# Patent

## Title
Optical component having a low-density silicon oxide layer as the outermost layer of an inorganic thin-film, method of manufacturing optical component and electronic apparatus

## Abstract

An optical component includes: a multilayer inorganic thin-film on a substrate, wherein the inorganic thin-film is formed by laminating a plurality of layers made of silicon oxide and a plurality of layers made of metal oxide, the metal oxide is metal oxide containing any one of zirconium, tantalum, and titanium, the layers made of silicon oxide include a low-density silicon oxide layer and a high-density silicon oxide layer having a density higher than the low-density silicon oxide layer, the outermost layer of the inorganic thin-film is the low-density silicon oxide layer, and the surface roughness of the outermost layer of the inorganic thin-film is equal to or greater than 0.55 nm and equal to or smaller than 0.7 nm.

## Background
BACKGROUND
1. Technical Field
The present invention relates to an optical component, such as an optical multilayer filter, a method of manufacturing an optical component, and an electronic apparatus including the optical component.
2. Related Art
In an electronic apparatus, for example, an imaging apparatus, such as a digital camera, a reproducing apparatus, such as a pickup, or a video apparatus, such as a projector, in general, dust-proof glass formed with an anti-reflection film, or an optical multilayer filter, such as an IR-UV cut filter, an IR cut filter, or a low-pass filter, is used. An optical component, such as dust-proof glass or an optical multilayer filter, has a structure in which a low-refractive-index inorganic thin-film made of silicon oxide or the like and a high-refractive-index inorganic thin-film made of titanium oxide or the like are alternately laminated on a substrate made of glass or quartz through deposition or the like.
In the related art, a multilayer filter is known which can obtain an antistatic effect without causing deterioration of the optical properties. This multilayer filter is structured such that a thin film made of silicon oxide and a thin film made of titanium oxide are alternately laminated to form an inorganic thin-film, the outermost silicon oxide layer of the inorganic thin-film has a low density of 1.09 to 2.04 g/cm3, and the silicon oxide other than the outermost layer has a density equal to or greater than 2.21 g/cm3 which is greater than the density of the outermost layer (Japanese Patent No. 4207063).
According to the related art described in Japanese Patent No. 4207083, in order to form the inorganic thin-film, film formation other than the outermost layer is performed through ion-assisted electron beam deposition with an acceleration current of 1000 mV and an acceleration voltage of 1200 mA, and film formation of silicon oxide of the outermost layer is performed through electron beam deposition without ion assist.
According to the related art described in Japanese Patent No. 4207083, with reduction in the surface resistance of the outermost layer, an antistatic effect can be obtained, increasing dust-proof performance.
However, with an increase in the number of pixels of the imaging apparatus or the video apparatus, small foreign particles or grit may adhere and may adversely affect the products. For this reason, there is demand for high dust-proof performance.
SUMMARY
An advantage of some aspects of the invention is that it provides an optical component having high dust-proof performance, a method of manufacturing an optical component, and an electronic apparatus.
The invention can be implemented by the following forms and application examples.
APPLICATION EXAMPLE 1
This application example of the invention provides an optical component having a multilayer inorganic thin-film on a substrate. The inorganic thin-film is formed by laminating a plurality of layers made of silicon oxide and a plurality of layers made of metal oxide. The metal oxide is metal oxide containing any one of zirconium, tantalum, and titanium. The layers made of silicon oxide include a low-density silicon oxide layer and a high-density silicon oxide layer having a density higher than the low-density silicon oxide layer. The outermost layer of the inorganic thin-film is the low-density silicon oxide layer. The surface roughness of the outermost layer of the inorganic thin-film is equal to or greater than 0.55 nm and equal to or smaller than 0.7 nm.
With this configuration, since the layer forming the outermost layer of the inorganic thin-film is the low-density silicon oxide layer, the insulation property of the thin film of silicon oxide which intrinsically exhibits high insulation performance is reduced, and conductivity increases.
