# Patent

## Title
Oxide sintered body and sputtering target

## Abstract

An oxide sintered body is obtained by mixing and sintering a zinc oxide, an indium oxide, a gallium oxide and a tin oxide. The oxide sintered body has a relative density of 85% or more, and has volume ratios satisfying the following expressions (1) to (3), respectively, as determined by X•ray diffractometry: (1) (Zn2SnO4 phase+InGaZnO4 phase)/(Zn2SnO4 phase+InGaZnO4 phase+In2O3 phase+SnO2 phase+(ZnO)mIn2O3, phase)≧75% by volume; (2) Zn2SnO4 phase/(Zn2SnO4 phase+InGaZnO4 phase+In2O3 phase+SnO2 phase+(ZnO)mIn2O3 phase)≧30% by volume; and (3) InGaZnO4 phase/(Zn2SnO4 phase+InGaZnO4 phase+In2O3 phase+SnO2 phase+(ZnO)mIn2O3 phase)≧10% by volume, and m represents an integer of 2 to 5.

## Background
TECHNICAL FIELD
The present invention relates to an oxide sintered body and sputtering target for use in deposition, by a sputtering method, of oxide semiconductor thin films of thin-film transistors (TFTs) to be used in display devices such as liquid crystal displays and organic EL displays.
BACKGROUND ART
Amorphous (noncrystalline) oxide semiconductors for use in TFTs have higher carrier mobility and larger optical band gaps and can be deposited at lower temperatures as compared with the cases of general amorphous silicon (a-Si). Therefore, the amorphous oxide semiconductors are expected to be applied to next-generation displays which are required to have large sizes and high resolutions and to achieve high-speed drive; and to resin substrates which have low thermal stability. As compositions of oxide semiconductors suitable for these applications, for example, In-containing amorphous oxide semiconductors [In—Ga—Zn—O (IGZO) etc.] have been proposed.
For deposition of the above oxide semiconductor (film), a sputtering method has been preferably employed, in which a sputtering target (hereinafter sometimes referred to as “target material”) composed of the same materials as the film is subjected to sputtering. In the sputtering method, for stabilization of properties of thin films as products and for efficient production, for example, it is important to prevent abnormal discharge or the like during sputtering, and various techniques have been proposed.
For example, Patent Document 1 proposes a technique of suppressing abnormal discharge by refining average grain size of grains, for an ITO target.
Furthermore, Patent Document 2 proposes a technique of increasing conductivity of a target material, thereby suppressing abnormal discharge during sputtering, by subjecting an In—Zn—O-based composite oxide to an annealing treatment in a reducing atmosphere after sintering.
CITATION LIST
Patent Documents
Patent Document 1: JP-A-7-243036
Patent Document 2: Japanese Patent No. 3746094
SUMMARY OF THE INVENTION
Technical Problems
With recent progress in performance of display devices, an improvement in properties of oxide semiconductor thin films and stabilization of the properties have been requested and also it is required to produce the display devices more efficiently. Therefore, a sputtering target for use in the production of the oxide semiconductor films for display devices and an oxide sintered body as a raw material thereof have been desired to have a composition which corresponds to high carrier mobility to be required. In consideration of productivity, production costs and the like, it is also important to further suppress abnormal discharge (arching) during the sputtering step. Accordingly, it is required to improve the target material and the oxide sintered body as a raw material thereof.
The present invention has been made under these circumstances, and an object thereof is to provide an oxide sintered body and sputtering target which are preferably used for the production of oxide semiconductor films for display devices, which enable the suppression of abnormal discharge and also the stable deposition of the oxide semiconductor films by a sputtering method.
Solution to Problems
The present invention provides the following oxide sintered body and sputtering target.
<1> An oxide sintered body obtained by mixing and sintering a zinc oxide; an indium oxide; a gallium oxide; and a tin oxide,
wherein the oxide sintered body has a relative density of 85% or more, and
the oxide sintered body has volume ratios of a Zn2SnO4 phase and an InGaZnO4 phase, which satisfy the following expressions (1) to (3), respectively, as determined by X-ray diffractometry:

(Zn2SnO4 phase+InGaZnO4 phase)/(Zn2SnO4 phase+InGaZnO4 phase+In2O3 phase+SnO2 phase+(ZnO)mIn2O3 phase)≧75% by volume  (1)

Zn2SnO4 phase/(Zn2SnO4 phase+InGaZnO4 phase+In2O3 phase+SnO2 phase+(ZnO)mIn2O3 phase)≧30% by volume  (2)

InGaZnO4 phase/(Zn2SnO4 phase+InGaZnO4 phase+In2O3 phase+SnO2 phase+(ZnO)mIn2O3 phase)≧10% by volume  (3)

wherein m represents an integer of 2 or more and 5 or less.
<2> The oxide sintered body according to <1>, which satisfies the following expressions (4) to (6) when content ratios (atomic %) of zinc, indium, gallium, and tin to all metal elements contained in the oxide sintered body are taken as [Zn], [In], [Ga], and [Sn], respectively:

40 atomic %≦[Zn]≦50 atomic %  (4)

30 atomic %≦([In]+[Ga])≦45 atomic %  (5)

wherein [In] is 4 atomic % or more, and [Ga] is 5 atomic % or more,

15 atomic %≦[Sn]≦25 atomic %  (6).

