed of film formation increases, and the operation time is shortened, thereby increasing the number of products for a predetermined time. Further, when film formation is performed at the same film formation speed, electron beam energy is reduced, and the replacement timing of a filament of an electron gun or the like is delayed, such that the number of times of maintenance is reduced and productivity is improved. As a result, production costs can be reduced.
Next, another aspect of the present invention will be described.
[ZnO Vapor Deposition Material]
A ZnO vapor deposition material of this aspect is a ZnO vapor deposition material for formation of a transparent conductive film which is composed of a ZnO sintered body having a ZnO purity equal to or greater than 98%, wherein the sintered body contains one or more additive elements selected from the group consisting of Y, La, Sc, Ce, Pr, Nd, Pm, and Sm, and the sintered body is a porous sintered body having a porosity of 3 to 50%.
The inventors have investigated in detail the effect on conductivity due to additive species and the content in a ZnO vapor deposition material and a ZnO film formed by using the vapor deposition material, and have found that there is a significant level of influence on conductivity due to the species and content of one or more additive elements selected from the group consisting of Y, La, Sc, Ce, Pr, Nd, Pm, and Sm in the porous ZnO sintered body. Based on the above-described knowledge, the ZnO vapor deposition material according to this aspect contains ZnO as a major component, and also contains the additive elements, such that excess electrons contributing to conduction are developed in large amounts and maintained, thereby forming a ZnO film having high conductivity.
The ZnO vapor deposition material of this aspect is composed of a ZnO sintered body having a ZnO purity equal to or greater than 98%, preferably equal to or greater than 98.4%, and more preferably equal to or greater than 99%. If the ZnO purity is smaller than 98%, the conductivity is lowered by the effect of impurities. The ZnO sintered body may be monocrystal or polycrystal.
The ZnO sintered body contains one or more additive elements selected from the group consisting of Y, La, Sc, Ce, Pr, Nd, Pm, and Sm. The additive element includes a misch metal (also indicated by Mm) which is a mixture with La, Ce, or Nd as a major component.
As the concentration of the additive elements in the porous ZnO sintered body increases, the conductivity of the ZnO film becomes better, and if the concentration further increases, the conductivity adversely deteriorates. Thus, there is an optimum concentration range for obtaining a ZnO film having high conductivity. Specifically, the content of the additive elements is appropriately in a range of 2 to 20% by mass, and preferably, in a range of 3 to 6% by mass. If the content of the additive elements is lower than 2% by mass, the conductivity is not improved. If the content of the additive elements exceeds 20% by mass, the conductivity is lowered and the permeability is deteriorated.
Since a very small amount of the additive elements is contained, the additive elements do not exist as granular precipitates in grain boundaries or grains in the ZnO matrix but are uniformly dispersed in the ZnO sintered body. The additive elements exist in the ZnO vapor deposition material as oxide. For example, Y is present as Y2O3, and La is present as La2O3. Sc is present as Sc2O3, and Ce is present as CeO2 or Ce2O3. Pr is present as Pr6O11, and Nd is present as Nd2O3. Pm is present as Pm2O3, and Sm is present as Sm2O3.
The ZnO vapor deposition material of this aspect contains a tri- or quadri- or more valent rare earth element, and the rare earth element can cause excess carrier electrons to be generated with respect to divalent Zn. When a rare earth element is added to the ZnO vapor deposition material, compositional shift at the time of deposition is unlikely to occur, and a desired composition ratio can be maintained when a film is formed.
In general, as a mechanism for obtaining the conductivity, oxygen defect is used, as well as compulsive injection of carrier electrons. Usually, oxygen gas is introduced in a vapor deposition method, but generally oxygen in the film composition is insufficient. At the time of transparent conductive film formation, a technique is conventionally used in which resistance is lowered by generating oxygen defect. However, in the case of adding a rare earth element, it is easy to control because the element is excellent in evaporation performance. With this advantage, the present invention uses an additive element other than Al or Ga, thereby obtaining conductivity like ITO.
The ZnO vapor deposition material of this aspect is composed of a porous ZnO sintered body having a porosity of 3 to 50%. The porosity of the sintered body is appropriately in a range of 3 to 50%, preferably in a range of 5 to 30%, more preferably in a range of 10 to 30%, and still more preferably in a range of 20 to 30%. If the porosity is smaller than 3%, it is not preferable since, at the time of film formation by an electron beam deposition method or an ion plating method, the evaporation speed of the vapor deposition material does not increase, and as a result, the speed of film formation decreases, which results in an increase in production costs. If the porosity exceeds 50%, the strength of the porous sintered body is lowered, and it is difficult to obtain sufficient mechanical strength. If the porosity is equal to or greater than 10%, the evaporation speed can be improved. Further, if the porosity is equal to or greater than 20%, a vapor deposition material having an evaporation speed about two times higher than the conventional ZnO vapor deposition material can be obtained.
In the porous ZnO sintered body of this aspect, the pores preferably have an average pore diameter of 0.1 to 500 μm. If the average pore diameter of the pores is within the above-described range, the evaporation speed can be further increased. If the pore diameter is smaller than 0.1 μm, there is no merit in the pores. If the pore diameter exceeds 500 μm, it is not preferable because the strength of the sintered body is lowered, which causes damages due to EB (electron beam) irradiation, that is, splash.
The term “pore diameter” (the inner diameter of the pore) refers to, for example, the maximum value of the internal dimensions in the pores when the sectional portion of the vapor deposition material is observed by observation means, such as SEM or the like. As the evaluation method of the pores, measurement of porosity by a substitution method, measurement of porosity by microscopy, measurement of surface area and micropore distribution by gas absorption, measurement of surface area and micropore distribution by a mercury intrusion method, measurement of surface area by a gas permeation method, or measurement of micropore distribution by an X-ray small-angle scattering method may be used.
The pores are preferably rounded, and in terms of improvement in the evaporation speed, micropores are preferably formed at the surface of the pores. For the evaluation method of the pores, the surface area is preferably in a range of 5 to 40 m2/g, and at least one peak of the micropore distribution is present within a range of 1 to 100 μm. Portions (frame portion) other than the pores are preferably substantially sintered. For example, the frame portion of the porous sintered body preferably has a density equal to or greater than 98%.
In the porous ZnO sintered body of this aspect, it is preferable that grains preferably have an average crystal grain size of 1 to 500 μm, and rounded pores of about 0.1 to 500 μm are provided in the sintered body. The porous ZnO sintered body has a fine crystal structure in which the average crystal grain size is within the above-described range, and the occurrence of defects in the boundary of crystal grains can be reduced. Thus, the formed ZnO film has excellent film characteristics, such as ZnO film density, thickness distribution, refractive index, sputtering resistance, discharge characteristics (discharge voltage, discharge responsiveness, and the like), insulation characteristics, and the like. If the average crystal grain size is smaller than 1 μm, the speed of film formation is lowered. If the average crystal grain size exceeds 500 μm, the deposition rate of the additive element is not uniform. The average crystal grain size is preferably in a range of 5 to 40 μm, and more preferably, in a range of 10 to 30 μm.
The ZnO vapor deposition material of this aspect is preferably molded in the form of disc-like or circular pellets. When the vapor deposition material has a circular shape, the diameter of the vapor deposition material is appropriately in a range of 5 to 30 mm, and preferably, in a range of 5 to 15 mm. This is because, if the diameter is excessively small and smaller than 5 mm, splash occurs, and if the diameter exceeds 30 mm, it is difficult to handle the vapor deposition material in an actual production process. When the vapor deposition material is disk-like, the diameter of the vapor deposition material is appropriately in a range of 5 to 50 mm, and preferably, in a range of 5 to 10 mm. The height of the vapor deposition material is in a range of 1 to 30 mm, and preferably, in a range of 2 to 5 mm. This is because, if the diameter is excessively small and smaller than 5 mm or the height is excessively small and smaller than 1 mm, splash occurs, and if the diameter exceeds 50 mm or the height exceeds 30 mm, upon deposition, a uniform film is not formed and the film formation speed is lowered due to the decrease in the filling ratio to a hearth (vapor deposition material crucible).
Hereinafter, a process for producing a ZnO vapor deposition material according to this aspect will be described.
[Production Process]
The ZnO vapor deposition material according to this aspect can be produced by mixing ZnO powder having a purity equal to or greater than 98%, an oxide powder of additive elements, a binder, and an organic solvent to prepare a slurry with a concentration of 30 to 75% by mass, blowing gas into the slurry to obtain a gas-containing slurry, spray-drying the gas-containing slurry to obtain a porous granulation powder having an average grain size of 50 to 300 μm, molding the porous granulation powder to obtain a porous molded body, and sintering the porous molded body at a predetermined temperature to obtain a porous ZnO sintered body.
The ZnO powder preferably has purity equal to or greater than 98%, more preferably, equal to or greater than 98.4%, and still more preferably, equal to or greater than 99%. If the ZnO powder has purity equal to or greater than 98%, reduction of conductivity by the effect of impurities can be suppressed. The average grain size of the ZnO powder is in a range of 0.1 to 10 μm. When the average grain size of the ZnO powder is smaller than 0.1 μm, the powder is excessively fine and aggregated, so there is a tendency that the handling of the powder becomes worse, and it is difficult to prepare a high-concentration slurry. When the average grain size exceeds 10 μm, there is a tendency that it is difficult to control the micro-structure, and a dense pellet is hard to obtain. If the average grain size of the ZnO powder is adjusted to the above-described range, a desired sintered body is also obtained without using a sintering auxiliary agent.
With regard to the oxide powder of the additive element, considering the prevention of maldistribution of the powder, reactivity with a ZnO matrix, and the purity of a compound of the additive element, it is preferable to add oxide grains whose primary grain size is of a nanometer scale. The oxide powder of the additive element preferably has an average grain size of 0.01 to 1 μm, and still more preferably, the average grain size is in a range of 0.05 to 0.5 μm. If the oxide powder of the additive element having this average grain size is used, it is beneficial in terms of the uniform dispersion of the oxide powder of the additive element.
Oxide powder is used in such an amount that the content of the additive elements in the ZnO sintered body is in a range of 2 to 20% by mass, and preferably, in a range of 3 to 6% by mass, and oxide powder of the additive elements are mixed in ZnO powder to prepare raw powder.
For a binder, polyethylene glycol, polyvinyl butyral, or the like may be used. It is preferable to add the binder at 0.2 to 2.5% by mass. For an organic solvent, ethanol, propanol, or the like may be used.
The raw powder, the binder, and the organic solvent are mixed to prepare a slurry with a concentration of 30 to 75% by mass, and preferably, 40 to 65% by mass. If the slurry concentration exceeds 75% by mass, since the slurry is a non-aqueous system, stable granulation is difficult. If the slurry concentration is less than 30% by mass, it is difficult to obtain a dense ZnO sintered body having a uniform composition. If the slurry concentration is adjusted within the above-described range, the viscosity of the slurry is in a range of 200 to 1000 cps. Therefore, powder granulation using a spray drier can be performed stably. Further, the density of a molded body increases, such that a dense sintered body can be obtained.
Wet blending of raw powder, a binder, and an organic solvent, and in particular, wet blending of raw powder and an organic solvent as a dispersion medium is preferably performed by a wet ball mill or a stirring mill. In the case of using a ZrO2 ball in the wet ball mill, wet blending is preferably performed using a large number of ZrO2 balls having a diameter of 5 to 10 mm for 8 to 24 hours, and preferably, for 20 to 24 hours. If the diameter of the ZrO2 ball is smaller than 5 mm, blending may be insufficient. If the diameter of the ZrO2 ball exceeds 10 mm, impurities are increased. Even though the blending time is long, up to 24 hours, impurities are hardly generated due to milling. On the other hand, when a resin ball with a metal support is used in the wet ball mill, a ball having a diameter of 10 to 15 mm is preferably used.
In the stirring mill, wet blending is preferably performed using a ZrO2 ball having a diameter of 1 to 3 mm for 0.5 to 1 hour. If the diameter of the ZrO2 ball is smaller than 1 mm, blending is insufficient. If the diameter exceeds 3 mm, impurities are increased. If the blending time exceeds 1 hour, while raw materials are mixed, milling leads to the generation of impurities. Sufficient blending can be done within 1 hour. Blending/granulation of powder and additives may be performed by a general tumbling granulation method. In this case, it is not necessary to perform a separation operation from the balls or the like after the process, and thus the process is simplified.
In the production process of this aspect, as a first step for obtaining a porous sintered body, gas is blown and mixed into the slurry to prepare a gas-containing slurry. Gas blowing and mixing is preferably performed by blowing using a mechanical pump, gas pressure, or the like. As the gas, air, an insoluble gas, a non-aqueous gas, or the like may be used.
The gas-containing slurry is spray-dried. The spray drying is preferably performed at 150 to 250° C. for 3 hours by using a spray drier. Since gas is blown into the slurry, the granulation powder obtained by spray-drying the slurry is porous. Through the spray drying, a porous granulation powder having an average grain size of 50 to 300 μm can be obtained.
In the production process of this aspect, as a second step for obtaining a porous sintered body, a slurry is prepared in which a foaming agent is mixed. For the foaming agent, an organic foaming agent or an inorganic foaming agent may be used. For the organic foaming agent, azodicarboxylamide, dinitrosobenta methylene tetramine, or the like is used, and for the inorganic foaming agent, carbonate or the like is used. The foaming agent may be mixed with ZnO powder, oxide powder of the first additive element, and Al2O3 powder, or may be added upon slurry preparation.
The foaming agent-containing slurry is spray-dried. The spray drying is preferably performed at 150 to 250° C. for 3 hours by using a spray drier. The foaming agent contained in the slurry is foamed and dissolved upon this spray drying, such that resultant granulation powder is made porous. Through the spray drying, a porous granulation powder having an average grain size of 50 to 300 μm can be obtained.
In the production process of this aspect, as a third step for obtaining a porous sintered body, a slurry is prepared in which an additive, which will be volatized and dissolved upon sintering, is mixed. Examples of the additive include butyral capable of being dissolved in a solvent, and a cellulose-based additive, a polyvinyl-based additive, a polyester-based additive, a polyethylene-based additive, and the like capable of being dissolved in an alcohol-based solvent. Examples of the additive which will not be dissolved in the alcohol-based solvent include a starch-based additive and a polystyrene-based additive having an average grain size of about several μm to 500 μm. It is preferable that butyral is mixed in the slurry at about 20% by mass, or starch is mixed in the slurry at about 20% by mass.
If the slurry contains the additive, the additive is volatized and dissolved upon sintering to form pores, thereby obtaining a porous sintered body. The diameter and shape of the pores can be controlled by adjusting the kind and amount of the additive. For example, when a butyral-based additive is used, pores having a pore diameter of 0.1 μm to 10 μm order can be formed. When starch is used, pores having the same pore diameter as the grain size of starch and the same shape as starch can be formed. Thus, when starch is used, the pore diameter and shape of the pores can be more easily controlled.
Specifically, in the case of the ZnO vapor deposition material of this aspect, a vapor deposition material using a butyral-based additive can obtain a deposition speed about 1.3 times higher than the evaporation speed of the conventional ZnO vapor deposition material having relative density equal to or greater than about 98%, and a vapor deposition material using starch having an average grain size of 0.1 to 500 μm can obtain an evaporation speed about 2.5 times higher than the evaporation speed of the conventional ZnO vapor deposition material having relative density equal to or greater than about 98%. Therefore, a high speed of film formation can be obtained.
In the production process of this aspect, as a fourth step for obtaining a porous sintered body, a slurry using ZnO powder having a grain size distribution within a predetermined range is prepared. Specifically, ZnO powder having an average grain size of 10 to 500 μm and a grain size distribution within a range of ±10% of the average grain size is used. If the grain size distribution of ZnO powder is outside the range of ±10% of the average grain size, the porosity is lowered. More preferably, the grain size distribution is within a range of ±5% of the average grain size. The preferred grain size of oxide powder of the first additive element and Al2O3 powder is significantly smaller than that of ZnO powder, and the usage is smaller than that of ZnO powder, so oxide powder of the first additive element and Al2O3 powder may be outside the limitation of the grain size distribution.
The slurry using ZnO powder with a controlled grain size distribution is spray-dried. The spray drying is preferably performed at 150 to 250° C. for 3 hours by using a spray drier. In the slurry to be spray-dried, ZnO powder having an average grain size of 10 to 500 μm and a grain size distribution within a range of ±10% of the average grain size is used, and no fine ZnO powder is substantially contained. Thus, there are no cases where fine ZnO grains fill the gaps between ZnO grains, so the gaps between ZnO grains remain as pores, and granulation powder becomes porous. Through the spray drying, a porous granulation powder having an average grain size of 50 to 300 μm can be obtained.
After the slurry is spray-dried to obtain a granulation powder having an average grain size of 50 to 300 μm, the granulation powder is molded under a predetermined pressure. If the average grain size of the granulation powder is smaller than 50 μm, moldability deteriorates, and if the average grain size is larger than 300 μm, the density of the molded body is lowered, and the strength is likely to be insufficient.
For a pressing molding device, a uniaxial press device, a cold isostatic press (CIP) molding device, or other devices may be used. The molding pressure is appropriately in a range of 100 to 2000 kgf/cm2 (9.8 to 196 MPa), and preferably, 100 to 1000 kgf/cm2 (9.8 to 98 MPa). Molding is performed under pressure within the above-described range, such that the density of the molded body can be increased, deformation after sintering can be suppressed, and postprocessing is not required.
Next, the molded body is sintered. Before sintering, the molded body is preferably degreased at a temperature of 350 to 620° C. Through this degreasing, spots on the molded body after sintering can be suppressed. The degreasing is preferably performed for a sufficient time.
Sintering is performed in an atmosphere of air, an inactive gas, a vacuum, or a reductive gas at a temperature equal to or higher than 1000° C., and preferably, at a temperature of 1200 to 1400° C. for 1 to 10 hours, and preferably, for 2 to 5 hours. The sintering is performed under air pressure, but in the case of pressure sintering, such as hot press (HP) sintering or hot isostatic press (HIP) sintering, the sintering is preferably performed in an atmosphere of inactive gas, vacuum, or reductive gas at a temperature equal to or higher than 1000° C. for 1 to 5 hours.
A ZnO film is formed on the surface of the substrate by a vacuum film formation method with a ZnO vapor deposition material composed of the resultant porous sintered body as a target material. As the vacuum film formation method suitable for forming a film using the ZnO vapor deposition material of this aspect, an electron beam deposition method, an ion plating method, a sputtering method, or a plasma deposition method may be used. A ZnO film of this aspect formed by the film formation method uses the ZnO vapor deposition material containing the additive elements, so the ZnO film having high conductivity and visible light permeability is obtained.
According to the production process of this aspect, in any of the first step of mixing gas in the slurry, the second step of preparing the foaming agent-containing slurry, the third step of preparing the slurry containing the additive which will be volatized and dissolved upon sintering, and the fourth step of preparing the slurry using ZnO powder having a grain size distribution within a predetermined range, the porosity, pore diameter, and pore shape can be easily controlled. Therefore, a vapor deposition material having optimum pores can be produced. As a result, even when a large number of pore states are required by the production conditions or the like, an optimum vapor deposition material can be provided to cope with the requirements.
The ZnO vapor deposition material of this aspect is composed mainly of a porous sintered body having a porosity of 5 to 30% and a pore diameter of 0.1 to 500 μm, so when a ZnO transparent conductive film is formed by an electron beam deposition method or an ion plating method using the ZnO vapor deposition material, the evaporation speed can be improved. That is, when film formation is performed with the same electron beam energy, the speed of film formation increases, and the operation time is shortened, thereby increasing the number of products for a predetermined time. Further, when film formation is performed at the same film formation speed, electron beam energy is reduced, and the replacement timing of a filament of an electron gun or the like is delayed, such that the number of times of maintenance is reduced and productivity is improved. As a result, production costs can be reduced.
EXAMPLES
Hereinafter, Example A Group of the present invention will be described together with Comparative Example A Group. In Example A and Comparative Example A, commercially available ZnO powder (having a purity equal to or greater than 99% and an average grain size of 0.3 μm), CeO2 powder (having a purity equal to or greater than 99% and an average grain size of 0.3 μm), and Al2O3 powder (having a purity equal to or greater than 99% and an average grain size of 0.3 μm) were used. In any case, a slurry was prepared by using a ball mill (with a nylon-coated steel ball having a diameter of 5 to 20 mm), and wet blending was performed for 24 hours. In any case, a uniaxial molding press device was used as the molding device, and molded bodies having an outer diameter of 6.7 mmφ and a thickness of 2.0 mm were molded under pressure of 100 kgf/cm2 (9.8 MPa). The molded bodies were put in an electric furnace and calcinated under air pressure at 1300° C. for 3 hours, thereby obtaining sintered body pellets.
In Example A and Comparative Example A, the porosity was measured by a substitution method. The measurement of the average pore diameter and the crystal grain size was performed by SEM (Scanning Electron Microscopy). The evaporation speed was measured by a quartz crystal thickness monitor provided obliquely above the hearth. The specific resistance was measured by a four-terminal four-probe method with the application of a constant current at 25° C. in an atmosphere by using Loresta (trademark) from Mitsubishi Chemical Corporation (HP MCP-T410, probe in series, 1.5 mm pitch) as the measuring instrument. The visible light permeability was measured by placing the substrate after film formation vertically to measurement light for a visible wavelength band (380 to 780 nm) by using a spectrophotometer U-4000 manufactured by Hitachi, Ltd. as the measuring instrument.
Example A 1
1% by mass of polyvinyl butyral as a binder was added to 100 g of a raw powder containing 91 g of ZnO powder, 6.2 g of CeO2 powder, and 2.8 g of Al2O3 powder, and methylated alcohol as a dispersion medium was further added, thereby obtaining a slurry with a concentration of 30% by mass. Next, the slurry was put in a ball mill, air was blown into the slurry, and wet blending was performed, thereby obtaining a gas-containing slurry. The slurry was dry-comminuted after the dispersion medium in the slurry was vaporized by a vacuum drier at 80° C., thereby obtaining porous granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and a molded body was calcinated, thereby producing porous sintered body pellets (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 1.
Example A2
An organic foaming agent and an inorganic foaming agent were added to 100 g of the same raw powder as in Example A1, 1% by mass of polyvinyl butyral as a binder was added, and methylated alcohol was further added as a dispersion medium, thereby obtaining a slurry (viscosity 200 to 4000 cps) with a concentration of 30% by mass. For the organic foaming agent, azodicarboxylamide and dinitrosobenta methylene tetramine were used, and for the inorganic foaming agent, carbonate was used. The foaming agent-containing slurry was put in a ball mill, wet blending was performed, then, the slurry was dry-comminuted after the dispersion medium in the slurry was vaporized by a vacuum drier at 80° C., thereby obtaining porous granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure and calcinated, thereby producing porous sintered body pellets (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 1.
Example A3
An additive which will be volatized and dissolved upon calcination was added to 100 g of the same raw powder as in Example A1, 1% by mass of polyvinyl butyral was added as a binder, and methylated alcohol was further added as a dispersion medium, thereby obtaining a slurry (viscosity 200 to 4000 cps) with a concentration of 30% by mass. For the additive which will be volatized and dissolved upon calcination, 20% by mass of polyvinyl butyral was used. The additive-containing slurry was put in a ball mill, wet blending was performed, then, the slurry was dry-comminuted after the dispersion medium in the slurry was vaporized by a vacuum drier at 80° C., thereby obtaining granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated such that the additive was volatized and dissolved, thereby producing porous sintered body pellets (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 1.
Example A4
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example A3 except that, for the additive which will be volatized and dissolved upon calcination, 20% by mass of starch having a grain size of 50 μm was used. The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 1.
Example A5
The same raw powder as in Example A1 was used, and ZnO powder was filtered such that ZnO powder having an average grain size of 60 μm and a grain size distribution within a range of 55 to 65 μm was obtained. 1% by mass of polyvinyl butyral as a binder and also 30% by mass of methylated alcohol as an organic solvent were added to raw powder containing the ZnO powder and then mixed, thereby preparing a slurry in which the concentration of ZnO powder was 30% by mass. Next, the slurry was spray-dried, thereby obtaining porous granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby producing porous sintered body pellets (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 1.
Comparative Example A1
The same raw powder as in Example A1 was used, a slurry was prepared in the same manner as in Example A 1 except that introduction of air into the slurry, addition of a foaming agent, and use of an additive which will be volatized and dissolved upon calcination were not performed, and the slurry was spray-dried, thereby obtaining granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby preparing a sintered body pellet (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 1.
Comparative Example A2
A slurry was prepared in the same manner as in Comparative Example A1 except that 100 g of ZnO powder containing no CeO2 powder and Al2O3 powder was used, and the slurry was spray-dried, thereby obtaining granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby preparing a sintered body pellet (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 1.
[Deposition Test A]
A deposition test A was carried out using the ZnO vapor deposition materials of Examples A1 to A5 and the ZnO vapor deposition materials of Comparative Examples A1 and A2. A vapor deposition material as a sample was put in the hearth (diameter 50 mm, depth 25 mm) of the electron beam deposition device, adjustment was done in an atmosphere of an ultimate vacuum 2.66×10−4 Pa (2.0×10−6 Torr) and O2 partial pressure 1.33×10−2 Pa (1.0×10−4 Torr), and an electron beam with an acceleration voltage of 10 kV and a beam scan area of about 40 mmφ was irradiated to heat the ZnO vapor deposition material, thereby forming a ZnO film. The evaporation speed was measured by a quartz crystal thickness monitor provided obliquely above the hearth. The results are shown in Table 1. As shown in Table 1, in Examples A1 to A5, the deposition speed is about 1.1 to 2 times higher than in Comparative Examples A1 and A2, and the evaporation speed is higher.
[Moisture Resistance Test A]
For the samples of Examples A1 to A5 and Comparative Examples A1 and A2, a moisture resistance test A was performed. In the moisture resistance test A, the resistance value of a film was measured hourly for 2000 hours in an atmosphere of humidity 60% and temperature 90° C. The results are shown in Table 2. As shown in Table 2, with regard to the moisture resistance of a ZnO film formed of a ZnO vapor deposition material containing Ce and Al, the deterioration rate of specific resistance is several times lower than a ZnO film containing no Ce and Al. This indicates that a ZnO film containing Ce and Al is several times more stable.
Examples A6 to A8
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example A1 except that adjustment was done such that the Ce content was 0.2% by mass, the Al content was 0.1% by mass, and the porosity was in a range of 8 to 31%.
Examples A9 to A11
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example A1 except that adjustment was done such that the Ce content was 14.9% by mass, the Al content was 10% by mass, and the porosity was in a range of 9 to 30%.
Comparative Example A3
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Examples A6 to A8 except that adjustment was done such that the porosity was 2%.
Comparative Example A4
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Examples A9 to A11 except that adjustment was done such that the porosity was 2%.
Comparative Examples A5 to A8
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example A1 except that adjustment was done such that the Ce content was 20% by mass, the Al content was 15% by mass, and the porosity was in a range of 2 to 29%.
For the samples of Examples A6 to A11 and Comparative Examples A3 to A8, the deposition test A was performed. The results are shown in Table 3. As shown in Table 3, similar to Table 1, in Examples A6 to A11, the ZnO vapor deposition material has a high evaporation speed and excellent specific resistance, as compared with Comparative Example A Group. On the other hand, in Comparative Examples A2, A3, A4, and A8 having a small porosity, the evaporation speed is considerably low at 13.0 to 14.7. In Comparative Examples A5 to A8 in which the Ce content and the Al content are high, the ZnO film has very large specific resistance and considerably low permeability.