The thin film of silicon oxide of the outermost layer has a surface roughness equal to or greater than 0.55 nm and equal to or smaller than 0.7 nm which is a great improvement on the surface roughness (0.8 nm to 0.95 nm) of the outermost layer in Japanese Patent No. 4207083, improving dust-proof performance. That is, according to the related art described in Japanese Patent No. 4207083, since film formation is performed through electron beam deposition without ion assist, it may be supposed that the surface roughness of the thin film of silicon oxide of the outermost layer is deteriorated. In contrast, according to this application example, the surface roughness of the layer of silicon oxide of the outermost layer is improved and the layer is smoothened. Thus, grit or dust is less likely to adhere to the surface, and dust-proof performance increases. The surface-roughness described in the detailed statement of this invention is arithmetic mean rough Ra.
APPLICATION EXAMPLE 2
In the optical component according to the above application example of the invention, the layer of metal oxide near the outermost layer may include a layer of zirconium oxide, and the surface roughness of the outermost layer of the inorganic thin-film may be equal to or greater than 0.6 nm and equal to or smaller than 0.7 nm.
With this configuration, the surface roughness of the outermost silicon oxide layer is a great improvement on the surface roughness of the outermost layer in Japanese Patent No. 4207083, further improving dust-proof performance.
The zirconium oxide (also referred to as zirconia) forming one layer in this example has reduced surface detachment energy because Zr has electronegativity smaller than Ti of the titanium oxide forming one thin film in the related art. As a result, in this example, dust-proof performance increases compared to the related art. The outermost layer means a layer which is the furthest away from the substrate from among the layers forming the inorganic thin-film. The outermost layer may or may not form the surface of the optical component.
APPLICATION EXAMPLE 3
In the optical component according to the above application example of the invention, the layers of zirconium oxide may include a low-density zirconium oxide layer and a high-density zirconium oxide layer having a density higher than the low-density zirconium oxide layer, and at least a layer adjacent to the outermost layer of the inorganic thin-film may be the low-density zirconium oxide layer.
With this configuration, since the outermost silicon oxide layer and the underlying zirconium oxide layer are both low-density layers, the insulation property can be further reduced, improving conductivity.
APPLICATION EXAMPLE 4
In the optical component according to the above application example of the invention, the low-density silicon oxide layer may have a density equal to or higher than 2.00 g/cm3 and equal to or lower than 2.20 g/cm3, and the low-density zirconium oxide layer may have a density equal to or higher than 4.8 g/cm3 and equal to or lower than 5.4 g/cm3.
With this configuration, the reasonable density ranges of the low-density silicon oxide layer and the low-density zirconium oxide layer are set, reliably improving conductivity. That is, if the density of the low-density silicon oxide layer exceeds 2.20 g/cm3, there is no effect of reduction in the density of the layer. If the density of the low-density silicon oxide layer is lower than 2.00 g/cm3, film formation is difficult. Similarly, if the density of the low-density zirconium oxide layer exceeds 5.4 g/cm3, there is no effect of reduction in the density of the layer. If the density of the low-density zirconium oxide layer is lower than 4.8 g/cm3, adhesiveness is degraded, and there are problems, such as film separation, making it difficult to perform film formation.
APPLICATION EXAMPLE 5
In the optical component according to the above application example of the invention, the layer of metal oxide near the outermost layer may include a layer of tantalum oxide, and the surface roughness of the outermost layer of the inorganic thin-film may be equal to or greater than 0.55 nm and equal to or smaller than 0.65 nm.
With this configuration, the surface roughness of the outermost silicon oxide layer is a significantly greater improvement on the surface roughness of the outermost layer in Japanese Patent No. 4207083, further improving dust-proof performance.
The tantalum oxide forming one layer in this example has reduced surface detachment energy because Ta has electronegativity smaller than Ti of the titanium oxide forming one thin film in the related art. As a result, in this example, dust-proof performance increases compared to the related art. The outermost layer means a layer which is the furthest away from the substrate from among the layers forming the inorganic thin-film. The outermost layer may or may not form the surface of the optical component.