<3> The oxide sintered body according to <1> or <2>, wherein the relative density is 110% or less.
<4> The oxide sintered body according to any one of <1> to <3>, wherein the volume ratio of the Zn2SnO4 phase and the InGaZnO4 phase satisfies the following expression (1′):

(Zn2SnO4 phase+InGaZnO4 phase)/(Zn2SnO4 phase+InGaZnO4 phase+In2O3 phase+SnO2 phase+(ZnO)mIn2O3 phase)≦100% by volume  (1′).

<5> The oxide sintered body according to any one of <1> to <4>, wherein the volume ratio of the Zn2SnO4 phase satisfies the following expression (2′):

Zn2SnO4 phase/(Zn2SnO4 phase+InGaZnO4 phase+In2O3 phase+SnO2 phase+(ZnO)mIn2O3 phase)≦90% by volume  (2′).

<6> The oxide sintered body according to any one of <1> to <5>, wherein the volume ratio of the InGaZnO4 phase satisfies the following expression (3′):

InGaZnO4 phase/(Zn2SnO4 phase+InGaZnO4 phase+In2O3 phase+SnO2 phase+(ZnO)mIn2O3 phase)≦60% by volume  (3′).

<7> The oxide sintered body according to any one of <1> to <6>, wherein the oxide sintered body has an average grain size of 30 μm or less.
<8> The oxide sintered body according to <7>, wherein the oxide sintered body has the average grain size of 3 μm or more.
<9> A sputtering target obtained from the oxide sintered body according to any one of <1> to <8>, which has a resistivity of 1 Ω·cm or less.
<10> The sputtering target according to <9>, wherein the resistivity is 10−7 Ω·cm or more.
Advantageous Effects of the Invention
According to the present invention, it is possible to provide an oxide sintered body and sputtering target, which enable the suppression of abnormal discharge during the deposition of oxide semiconductor films, and the stable deposition by a sputtering method.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates basic steps for the production of an oxide sintered body and sputtering target according to the present invention.
FIG. 2 is a graph illustrating one example of the sintering step for use in the production method according to the present invention.



DESCRIPTION OF EMBODIMENTS
The present inventors have made intensive investigations to provide an oxide sintered body for a sputtering target, which enables stable deposition of films for a long period of time through the suppression of abnormal discharge during sputtering and which is suitable for the deposition of an oxide semiconductor film having high carrier mobility.
As a result, they have found that the intended object is achieved by allowing an oxide sintered body obtained by mixing and sintering a zinc oxide; an indium oxide; a gallium oxide; and a tin oxide, to contain a Zn2SnO4 phase and an InGaZnSnO4 phase as a main phase in predetermined ratios, as determined by X-ray diffractometry, and to have a relative density of 85% or more.
Moreover, for achieving the above object, they have found that it is also effective to appropriately control the content of each metal element contained in the oxide sintered body, or control the average grain size.
Specifically, they have found that (a) an oxide sintered body containing a zinc oxide, an indium oxide, a gallium oxide and a tin oxide in which, for the phase constitution as determined by X-ray diffractometry, the ratios of the Zn2SnO4 phase and InGaZnO4 phase are controlled has an effect of suppressing abnormal discharge during sputtering, (b) the effect of suppressing the occurrence of abnormal discharge during sputtering can be further enhanced by increasing the relative density. Further, they have found that (c) it is desirable to appropriately control the content of each metal element contained in the oxide sintered body, in order to obtain the oxide sintered body having such phase composition, and (d) refining of the average grain size of the oxide sintered body is further effective in suppressing abnormal discharge. Thus, they have accomplished the present invention.
The oxide sintered body according to the present invention is an oxide sintered body (IGZTO) obtained by mixing and sintering a zinc oxide; an indium oxide; a gallium oxide; and a tin oxide. The sintered body affords a deposited oxide semiconductor film that tends to exhibit high carrier mobility and high etching resistance, as compared with the case of conventional In—Ga—Zn—O (IGZO).
Furthermore, by appropriately controlling the composition of the compound phases and relative density of the oxide sintered body, the abnormal discharge during sputtering can be suppressed and an oxide semiconductor film having further high carrier mobility can be deposited.
Next, the constitution of the oxide sintered body according to the present invention will be explained in detail. In the present invention, the oxide sintered body contains a Zn2SnO4 phase and InGaZnO4 phase, as a main phase, in predetermined ratios, as determined by X-ray diffractometry.
Conditions for X-ray diffractometry in the present invention are as follows.
Analyzer: “X-ray Diffractometer RINT-1500” manufactured by Rigaku Corporation
Analysis Conditions

    
    
        Target: Cu
        Monochromatization: Use of monochromator (Kα)
        Target output: 40 kV, 200 mA
        (Continuous Measurement): θ/2θ Scanning
        Slits: Divergence slit: 1⁄2°, Scattering slit: 1⁄2°, Receiving slit: 0.15 mm
        Monochromator receiving slit: 0.6 mm
        Scanning speed: 2°/min
        Sampling interval: 0.02°
        Measurement angle (2θ): 5° to 90°
    
    