TABLE 1







Deposition test A results using ZnO vapor deposition material


containing CeO2: 6.2% (Ce: 5.1%), Al2O3: 2.8% (Al: 1.5%)












ZnO Vapor






Deposition Material
Evaporation












Crystal
Speed
ZnO Film



















Pore
Grain
20
60
100
Specific
Perme-




Porosity
Diameter
size
mA
mA
mA
Resistance
ability
Remarks




















Example A1
18
24
60
6.4
18.3
31.2
3.8 × 10−4
88
Air Blow


Example A2
24
30
48
8.3
24.7
36.9
4.0 × 10−4
89
Foaming Agent


Example A3
27
35
41
8.5
25.8
43.5
4.1 × 10−4
88
Volatized Upon


Example A4
30
46
37
9.1
26.4
46.3
4.1 × 10−4
87
Calcination


Example A5
9
10
62
5.9
18.1
25.9
3.8 × 10−4
88


Comparative
2.0
3.5
86
5.3
15.0
23.7
3.7 × 10−4
89


Example A1


Comparative
1.8
3.2
103
5.2
14.7
23.5
3.7 × 10−2
89
No Ce and


Example A2








Al Added





(Note)


Porosity is %, pore diameter is average pore diameter μm, crystal grain size is average crystal grain size μm, evaporation speed is A/sec, specific resistance is Ω · cm, and permeability is visible light permeability %













TABLE 2







Moisture Resistance Test A Result











Specific Resistance



Specific Resistance
Deterioration Rate












After Film
After
After
After



Formation (0 hr)
500 hr
100 hr
2000 hr















Example A1
1
1.01
1.03
1.05


Example A2
1
1.00
1.02
1.04


Example A3
1
1.03
1.04
1.07


Example A4
1
1.02
1.05
1.06


Example A5
1
1.02
1.01
1.03


Comparative
1
1.01
1.00
1.01


Example A1


Comparative
1
1.22
1.38
1.49


Example A2





(Note)


Deterioration rate of specific resistance represents change rate with setting 1 for after film formation.

