APPLICATION EXAMPLE 6
In the optical component according to the above application example of the invention, the layers of tantalum oxide may include a low-density tantalum oxide layer and a high-density tantalum oxide layer having a density higher than the low-density tantalum oxide layer, and at least a layer adjacent to the outermost layer of the inorganic thin-film may be the low-density tantalum oxide layer.
With this configuration, since the outermost silicon oxide layer and the underlying tantalum oxide layer are both low-density layers, the insulation property can be further reduced, improving conductivity.
APPLICATION EXAMPLE 7
In the optical component according to the above application example of the invention, the low-density silicon oxide layer may have a density equal to or higher than 2.00 g/cm3 and equal to or lower than 2.15 g/cm3, and the low-density tantalum oxide layer may have a density equal to or higher than 7.7 g/cm3 and equal to or lower than 8.0 g/cm3.
With this configuration, the reasonable density ranges of the low-density silicon oxide layer and the low-density tantalum oxide layer are set, reliably improving conductivity. That is, if the density of the low-density silicon oxide layer exceeds 2.15 g/cm3, there is no effect of reduction in the density of the layer. If the density of the low-density silicon oxide layer is lower than 2.00 g/cm3, film formation is difficult. Similarly, if the density of the low-density tantalum oxide layer exceeds 8.00 g/cm3, there is no effect of reduction in the density of the layer. If the density of the low-density tantalum oxide layer is lower than 7.70 g/cm3, transparency is lost, making it impossible to use the resultant thin-film as an optical thin-film which should have high transparency.
APPLICATION EXAMPLE 8
In the optical component according to the above application example of the invention, the layer of metal oxide near the outermost layer may include a layer of titanium oxide, and the surface roughness of the outermost layer of the inorganic thin-film may be equal to or greater than 0.6 nm and equal to or smaller than 0.7 nm.
With this configuration, the surface roughness of the outermost silicon oxide layer is a significantly greater improvement on the surface roughness of the outermost layer in Japanese Patent No. 4207083, further improving dust-proof performance.
APPLICATION EXAMPLE 9
In the optical component according to the above application example of the invention, the layers of titanium oxide may include a low-density titanium oxide layer and a high-density titanium oxide layer having a density higher than the low-density titanium oxide layer, and at least a layer adjacent to the outermost layer of the inorganic thin-film may be the low-density titanium oxide layer.
With this configuration, since the outermost silicon oxide layer and the underlying titanium oxide layer are both low-density layers, the insulation property can be further reduced, improving conductivity.
APPLICATION EXAMPLE 10
In the optical component according to the above application example of the invention, the low-density silicon oxide layer may have a density equal to or higher than 2.00 g/cm3 and equal to or lower than 2.15 g/cm3, and the low-density titanium oxide layer may have a density equal to or higher than 4.50 g/cm3 and equal to or lower than 4.75 g/cm3.
With this configuration, the reasonable density ranges of the low-density silicon oxide layer and the low-density titanium oxide layer are set, reliably improving conductivity. That is, if the density of the low-density silicon oxide layer exceeds 2.15 g/cm3, there is no effect of reduction in the density of the layer. If the density of the low-density silicon oxide layer is lower than 2.00 g/cm3, film formation is difficult. Similarly, if the density of the low-density titanium oxide layer exceeds 4.75 g/cm3, there is no effect of reduction in the density of the layer. If the density of the low-density titanium oxide layer is lower than 4.50 g/cm3, film formation is difficult.
APPLICATION EXAMPLE 11
In the optical component according to the above application example of the invention, the total thickness of the low-density silicon oxide layer and the low-density metal oxide layer may be equal to or smaller than 500 nm.
With this configuration, the total thickness of the low-density silicon oxide layer and the low-density metal oxide layer is equal to or smaller than 500 nm, and preferably, is equal to or smaller than 400 nm. Thus, the surface resistance of the outermost layer can be maintained without increasing the thickness more than necessary. That is, although it is preferable to increase the total thickness of a plurality of layers so as to reduce the surface resistance of the outermost layer, even when the total thickness exceeds 500 nm, the surface resistance does not substantially change, and there is no effect of maintaining the low surface resistance of the outermost layer.