For diffraction peaks obtained in the measurement, compound phases having crystal structures described in ICDD (International Center for Diffraction Data) cards are identified. The correspondence of individual compound phases to card numbers thereof is as follows:
Zn2SnO4 phase: 24-1470
InGaZnO4 phase: 38-1104
In2O3 phase: 06-0416
SnO2 phase: 41-1445
(ZnO)mIn2O3 phase: 20-1442 (m=2), 20-1439 (m=3), 20-1438 (m=4), 20-1440 (m=5).
Here, m in the (ZnO)mIn2O3 phase is an integer of 2 to 5. The reason why m is defined is that ZnO takes an arbitrary ratio relative to In2O3 in a compound where the ZnO phase and the In2O3 phase are bonded.
Next, compounds to be detected by the above X-ray diffractometry and identified in the present invention will be explained in detail.
(With regard to Zn2SnO4 compound and InGaZnO4 compound)
The Zn2SnO4 compound (phase) is formed through bonding of ZnO and SnO2 which constitute the oxide sintered body of the present invention. Moreover, the InGaZnO4 compound (phase) is an oxide to be formed through bonding of In, Ga and Zn which constitute the oxide sintered body of the present invention. In the present invention, the above compounds remarkably contribute to an improvement in relative density of the oxide sintered body and a reduction in resistivity thereof. As a result, stable direct-current discharge is continuously obtained and an effect of suppressing abnormal discharge is enhanced.
In the present invention, the above Zn2SnO4 phase and InGaZnO4 phase are contained as a main phase. As used herein, the term “main phase” means that the total of the ratios of the Zn2SnO4 phase and InGaZSnO4 phase are the largest among all compounds detected by the above X-ray diffractometry.
Moreover, the meaning of the above Zn2SnO4 phase and InGaZnO4 phase in the present invention also include those in which In, Ga, and/or Sn are dissolved in Zn2SnO4 and/or InGaZnO4.
In order to form an oxide sintered body which enables the suppression of abnormal discharge and stable deposition by a sputtering method, it is necessary that the volume ratios of the Zn2SnO4 phase and InGaZnO4 phase to the sum of the above compound phases (Zn2SnO4 phase, InGaZnO4 phase, In2O3 phase, SnO2 phase, and (ZnO)mIn2O3 phase) (m is an integer of 2 or more and 5 or less) identified by the above X-ray diffractometry satisfy the following (1) to (3).
(1): Ratio of [Zn2SnO4]+[InGaZnO4]((Zn2SnO4 phase+InGaZnO4 phase)/(Zn2SnO4 phase+InGaZnO4 phase+In2O3 phase+SnO2 phase+(ZnO)mIn2O3 phase); hereinafter referred to as “ratio (1)”)≧75% by volume (hereinafter “% by volume” of each phase is simply designated as “%”).
Since the occurrence rate of abnormal discharge increases as the ratio (1) decreases, the ratio should be 75% or more and is preferably 80% or more, more preferably 85% or more. On the other hand, with regard to the upper limit, in view of performance, the higher the ratio is, the better the performance is. For example, the ratio may be 100% but, from the viewpoint of easiness in production, the ratio is preferably 95% or less, more preferably 90% or less.
(2): Ratio of [Zn2SnO4](Zn2SnO4 phase/(Zn2SnO4 phase+InGaZnO4 phase+In2O3 phase+SnO2 phase+(ZnO)mIn2O3 phase); hereinafter referred to as “ratio (2)”)≧30%
Since the effect of suppressing abnormal discharge is sometimes not sufficiently obtained when the ratio (2) is small even if the above ratio (1) is satisfied, the ratio (2) should be 30% or more and is preferably 40% or more, more preferably 50% or more, further preferably 55% or more. On the other hand, the upper limit is not particularly limited but, from the viewpoint of securing the InGaZnO4 phase, the ratio is preferably 90% or less, more preferably 80% or less, further preferably 70% or less.
(3): Ratio of [InGaZnO4](InGaZnO4 phase/(Zn2SnO4 phase+InGaZnO4 phase+In2O3 phase+SnO2 phase+(ZnO)mIn2O3 phase); hereinafter referred to as “ratio (3)”)≧10%
Since the relative density cannot be increased and the effect of suppressing abnormal discharge is not sufficiently obtained in some cases when the ratio (3) is small even if the above ratios (1) and/or (2) are satisfied, the ratio (3) should be 10% or more and is preferably 12% or more, more preferably 15% or more. On the other hand, the upper limit is not particularly limited but, from the viewpoint of securing the Zn2SnO4 phase, the ratio is preferably 60% or less and, from the viewpoint of easiness in production, it is more preferably 30% or less, further preferably 25% or less.
The compound phases of the oxide sintered body of the present invention are desirably composed of substantially the Zn2SnO4 phase, the InGaZnO4 phase, the In2O3 phase, the SnO2 phase, and the (ZnO)mIn2O3 phase (m is an integer of 2 or more and 5 or less) and the ratio of these compound phases among all the compound phases is preferably 75% or more. Of these compound phases, the In2O3 phase, the SnO2 phase, and the (ZnO)mIn2O3 phase (m is an integer of 2 or more and 5 or less) may not be contained. As compound phases which may be contained, an InGaZn2O5 phase, a ZnGa2O4 phase, a (ZnO)mIn2O3 phase (m is an integer of 6 or more) and the like which are unavoidably formed in production may be contained in a ratio of 25% or less. Of these compound phases, the InGaZn2O5 phase is preferably not contained. The ratio of the compound phases unavoidably formed can be measured by XRD.
Furthermore, the relative density of the oxide sintered body of the present invention is 85% or more. When the relative density of the oxide sintered body is increased, not only the above effect of suppressing the occurrence of abnormal discharge can be further enhanced, but also an advantage of continuously maintaining stable discharge during target life and the other advantage can be attained. For obtaining such effects, it is necessary for the oxide sintered body of the present invention to have a relative density of at least 85% or more and the relative density is preferably 90% or more, more preferably 95% or more. The relative density is preferably 110% or less, more preferably 105% or less.
The relative density of the oxide sintered body is determined by the Archimedes' method.
In addition, in order to obtain an oxide sintered body having the above phase composition, which has high carrier mobility and an effect of suppressing the occurrence of abnormal discharge, it is desirable to appropriately control the content of each metal element contained in the oxide sintered body.
Specifically, when the content ratios (atomic %) of individual metal elements (zinc, indium, gallium, and tin) to all the metal elements, but excluding oxygen, which are contained in the oxide sintered body are taken as [Zn], [In], [Ga] and [Sn], respectively, the oxide sintered body desirably satisfies the following expressions (4) to (6):