TABLE 3










Evapora-




ZnO Vapor
tion
ZnO Film












Deposition Material
Speed
Specific
Perme-














Ce
Al
Porosity
60 mA
Resistance
ability

















Example A6
0.2
0.1
8
17.5
8.3 × 10−4
89


Example A7


17
20.8
8.3 × 10−4
88


Example A8


31
26.6
8.4 × 10−4
89


Comparative


2
14.1
8.7 × 10−4
88


Example A3


Example A9
14.9
10
9
17.0
7.3 × 10−4
86


Example A10


16
19.4
7.2 × 10−4
86


Example A11


30
25.3
7.4 × 10−4
85


Comparative


2
13.2
7.9 × 10−4
86


Example A4


Comparative
20
15
8
16.1
9.2 × 10−3
82


Example A5


Comparative


14
18.9
9.7 × 10−3
82


Example A6


Comparative


29
23.7
9.4 × 10−3
81


Example A7


Comparative


2
13.0
9.3 × 10−3
82


Example A8


Comparative
0
0
1.8
14.7
3.7 × 10−2
89


Example A2





(Note)


Porosity is %, pore diameter is average pore diameter μm, crystal grain size is average crystal grain size μm, evaporation speed is A/sec, specific resistance is Ω · cm, and permeability is visible light permeability %






Example B
Hereinafter, Example B Group of this aspect will be described together with Comparative Example B Group. In Example B and Comparative Example B, commercially available ZnO powder (having a purity equal to or greater than 99% and an average grain size of 0.3 μm), CeO2 powder (having a purity equal to or greater than 99% and an average grain size of 0.3 μm), and Ga2O3 powder (having a purity equal to or greater than 99% and an average grain size of 0.3 μm) were used. In any case, a slurry was prepared by using a ball mill (with a nylon-coated steel ball having a diameter of 5 to 20 mm), and wet blending was performed for 24 hours. In any case, a uniaxial molding press device was used as the molding device, and molded bodies having an outer diameter of 6.7 mmφ and a thickness of 2.0 mm were molded under pressure of 100 kgf/cm2 (9.8 MPa). The molded bodies were put in an electric furnace and calcinated under air pressure at 1300° C. for 3 hours, thereby obtaining sintered body pellets.
In Example B and Comparative Example B, the porosity was measured by a substitution method. The measurement of the average pore diameter and the crystal grain size was performed by SEM (Scanning Electron Microscopy). The evaporation speed was measured by a quartz crystal thickness monitor provided obliquely above the hearth. The specific resistance was measured by a four-terminal four-probe method with the application of a constant current at 25° C. in an atmosphere by using Loresta (trademark) from Mitsubishi Chemical Corporation (HP MCP-T410, probe in series, 1.5 mm pitch) as the measuring instrument. The visible light permeability was measured by placing the substrate after film formation vertically to measurement light for a visible wavelength band (380 to 780 nm) by using a spectrophotometer U-4000 manufactured by Hitachi, Ltd. as the measuring instrument.
Example B1
1% by mass of polyvinyl butyral as a binder was added to 100 g of a raw powder containing 91 g of ZnO powder, 6.2 g of CeO2 powder, and 2.8 g of Ga2O3 powder, and methylated alcohol as a dispersion medium was further added, thereby obtaining a slurry with a concentration of 30% by mass. Next, the slurry was put in a ball mill, air was blown into the slurry, and wet blending was performed, thereby obtaining a gas-containing slurry. The slurry was dry-comminuted after the dispersion medium in the slurry was vaporized by a vacuum drier at 80° C., thereby obtaining porous granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby producing porous sintered body pellets (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 4.
Example B2
An organic foaming agent and an inorganic foaming agent were added to 100 g of the same raw powder as in Example B1, 1% by mass of polyvinyl butyral as a binder was added, and methylated alcohol was further added as a dispersion medium, thereby obtaining a slurry (viscosity 200 to 4000 cps) with a concentration of 30% by mass. For the organic foaming agent, azodicarboxylamide and dinitrosobenta methylene tetramine were used, and for the inorganic foaming agent, carbonate was used. The foaming agent-containing slurry was put in a ball mill, wet blending was performed, then, the slurry was dry-comminuted after the dispersion medium in the slurry was vaporized by a vacuum drier at 80° C., thereby obtaining porous granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby producing porous sintered body pellets (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 4.
Example B3
An additive which will be volatized and dissolved upon calcination was added to 100 g of the same raw powder as in Example B1, 1% by mass of polyvinyl butyral was added as a binder, and methylated alcohol was further added as a dispersion medium, thereby obtaining a slurry (viscosity 200 to 4000 cps) with a concentration of 30% by mass. For the additive which will be volatized and dissolved upon calcination, 20% by mass of polyvinyl butyral was used. The additive-containing slurry was put in a ball mill, wet blending was performed, then, the slurry was dry-comminuted after the dispersion medium in the slurry was vaporized by a vacuum drier at 80° C., thereby obtaining granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated such that the additive was volatized and dissolved, thereby producing porous sintered body pellets (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 4.
Example B4
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example B3 except that, for the additive which will be volatized and dissolved upon calcination, 20% by mass of starch having a grain size of 50 μm was used. The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 4.
Example B5
The same raw powder as in Example B1 was used, and ZnO powder was filtered such that ZnO powder having an average grain size of 60 μm and a grain size distribution within a range of 55 to 65 μm was obtained. 1% by mass of polyvinyl butyral as a binder and also 30% by mass of methylated alcohol as an organic solvent were added to raw powder containing the ZnO powder and then mixed, thereby preparing a slurry in which the concentration of ZnO powder was 30% by mass. Next, the slurry was spray-dried, thereby obtaining porous granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby producing porous sintered body pellets (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 4.
Comparative Example B1
The same raw powder as in Example B1 was used, a slurry was prepared in the same manner as in Example B1 except that introduction of air into the slurry, addition of a foaming agent, and use of an additive which will be volatized and dissolved upon calcination were not performed, and the slurry was spray-dried, thereby obtaining granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby preparing a sintered body pellet (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 4.
Comparative Example B2
A slurry was prepared in the same manner as in Comparative Example B1 except that raw powder was used in which 6.2 g of CeO2 powder was added to 93.8 g of ZnO powder, and no Ga2O3 powder was added, and the slurry was spray-dried, thereby obtaining granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby preparing a sintered body pellet (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 4.
Comparative Example B3
A slurry was prepared in the same manner as in Comparative Example B1 except that 100 g of ZnO powder containing no CeO2 powder and Ga2O3 powder was used, and the slurry was spray-dried, thereby obtaining granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby preparing a sintered body pellet (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 4.
[Deposition Test B]
A deposition test B was carried out using the ZnO vapor deposition materials of Examples B1 to B5 and the ZnO vapor deposition materials of Comparative Examples B1 to B3. A vapor deposition material as a sample was put in the hearth (diameter 50 mm, depth 25 mm) of the electron beam deposition device, adjustment was done in an atmosphere of an ultimate vacuum 2.66×10−4 Pa (2.0×10−6 Torr) and O2 partial pressure 1.33×10−2 Pa (1.0×10−4 Torr), and an electron beam with an acceleration voltage of 10 kV and a beam scan area of about 40 mmφ was irradiated to heat the ZnO vapor deposition material, thereby forming a ZnO film. The evaporation speed was measured by a quartz crystal thickness monitor provided obliquely above the hearth. The results are shown in Table 5.
As shown in Tables 4 and 5, in Examples B1 to B5, the evaporation speed is high, as compared with Comparative Example B1. In Comparative Examples B2 to B3, the evaporation speed is the same as in Example B5, but the specific resistance is large and the conductivity is low.
[Moisture Resistance Test B]
For the samples of Examples B1 to B5 and Comparative Examples B1 and B3, a moisture resistance test B was performed. The moisture resistance test B was performed for 2000 hours in an atmosphere of humidity 60% and temperature 90° C. The specific resistance of a film was measured hourly. The results are shown in Table 6.
As shown in Table 6, with regard to the moisture resistance of a ZnO film formed of a ZnO vapor deposition material containing Ce and Ga, the deterioration rate of specific resistance is several times lower than a ZnO film containing no Ce and Ga. This indicates that a ZnO film containing Ce and Ga is several times more stable.
Examples B6 to B8
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example B1 except that adjustment was done such that the Ce content was 0.2% by mass, the Ga content was 0.1% by mass, and the porosity was in a range of 8 to 30%.
Examples B9 to B11
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example B1 except that adjustment was done such that the Ce content was 14.9% by mass, the Ga content was 10% by mass, and the porosity was in a range of 10 to 32%.
Comparative Example B4
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Examples B6 to B8 except that adjustment was done such that the porosity was 2%.
Comparative Example B5
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Examples B9 to B11 except that adjustment was done such that the porosity was 2%.
Comparative Examples B6 to B9
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example B1 except that adjustment was done such that the Ce content was 20% by mass, the Ga content was 15% by mass, and the porosity was in a range of 2 to 31%.
For the samples of Examples B6 to B11 and Comparative Examples B4 to B9, a deposition test B was performed. The results are shown in Table 7. As shown in Table 7, similar to Table 4, in Examples B6 to B11, the ZnO vapor deposition material has a high evaporation speed and excellent specific resistance, as compared with Comparative Example B. On the other hand, in Comparative Examples B4, B5, and B9 having a small porosity, the evaporation speed is considerably low at 13.0 to 14.1. In Comparative Examples B6 to B9 in which the Ce content and the Ga content are high, the ZnO film has very large specific resistance and considerably low permeability.







TABLE 4







Deposition test B results using ZnO vapor deposition material


containing CeO2: 6.2% (Ce: 5.1%) and Ga2O3: 2.8% (Ga: 2.3%)









ZnO Vapor



Deposition Material

















Crystal



Raw Powder



Grain



(% by mass)
Slurry
Porosity
Porosity
size
















Example B1
ZnO: 91%
Gas-
18.4%
24
56



CeO2: 6.2%
Containing



(Ce: 5.1%)
Slurry


Example B2
Ga2O3: 2.8%
Foaming
25.9%
31
46



(Ga: 2.3%)
Agent-




Containing




Slurry


Example B3

Additive-
28.4%
37
42




Containing




Slurry


Example B4

Additive-
31.3%
50
35




Containing




Slurry


Example B5

Slurry with
10.3%
11
59




Adjustment




of Grain Size




Distribution


Comparative
Same as
Slurry
1.9%
3.8
90


Example B1
Above
with No




Adjustment


Comparative
ZnO: 93.8%
Gas-
17.9%
22
45


Example B2
CeO2: 6.2%
Containing




Slurry


Comparative
ZnO Alone
Gas-
17.2%
23
43


Example B3
No Ce and
Containing



Ga Added
Slurry





(Note)


Porosity is %, pore diameter is average pore diameter μm, and crystal grain size is average crystal grain size μm
















TABLE 5









Ratio of
ZnO Film












Evaporation Speed
Evapora-

Visible














20
60
100
tion
Specific
Light



mA
mA
mA
Speed
Resistance
Permeability

















Example B1
6.4
18.3
31.2
1.4
3.3 × 10−4
89


Example B2
8.3
24.7
36.9
1.6
3.4 × 10−4
88


Example B3
8.5
25.8
43.5
1.9
3.5 × 10−4
87


Example B4
9.1
26.4
46.3
2.0
3.5 × 10−4
87


Example B5
5.9
18.1
25.9
1.1
3.4 × 10−4
88


Comparative
5.3
14.8
22.9
1
3.3 × 10−4
89


Example B1


Comparative
6.2
17.1
28.4
1.2
8.1 × 10−4
89


Example B2


Comparative
6.0
17.0
28.3
1.2
2.3 × 10−2
92


Example B3





(Note)


Evaporation speed is A/sec, specific resistance is Ω · cm, and permeability is visible light permeability % Ratio of evaporation speed is ratio to evaporation speed of Comparative Example B1 at 100 mA













TABLE 6







Moisture Resistance Test B Result










Specific Resistance
Specific Resistance



After Film
Deterioration Rate












Formation (0 hr)
500 hr
100 hr
2000 hr















Example B1
1
1.01
1.02
1.04


Example B2
1
1.02
1.04
1.07


Example B3
1
1.04
1.05
1.08


Example B4
1
1.01
1.03
1.05


Example B5
1
1.02
1.04
1..07


Comparative
1
1.02
1.03
1.06


Example B1


Comparative
1
1.30
1.39
1.53


Example B3





(Note)


Deterioration rate of specific resistance represents change rate with setting 1 for after film formation.

















TABLE 7










Evapora-




ZnO Vapor
tion
ZnO Film












Deposition Material
Speed
Specific
Perme-














Ce
Ga
Porosity
60 mA
Resistance
ability

















Example B6
0.2
0.1
8
17.5
5.5 × 10−4
88


Example B7


16
20.8
5.5 × 10−4
88


Example B8


30
26.6
5.6 × 10−4
89


Comparative


2
14.1
5.9 × 10−4
89


Example B4


Example B9
14.9
10
10
17.0
6.2 × 10−4
88


Example B10


15
19.4
6.5 × 10−4
86


Example B11


32
25.3
6.5 × 10−4
87


Comparative


2
13.2
6.4 × 10−4
87


Example B5


Comparative
20
15
7
16.1
7.7 × 10−3
84


Example B6


Comparative


17
18.9
7.3 × 10−3
82


Example B7


Comparative


31
23.7
7.4 × 10−3
83


Example B8


Comparative


2
13.0
7.6 × 10−3
84


Example B9


Comparative
0
0
1.8
14.5
2.4 × 10−2
90


Example B3





(Note)


Porosity is %, pore diameter is average pore diameter μm, crystal grain size is average crystal grain size μm, evaporation speed is A/sec, specific resistance is Ω · cm, and permeability is visible light permeability %