APPLICATION EXAMPLE 12
In the optical component according to the above application example of the invention, a fluorine-containing organic silicon compound film may be formed on the surface of the outermost layer of the inorganic thin-film.
With this configuration, the fluorine-containing organic silicon compound film is formed on the surface of the thin film of silicon oxide as the outermost layer, reducing surface energy and suppressing adhesion of grit.
APPLICATION EXAMPLE 13
In the optical component according to the above application example of the invention, the surface resistance of the inorganic thin-film may be equal to or smaller than 3.1×1010Ω/□ and equal to or greater than 9.1×109Ω/□.
With this configuration, since the surface resistance is sufficiently reduced, the dust-proof effect can be reliably obtained.
APPLICATION EXAMPLE 14
In the optical component according to the above application example of the invention, the surface resistance of the inorganic thin-film may be equal to or smaller than 1.4×1011Ω/□ and equal to or greater than 7.7×109Ω/□.
With this configuration, since the surface resistance is sufficiently reduced, the dust-proof effect can be reliably obtained.
APPLICATION EXAMPLE 15
In the optical component according to the above application example of the invention, the surface resistance of the inorganic thin-film may be equal to or smaller than 1.4×1011Ω/□ and equal to or greater than 5.7×1010Ω/□.
With this configuration, since the surface resistance is sufficiently reduced, the dust-proof effect can be reliably obtained.
APPLICATION EXAMPLE 16
This application example of the invention provides a method of manufacturing an optical component having the above-described configuration in which at least the outermost layer of the inorganic thin-film is formed through ion-assisted electron beam deposition with assist power having an acceleration voltage equal to or greater than 300 V and equal to or smaller than 450 V.
With this configuration, at least the outermost layer is formed through electron beam deposition (IAD) under the low ion assist condition that the acceleration voltage is equal to or greater than 300 V and equal to or smaller than 450 V. Thus, the surface roughness of the thin film of silicon oxide of the outermost layer can be improved to be equal to or greater than 0.65 nm and smaller than 0.80 nm compared to the related art. For this reason, it is possible to prevent grit or dust from adhering to the surface of the outermost layer, increasing dust-proof performance.
APPLICATION EXAMPLE 17
In the method of manufacturing an optical component according to the above application example of the invention, the plurality of layers may be five or more layers, and at least four adjacent layers including the outermost layer from among the layers may be formed through the ion-assisted electron beam deposition with assist power.
With this configuration, the number of films which will be formed with low assist power is within an appropriate range, performing reasonable film formation. Four or more layers are subjected to the electron beam deposition with low assist power because, if three or less layers are subjected to the electron beam deposition, the surface resistance is not sufficiently reduced and the dust-proof effect is not sufficiently obtained. If four or more layers are subjected to the electron beam deposition, since the surface resistance is sufficiently reduced, the dust-proof effect can be reliably obtained. When five or more layers are subjected to the electron beam deposition, since the surface resistance is not changed so much and there is little difference in the dust-proof effect, it will suffice that at least four layers are subjected to the electron beam deposition.
APPLICATION EXAMPLE 18
This application example of the invention provides an electronic apparatus. The electronic apparatus includes the above-described optical component, and a case which accommodates the optical component. The optical component is an IR-UV cut filter, and an imaging element is arranged to be opposite the IR-UV cut filter.
With this configuration, the IR-UV cut filter having high dust-proof performance is arranged to be opposite the imaging element, for example, a CCD. Thus, there is no case where grit or the like remains in an image captured by the CCD. Therefore, it is possible to provide a high-quality imaging apparatus.
APPLICATION EXAMPLE 19
This application example of the invention provides an electronic apparatus. The electronic apparatus includes the above-described optical component, and a case which accommodates the optical component. The optical component has an anti-reflection film and is arranged in an optical path between a laser light source and an objective lens opposite an optical disk.