40 atomic %≦[Zn]≦50 atomic %  (4)

30 atomic %≦([In]+[Ga])≦45 atomic %  (5)

wherein [In] is 4 atomic % or more and [Ga] is 5 atomic % or more,

15 atomic %≦[Sn]≦25 atomic %  (6).

In the present description, [Zn] means the content of Zn (atomic %; hereinafter “atomic %” of the content of each metal element is simply designated as “%”) relative to all the metal elements excluding oxygen (O) (Zn, In, Ga, and Sn). Similarly, [In], [Ga], and [Sn] mean individual content ratios (atomic %) of In, Ga, and Sn relative to all the metal elements excluding oxygen (O) (Zn, In, Ga, and Sn), respectively.
First, the above expression (4) defines the Zn ratio ([Zn]) in all the metal elements and is set from the viewpoint of mainly controlling the above Zn2SnO4 phase and InGaZnO4 phase to the above predetermined ratios (1) to (3). When [Zn] is too small, it becomes difficult to satisfy the ratios (1) to (3) of the above compound phases and the effect of suppressing abnormal discharge is not sufficiently obtained. Therefore, [Zn] is preferably 40% or more, more preferably 42% or more. On the other hand, when [Zn] is too large, the ratios of In, Ga, and Sn relatively decrease and desired ratios of the compound phases are not obtained, and thus, [Zn] is preferably 50% or less, more preferably 48% or less.
The above expression (5) defines the sum of the In ratio and the Ga ratio ([In]+[Ga]) in all the metal elements and is set from the viewpoint of mainly controlling the InGaZnO4 phase to the above predetermined ratios (1) and (3). When [In]+[Ga] is too small, it becomes difficult to satisfy the ratios (1) and (3) of the above compound phases. Therefore, [In]+[Ga] is preferably 30% or more, more preferably 32% or more. On the other hand, when [In]+[Ga] is too large, the ratio (2) of the above compound phases relatively decreases, and thus, [In]+[Ga] is preferably 45% or less, more preferably 43% or less.
Both of In and Ga are essential elements, and [In] is preferably 4% or more, more preferably 5% or more. When [In] is too small, the effect of increasing the relative density of the oxide sintered body and the reduction in resistivity cannot be achieved and the carrier mobility of the oxide semiconductor film after deposition also decreases.
Moreover, [Ga] is preferably 5% or more, more preferably 10% or more. When [Ga] is too small, the ratio (3) of the above compound phases relatively decreases in some cases.
The above expression (6) defines the Sn ratio ([Sn]) in all the metal elements and is set from the viewpoint of mainly controlling the above Zn2SnO4 phase to the above predetermined ratios (1) and (2). When [Sn] is too small, it becomes difficult to satisfy the ratios (1) and (2) of the above compound phases, and thus, [Sn] is preferably 15% or more, more preferably 16% or more. On the other hand, when [Sn] is too large, the ratio (3) of the above compound phases relatively decreases, and thus, [Sn] is preferably 25% or less, more preferably 22% or less.
It should be sufficient that the contents of the metal elements are controlled within the above ranges and the oxide sintered body of the present invention may contain oxides unavoidably formed during production.
Moreover, in order to further enhance the effect of suppressing abnormal discharge, it is desirable to refine the average grain size of grains of the oxide sintered body. Specifically, by controlling the average grain size of the grains observed by SEM (scanning electron microscope) on a fracture surface (any position of a cut surface when the oxide sintered body is cut at any position in a thickness direction) of the oxide sintered body (or a sputtering target using the oxide sintered body) to preferably 30 μm or less, the occurrence of abnormal discharge can be still further suppressed. The average grain size is more preferably 25 μm or less, further preferably 20 μm or less. On the other hand, the lower limit of the average grain size is not particularly limited but, since the relative density may decrease when the grains are exceedingly refined, the lower limit of the average grain size is preferably about 3 μm, and it is more preferably 5 μm or more.
With regard to the average grain size of the grains, the structure of the fracture surface of the oxide sintered body (or the sputtering target) is observed by SEM (magnification: 400 times), a straight line having a length of 100 μm is drawn in an arbitrary direction, the number (N) of grains contained in the straight line is determined, and a value calculated from [100/N] is taken as an average grain size on the straight line. In the present invention, 20 straight lines are drawn at intervals of 20 μm or more, “average grain sizes on individual straight lines” are calculated, and a value calculated from [the sum of average grain sizes on individual straight lines/20] is taken as the average grain size of the grains.
Furthermore, the sputtering target obtained using the oxide sintered body of the present invention has a resistivity of 1Ω·m or less, preferably 10−1 Ω·cm or less, more preferably 10−2 Ω·cm or less, further preferably 10−3 Ω·cm or less. It becomes possible to perform the deposition with the further suppression of the abnormal discharge during sputtering, and physical vapor deposition (sputtering method) using the sputtering target can be efficiently performed in production lines of display devices. Moreover, the resistivity of the sputtering target is preferably 10−7 Ω·cm or more, more preferably 10−6 Ω·cm or more, further preferably 10−5 Ω·cm or more.
The resistivity of the sputtering target is determined by the four-terminal method.
Next, a method of producing the oxide sintered body of the present invention will be explained.
The oxide sintered body of the present invention may be obtained by mixing and sintering a zinc oxide; an indium oxide; a gallium oxide; and a tin oxide, and the sputtering target can be produced by machining the oxide sintered body. FIG. 1 illustrates basic steps of subjecting oxide powders to (a) mixing/pulverization→(b) drying/granulation→(c) preforming→(d) degreasing→(e) air sintering and subjecting the resulting oxide sintered body to (f) machining→(g) bonding, thereby giving a sputtering target. Of the above steps, the present invention is characterized in that the sintering conditions are suitably controlled as described in detail below. The other steps are not particularly limited and generally used steps may be suitably selected. Respective steps will be explained below, but the present invention is by no means limited thereto.
Initially, a zinc oxide powder; an indium oxide powder; a gallium oxide powder; and a tin oxide powder are blended in predetermined ratios, followed by mixing and pulverizing. The material powders to be used preferably each have a purity of about 99.99% or more. This is because an impurity element, if present in a trace amount, may impair semiconducting properties of the oxide semiconductor film. The blending ratios of the material powders are preferably controlled so as to give ratios falling within the aforementioned ranges.