Example C
Hereinafter, Example C Group of this aspect will be described together with Comparative Example C Group. In Example C and Comparative Example C, commercially available ZnO powder (having a purity equal to or greater than 99% and an average grain size of 0.3 μm), CeO2 powder (having a purity equal to or greater than 99% and an average grain size of 0.3 μm), and Sc2O3 powder (having a purity equal to or greater than 99% and an average grain size of 0.3 μm) were used. In any case, a slurry was prepared by using a ball mill (with a nylon-coated steel ball having a diameter of 5 to 20 mm), and wet blending was performed for 24 hours. In any case, a uniaxial molding press device was used as the molding device, and molded bodies having an outer diameter of 6.7 mmφ and a thickness of 2.0 mm were molded under pressure of 100 kgf/cm2 (9.8 MPa). The molded bodies were put in an electric furnace and calcinated under air pressure at 1300° C. for 3 hours, thereby obtaining sintered body pellets.
In Example C and Comparative Example C, the porosity was measured by a substitution method. The measurement of the average pore diameter and the crystal grain size was performed by SEM (Scanning Electron Microscopy). The evaporation speed was measured by a quartz crystal thickness monitor provided obliquely above the hearth. The specific resistance was measured by a four-terminal four-probe method with the application of a constant current at 25° C. in an atmosphere by using Loresta (trademark) from Mitsubishi Chemical Corporation (HP MCP-T410, probe in series, 1.5 mm pitch) as the measuring instrument. The visible light permeability was measured by placing the substrate after film formation vertically to measurement light for a visible wavelength band (380 to 780 nm) by using a spectrophotometer U-4000 manufactured by Hitachi, Ltd. as the measuring instrument.
Example C1
1% by mass of polyvinyl butyral as a binder was added to 100 g of a raw powder containing 90.8 g of ZnO powder, 6.2 g of CeO2 powder, and 3.0 g of Sc2O3 powder, and methylated alcohol as a dispersion medium was further added, thereby obtaining a slurry with a concentration of 30% by mass. Next, the slurry was put in a ball mill, air was blown into the slurry, and wet blending was performed, thereby obtaining a gas-containing slurry. The slurry was dry-comminuted after the dispersion medium in the slurry was vaporized by a vacuum drier at 80° C., thereby obtaining porous granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby producing porous sintered body pellets (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 8.
Example C2
An organic foaming agent and an inorganic foaming agent were added to 100 g of the same raw powder as in Example C1, 1% by mass of polyvinyl butyral as a binder was added, and methylated alcohol was further added as a dispersion medium, thereby obtaining a slurry (viscosity 200 to 4000 cps) with a concentration of 30% by mass. For the organic foaming agent, azodicarboxylamide and dinitrosobenta methylene tetramine were used, and for the inorganic foaming agent, carbonate was used. The foaming agent-containing slurry was put in a ball mill, wet blending was performed, then, the slurry was dry-comminuted after the dispersion medium in the slurry was vaporized by a vacuum drier at 80° C., thereby obtaining porous granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby producing porous sintered body pellets (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 8.
Example C3
An additive which will be volatized and dissolved upon calcination was added to 100 g of the same raw powder as in Example C1, 1% by mass of polyvinyl butyral was added as a binder, and methylated alcohol was further added as a dispersion medium, thereby obtaining a slurry (viscosity 200 to 4000 cps) with a concentration of 30% by mass. For the additive which will be volatized and dissolved upon calcination, 20% by mass of polyvinyl butyral was used. The additive-containing slurry was put in a ball mill, wet blending was performed, then, the slurry was dry-comminuted after the dispersion medium in the slurry was vaporized by a vacuum drier at 80° C., thereby obtaining granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated such that the additive was volatized and dissolved, thereby producing porous sintered body pellets (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 8.
Example C4
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example C3 except that, for the additive which will be volatized and dissolved upon calcination, 20% by mass of starch having a grain size of 50 μm was used. The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 8.
Example C5
The same raw powder as in Example C1 was used, and ZnO powder was filtered such that ZnO powder having an average grain size of 60 μm and a grain size distribution within a range of 55 to 65 μm was obtained. 1% by mass of polyvinyl butyral as a binder and also 30% by mass of methylated alcohol as an organic solvent were added to raw powder containing the ZnO powder and then mixed, thereby preparing a slurry in which the concentration of ZnO powder was 30% by mass. Next, the slurry was spray-dried, thereby obtaining porous granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby producing porous sintered body pellets (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 8.
Comparative Example C1
The same raw powder as in Example C1 was used, a slurry was prepared in the same manner as in Example C1 except that introduction of air into the slurry, addition of a foaming agent, and use of an additive which will be volatized and dissolved upon calcination were not performed, and the slurry was spray-dried, thereby obtaining granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby preparing a sintered body pellet (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 8.
Comparative Example C2
A slurry was prepared in the same manner as in Example C1 except that raw powder was used in which 6.2 g of CeO2 powder was added to 93.8 g of ZnO powder and no Sc2O3 powder was added, and the slurry was spray-dried, thereby obtaining granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby preparing a sintered body pellet (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 8.
Comparative Example C3
A slurry was prepared in the same manner as in Example C1 except that 100 g of ZnO powder containing no CeO2 powder and Sc2O3 powder was used, and the slurry was spray-dried, thereby obtaining granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby preparing a sintered body pellet (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 8.
[Deposition Test C]
A deposition test C was carried out using the ZnO vapor deposition materials of Examples C1 to C5 and the ZnO vapor deposition materials of Comparative Examples C1 to C3. A vapor deposition material as a sample was put in the hearth (diameter 50 mm, depth 25 mm) of the electron beam deposition device, adjustment was done in an atmosphere of an ultimate vacuum 2.66×10−4 Pa (2.0×10−6 Torr) and O2 partial pressure 1.33×10−2 Pa (1.0×10−4 Torr), and an electron beam with an acceleration voltage of 10 kV and a beam scan area of about 40 mmφ was irradiated to heat the ZnO vapor deposition material, thereby forming a ZnO film. The evaporation speed was measured by a quartz crystal thickness monitor provided obliquely above the hearth. The results are shown in Table 9.
As shown in Tables 8 and 9, in Examples C1 to C5, the evaporation speed is higher than in Comparative Example C1. In Comparative Examples C2 and C3, the evaporation speed is the same as in Example C5, but the specific resistance is large and the conductivity is low.
[Moisture Resistance Test C]
For the samples of Examples C1 to C5 and Comparative Examples C1 and C3, a moisture resistance test C was performed. The moisture resistance test C was performed for 2000 hours in an atmosphere of humidity 60% and temperature 90° C. The specific resistance of a film was measured hourly. The results are shown in Table 10.
As shown in Table 10, with regard to the moisture resistance of a ZnO film formed of a ZnO vapor deposition material containing Ce and Sc, the deterioration rate of specific resistance is several times lower than a ZnO film containing no Ce and Sc. This indicates that a ZnO film containing Ce and Sc is several times more stable.
Examples C6 to C8
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example C1 except that adjustment was done such that the Ce content was 0.2% by mass, the Sc content was 0.1% by mass, and the porosity was in a range of 78 to 28%.
Examples C9 to C11
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example C1 except that adjustment was done such that the Ce content was 14.9% by mass, the Sc content was 10% by mass, and the porosity was in a range of 9 to 30%.
Comparative Example C4
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Examples C6 to C8 except that adjustment was done such that the porosity was 2%.
Comparative Example C5
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Examples C9 to C11 except that adjustment was done such that the porosity was 2%.
Comparative Examples C6 to C9
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example C1 except that adjustment was done such that the Ce content was 20% by mass, the Sc content was 15% by mass, and the porosity was in a range of 2 to 28%.
For the samples of Examples C6 to C11 and Comparative Examples C4 to C9, a deposition test C was performed. The results are shown in Table 11. As shown in Table 11, similar to Table 8, in Examples C6 to C11, the ZnO vapor deposition material has a high evaporation speed and excellent specific resistance, as compared with Comparative Example C. On the other hand, in Comparative Examples C4, C5, and C9 having a small porosity, the evaporation speed is considerably low at 13.8 to 14.9. In Comparative Examples C6 to C9 in which the Ce content and the Sc content are high, a ZnO film has very large specific resistance and considerably low permeability.







TABLE 8







Deposition test C results using ZnO vapor deposition material


containing CeO2: 6.2% (Ce: 5.1%) and Sc2O3: 2.8% (Sc: 2.3%)









ZnO Vapor



Deposition Material
















Pore
Crystal



Raw Powder


Diam-
Grain



(% by mass)
Slurry
Porosity
eter
size
















Example C1
ZnO: 90.8%
Gas-
18.2%
25
61



CeO2: 6.2%
Containing



(Ce: 5.1%)
Slurry


Example C2
Sc2O3: 3.0%
Foaming
25.3%
30
49



(Sc: 2.0%)
Agent-




Containing




Slurry


Example C3

Additive-
27.9%
38
43




Containing




Slurry


Example C4

Additive-
30.1%
48
32




Containing




Slurry


Example C5

Slurry with
9.8%
12
56




Adjustment




of Grain Size




Distribution


Comparative
Same as
Slurry
1.8%
4
104


Example C1
Above
with No




Adjustment


Comparative
ZnO: 93.8%
Gas-
17.9%
22
45


Example C2
CeO2: 6.2%
Containing




Slurry


Comparative
ZnO Alone
Gas-
17.2%
23
43


Example C3
No Ce and
Containing



Sc Added
Slurry





(Note)


Porosity is %, pore diameter is average pore diameter μm, and crystal grain size is average crystal grain size μm
















TABLE 9









Ratio of
ZnO Film












Evaporation Speed
Evapora-

Visible














20
60
100
tion
Specific
Light



mA
mA
mA
Speed
Resistance
Permeability

















Example C1
6.5
18.5
32.9
1.3
3.9 × 10−4
89


Example C2
8.5
25.2
37.5
1.5
3.9 × 10−4
89


Example C3
8.9
25.9
44.8
1.8
3.9 × 10−4
88


Example C4
9.4
27.8
48.1
2.0
3.9 × 10−4
88


Example C5
6.2
19.0
26.8
1.1
3.9 × 10−4
89


Comparative
5.5
15.8
24.5
1
3.9 × 10−4
89


Example C1


Comparative
6.2
17.1
28.4
1.2
8.1 × 10−4
89


Example C2


Comparative
6.0
17.0
28.3
1.2
2.3 × 10−2
92


Example C3





(Note)


Evaporation speed is A/sec, specific resistance is Ω · cm, and visible light permeability is % Ratio of evaporation speed is ratio to evaporation speed of Comparative Example C1 at 100 mA













TABLE 10







Moisture Resistance Test C Result











Specific Resistance



Specific Resistance
Deterioration Rate












After Film
After
After
After



Formation (0 hr)
500 hr
100 hr
2000 hr















Example C1
1
1.02
1.03
1.05


Example C2
1
1.02
1.04
1.06


Example C3
1
1.03
1.06
1.09


Example C4
1
1.02
1.03
1.06


Example C5
1
1.03
1.04
1.06


Comparative
1
1.01
1.03
1.04


Example C1


Comparative
1
1.29
1.38
1.49


Example C3





(Note)


Deterioration rate of specific resistance represents change rate with setting 1 for after film formation.

















TABLE 11










Evapora-




ZnO Vapor
tion
ZnO Film












Deposition Material
Speed
Specific
Perme-














Ce
Sc
Porosity
60 mA
Resistance
ability

















Example C6
0.2
0.1
7
18.2
6.3 × 10−4
89


Example C7


14
19.8
6.2 × 10−4
89


Example C8


28
27.3
6.4 × 10−4
89


Comparative


2
14.9
6.7 × 10−4
88


Example C4


Example C9
14.9
10
9
18.2
9.3 × 10−4
87


Example C10


15
19.7
9.5 × 10−4
86


Example C11


30
25.0
9.7 × 10−4
86


Comparative


2
14.1
9.6 × 10−4
86


Example C5


Comparative
20
15
6
15.0
1.1 × 10−2
83


Example C6


Comparative


16
18.2
1.2 × 10−2
81


Example C7


Comparative


28
22.6
1.2 × 10−2
82


Example C8


Comparative


2
13.8
1.3 × 10−2
83


Example C9


Comparative
0
0
1.8
14.5
2.4 × 10−2
90


Example C3





(Note)


Porosity is %, pore diameter is average pore diameter μm, crystal grain size is average crystal grain size μm, evaporation speed is A/sec, specific resistance is Ω · cm, and permeability is visible light permeability %






Example D
Hereinafter, Example D Group of this aspect will be described together with Comparative Example D Group. In Example D and Comparative Example D, commercially available ZnO powder (having a purity equal to or greater than 99% and average grain size of 0.3 μm), CeO2 powder (having a purity equal to or greater than 99% and an average grain size of 0.3 μm), and B2O3 powder (having a purity equal to or greater than 99% and an average grain size of 0.3 μm) were used. In any case, a slurry was prepared by using a ball mill (with a nylon-coated steel ball having a diameter of 5 to 20 mm), and wet blending was performed for 24 hours. In any case, a uniaxial molding press device was used as the molding device, and molded bodies having an outer diameter of 6.7 mmφ and a thickness of 2.0 mm were molded under pressure of 100 kgf/cm2 (9.8 MPa). The molded bodies were put in an electric furnace and calcinated under air pressure at 1300° C. for 3 hours, thereby obtaining sintered body pellets.
In Example D and Comparative Example D, the porosity was measured by a substitution method. The measurement of the average pore diameter and the crystal grain size was performed by SEM (Scanning Electron Microscopy). The evaporation speed was measured by a quartz crystal thickness monitor provided obliquely above the hearth. The specific resistance was measured by a four-terminal four-probe method with the application of a constant current at 25° C. in an atmosphere by using Loresta (trademark) from Mitsubishi Chemical Corporation (HP MCP-T410, probe in series, 1.5 mm pitch) as the measuring instrument. The visible light permeability was measured by placing the substrate after film formation vertically to measurement light for a visible wavelength band (380 to 780 nm) by using a spectrophotometer U-4000 manufactured by Hitachi, Ltd. as the measuring instrument.
Example D1
1% by mass of polyvinyl butyral as a binder was added to 100 g of a raw powder containing 90 g of ZnO powder, 6.2 g of CeO2 powder, and 3.8 g of B2O3 powder, and methylated alcohol as a dispersion medium was further added, thereby obtaining a slurry with a concentration of 30% by mass. Next, the slurry was put in a ball mill, air was blown into the slurry, and wet blending was performed, thereby obtaining a gas-containing slurry. The slurry was dry-comminuted after the dispersion medium in the slurry was vaporized by a vacuum drier at 80° C., thereby obtaining porous granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby producing porous sintered body pellets (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 12.
Example D2
An organic foaming agent and an inorganic foaming agent were added to 100 g of the same raw powder as in Example D1, 1% by mass of polyvinyl butyral as a binder was added, and methylated alcohol was further added as a dispersion medium, thereby obtaining a slurry (viscosity 200 to 4000 cps) with a concentration of 30% by mass. For the organic foaming agent, azodicarboxylamide and dinitrosobenta methylene tetramine were used, and for the inorganic foaming agent, carbonate was used. The foaming agent-containing slurry was put in a ball mill, wet blending was performed, then, the slurry was dry-comminuted after the dispersion medium in the slurry was vaporized by a vacuum drier at 80° C., thereby obtaining porous granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby producing porous sintered body pellets (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 12.
Example D3
An additive which will be volatized and dissolved upon calcination was added to 100 g of the same raw powder as in Example D1, 1% by mass of polyvinyl butyral was added as a binder, and methylated alcohol was further added as a dispersion medium, thereby obtaining a slurry (viscosity 200 to 4000 cps) with a concentration of 30% by mass. For the additive which will be volatized and dissolved upon calcination, 20% by mass of polyvinyl butyral was used. The additive-containing slurry was put in a ball mill, wet blending was performed, then, the slurry was dry-comminuted after the dispersion medium in the slurry was vaporized by a vacuum drier at 80° C., thereby obtaining granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated such that the additive was volatized and dissolved, thereby producing porous sintered body pellets (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 12.
Example D4
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example D3 except that, for the additive which will be volatized and dissolved upon calcination, 20% by mass of starch having a grain size of 50 μm was used. The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 12.
Example D5
The same raw powder as in Example D1 was used, and ZnO powder was filtered such that ZnO powder having an average grain size of 60 μm and a grain size distribution within a range of 55 to 65 μm was obtained. 1% by mass of polyvinyl butyral as a binder and also 30% by mass of methylated alcohol as an organic solvent were added to raw powder containing the ZnO powder and then mixed, thereby preparing a slurry in which the concentration of ZnO powder was 30% by mass. Next, the slurry was spray-dried, thereby obtaining porous granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby producing porous sintered body pellets (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 12.
Comparative Example D1
The same raw powder as in Example D1 was used, a slurry was prepared in the same manner as in Example D1 except that introduction of air into the slurry, addition of a foaming agent, and use of an additive which will be volatized and dissolved upon calcination were not performed, and the slurry was spray-dried, thereby obtaining granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby preparing a sintered body pellet (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 12.
Comparative Example D2
A slurry was prepared in the same manner as in Example D1 except that raw powder was used in which 6.2 g of CeO2 powder was added to 93.8 g of ZnO powder and no B2O3 powder was added, and the slurry was spray-dried, thereby obtaining granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby preparing a sintered body pellet (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 12.
Comparative Example D3
A slurry was prepared in the same manner as in Example D1 except that 100 g of ZnO powder containing no CeO2 powder and B2O3 powder was used, and the slurry was spray-dried, thereby obtaining granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby preparing a sintered body pellet (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 12.
[Deposition Test D]
A deposition test D was carried out using the ZnO vapor deposition materials of Examples D1 to D5 and the ZnO vapor deposition materials of Comparative Examples D1 to D3. A vapor deposition material as a sample was put in the hearth (diameter 50 mm, depth 25 mm) of the electron beam deposition device, adjustment was done in an atmosphere of an ultimate vacuum 2.66×10−4 Pa (2.0×10−6 Torr) and O2 partial pressure 1.33×10−2 Pa (1.0×10−4 Torr), and an electron beam with an acceleration voltage of 10 kV and a beam scan area of about 40 mmφ was irradiated to heat the ZnO vapor deposition material, thereby forming a ZnO film. The evaporation speed was measured by a quartz crystal thickness monitor provided obliquely above the hearth. The results are shown in Table 13.
As shown in Tables 12 and 13, in Examples D1 to D5, the evaporation speed is higher than in Comparative Example D1. In Comparative Examples D2 and D3, the evaporation speed is the same as in Example D5, but the specific resistance is large and the conductivity is low.
[Moisture Resistance Test D]
For the samples of Examples D1 to D5 and Comparative Examples D1 and D3, a moisture resistance test D was performed. The moisture resistance test D was performed for 2000 hours in an atmosphere of humidity 60% and temperature 90° C. The specific resistance of a film was measured hourly. The results are shown in Table 14.
As shown in Table 14, with regard to the moisture resistance of a ZnO film formed of a ZnO vapor deposition material containing Ce and B, the deterioration rate of specific resistance is several times lower than a ZnO film containing no Ce and B. This indicates that a ZnO film containing Ce and B is several times more stable.
Examples D6 to D8
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example D1 except that adjustment was done such that the Ce content was 0.2% by mass, the B content was 0.1% by mass, and the porosity was in a range of 9 to 30%.
Examples D9 to D11
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example D1 except that adjustment was done such that the Ce content was 14.9% by mass, the B content was 10% by mass, and the porosity was in a range of 10 to 33%.
Comparative Example D4
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Examples D6 to D8 except that adjustment wad done such that the porosity was 2%.
Comparative Example D5
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Examples D9 to D11 except that adjustment was done such that the porosity was 2%.
Comparative Examples D6 to D9
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example D1 except that adjustment was done such that the Ce content was 20% by mass, the B content was 15% by mass, and porosity was in a range of 2 to 31%.
For the samples of Examples D6 to D11 and Comparative Examples D4 to D9, a deposition test D was performed. The results are shown in Table 15. As shown in Table 15, similar to Table 12, in Examples D6 to D11, a ZnO vapor deposition material has high evaporation speed and excellent specific resistance, as compared with Comparative Example D. On the other hand, in Comparative Examples D4, D5, and D9 having a small porosity, the evaporation speed is considerably low at 14.0 to 14.5. In Comparative Examples D6 to D9 in which the Ce content and the B content are high, a ZnO film has very large specific resistance and considerably low permeability.