With this configuration, anti-reflection an film-equipped optical component having high dust-proof performance, for example, a beam splitter is arranged between the laser light source and the objective lens. Thus, it is possible to suppress deterioration in the reproduction of information recorded on the optical disk or recording of information onto the optical disk by the laser light source or the objective lens due to adhesion of grit. Therefore, it is possible to provide an optical pickup apparatus having high accuracy.
APPLICATION EXAMPLE 20
This application example of the invention provides an electronic apparatus. The electronic apparatus includes the above-described optical component, and a case which accommodates the optical component. The optical component has an anti-reflection film and is arranged in an optical path between a light source and a dichroic prism.
With this configuration, an anti-reflection film-equipped optical component having high dust-proof performance, for example, dust-proof glass is arranged between the light source and the dichroic prism. Thus, it is possible to provide a projector which projects an image with high accuracy through the laser light source, the dichroic prism, and the like.



BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be described with reference to the accompanying drawings, wherein like members reference like elements.
FIG. 1 is a schematic view showing an electronic apparatus according to a first embodiment of the invention.
FIG. 2 is a sectional view of an optical component of the first embodiment.
FIG. 3 is a schematic view of an apparatus for forming a film on a substrate.
FIG. 4 is a schematic view showing an electronic apparatus according to a second embodiment of the invention.
FIG. 5 is a schematic view of an optical component of the second embodiment.
FIG. 6 is a schematic view showing an electronic apparatus according to a third embodiment of the invention.
FIG. 7A is a schematic view of a surface resistance measurement instrument.
FIG. 7B is a schematic view of a surface electrometer.
FIG. 8 is a graph showing the relationship between a film thickness and surface resistance in Example 1.
FIG. 9 is a graph showing the relationship between time and a residual charge quantity in Example 1, Comparative Example 5, and Comparative Example 7.
FIG. 10 is a graph showing the relationship between a film thickness and surface resistance in Example 5.
FIG. 11 is a graph showing the relationship between a film thickness and surface resistance in Example 9.
FIG. 12 is a graph showing the relationship between time and a residual charge quantity in Example 9 and Comparative Example 25.
FIG. 13 is a graph showing the relationship between a film thickness and surface resistance in Example 13.
FIG. 14 is a graph showing surface resistance in Example 17, Comparative Example 37, and Comparative Example 39.
FIG. 15 is a graph showing the relationship between a film thickness and surface resistance in Example 17.
FIG. 16 is a graph showing the relationship between time and a residual charge quantity in Example 17, Comparative Example 37, and Comparative Example 39.
FIG. 17 is a graph showing the relationship between a film thickness and surface resistance in Example 21.



DESCRIPTION OF EXEMPLARY EMBODIMENTS
Hereinafter, embodiments of the invention will be described with reference to the drawings. In the embodiments, the same constituent elements are represented by the same reference numerals, and description thereof will be omitted or simplified.
First Embodiment
First, a first embodiment will be described with reference to FIGS. 1 and 2.
In the first embodiment, an example will be described where an electronic apparatus is a projector, and an optical component which is incorporated into the projector is dust-proof glass.
FIG. 1 is a schematic configuration diagram of a projector.
In FIG. 1, a projector 100 includes an integrator illumination optical system 110, a color separation optical system 120, a relay optical system 130, an electro-optical device 140 which modulates a light flux emitted from a light source in accordance with image information, and a projection lens 150 which projects the light flux modulated by the electro-optical device 140 on a magnified scale.
The integrator illumination optical system 110 is an optical system which substantially uniformly illuminates the image forming regions of three transmissive liquid crystal panels 141 (liquid crystal panels 141R, 141G, and 141B for respective light components of red, green, and blue) constituting the electro-optical device 140. The integrator illumination optical system 110 includes a light source device 111, a first lens array 112, a second lens array 113, a polarization conversion element 114, and a superimposing lens 115.
The light source device 111 includes a light source lamp 116 and a reflector 117. A radiant light beam emitted from the light source lamp 116 is reflected by the reflector 117 and becomes a parallel light beam, and the parallel light beam is emitted to the outside.
The first lens array 112 has the configuration that small lenses which substantially have a rectangular contour when viewed from the optical axis direction are arranged in a matrix.