The (a) mixing/pulverization are preferably performed in a ball mill by placing the material powders together with water in the mill. A ball or bead to be used in these steps is preferably formed of a material, for example, a nylon, alumina, or zirconia. On this occasion, a dispersant may be mixed for the purpose of homogeneous mixing and a binder may be mixed for securing easiness of the subsequent forming step.
Next, a mixed powder obtained in the above step is preferably subjected to (b) drying/granulation by means of, for example, a spray drier.
After drying/granulation, (c) preforming is performed. For the forming, the powder after drying/granulation is charged into a die having predetermined dimensions and is preformed through a die press. Since the preforming is performed for the purpose of improving handling properties when setting, it should be sufficient to form a compact by applying a pressure of about 0.5 to 1.0 tonf/cm2. After that, the forming (substantial forming) is performed by CIP (cold isostatic pressing). In order to increase the relative density of the sintered body, it is preferable to control the pressure during forming to about 1 tonf/cm2 or more.
In the case where a dispersant or binder is added to the mixed powder, it is desirable to perform (d) degreasing by heating the compact for the purpose of removing the dispersant and the binder. The heating conditions are not particularly limited as long as the purpose of degreasing can be achieved but, for example, the compact may be kept in the air at about 500° C. for about 5 hours.
After degreasing, the compact is set in a graphite die having a desired shape, followed by sintering by (e) air sintering.
In the present invention, sintering is preferably performed at a sintering temperature of 1350 to 1600° C. for a retention time of 1 to 50 hours at the temperature (FIG. 2). By using the temperature range and retention time, the sintered body having compound phases satisfying the aforementioned ratios (1) to (3) is obtained. When the sintering temperature is low, the sintered body cannot be sufficiently densified and the effect of suppressing abnormal discharge is not obtained. On the other hand, when the sintering temperature is too high, the grains are coarsened and the average grain size of the grains cannot be controlled to the predetermined range, and the abnormal discharge cannot be controlled. Therefore, it is desirable that the sintering temperature is controlled to 1350° C. or higher, preferably 1400° C. or higher, more preferably 1500° C. or higher, and preferably 1600° C. or lower, more preferably 1550° C. or lower, more preferably 1500° C. or lower.
Moreover, when the retention time at the above sintering temperature is too long, the grains grow and are coarsened, so that the average grain size of the grains cannot be controlled to the predetermined range. On the other hand, when the retention time is too short, the sintered body cannot be sufficiently densified. Therefore, it is desirable to control the retention time to 1 hour or more, preferably 8 hours or more, more preferably 12 hours, and preferably 50 hours or less, more preferably 40 hours or less, more preferably 30 hours or less.
Also in the present invention, after forming, an average temperature-elevating rate (HR) to the above sintering temperature is preferably controlled to 100° C./hr or less. When the average temperature-elevating rate exceeds 100° C./hr, abnormal growth of the grains occurs. Also, the relative density may not sufficiently be increased. The average temperature-elevating rate is preferably 80° C./hr or less, further preferably 50° C./hr or less. On the other hand, the lower limit of the average temperature-elevating rate is not particularly limited but, from the viewpoint of productivity, it is preferably 10° C./hr or more, more preferably 20° C./hr or more.
In the sintering step, as the sintering atmosphere, an oxygen gas atmosphere (for example, air atmosphere), or an oxygen gas pressurized atmosphere is preferable. Moreover, the pressure of the atmosphere gas is desirably controlled to the atmospheric pressure for suppressing evaporation of zinc oxide having high vapor pressure. The oxide sintered body obtained as above has a relative density of 85% or more.
After the oxide sintered body is obtained as described above, it is subjected to (f) machining→(g) bonding according to common procedures, thereby obtaining a sputtering target of the present invention. The thus obtained sputtering target is also very satisfactory in resistivity and has a resistivity of about 1 Ω·cm or less.
EXAMPLES
The present invention will be explained in further detail below with reference to Examples. The present invention is not limited to the following Examples and it is possible to carry out the present invention with appropriate changes within the range where they do not depart from the gist of the present invention, and all of them fall within the scope of the present invention.
(Preparation of Sputtering Target)
An indium oxide powder (In2O3) having a purity of 99.99%, a zinc oxide powder (ZnO) having a purity of 99.99%, a gallium oxide powder (Ga2O3) having a purity of 99.99%, and a tin oxide powder (SnO2) having a purity of 99.99% were blended in ratios shown in Table 2, and water and a dispersant (ammonium polycarboxylate) were added thereto, followed by mixing in a zirconia ball mill for 24 hours. Then, the mixed powder obtained in the above step was dried and granulated.
After the powder thus obtained was preformed through a die press (forming pressure: 1.0 ton/cm2, size of compact: φ110×t13 mm, where t is thickness), the substantial forming was performed by CIP (cold isostatic pressing) under the forming pressure of 3 tonf/cm2.
The temperature of the compact thus obtained was elevated to 500° C. in the air atmosphere under normal pressure and the temperature was kept for 5 hours, thereby performing degreasing.
The resulting compact was set in a sintering furnace and was sintered under conditions (A to F) shown in Table 3. The resulting sintered body was machined into dimensions of φ100×t5 mm, followed by bonding to a Cu backing plate, thereby preparing a sputtering target.
(Preparation of Thin-Film Transistor)
The sputtering target thus obtained was set in a sputtering apparatus and an oxide semiconductor film was formed on a glass substrate (size: 100 mm×100 mm×0.50 mm) by a DC (direct-current) magnetron sputtering method. The sputtering conditions were as follows: a DC sputtering power of 150 W, an atmosphere of Ar/0.1% by volume O2, a pressure of 0.8 mTorr. Further, using a thin film deposited under these conditions, a thin-film transistor having a channel length of 10 μm and a channel width of 100 μm was prepared.
(Measurement of Relative Density)
The relative density was calculated according to the Archimedes' method after the target was taken out from the backing plate after sputtering and polished. When the relative density was 85% or more, the sample was evaluated as passed (see “Relative density (%)” in Table 4).
The relative density is a percent value obtained by dividing the density (g/cm3) as measured by the Archimedes' method by theoretical density p (g/cm3), and the theoretical density p was calculated as follows.