TABLE 12







Deposition test D results using ZnO vapor deposition material


containing CeO2: 6.2% (Ce: 5.1%) and B2O3: 2.8% (B: 1.0%)









ZnO Vapor



Deposition Material
















Pore
Crystal



Raw Powder


Diam-
Grain



(% by mass)
Slurry
Porosity
eter
size
















Example D1
ZnO: 90%
Gas-
17.9%
25
53



CeO2: 6.2%
Containing



(Ce: 5.1%)
Slurry


Example D2
B2O3: 3.8%
Foaming
24.7%
32
49



(B: 1.0%)
Agent-




Containing




Slurry


Example D3

Additive-
28.1%
39
42




Containing




Slurry


Example D4

Additive-
30.4%
54
37




Containing




Slurry


Example D5

Slurry with
10.9%
15
60




Adjustment




of Grain Size




Distribution


Comparative
Same as
Slurry
1.8%
5
118


Example D1
Above
with No




Adjustment


Comparative
ZnO: 93.8%
Gas-
17.9%
22
45


Example D2
CeO2: 6.2%
Containing




Slurry


Comparative
ZnO Alone
Gas-
17.2%
23
43


Example D3
No Ce and
Containing



B Added
Slurry





(Note)


Porosity is %, pore diameter is average pore diameter μm, and crystal grain size is average crystal grain size μm
















TABLE 13









Ratio of
ZnO Film












Evaporation Speed
Evapora-

Visible














20
60
100
tion
Specific
Light



mA
mA
mA
Speed
Resistance
Permeability

















Example D1
6.7
17.5
32.1
1.3
4.5 × 10−4
88


Example D2
8.3
24.1
37.7
1.5
4.4 × 10−4
88


Example D3
8.2
24.9
45.7
1.9
4.5 × 10−4
87


Example D4
9.8
26.8
48.1
2.0
4.7 × 10−4
87


Example D5
5.4
18.3
26.7
1.1
4.9 × 10−4
88


Comparative
5.4
15.4
24.5
1
4.6 × 10−4
87


Example D1


Comparative
6.2
17.1
28.4
1.2
8.1 × 10−4
89


Example D2


Comparative
6.0
17.0
28.3
1.2
2.3 × 10−2
92


Example D3





(Note)


Evaporation speed is A/sec, specific resistance is Ω · cm, and visible light permeability is % Ratio of evaporation speed is ratio to evaporation speed of Comparative Example D1 at 100 mA













TABLE 14







Moisture Resistance Test D Result











Specific Resistance



Specific Resistance
Deterioration Rate












After Film
After
After
After



Formation (0 hr)
500 hr
100 hr
2000 hr















Example D1
1
1.01
1.02
1.04


Example D2
1
1.03
1.03
1.04


Example D3
1
1.02
1.06
1.08


Example D4
1
1.02
1.04
1.06


Example D5
1
1.02
1.03
1.05


Comparative
1
1.02
1.03
1.05


Example D1


Comparative
1
1.29
1.38
1.49


Example D3





(Note)


Deterioration rate of specific resistance represents change rate with setting 1 for after film formation.

















TABLE 15










Evapora-




ZnO Vapor
tion
ZnO Film












Deposition Material
Speed
Specific
Perme-














Ce
B
Porosity
60 mA
Resistance
ability

















Example D6
0.2
0.1
9
19.2
6.0 × 10−4
89


Example D7


16
19.5
6.1 × 10−4
88


Example D8


30
28.1
6.3 × 10−4
89


Comparative


2
14.5
6.4 × 10−4
88


Example D4


Example D9
14.9
10
10
17.8
8.3 × 10−4
84


Example D10


17
18.2
8.2 × 10−4
85


Example D11


33
24.3
8.6 × 10−4
85


Comparative


2
14.0
8.9 × 10−4
84


Example D5


Comparative
20
15
7
15.9
1.3 × 10−2
82


Example D6


Comparative


16
17.7
1.6 × 10−2
82


Example D7


Comparative


31
21.8
1.4 × 10−2
82


Example D8


Comparative


2
14.5
1.8 × 10−2
81


Example D9


Comparative
0
0
1.8
14.5
2.4 × 10−2
90


Example D3





(Note)


Porosity is %, pore diameter is average pore diameter μm, crystal grain size is average crystal grain size μm, evaporation speed is A/sec, specific resistance is Ω · cm, and permeability is visible light permeability %






Example E
Hereinafter, Example E Group of this aspect will be described together with Comparative Example E Group. In Example E and Comparative Example E, commercially available ZnO powder, La2O3 powder, B2O3 powder, Al2O3 powder, Ga2O3 powder, and Sc2O3 powder were used. Any powder has purity equal to or greater than 99% and an average grain size of 0.3 μm.
In any case, a slurry was prepared by using a ball mill (with a nylon-coated steel ball having a diameter of 5 to 20 mm), and wet blending was performed for 24 hours. In any case, a uniaxial molding press device was used as the molding device, and molded bodies having an outer diameter of 6.7 mmφ and a thickness of 2.0 mm were molded under pressure of 100 kgf/cm2 (9.8 MPa). The molded bodies were put in an electric furnace and calcinated under air pressure at 1300° C. for 3 hours, thereby obtaining sintered body pellets.
In Example E and Comparative Example E, the porosity was measured by a substitution method. The measurement of the average pore diameter and the crystal grain size was performed by SEM (Scanning Electron Microscopy). The evaporation speed was measured by a quartz crystal thickness monitor provided obliquely above the hearth. The specific resistance was measured by a four-terminal four-probe method with the application of a constant current at 25° C. in an atmosphere by using Loresta (trademark) from Mitsubishi Chemical Corporation (HP MCP-T410, probe in series, 1.5 mm pitch) as the measuring instrument. The visible light permeability was measured by placing the substrate after film formation vertically to measurement light for a visible wavelength band (380 to 780 nm) by using a spectrophotometer U-4000 manufactured by Hitachi, Ltd. as the measuring instrument.
Example E1
1% by mass of polyvinyl butyral as a binder was added to 100 g of a raw powder containing 90.4 g of ZnO powder, 5.8 g of La2O3 powder, and 3.8 g of B2O3 powder, and methylated alcohol as a dispersion medium was further added, thereby obtaining a slurry with a concentration of 30% by mass. Next, the slurry was put in a ball mill, air was blown into the slurry, and wet blending was performed, thereby obtaining a gas-containing slurry. The slurry was dry-comminuted after the dispersion medium in the slurry was vaporized by a vacuum drier at 80° C., thereby obtaining porous granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby producing porous sintered body pellets (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 16.
Example E2
An organic foaming agent and an inorganic foaming agent were added to 100 g of a raw powder containing 91.4 g of ZnO powder, 5.8 g of La2O3 powder, and 2.8 g of Al2O3 powder, 1% by mass of polyvinyl butyral as a binder was added, and methylated alcohol was further added as a dispersion medium, thereby obtaining a slurry (viscosity 200 to 4000 cps) with a concentration of 30% by mass. For the organic foaming agent, azodicarboxylamide and dinitrosobenta methylene tetramine were used, and for the inorganic foaming agent, carbonate was used. The foaming agent-containing slurry was put in a ball mill, wet blending was performed, then, the slurry was dry-comminuted after the dispersion medium in the slurry was vaporized by a vacuum drier at 80° C., thereby obtaining porous granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby producing porous sintered body pellets (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 16.
Example E3
An additive which will be volatized and dissolved upon calcination was added to 100 g of a raw powder containing 91.4 g of ZnO powder, 5.8 g of La2O3 powder, and 2.8 g of Ga2O3 powder, 1% by mass of polyvinyl butyral was added as a binder, and methylated alcohol was further added as a dispersion medium, thereby obtaining a slurry (viscosity 200 to 4000 cps) with a concentration of 30% by mass. For the additive which will be volatized and dissolved upon calcination, 20% by mass of polyvinyl butyral was used. The additive-containing slurry was put in a ball mill, wet blending was performed, then, the slurry was dry-comminuted after the dispersion medium in the slurry was vaporized by a vacuum drier at 80° C., thereby obtaining granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated such that the additive was volatized and dissolved, thereby producing porous sintered body pellets (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 16.
Example E4
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example E3 except that 100 g of a raw powder containing 91.2 g of ZnO powder, 5.8 g of La2O3 powder, and 3.0 g of Sc2O3 powder was used and, for the additive which will be volatized and dissolved upon calcination, 20% by mass of starch having a grain size of 50 μm was used. The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 16.
Example E5
The same raw powder as in Example E1 was used, and ZnO powder was filtered such that ZnO powder having an average grain size of 60 μm and a grain size distribution within a range of 55 to 65 μm was obtained. 1% by mass of polyvinyl butyral as a binder and also 30% by mass of methylated alcohol as an organic solvent were added to raw powder containing the ZnO powder and then mixed, thereby preparing a slurry in which the concentration of ZnO powder was 30% by mass. Next, the slurry was spray-dried, thereby obtaining porous granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby producing porous sintered body pellets (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 16.
Comparative Example E1
The same raw powder as in Example E1 was used, a slurry was prepared in the same manner as in Example E1 except that introduction of air into the slurry, addition of a foaming agent, and use of an additive which will be volatized and dissolved upon calcination were not performed, and the slurry was spray-dried, thereby obtaining granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby preparing a sintered body pellet (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 16.
Comparative Example E2
A slurry was prepared in the same manner as in Example E1 except that raw powder was used in which 5.8 g of La2O3 powder was added to 95.2 g of ZnO powder and no oxide powder of the second additive element was added, and the slurry was spray-dried, thereby obtaining granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby preparing a sintered body pellet (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 16.
Comparative Example E3
A slurry was prepared in the same manner as in Example E1 except that 100 g of ZnO powder containing no LaO2 powder as a first additive element and no oxide powder of the second additive element was used, and the slurry was spray-dried, thereby obtaining granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby preparing a sintered body pellet (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 16.
[Deposition Test E]
A deposition test E was carried out using the ZnO vapor deposition materials of Examples E1 to E5 and the ZnO vapor deposition materials of Comparative Examples E1 to E3. A vapor deposition material as a sample was put in the hearth (diameter 50 mm, depth 25 mm) of the electron beam deposition device, adjustment was done in an atmosphere of an ultimate vacuum 2.66×10 Pa (2.0×10−6 Ton) and O2 partial pressure 1.33×10−2 Pa (1.0×10−4 Torr), and an electron beam with an acceleration voltage of 10 kV and a beam scan area of about 40 mmφ was irradiated to heat the ZnO vapor deposition material, thereby forming a ZnO film. The evaporation speed was measured by a quartz crystal thickness monitor provided obliquely above the hearth. The results are shown in Table 17.
As shown in Tables 16 and 17, in Examples E1 to E5, the evaporation speed is higher than in Comparative Example E1. In Comparative Examples E2 and E3, the evaporation speed is the same as in Example E5, but the specific resistance is large and the conductivity is low.
[Moisture Resistance Test E]
For the samples of Examples E1 to E5 and Comparative Examples E1 and E3, a moisture resistance test E was performed. The moisture resistance test E was performed for 2000 hours in an atmosphere of humidity 60% and temperature 90° C. The specific resistance of a film was measured hourly. The results are shown in Table 18.
As shown in Table 18, with regard to the moisture resistance of a ZnO film formed of a ZnO vapor deposition material containing La and B, Al, Ga, or Sc, the deterioration rate of specific resistance is several times lower than a ZnO film containing no elements described above. This indicates that a ZnO film containing La and B, Al, Ga, or Sc is several times more stable.
Examples E6 to E8
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example E1 except that adjustment was done such that the La content was 0.2% by mass, the B content was 0.1% by mass, and the porosity was in a range of 10 to 28%.
Examples E9 to E11
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example E1 except that adjustment was done such that the La content was 14.9% by mass, the Al content was 10% by mass, and the porosity was in a range of 8 to 32%.
Comparative Example E4
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Examples E6 to E8 except that adjustment was done such that the porosity was 2%.
Comparative Example E5
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Examples E9 to E11 except that adjustment was done such that the porosity was 2%.
Comparative Examples E6 to E9
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example E1 except that adjustment was done such that the La content was 20% by mass, the Ga content was 15% by mass, and the porosity was in a range of 2 to 30%.
For the samples of Examples E6 to E11 and Comparative Examples E4 to E9, a deposition test E was performed. The results are shown in Table 19. As shown in Table 19, similar to Table 16, in Examples E6 to E11, the ZnO vapor deposition material has a high evaporation speed and excellent specific resistance, as compared with Comparative Example E. On the other hand, in Comparative Examples E4, E5, and E9 having a small porosity, the evaporation speed is considerably low at 13.0 to 14.1. In Comparative Examples E6 to E9 in which the La content and the Ga content are high, a ZnO film has very large specific resistance and considerably low permeability.