The second lens array 113 substantially has the same configuration as the first lens array 112, that is, has the configuration that small lenses are arranged in a matrix. The second lens array 113 has a function of forming an image of each small lens of the first lens array 112 on the corresponding transmissive liquid crystal panel 141 along with the superimposing lens 115.
The polarization conversion element 114 is arranged between the second lens array 113 and the superimposing lens 115 and also combined with the second lens array 113 as a single unit. The polarization conversion element 114 converts light from the second lens array 113 to one kind of polarized light. The color separation optical system 120 includes two dichroic mirrors 121 and 122 and a reflecting mirror 123. The color separation optical system 120 separates a plurality of partial light fluxes emitted from the integrator illumination optical system 110 into light components of three colors of red (R), green (G), and blue (B) by the dichroic mirrors 121 and 122.
The relay optical system 130 includes an incidence-side lens 131, a relay lens 133, and reflecting mirrors 132 and 134. The relay optical system 130 has a function of guiding the red light component as a color light component separated by the color separation optical system 120 to the transmissive liquid crystal panel 141R.
Out of the red light component and the green light component having transmitted the dichroic mirror 121, the green light component is reflected by the dichroic mirror 122, passes through a field lens 151, and reaches the transmissive liquid crystal panel 141G for green. The red light component transmits the dichroic mirror 122, passes through the relay optical system 130 and the field lens 151, and reaches the transmissive liquid crystal panel 141R for red.
The electro-optical device 140 modulates incident light fluxes in accordance with image information to form a color image. The electro-optical device 140 includes the transmissive liquid crystal panels 141R, 141G, and 141B serving as a light modulation device, dust-proof glasses 10 provided on the light incidence surfaces of the respective transmissive liquid crystal panels 141R, 141G, and 141B, and a cross dichroic prism 142.
The cross dichroic prism 142 combines the optical images modulated for the respective color light components to form a color image. A dielectric multilayer film which reflects the red light component and a dielectric multilayer film which reflects the blue light component are substantially provided in an X shape along the interface of four right angle prisms, and the three color light components are combined by the dielectric multilayer films.
FIG. 2 shows the schematic configuration of the dust-proof glass 10.
In FIG. 2, the dust-proof glass 10 is structured such that an anti-reflection film 2 is provided on the light incidence surface of a substrate 1, and a fluorine-containing organic silicon compound film 3 is provided on the surface of the anti-reflection film 2 as necessary. That is, the fluorine-containing organic silicon compound film 3 may or may not be provided on the surface of the anti-reflection film 2. For the substrate 1, for example, quartz, crystal, inorganic alkali glass, or the like may be used.
The anti-reflection film 2 has the five-layer structure that a low-refractive-index silicon oxide (SiO2) layer 2A and a high-refractive-index metal oxide layer 2B are alternately laminated.
A first layer which is the furthest away from the substrate 1 is an outermost layer 2S, and the outermost layer 2S is the silicon oxide layer 2A. A second layer 22 near the outermost layer 2S is the metal oxide layer 2B. A third layer 23 near the second layer 22 is the silicon oxide layer 2A, and a fourth layer 24 near the third layer 23 is the metal oxide layer 2B. A fifth layer 25 near the fourth layer 24 is in contact with the substrate 1, and the fifth layer 25 is the silicon oxide layer 2A.
The metal oxide constituting the metal oxide layer 2B is a metal oxide containing any one of zirconium, tantalum, or titanium.
The silicon oxide layer 2A is constituted by any one of a low-density layer and a high-density layer having a density higher than the low-density layer. The silicon oxide layer 2A as the outermost layer 2S is a low-density layer. The silicon oxide layer 2A constituting the third layer 23 may be a low-density layer or a high-density layer having a density higher than the low-density layer. The silicon oxide layer 2A constituting the first layer 21 is a high-density layer.
Since the fluorine-containing organic silicon compound film 3 has a small thickness and the underlying silicon oxide layer 2A of the outermost layer 2S is a low-density layer, the insulation property is low. For this reason, electric charges which are generated on the surface of the fluorine-containing organic silicon compound film 3 can escape to the outside through a ground wire (not shown).