  
    
      
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          ⁢
          1
        
        ]
      
    
  




Here, W1 is a blending amount of ZnO [wt %], W2 is a blending amount of In2O3 [wt %], W3 is a blending amount of Ga2O3 [wt %], and W4 is a blending amount of SnO2 [wt %].
(Measurement of Resistivity)
The resistivity of the sintered body was measured for the above-prepared sputtering target by the four-terminal method. When the resistivity is 1 Ω·cm or less, the sample was evaluated as passed.
(Average Grain Size of Grains)
With regard to the average grain size of grains, the structure of fracture surface (any position of a cut surface when the oxide sintered body is cut at any position in a thickness direction) of an oxide sintered body surface was observed by SEM (magnification: 40 times), a straight line having a length of 100 μm was drawn in an arbitrary direction, the number (N) of grains contained in the straight line was determined, and a value calculated from [100/N] was taken as an average grain size on the straight line. Similarly, 20 straight lines were drawn at intervals of 20 to 30 μm and average grain sizes on individual straight lines were calculated, and a value calculated from [the sum of average grain sizes on individual straight lines/20] was taken as the average grain size of grains. Grains having an average grain size of 30 μm or less were evaluated as passed (see “Average grain size (μm)” in Table 4).
(Ratio of Compound Phase)
The ratio of each compound phase was determined by taken out the target from the backing plate after sputtering, cutting out a test piece having 10 mm square, and measuring strength of diffraction lines by X-ray diffractometry.
Analyzer: “X-ray Diffractometer RINT-1500” manufactured by Rigaku Corporation
Analysis Conditions:

    
    