TABLE 16









ZnO Vapor



Deposition Material
















Pore
Crystal



Raw Powder


Diam-
Grain



(% by mass)
Slurry
Porosity
eter
size
















Example E1
ZnO 90.4%,
Gas-
16.3%
23
60



La2O3 5.8%,
Containing



B2O3 3.8%
Slurry



(La: 4.9%),



(B: 1.2%)


Example E2
ZnO 91.4%,
Foaming
26.7%
34
52



La2O3 5.8%,
Agent-



Al2O3 2.8%
Containing



(La: 4.9%),
Slurry



(Al: 1.5%)


Example E3
ZnO 91.4%,
Additive-
30.9%
45
51



La2O3 5.8%,
Containing



Ga2O3 2.8%
Slurry



(La: 4.9%),



(Ga: 2.3%)


Example E4
ZnO 91.2%,
Additive-
31.6%
64
45



La2O3 5.8%,
Containing



Sc2O3 3.0%
Slurry



(La: 4.9%),



(Sc: 2.0%)


Example E5
ZnO 90.4%,
Slurry with
9.8%
23
57



La2O3 5.8%,
Adjustment



B2O3 3.8%
of Grain Size



(La: 4.9%),
Distribution



(B: 1.2%)


Comparative
ZnO 90.4%,
Slurry
2.2%
5
89


Example E1
La2O3 5.8%,
with No



B2O3 3.8%
Adjustment



(La: 4.9%),



(B: 1.2%)


Comparative
ZnO 95.2%,
Gas-
18.6%
21
50


Example E2
La2O3 5.8%
Containing



(La: 4.9%)
Slurry


Comparative
ZnO Alone
Gas-
17.2%
23
43


Example E3
No Second
Containing



Additive
Slurry



Element



Added





(Note)


Porosity is %, pore diameter is average pore diameter μm, and crystal grain size is average crystal grain size μm
















TABLE 17









Ratio of
ZnO Film












Evaporation Speed
Evapora-

Visible














20
60
100
tion
Specific
Light



mA
mA
mA
Speed
Resistance
Permeability

















Example E1
6.2
17.9
31.0
1.4
8.2 × 10−4
90


Example E2
8.5
24.3
36.6
1.7
7.4 × 10−4
90


Example E3
8.7
24.8
43.1
2.0
7.2 × 10−4
89


Example E4
9.2
25.3
45.9
2.1
6.8 × 10−4
89


Example E5
5.4
17.7
24.8
1.1
8.1 × 10−4
90


Comparative
4.8
12.8
21.8
1

90


Example E1


Comparative
6.1
17.2
28.5
1.3
8.4 × 10−4
91


Example E2


Comparative
6.0
17.0
28.3
1.3
2.3 × 10−2
92


Example E3





(Note)


Evaporation speed is A/sec, specific resistance is Ω · cm, and visible light permeability is % Ratio of evaporation speed is ratio to evaporation speed of Comparative Example E1 at 100 mA













TABLE 18







Moisture Resistance Test E Result











Specific Resistance



Specific Resistance
Deterioration Rate












After Film
After
After
After



Formation (0 hr)
500 hr
100 hr
2000 hr















Example E1
1
1.03
1.05
1.08


Example E2
1
1.03
1.05
1.07


Example E3
1
1.04
1.07
1.09


Example E4
1
1.03
1.06
1.08


Example E5
1
1.04
1.05
1.07


Comparative
1
1.03
1.05
1.09


Example E1


Comparative
1
1.29
1.38
1.49


Example E3





(Note)


Deterioration rate of specific resistance represents change rate with setting 1 for after film formation.

















TABLE 19










Evapora-




ZnO Vapor
tion
ZnO Film












Deposition Material
Speed
Specific
Perme-














La

Porosity
60 mA
Resistance
ability

















Example E6
0.2
B
10
19.1
7.4 × 10−4
89


Example E7

0.1
15
19.3
7.6 × 10−4
88


Example E8


28
27.4
7.9 × 10−4
88


Comparative


2
14.1
7.7 × 10−4
88


Example E4


Example E9
14.9
Al
8
16.9
9.9 × 10−4
86


Example E10

10
14
17.4
9.5 × 10−4
85


Example E11


32
23.1
9.3 × 10−4
86


Comparative


2
14.2
8.9 × 10−4
85


Example E5


Comparative
20
Ga
5
16.2
1.4 × 10−2
83


Example E6

15


Comparative


16
17.3
1.5 × 10−2
84


Example E7


Comparative


30
22.1
1.8 × 10−2
83


Example E8


Comparative


2
14.7
1.9 × 10−2
82


Example E9


Comparative
0
0
1.8
14.5
2.4 × 10−2
90


Example E3





(Note)


Porosity is %, pore diameter is average pore diameter μm, crystal grain size is average crystal grain size μm, evaporation speed is A/sec, specific resistance is Ω · cm, and permeability is visible light permeability %






Example F
Hereinafter, Example F Group of this aspect will be described together with Comparative Example F Group. In Example F and Comparative Example F, commercially available ZnO powder, Y2O3 powder, B2O3 powder, Al2O3 powder, Ga2O3 powder, and Sc2O3 powder were used. Any powder has purity equal to or greater than 99% and an average grain size of 0.3 μm.
In any case, a slurry was prepared by using a ball mill (with a nylon-coated steel ball having a diameter of 5 to 20 mm), and wet blending was performed for 24 hours. In any case, a uniaxial molding press device was used as the molding device, and molded bodies having an outer diameter of 6.7 mmφ and a thickness of 2.0 mm were molded under pressure of 100 kgf/cm2 (9.8 MPa). The molded bodies were put in an electric furnace and calcinated under air pressure at 1300° C. for 3 hours, thereby obtaining sintered body pellets.
In Example F and Comparative Example F, the porosity was measured by a substitution method. The measurement of the average pore diameter and the crystal grain size was performed by SEM (Scanning Electron Microscopy). The evaporation speed was measured by a quartz crystal thickness monitor provided obliquely above the hearth. The specific resistance was measured by a four-terminal four-probe method with the application of a constant current at 25° C. in an atmosphere by using Loresta (trademark) from Mitsubishi Chemical Corporation (HP MCP-T410, probe in series, 1.5 mm pitch) as the measuring instrument. The visible light permeability was measured by placing the substrate after film formation vertically to measurement light for a visible wavelength band (380 to 780 nm) by using a spectrophotometer U-4000 manufactured by Hitachi, Ltd. as the measuring instrument.
Example F1
1% by mass of polyvinyl butyral as a binder was added to 100 g of a raw powder containing 91.2 g of ZnO powder, 5.0 g of Y2O3 powder, and 3.8 g of B2O3 powder, and methylated alcohol as a dispersion medium was further added, thereby obtaining a slurry with a concentration of 30% by mass. Next, the slurry was put in a ball mill, air was blown into the slurry, and wet blending was performed, thereby obtaining a gas-containing slurry. The slurry was dry-comminuted after the dispersion medium in the slurry was vaporized by a vacuum drier at 80° C., thereby obtaining porous granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby producing porous sintered body pellets (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 20.
Example F2
An organic foaming agent and an inorganic foaming agent were added to 100 g of a raw powder containing 92.2 g of ZnO powder, 5.0 g of Y2O3 powder, and 2.8 g of Al2O3 powder, 1% by mass of polyvinyl butyral as a binder was added, and methylated alcohol was further added as a dispersion medium, thereby obtaining a slurry (viscosity 200 to 4000 cps) with a concentration of 30% by mass. For the organic foaming agent, azodicarboxylamide and dinitrosobenta methylene tetramine were used, and for the inorganic foaming agent, carbonate was used. The foaming agent-containing slurry was put in a ball mill, wet blending was performed, then, the slurry was dry-comminuted after the dispersion medium in the slurry was vaporized by a vacuum drier at 80° C., thereby obtaining porous granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby producing porous sintered body pellets (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 20.
Example F3
An additive which will be volatized and dissolved upon calcination was added to 100 g of a raw powder containing 92.2 g of ZnO powder, 5.0 g of Y2O3 powder, and 2.8 g of Ga2O3 powder, 1% by mass of polyvinyl butyral was added as a binder, and methylated alcohol was further added as a dispersion medium, thereby obtaining a slurry (viscosity 200 to 4000 cps) with a concentration of 30% by mass. For the additive which will be volatized and dissolved upon calcination, 20% by mass of polyvinyl butyral was used. The additive-containing slurry was put in a ball mill, wet blending was performed, then, the slurry was dry-comminuted after the dispersion medium in the slurry was vaporized by a vacuum drier at 80° C., thereby obtaining granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated such that the additive was volatized and dissolved, thereby producing porous sintered body pellets (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 20.
Example F4
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example F3 except that 100 g of a raw powder containing 92.0 g of ZnO powder, 5.0 g of Y2O3 powder, and 3.0 g of Sc2O3 powder was used and, for the additive which will be volatized and dissolved upon calcination, 20% by mass of starch having a grain size of 50 μm was used. The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 20.
Example F5
The same raw powder as in Example F1 was used, and ZnO powder was filtered such that ZnO powder having an average grain size of 60 μm and a grain size distribution within a range of 55 to 65 μm was obtained. 1% by mass of polyvinyl butyral as a binder and also 30% by mass of methylated alcohol as an organic solvent were added to raw powder containing the ZnO powder and then mixed, thereby preparing a slurry in which the concentration of ZnO powder was 30% by mass. Next, the slurry was spray-dried, thereby obtaining porous granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby producing porous sintered body pellets (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 20.
Comparative Example F1
The same raw powder as in Example F1 was used, a slurry was prepared in the same manner as in Example F1 except that introduction of air into the slurry, addition of a foaming agent, and use of an additive which will be volatized and dissolved upon calcination were not performed, and the slurry was spray-dried, thereby obtaining granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby preparing a sintered body pellet (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 20.
Comparative Example F2
A slurry was prepared in the same manner as in Example F1 except that raw powder was used in which 5.0 g of Y2O3 powder was added to 95 g of ZnO powder and no oxide powder of the second additive element was added, and the slurry was spray-dried, thereby obtaining granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby preparing a sintered body pellet (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 20.
Comparative Example F3
A slurry was prepared in the same manner as in Example F1 except that 100 g of ZnO powder containing no YO2 powder as a first additive element and no oxide powder of the second additive element was used, and the slurry was spray-dried, thereby obtaining granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby preparing a sintered body pellet (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 20.
[Deposition Test F]
A deposition test F was carried out using the ZnO vapor deposition materials of Examples F1 to F5 and the ZnO vapor deposition materials of Comparative Examples F1 to F3. A vapor deposition material as a sample was put in the hearth (diameter 50 mm, depth 25 mm) of the electron beam deposition device, adjustment was done in an atmosphere of an ultimate vacuum 2.66×10−4 Pa (2.0×10−6 Torr) and O2 partial pressure 1.33×10−2 Pa (1.0×10−4 Torr), and an electron beam with an acceleration voltage of 10 kV and a beam scan area of about 40 mmφ was irradiated to heat the ZnO vapor deposition material, thereby forming a ZnO film. The evaporation speed was measured by a quartz crystal thickness monitor provided obliquely above the hearth. The results are shown in Table 21.
As shown in Tables 20 and 21, in Examples F1 to F5, the evaporation speed is higher than in Comparative Example F1. In Comparative Examples F2 and F3, the evaporation speed is the same as in Example F5, but the specific resistance is large and the conductivity is low.
[Moisture Resistance Test F]
For the samples of Examples F1 to F5 and Comparative Examples F1 and F3, a moisture resistance test F was performed. The moisture resistance test F was performed for 2000 hours in an atmosphere of humidity 60% and temperature 90° C. The specific resistance of a film was measured hourly. The results are shown in Table 22.
As shown in Table 22, with regard to the moisture resistance of a ZnO film formed of a ZnO vapor deposition material containing Y and B, Al, Ga, or Sc, the deterioration rate of specific resistance is several times lower than a ZnO film containing no elements described above. This indicates that a ZnO film containing Y and B, Al, Ga, or Sc is several times more stable.
Examples F6 to F8
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example F1 except that adjustment was done such that the Y content was 0.2% by mass, the B content was 0.1% by mass, and the porosity was in a range of 9 to 30%.
Examples F9 to F11
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example F1 except that adjustment was done such that the Y content was 14.9% by mass, the Al content was 10% by mass, and the porosity was in a range of 9 to 30%.
Comparative Example F4
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Examples F6 to F8 except that adjustment was done such that the porosity was 2%.
Comparative Example F5
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Examples F9 to F11 except that adjustment was done such that the porosity was 2%.
Comparative Examples F6 to F9
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example F1 except that adjustment was done such that the Y content was 20% by mass, the Ga content was 15% by mass, and the porosity was in a range of 5 to 29%.
For the samples of Examples F6 to F11 and Comparative Examples F4 to F9, a deposition test F was performed. The results are shown in Table 23. As shown in Table 23, similar to Table 20, in Examples F6 to F11, the ZnO vapor deposition material has a high evaporation speed and excellent specific resistance, as compared with Comparative Example F. On the other hand, in Comparative Examples F4, F5, and F9 having a small porosity, the evaporation speed is considerably low at 14.2 to 14.4. In Comparative Examples F6 to F9 in which the Ce content and the Ga content are high, a ZnO film has very large specific resistance and considerably low permeability.









TABLE 20









ZnO Vapor



Deposition Material
















Pore
Crystal



Raw Powder


Diam-
Grain



(% by mass)
Slurry
Porosity
eter
size
















Example F1
ZnO 91.2%,
Gas-
17.5%
25
57



Y2O3 5.0%,
Containing



B2O3 3.8%
Slurry



(Y: 3.9%),



(B: 1.2%)


Example F2
ZnO 92.2%,
Foaming
24.8%
34
48



Y2O3 5.0%,
Agent-



Al2O3 2.8%
Containing



(Y: 3.9%),
Slurry



(Al: 1.5%)


Example F3
ZnO 92.2%,
Additive-
27.9%
42
42



Y2O3 5.0%,
Containing



Ga2O3 2.8%
Slurry



(Y: 3.9%),



(Ga: 2.3%)


Example F4
ZnO 92.0%,
Additive-
29.7%
48
34



Y2O3 5.0%,
Containing



Sc2O3 3.0%
Slurry



(Y: 3.9%),



(Sc: 2.0%)


Example F5
ZnO 91.2%,
Slurry with
9.8%
10
58



Y2O3 5.0%,
Adjustment



B2O3 3.8%
of Grain Size



(Y: 3.9%),
Distribution



(B: 1.2%)


Comparative
ZnO 91.2%,
Slurry
1.7%
4
92


Example F1
Y2O3 5.0%,
with No



B2O3 3.8%
Adjustment



(Y: 3.9%),



(B: 1.2%)


Comparative
ZnO 95.0%,
Gas-
17.2%
22
44


Example F2
Y2O3 5.0%
Containing



(Y: 3.9%)
Slurry


Comparative
ZnO Alone
Gas-
17.2%
23
43


Example F3
No Second
Containing



Additive
Slurry



Element



Added





(Note)


Porosity is %, pore diameter is average pore diameter μm, and crystal grain size is average crystal grain size μm
















TABLE 21









Ratio of
ZnO Film












Evaporation Speed
Evapora-

Visible














20
60
100
tion
Specific
Light



mA
mA
mA
Speed
Resistance
Permeability

















Example F1
6.1
17.7
30.7
1.3
6.8 × 10−4
90


Example F2
8.2
24.1
36.3
1.5
6.3 × 10−4
89


Example F3
8.3
25.0
42.1
1.8
6.0 × 10−4
89


Example F4
9.0
26.1
45.8
1.9
6.1 × 10−4
89


Example F5
5.8
17.8
25.2
1.1
6.7 × 10−4
90


Comparative
5.2
14.7
23.5
1
6.7 × 10−4
90


Example F1


Comparative
5.9
16.8
27.9
1.2
9.5 × 10−4
89


Example F2


Comparative
6.0
17.0
28.3
1.2
2.3 × 10−2
92


Example F3





(Note)


Evaporation speed is A/sec, specific resistance is Ω · cm, and visible light permeability is % Ratio of evaporation speed is ratio to evaporation speed of Comparative Example F1 at 100 mA













TABLE 22







Moisture Resistance Test F Result











Specific Resistance



Specific Resistance
Deterioration Rate












After Film
After
After
After



Formation (0 hr)
500 hr
100 hr
2000 hr















Example F1
1
1.03
1.05
1.08


Example F2
1
1.03
1.05
1.07


Example F3
1
1.04
1.07
1.09


Example F4
1
1.03
1.06
1.08


Example F5
1
1.04
1.05
1.07


Comparative
1
1.03
1.05
1.09


Example F1


Comparative
1
1.29
1.38
1.49


Example F3





(Note)


Deterioration rate of specific resistance represents change rate with setting 1 for after film formation.

















TABLE 23










Evapora-




ZnO Vapor
tion
ZnO Film












Deposition Material
Speed
Specific
Perme-














Y

Porosity
60 mA
Resistance
ability

















Example F6
0.2
B
9
19.9
7.1 × 10−4
87


Example F7

0.1
14
20.4
7.3 × 10−4
87


Example F8


30
28.8
7.2 × 10−4
88


Comparative


2
14.4
7.4 × 10−4
87


Example F4


Example F9
14.9
Al
9
17.1
8.9 × 10−4
85


Example F10

10
15
17.9
9.0 × 10−4
85


Example F11


30
23.0
9.1 × 10−4
85


Comparative


2
14.2
8.8 × 10−4
84


Example F5


Comparative
20
Ga
5
15.9
1.5 × 10−2
84


Example F6

15


Comparative


14
16.7
1.6 × 10−2
84


Example F7


Comparative


29
21.8
1.2 × 10−2
83


Example F8


Comparative


2
14.3
1.5 × 10−2
83


Example F9


Comparative
0
0
1.8
14.5
2.4 × 10−2
90


Example F3





(Note)


Porosity is %, pore diameter is average pore diameter μm, crystal grain size is average crystal grain size μm, evaporation speed is A/sec, specific resistance is Ω · cm, and permeability is visible light permeability %






Example G
Hereinafter, Example G Group of this aspect will be described together with Comparative Example G Group. In Example G and Comparative Example G, commercially available ZnO powder, Pr6O11 powder, B2O3 powder, Al2O3 powder, Ga2O3 powder, and Sc2O3 powder were used. Any powder has purity equal to or greater than 99% and an average grain size of 0.3 μm.
In any case, a slurry was prepared by using a ball mill (with a nylon-coated steel ball having a diameter of 5 to 20 mm), and wet blending was performed for 24 hours. In any case, a uniaxial molding press device was used as the molding device, and molded bodies having an outer diameter of 6.7 mmφ and a thickness of 2.0 mm were molded under pressure of 100 kgf/cm2 (9.8 MPa). The molded bodies were put in an electric furnace and calcinated under air pressure at 1300° C. for 3 hours, thereby obtaining sintered body pellets.
In Example G and Comparative Example G, the porosity was measured by a substitution method. The measurement of the average pore diameter and the crystal grain size was performed by SEM (Scanning Electron Microscopy). The evaporation speed was measured by a quartz crystal thickness monitor provided obliquely above the hearth. The specific resistance was measured by a four-terminal four-probe method with the application of a constant current at 25° C. in an atmosphere by using Loresta (trademark) from Mitsubishi Chemical Corporation (HP MCP-T410, probe in series, 1.5 mm pitch) as the measuring instrument. The visible light permeability was measured by placing the substrate after film formation vertically to measurement light for a visible wavelength band (380 to 780 nm) by using a spectrophotometer U-4000 manufactured by Hitachi, Ltd. as the measuring instrument.
Example G1
1% by mass of polyvinyl butyral as a binder was added to 100 g of a raw powder containing 91.2 g of ZnO powder, 5.0 g of Pr6O11 powder, and 3.8 g of B2O3 powder, and methylated alcohol as a dispersion medium was further added, thereby obtaining a slurry with a concentration of 30% by mass. Next, the slurry was put in a ball mill, air was blown into the slurry, and wet blending was performed, thereby obtaining a gas-containing slurry. The slurry was dry-comminuted after the dispersion medium in the slurry was vaporized by a vacuum drier at 80° C., thereby obtaining porous granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby producing porous sintered body pellets (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 24.
Example G2
An organic foaming agent and an inorganic foaming agent were added to 100 g of a raw powder containing 92.2 g of ZnO powder, 5.0 g of Pr6O11 powder, and 2.8 g of Al2O3 powder, 1% by mass of polyvinyl butyral as a binder was added, and methylated alcohol was further added as a dispersion medium, thereby obtaining a slurry (viscosity 200 to 4000 cps) with a concentration of 30% by mass. For the organic foaming agent, azodicarboxylamide and dinitrosobenta methylene tetramine were used, and for the inorganic foaming agent, carbonate was used. The foaming agent-containing slurry was put in a ball mill, wet blending was performed, then, the slurry was dry-comminuted after the dispersion medium in the slurry was vaporized by a vacuum drier at 80° C., thereby obtaining porous granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby producing porous sintered body pellets (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 24.
Example G3
An additive which will be volatized and dissolved upon calcination was added to 100 g of a raw powder containing 92.2 g of ZnO powder, 5.0 g of Pr6O11 powder, and 2.8 g of Ga2O3 powder, 1% by mass of polyvinyl butyral was added as a binder, and methylated alcohol was further added as a dispersion medium, thereby obtaining a slurry (viscosity 200 to 4000 cps) with a concentration of 30% by mass. For the additive which will be volatized and dissolved upon calcination, 20% by mass of polyvinyl butyral was used. The additive-containing slurry was put in a ball mill, wet blending was performed, then, the slurry was dry-comminuted after the dispersion medium in the slurry was vaporized by a vacuum drier at 80° C., thereby obtaining granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated such that the additive was volatized and dissolved, thereby producing porous sintered body pellets (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 24.
Example G4
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example G3 except that 100 g of a raw powder containing 92.0 g of ZnO powder, 5.0 g of Pr6O11 powder, and 3.0 g of Sc2O3 powder was used and, for the additive which will be volatized and dissolved upon calcination, 20% by mass of starch having a grain size of 50 μm was used. The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 24.
Example G5
The same raw powder as in Example G1 was used, and ZnO powder was filtered such that ZnO powder having an average grain size of 60 μm and a grain size distribution within a range of 55 to 65 μm was obtained. 1% by mass of polyvinyl butyral as a binder and also 30% by mass of methylated alcohol as an organic solvent were added to raw powder containing the ZnO powder and then mixed, thereby preparing a slurry in which the concentration of ZnO powder was 30% by mass. Next, the slurry was spray-dried, thereby obtaining porous granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby producing porous sintered body pellets (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 24.
Comparative Example G1
The same raw powder as in Example G1 was used, a slurry was prepared in the same manner as in Example G1 except that introduction of air into the slurry, addition of a foaming agent, and use of an additive which will be volatized and dissolved upon calcination were not performed, and the slurry was spray-dried, thereby obtaining granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby preparing a sintered body pellet (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 24.
Comparative Example G2
A slurry was prepared in the same manner as in Example G1 except that raw powder was used in which 5.0 g of Pr6O11 powder was added to 95 g of ZnO powder and no oxide powder of the second additive element was added, and the slurry was spray-dried, thereby obtaining granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby preparing a sintered body pellet (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 24.
Comparative Example G3
A slurry was prepared in the same manner as in Example G1 except that 100 g of ZnO powder containing no oxide powder of the first additive element and no oxide powder the second additive element was used, and the slurry was spray-dried, thereby obtaining granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby preparing a sintered body pellet (ZnO vapor deposition material). The porosity, average pore diameter, and average crystal grain size of the sintered body are shown in Table 24.
[Deposition Test G]
A deposition test G was carried out using the ZnO vapor deposition materials of Examples G1 to G5 and the ZnO vapor deposition materials of Comparative Examples G1 to G3. A vapor deposition material as a sample was put in the hearth (diameter 50 mm, depth 25 mm) of the electron beam deposition device, adjustment was done in an atmosphere of an ultimate vacuum 2.66×10−4 Pa (2.0×10−6 Torr) and O2 partial pressure 1.33×10−2 Pa (1.0×10−4 Torr), and an electron beam with an acceleration voltage of 10 kV and a beam scan area of about 40 mmφ was irradiated to heat the ZnO vapor deposition material, thereby forming a ZnO film. The evaporation speed was measured by a quartz crystal thickness monitor provided obliquely above the hearth. The results are shown in Table 25.
As shown in Tables 24 and 25, in Examples G1 to G5, the evaporation speed is higher than in Comparative Example G1. In Comparative Examples G2 and G3, the evaporation speed is the same as in Example G5, but the specific resistance is large and the conductivity is low.
[Moisture Resistance Test G]
For the samples of Examples G1 to G5 and Comparative Examples G1 and G3, a moisture resistance test G was performed. The moisture resistance test G was performed for 2000 hours in an atmosphere of humidity 60% and temperature 90° C. The specific resistance of a film was measured hourly. The results are shown in Table 26.
As shown in Table 26, with regard to the moisture resistance of a ZnO film formed of a ZnO vapor deposition material containing Pr and B, Al, Ga, or Sc, the deterioration rate of specific resistance is several times lower than a ZnO film containing no elements described above. This indicates that a ZnO film containing Pr and B, Al, Ga, or Sc is several times more stable.
Examples G6 to G8
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example G1 except that adjustment was done such that the Pr content was 0.2% by mass, the B content was 0.1% by mass, and the porosity was in a range of 10 to 31%.
Examples G9 to G11
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example G1 except that adjustment was done such that the Pr content was 14.9% by mass, the Al content was 10% by mass, and the porosity was in a range of 9 to 32%.
Comparative Example G4
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Examples G6 to G8 except that adjustment was done such that the porosity was 2%.
Comparative Example G5
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Examples G9 to G11 except that adjustment was done such that the porosity was 2%.
Comparative Examples G6 to G9
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example G1 except that adjustment was done such that the Pr content was 20% by mass, the Ga content was 15% by mass, and the porosity was in a range of 2 to 31%.
For the samples of Examples G6 to G11 and Comparative Examples G4 to G9, a deposition test G was performed. The results are shown in Table 27. As shown in Table 27, similar to Table 24, in Examples G6 to G11, the ZnO vapor deposition material has a high evaporation speed and excellent specific resistance, as compared with Comparative Example G. On the other hand, in Comparative Examples G4, G5, and G9 having a small porosity, the evaporation speed is considerably low at 14.2 to 14.4. In Comparative Examples G6 to G9 in which the Pr content and the Ga content are high, a ZnO film has very large specific resistance and considerably low permeability.









TABLE 24









ZnO Vapor



Deposition Material
















Pore
Crystal



Raw Powder


Diam-
Grain



(% by mass)
Slurry
Porosity
eter
size
















Example G1
ZnO 91.2%,
Gas-
18.1%
25
59



Pr6O11 5.0%,
Containing



B2O3 3.8%
Slurry



(Pr: 4.1%),



(B: 1.2%)


Example G2
ZnO 92.2%,
Foaming
25.2%
34
48



Pr6O11 5.0%,
Agent-



Al2O3 2.8%
Containing



(Pr: 4.1%),
Slurry



(Al: 1.5%)


Example G3
ZnO 92.2%,
Additive-
28.3%
40
44



Pr6O11 5.0%,
Containing



Ga2O3 2.8%
Slurry



(Pr: 4.1%),



(Ga: 2.3%)


Example G4
ZnO 92.0%,
Additive-
29.8%
52
34



Pr6O11 5.0%,
Containing



Sc2O3 3.0%
Slurry



(Pr: 4.1%),



(Sc: 2.0%)


Example G5
ZnO 91.2%,
Slurry with
10.5%
10
60



Pr6O11 5.0%,
Adjustment



B2O3 3.8%
of Grain Size



(Pr: 4.1%),
Distribution



(B: 1.2%)


Comparative
ZnO 91.2%,
Slurry
1.8%
4
94


Example G1
Pr6O11 5.0%,
with No



B2O3 3.8%
Adjustment



(Pr: 4.1%),



(B: 1.2%)


Comparative
ZnO 95.0%,
Gas-
17.3%
23
44


Example G2
Pr6O11 5.0%
Containing



(Pr: 4.1%)
Slurry


Comparative
ZnO Alone
Gas-
17.2%
23
43


Example G3
No Second
Containing



Additive
Slurry



Element



Added





(Note)


Porosity is %, pore diameter is average pore diameter μm, and crystal grain size is average crystal grain size μm
















TABLE 25









Ratio of
ZnO Film












Evaporation Speed
Evapora-

Visible














20
60
100
tion
Specific
Light



mA
mA
mA
Speed
Resistance
Permeability

















Example G1
6.7
18.9
31.8
1.4
8.1 × 10−4
92


Example G2
8.5
25.4
37.8
1.6
8.1 × 10−4
91


Example G3
8.7
26.6
44.7
1.9
8.1 × 10−4
90


Example G4
9.3
26.9
48.0
2.0
8.1 × 10−4
90


Example G5
6.0
18.9
26.9
1.1
8.1 × 10−4
92


Comparative
5.2
14.7
23.5
1
8.1 × 10−4
92


Example G1


Comparative
6.1
17.2
28.6
1.2
1.8 × 10−3
92


Example G2


Comparative
6.0
17.0
28.3
1.2
2.3 × 10−2
92


Example G3





(Note)


Evaporation speed is A/sec, specific resistance is Ω · cm, and visible light permeability is % Ratio of evaporation speed is ratio to evaporation speed of Comparative Example G1 at 100 mA













TABLE 26







Moisture Resistance Test G Results











Specific Resistance



Specific Resistance
Deterioration Rate












After Film
After
After
After



Formation (0 hr)
500 hr
100 hr
2000 hr















Example G1
1
1.05
1.07
1.09


Example G2
1
1.04
1.08
1.11


Example G3
1
1.05
1.07
1.10


Example G4
1
1.05
1.09
1.11


Example G5
1
1.04
1.07
1.09


Comparative
1
1.04
1.07
1.10


Example G1


Comparative
1
1.29
1.38
1.49


Example G3





(Note)


Deterioration rate of specific resistance represents change rate with setting 1 for after film formation.

