        Target: Cu
        Monochromatization: Use of monochromator (Kα)
        Target output: 40 kV, 200 mA
        (Continuous Measurement): θ/2θ Scanning
        Slits: Divergence slit: 1⁄2°, Scattering slit: 1⁄2°, Receiving slit: 0.15 mm
        Monochromator receiving slit: 0.6 mm
        Scanning speed: 2°/min
        Sampling interval: 0.02°
        Measurement angle (2θ): 5° to 90°
    
    


For diffraction peaks obtained in the measurement, the peaks of the individual compound phases as shown in Table 1 were identified based on ICDD (International Center for Diffraction Data) cards and height of the diffraction peaks was measured. As these peaks, among the compound phases, peaks having high diffraction strength and showing less overlap with the peaks of the other compound phases as far as possible were selected. Measured values of peak height of designated peaks for individual compound phases were taken as I[Zn2SnO4], I[InGaZnO4], I[InGaZn2O5], I[In2O3], I[SnO2] and I[(ZnO)mIn2O3](“I” means that the value is a measured value), respectively, and the volume ratios were determined according to the following expressions (volume ratios (%) of A, B and A+B in Table 4).

[Zn2SnO4]+[InGaZnO4]=(I[Zn2SnO4]+I[InGaZnO4])/(I[Zn2SnO4]+I[InGaZnO4]+I[In2O3]+I[SnO2]+I[(ZnO)mIn2O3])×100  (1)

[Zn2SnO4]═I[Zn2SnO4]/(I[Zn2SnO4]+I[InGaZnO4]+I[In2O3]+I[SnO2]+I[(ZnO)mIn2O3])×100  (2)

[InGaZnO4]═I[InGaZnO4]/(I[Zn2SnO4]+I[InGaZnO4]+I[In2O3]+I[SnO2]+I[(ZnO)mIn2O3])×100  (3)

In all samples, the peaks of (ZnO)mIn2O3 where m=2, 3 and 4 could be negligible, and thus, I[(ZnO)5In2O3] was taken as I[(ZnO)mIn2O3]. In addition, peaks of compound phases other than the above ones were hardly observed.
With regard to the ratios of compound phases, one having [Zn2SnO4] of 30% or more, [InGaZnO4] of 10% or more, and [Zn2SnO4]+[InGaZnO4] of 75% or more was evaluated as passed (see “A”, “B” and “A+B” in Table 4).
(Evaluation of Abnormal Discharge)
The above sintered body was machined into a shape of 4 inches in diameter and 5 mm in thickness and was bonded to a backing plate to obtain a sputtering target. The sputtering target thus obtained was set in a sputtering apparatus, followed by DC (direct-current) magnetron sputtering. The sputtering conditions are as follows: a DC sputtering power of 150 W, an atmosphere of Ar/0.1% by volume O2, a pressure of 0.8 mTorr. The number of times of occurrence of arching per 100 minutes on this occasion was counted, and a sample showing that the number of times was 2 or less was evaluated as passed (see “Number of times of abnormal discharge” in Table 4).
The results are shown in Table 4.











TABLE 1








ICDD card No.
Peak position



Crystal phase
to be referred to
to be measured









Zn2SnO4
24-1470
around 34°



InGaZnO4
38-1104
around 31°



In2O3
06-0416
around 24°



SnO2
41-1445
around 26°



(ZnO)5In2O3
20-1440
around 31°




















TABLE 2









[In] + [Ga]















Component
[Zn]
[In]
[Ga]
Sum
[Sn]


















a
47.2
16.6
16.8
33.4
19.4



b
42.3
6.5
35.0
41.5
16.3



c
56.7
10.0
10.0
20.0
23.3



d
27.0
38.3
29.1
67.4
5.6







Content ratio (atomic %)

















TABLE 3








Average




Sintering
Retention
temperature-


Production
temperature T
time t
elevating rate HR


conditions
(° C.)
(hour)
(° C./hour)
Atmosphere



















A
1550
2
50
Air


B
1500
8
50
Air


C
1400
12
50
Air


D
1500
0
50
Air


E
1300
8
50
Air


F
1500
8
200
Air

























TABLE 4














Number of





Relative
Average grain
A: [Zn2SnO4] phase
B: [InGaZnO4] phase


times of




Production
density
size
Volume ratio
Volume ratio
A + B
Resistivity
abnormal


No.
Component
conditions
(%)
(μm)
(%)
(%)
(%)
(Ω · cm)
discharge
























1
a
A
96
20
69
17
86
10{circumflex over ( )}(−3)
1


2
a
B
93
12
66
18
84
10{circumflex over ( )}(−3)
0


3
a
C
86
10
55
21
76
10{circumflex over ( )}(−1)
1


4
a
D
79
8
50
20
70
 1
5


5
a
E
71
7
38
12
50
10
4


6
a
F
91
35
65
15
80
10{circumflex over ( )}(−2)
3


7
b
A
95
23
41
50
91
10{circumflex over ( )}(−2)
2


8
c
A
82
25
98
0
98
10{circumflex over ( )}(4)
4


9
d
A
100
10
0
73
73
10{circumflex over ( )}(−3)
3









In Nos. 1 to 3 and 7 where preferable compositions and production conditions in the present invention were satisfied, abnormal discharge was suppressed. Namely, upon sputtering, abnormal discharge occurred twice or less and it was confirmed that discharge was stably performed. Also, with regard to the relative density and resistivity of the sputtering targets thus obtained, good results were obtained.
On the other hand, in Nos. 4 to 6 where preferable production conditions in the present invention were not satisfied and in Nos. 8 and 9 where preferable compositions were not satisfied, abnormal discharge frequently occurred and desired effects were not able to be obtained.
Specifically, in No. 4 which is an example where the retention time t in the sintering step fallen out of the definition of the present invention, the relative density of the sintered body was low and also the volume ratio of the compound phases ([Zn2SnO4] phase+[InGaZnO4] phase) was also low, and thus, abnormal discharge occurred many times. In No. 5 which is an example where the sintering temperature T in the sintering step fallen out of the definition of the present invention, the relative density of the sintered body was low and also the volume ratios of the compound phases ([Zn2SnO4] phase+[InGaZnO4] phase, and [Zn2SnO4] phase) were also low, and thus, the resistivity was high and abnormal discharge occurred many times. In No. 6 which is an example where the average temperature-elevating rate HR fallen out of the definition of the present invention and the average grain size was large, abnormal discharge occurred many times.
The compositions of Nos. 8 and 9 each fallen out of the predetermined range with regard to the content ratios of the metal elements and also the volume ratios of the compound phases ([Zn2SnO4] phase, and [InGaZnO4] phase) fallen out of the definition of the present invention. As a result, abnormal discharge occurred many times in Nos. 8 and 9.
While the present invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
The present application is based on Japanese Patent Application No. 2012-203577 filed on Sep. 14, 2012, and the contents thereof are incorporated herein by reference.
INDUSTRIAL APPLICABILITY
According to the present invention, it is possible to provide an oxide sintered body and sputtering target, which enable the suppression of abnormal discharge during the deposition of the oxide semiconductor films, and stable deposition by a sputtering method.

## Claims

1. An oxide sintered body, obtained by a process comprising mixing and sintering a zinc oxide; an indium oxide; a gallium oxide; and a tin oxide,
wherein
the oxide sintered body has a relative density of 85% or more,
the oxide sintered body has an average grain size of 30 μm or less,
the oxide sintered body comprises a Zn2SnO4 phase and an InGaZnO4 phase as a main phase, and
a volume ratio of the Zn2SnO4 phase and a volume ratio of the InGaZnO4 phase, as determined by X-ray diffractometry, satisfy the following expressions (1) to (3):


(Zn2SnO4 phase+InGaZnO4 phase)/(Zn2SnO4 phase+InGaZnO4 phase+In2O3 phase+SnO2 phase+(ZnO)mIn2O3 phase)≧75%  (1),



Zn2SnO4 phase/(Zn2SnO4 phase+InGaZnO4 phase+In2O3 phase+SnO2 phase+(ZnO)mIn2O3 phase)≧30%  (2),



InGaZnO4 phase/(Zn2SnO4 phase+InGaZnO4 phase+In2O3 phase+SnO2 phase+(ZnO)mIn2O3 phase)≧10%  (3),



where m is an integer of 2 or more and 5 or less.

2. The oxide sintered body according to claim 1, wherein [Zn], [In], [Ga], and [Sn], which are content ratios by atomic % of zinc, indium, gallium, and tin to all metal elements contained in the oxide sintered body, respectively, satisfy the following expressions (4) to (6):


40 atomic %≦[Zn]≦50 atomic %  (4),



30 atomic %≦([In]+[Ga])≦45 atomic %  (5),



wherein [In] is 4 atomic % or more, and [Ga] is 5 atomic % or more, and



15 atomic %≦[Sn]≦25 atomic %  (6).

3. The oxide sintered body according to claim 1, wherein the relative density is 110% or less.

4. The oxide sintered body according to claim 1, wherein a combined volume ratio of the Zn2SnO4 phase and the InGaZnO4 phase satisfies the following expression (1′):


(Zn2SnO4 phase+InGaZnO4 phase)/(Zn2SnO4 phase+InGaZnO4 phase+In2O3 phase+SnO2 phase+(ZnO)mIn2O3 phase)≦100%  (1′).

5. The oxide sintered body according to claim 1, wherein the volume ratio of the Zn2SnO4 phase satisfies the following expression (2′):


Zn2SnO4 phase/(Zn2SnO4 phase+InGaZnO4 phase+In2O3 phase+SnO2 phase+(ZnO)mIn2O3 phase)≦90%  (2′).

6. The oxide sintered body according to claim 1, wherein the volume ratio of the InGaZnO4 phase satisfies the following expression (3′):


InGaZnO4 phase/(Zn2SnO4 phase+InGaZnO4 phase+In2O3 phase+SnO2 phase+(ZnO)mIn2O3 phase)≦60%  (3′).

7. The oxide sintered body according to claim 1, which has the average grain size of 3 μm or more.

8. A sputtering target, obtained from the oxide sintered body according to claim 1, wherein the sputtering target has a resistivity of 1 Ω·cm or less.

9. The sputtering target according to claim 8, wherein the resistivity is 10−7 ∩·cm or more.

10. The oxide sintered body according to claim 1, wherein a total ratio of the Zn2SnO4 phase, the InGaZnO4 phase, the In2O3 phase, the SnO2 phase, and the (ZnO)mIn2O3 phase is 75% or more, relative to all compound phases in the oxide sintered body.