TABLE 27










Evapora-




ZnO Vapor
tion
ZnO Film












Deposition Material
Speed
Specific
Perme-














Pr

Porosity
60 mA
Resistance
ability

















Example G6
0.2
B
10
19.9
9.1 × 10−4
86


Example G7

0.1
15
20.4
9.3 × 10−4
86


Example G8


31
28.8
9.2 × 10−4
87


Comparative


2
14.4
9.4 × 10−4
86


Example G4


Example G9
14.9
Al
9
17.1
1.2 × 10−3
85


Example G10

10
16
17.9
1.4 × 10−3
85


Example G11


32
23.0
1.3 × 10−3
86


Comparative


2
14.2
1.2 × 10−3
85


Example G5


Comparative
20
Ga
4
15.9
1.9 × 10−2
83


Example G6

15


Comparative


15
16.7
1.8 × 10−2
83


Example G7


Comparative


31
21.8
1.7 × 10−2
82


Example G8


Comparative


2
14.3
1.9 × 10−2
83


Example G9


Comparative
0
0
1.8
14.5
2.4 × 10−2
90


Example G3





(Note)


Porosity is %, pore diameter is average pore diameter μm, crystal grain size is average crystal grain size μm, evaporation speed is A/sec, specific resistance is Ω · cm, and permeability is visible light permeability %






Example H
Hereinafter, Example H Group of this aspect will be described together with Comparative Example H Group. In Example H and Comparative Example H, commercially available ZnO powder, Ce oxide powder, Y oxide powder, La oxide powder, Pr oxide powder, Nd oxide powder, Pm oxide powder, and Sm oxide powder were used. Any powder has purity equal to or greater than 99% and an average grain size of 0.3 μm.
A slurry was prepared by using a ball mill (with a nylon-coated steel ball having a diameter of 5 to 20 mm), and wet blending was performed for 24 hours. In any case, a uniaxial molding press device was used as a molding device, and a molded body was molded under pressure of 100 kgf/cm2 (9.8 MPa). The molded bodies were put in an electric furnace and calcinated under air pressure at 1300° C. for 3 hours, thereby forming a plate-shaped (vertical 5 mm×horizontal 5 mm×thickness 2 mm) sintered body (ZnO vapor deposition material). In Example H and Comparative Example H, the porosity was measured by a substitution method. The measurement of the average pore diameter and the crystal grain size was performed by SEM (Scanning Electron Microscopy). The evaporation speed upon film formation was measured by a quartz crystal thickness monitor provided obliquely above the hearth.
A ZnO film was formed of the ZnO vapor deposition material to have a thickness of 200 nm on a glass substrate by an electron beam deposition method. The film formation conditions were that an ultimate vacuum was 1.0×10−4 Pa, oxygen gas partial pressure was 1.0×10−2 Pa, and substrate temperature was 200° C. The evaporation speed upon film formation was measured by a quartz crystal thickness monitor provided obliquely above the hearth. The specific resistance and visible light permeability of the formed ZnO film were measured. The specific resistance was measured by a four-terminal four-probe method with the application of a constant current at a so-called normal temperature of 25° C. in an atmosphere by using Loresta (trademark) from Mitsubishi Chemical Corporation (HP MCP-T410, probe in series, 1.5 mm pitch) as the measuring instrument. The permeability was measured by placing the substrate after film formation vertically to measurement light for a visible wavelength band (380 to 780 nm) by using a spectrophotometer U-4000 manufactured by Hitachi, Ltd. as the measuring instrument. The results were shown in Tables 28 and 29.
Example H1
1% by mass of polyvinyl butyral as a binder was added to 100 g of a raw powder containing 93.8 g of ZnO powder and 6.2 g of CeO2 powder, and methylated alcohol as a dispersion medium was further added, thereby obtaining a slurry with a concentration of 30% by mass. Next, the slurry was put in a ball mill, air was blown into the slurry, and wet blending was performed, thereby obtaining a gas-containing slurry. The slurry was dry-comminuted after the dispersion medium in the slurry was vaporized by a vacuum drier at 80° C., thereby obtaining porous granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby producing porous sintered body pellets (ZnO vapor deposition material). A ZnO Film was formed of the ZnO vapor deposition material.
Example H2
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example H1 except that 5.0 g of Sc2O3 powder was used instead of CeO2 powder, and a foaming agent was added instead of blowing air into the slurry. A ZnO film was formed of the ZnO vapor deposition material.
Example H3
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example H1 except that 5.0 g of Y2O3 powder was used instead of CeO2 powder, and a foaming agent was added instead of blowing air into the slurry. A ZnO film was formed of the ZnO vapor deposition material.
Example H4
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example H1 except that 5.8 g of La2O3 powder was used instead of CeO2 powder, and an additive which will be volatized and dissolved upon calcination was added instead of blowing air into the slurry. A ZnO film was formed of the ZnO vapor deposition material.
Example H5
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example H1 except that 5.0 g of Pr6O11 powder was used instead of CeO2 powder, and starch was used as an additive, which will be volatized and dissolved upon calcination, instead of blowing air into the slurry. A ZnO film was formed of the ZnO vapor deposition material.
Example H6
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example H1 except that 5.0 g of Nd2O3 powder was used instead of CeO2 powder, and an additive which will be volatized and dissolved upon calcination was used instead of blowing air into the slurry. A ZnO film was formed of the ZnO vapor deposition material.
Example H7
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example H1 except that 5.0 g of Pm2O3 powder was used instead of CeO2 powder, and a foaming agent was added instead of blowing air into the slurry. A ZnO film was formed of the ZnO vapor deposition material.
Example H8
5.0 g of Sm2O3 powder was used instead of CeO2 powder, and ZnO powder was filtered such that ZnO powder having an average grain size of 60 μm and a grain size distribution of 55 to 65 μm was obtained instead of blowing air into the slurry. 1% by mass of polyvinyl butyral as a binder and 30% by mass of methylated alcohol as an organic solvent were added to mixed raw powder of the ZnO powder and Sm oxide powder and mixed, thereby preparing a slurry in which the concentration of ZnO powder was 30% by mass. Next, the slurry was spray-dried, thereby obtaining porous granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby producing porous sintered body pellets (ZnO vapor deposition material). A ZnO film was formed of the ZnO vapor deposition material.
Comparative Example H1
The same raw powder as in Example H1 was used, a slurry was prepared in the same manner as in Example H1 except that introduction of air into the slurry, addition of a foaming agent, and use of an additive which will be volatized and dissolved upon calcination were not performed, and the slurry was spray-dried, thereby obtaining granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby preparing a sintered body pellet (ZnO vapor deposition material). A ZnO film was formed of the ZnO vapor deposition material.
Comparative Example H2
A slurry was prepared in the same manner as in Example H1 except that 100 g of ZnO powder was used and no oxide powder of the additive elements was added, and the slurry was spray-dried, thereby obtaining granulation powder having an average grain size of 200 μm. The granulation powder was molded under a predetermined pressure, and the molded bodies were calcinated, thereby preparing a sintered body pellet (ZnO vapor deposition material). A ZnO film was formed of the ZnO vapor deposition material.
[Deposition Test]
A deposition test was carried out using the ZnO vapor deposition materials of Examples H1 to H5 and the ZnO vapor deposition materials of Comparative Examples H1 to H3. A vapor deposition material as a sample was put in the hearth (diameter 50 mm, depth 25 mm) of the electron beam deposition device, adjustment was done in an atmosphere of an ultimate vacuum 2.66×10−4 Pa (2.0×10−6 Ton) and O2 partial pressure 1.33×10−2 Pa (1.0×10−4 Torr), and an electron beam with an acceleration voltage of 10 kV and a beam scan area of about 40 mmφ was irradiated to heat the ZnO vapor deposition material, thereby forming a ZnO film. The evaporation speed was measured by a quartz crystal thickness monitor provided obliquely above the hearth. The results are shown in Table 29.
As shown in Tables 28 and 29, in Examples H1 to H5, the evaporation speed is higher than in Comparative Example H1. In Comparative Examples H2 and H3, the evaporation speed is the same as in Example H5, but the specific resistance is large and the conductivity is low.
[Moisture Resistance Test]
For the samples of Examples H1 to H5 and Comparative Examples H1 and H2, a moisture resistance test was performed. The moisture resistance test was performed for 2000 hours in an atmosphere of humidity 60% and temperature 90° C. The specific resistance of a film was measured hourly. The results are shown in Table 30.
As shown in Table 30, with regard to the moisture resistance of a ZnO film formed of a ZnO vapor deposition material containing Ce, Sc, Y, La, Pr, Nd, Pm, or Sm, the deterioration rate of specific resistance is several times lower than a ZnO film containing no elements described above. This indicates that a ZnO film containing Ce, Sc, Y, La, Pr, Nd, Pm, or Sm is several times more stable.
Examples H6 to H8
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example H1 except that adjustment was done such that the Ce content was 0.2% by mass, the Nd content was 0.1% by mass, and the porosity was in a range of 10 to 29%.
Examples H9 to H11
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example H1 except that adjustment was done such that the Ce content was 14.9% by mass, the Pm content was 10% by mass, and the porosity was in a range of 10 to 31%.
Comparative Example H4
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Examples H6 to H8 except that adjustment was done such that the porosity was 2%.
Comparative Example H5
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Examples H9 to H11 except that adjustment was done such that the porosity was 2%.
Comparative Examples H6 to H9
A porous sintered body pellet (ZnO vapor deposition material) was produced in the same manner as in Example H1 except that adjustment was done such that the Ce content was 20% by mass, the Sm content was 15% by mass, and the porosity was in a range of 8 to 30%.
For the samples of Examples H6 to H11 and Comparative Examples H4 to H9, a deposition test was performed. The results are shown in Table 31. As shown in Table 31, similar to Table 28, in Examples H6 to H11, the ZnO vapor deposition material has a high evaporation speed and excellent specific resistance, as compared with Comparative Example H. On the other hand, in Comparative Examples H4, H5, and H9 having a small porosity, the evaporation speed is considerably low at 14.8 to 14.9. In Comparative Examples H6 to H9 in which the Ce content and the Sm content are high, a ZnO film has very large specific resistance and considerably low permeability.









TABLE 28









ZnO Vapor



Deposition Material
















Pore
Crystal



Raw Powder


Diam-
Grain



(% by mass)
Slurry
Porosity
eter
size
















Example H1
ZnO 93.8%,
Gas-
17.9%
22
45



CeO2 6.2%
Containing




Slurry


Example H2
ZnO 95.0%,
Foaming
26.0%
32
47



Sc2O3 5.0%
Agent-




Containing




Slurry


Example H3
ZnO 95.0%,
Additive-
29.8%
40
42



Y2O3 5.0%
Containing




Slurry


Example H4
ZnO 94.2%,
Additive-
31.2%
48
35



La2O3 5.8%
Containing




Slurry


Example H5
ZnO 95.0%,
Additive-
30.4%
47
38



Pr6O11 5.0%
Containing




Slurry


Example H6
ZnO 95.0%,
Additive-
30.9%
48
37



Nd2O3 5.0%
Containing




Slurry


Example H7
ZnO 95.0%,
Foaming
29.6%
42
40



Pm2O3 5.0%
Agent-




Containing




Slurry


Example H8
ZnO 95.0%,
Slurry with
11.2%
55
57



Sm2O3 5.0%
Adjustment




of Grain Size




Distribution


Comparative
Same As
Slurry
1.7%
4
94


Example H1
Example H1
with No




Adjustment


Comparative
ZnO Alone
Gas-
17.2%
23
43


Example H2
No Additive
Containing



Element
Slurry



Added





(Note)


Porosity is %, pore diameter is average pore diameter μm, and crystal grain size is average crystal grain size μm
















TABLE 29









Ratio of
ZnO Film












Evaporation Speed
Evapora-

Visible














20
60
100
tion
Specific
Light



mA
mA
mA
Speed
Resistance
Permeability

















Example H1
6.2
17.1
28.4
1.2
8.1 × 10−4
89


Example H2
8.3
24.7
36.9
1.6
9.2 × 10−4
87


Example H3
8.8
24.7
43.9
1.9
9.5 × 10−4
89


Example H4
9.6
27.2
48.3
2.1
8.4 × 10−4
91


Example H5
9.3
26.1
47.2
2.0
1.8 × 10−3
92


Example H6
9.5
26.9
48.1
2.1
2.3 × 10−3
90


Example H7
9.1
25.7
45.3
1.9
3.1 × 10−3
89


Example H8
5.9
16.9
25.9
1.1
2.9 × 10−3
91


Comparative
5.1
14.2
23.3
1
8.4 × 10−4
89


Example H1


Comparative
6.3
17.1
28.3
1.2
2.3 × 10−2
92


Example H2





(Note)


Evaporation speed is A/sec, specific resistance is Ω · cm, and visible light permeability is % Ratio of evaporation speed is ratio to evaporation speed of Comparative Example H1 at 100 mA













TABLE 30







Moisture Resistance Test Results











Specific Resistance



Specific Resistance
Deterioration Rate












After Film
After
After
After



formation (0 hr)
500 hr
100 hr
2000 hr















Example H1
1
1.02
1.04
1.06


Example H2
1
1.03
1.05
1.08


Example H3
1
1.02
1.05
1.07


Example H4
1
1.03
1.05
1.08


Example H5
1
1.04
1.06
1.08


Comparative
1
1.02
1.03
1.04


Example H1


Comparative
1
1.29
1.38
1.49


Example H2





(Note)


Deterioration rate of specific resistance represents change rate with setting 1 for after film formation.

















TABLE 31










Evapora-




ZnO Vapor
tion
ZnO Film












Deposition Material
Speed
Specific
Perme-














Ce

Porosity
60 mA
Resistance
ability

















Example H6
0.2
Nd
10
20.4
8.1 × 10−4
89


Example H7

0.1
14
22.8
8.8 × 10−4
89


Example H8


29
30.1
8.6 × 10−4
88


Comparative


2
14.9
8.3 × 10−4
89


Example H3


Example H9
14.9
Pm
10
19.8
7.2 × 10−3
86


Example H10

10
17
21.4
7.5 × 10−3
86


Example H11


31
24.4
7.9 × 10−3
85


Comparative


2
14.9
7.5 × 10−3
86


Example H4


Comparative
20
Sm
8
17.4
9.3 × 10−2
84


Example H5

15


Comparative


15
18.2
9.4 × 10−2
83


Example H6


Comparative


30
22.9
9.1 × 10−2
82


Example H7


Comparative


2
14.8
9.5 × 10−2
83


Example H8


Comparative
0
0
1.8
14.5
2.4 × 10−2
90


Example H2





(Note)


Porosity is %, pore diameter is average pore diameter μm, crystal grain size is average crystal grain size μm, evaporation speed is A/sec, specific resistance is Ω · cm, and permeability is visible light permeability %






INDUSTRIAL APPLICABILITY
According to the present invention, it is possible to form a ZnO film having high permeability, excellent denseness, and high durability. Further, it is possible to obtain a film having excellent moisture resistance and gas and vapor barrier properties. Therefore, the present invention is industrially applicable.

## Claims

1. A ZnO vapor deposition material for formation of a transparent conductive film comprising:
a porous ZnO sintered body containing Ce and Ga,
wherein the Ce content is higher than the Ga content, the Ce content is in a range of 0.1 to 14.9% by mass, the Ga content is in a range of 0.1 to 10% by mass, and the sintered body has a porosity of 20 to 50%.

2. The ZnO vapor deposition material described in claim 1, wherein the total content of Ce and Ga is in a range of 0.2 to 15% by mass.

3. The ZnO vapor deposition material described in claim 1, wherein the porous ZnO sintered body has pores having an average pore diameter of 0.1 to 500 μm.

4. The ZnO vapor deposition material described in claim 1, wherein the porous ZnO sintered body is a sintered body of grains having an average crystal grain size of 1 to 500 μm.

5. The ZnO vapor deposition material described in claim 1, wherein the porous ZnO sintered body is polycrystal or monocrystal.

6. The ZnO vapor deposition material described in claim 1, wherein the Ce content is in a range of 3 to 6% by mass.

7. The ZnO vapor deposition material described in claim 1, wherein the Ga content is in a range of 1 to 3% by mass.

8. The ZnO vapor deposition material described in claim 1, wherein the porosity of the sintered body is in a range of 20 to 30%.

9. The ZnO vapor deposition material described in claim 1, wherein the surface area of the porous ZnO sintered body is in a range of 5 to 40 m2/g.

10. The ZnO vapor deposition material described in claim 1, wherein the porous ZnO sintered body has an average crystal grain size of 5 to 40 μm.

11. The ZnO vapor deposition material described in claim 1, wherein the porous ZnO sintered body is molded in the form of pellets.