The density of the silicon oxide layer 2A or the surface roughness of the outermost layer 2S differs depending on the material of the metal oxide layer 2B.
When the metal oxide is zirconium oxide (ZrO2), the density of the low-density silicon oxide layer 2A is equal to or higher than 2.00 g/cm3 and equal to or lower than 2.20 g/cm3. It will suffice that the density of the high-density silicon oxide layer 2A exceeds 2.20 g/cm3. The surface roughness of the outermost layer 2S is equal to or greater than 0.65 nm and equal to or smaller than 0.80 nm.
The metal oxide layer 2B constituting the second layer 22 may be a low-density layer or a high-density layer. Similarly to the second layer 22, the metal oxide layer 2B constituting the fourth layer 24 may be a low-density layer or a high-density layer.
The low-density layer constituting the metal oxide layer 2B made of zirconium oxide has a density equal to or higher than 4.8 g/cm3 and equal to or lower than 5.4 g/cm3. It will suffice that the density of the high-density layer constituting the metal oxide layer 2B made of zirconium oxide exceeds 5.4 g/cm3.
Although the second layer 22 to the fifth layer 25 may be low-density layers or high-density layers, in this embodiment, it is necessary that at least one of the third layer 23 and the fifth layer 25 other than the outermost layer 2S is a high-density layer. For example, the fifth layer 25 may be a high-density layer and other layers may be low-density layers.
The total thickness of the anti-reflection film 2 including the first layer 21 to the fifth layer 25 is equal to or smaller than 500 nm, and preferably, equal to or smaller than 400 nm.
When the metal oxide is tantalum oxide (Ta2O5), the density of the low-density silicon oxide layer 2A is equal to or higher than 2.00 g/cm3 and equal to or lower than 2.15 g/cm3. It will suffice that the density of the high-density silicon oxide layer 2A exceeds 2.15 g/cm3. The surface roughness of the outermost layer 2S is equal to or greater than 0.55 nm and equal to or smaller than 0.65 nm.
The metal oxide layer 2B constituting the second layer 22 may be a low-density layer or a high-density layer. Similarly to the second layer 22, the metal oxide layer 2B constituting the fourth layer 24 may be a low-density layer or a high-density layer.
The low-density layer constituting the metal oxide layer 2B made of tantalum oxide has a density equal to or higher than 7.7 g/cm3 and equal to or lower than 8.00 g/cm3. It will suffice that the density of the high-density layer constituting the metal oxide layer 2B made of tantalum oxide exceeds 8.00 g/cm3.
Although the second layer 22 to the fifth layer 25 may be low-density layers or high-density layers, in this embodiment, it is necessary that at least one of the third layer 23 and the fifth layer 25 other than the outermost layer 2S is a high-density layer. For example, the fifth layer 25 may be a high-density layer and other layers may below-density layers.
The total thickness of the anti-reflection film 2 including the first layer 21 to the fifth layer 25 is equal to or smaller than 500 nm, and preferably, equal to or smaller than 400 nm.
When the metal oxide is titanium oxide (TiO2), the density of the low-density silicon oxide layer 2A is equal to or higher than 2.00 g/cm3 and equal to or lower than 2.15 g/cm3. It will suffice that the density of the high-density silicon oxide layer 2A exceeds 2.15 g/cm3. The surface roughness of the outermost layer 2S is equal to or greater than 0.6 nm and equal to or smaller than 0.7 nm.
The metal oxide layer 2B constituting the second layer 22 may be a low-density layer or a high-density layer. Similarly to the second layer 22, the metal oxide layer 2B constituting the fourth layer 24 may be a low-density layer or a high-density layer.
The low-density layer constituting the metal oxide layer 2B made of titanium oxide has a density equal to or higher than 4.50 g/cm3 and equal to or lower than 4.75 g/cm3. It will suffice that the density of the high-density layer constituting the metal oxide layer 2B made of titanium oxide exceeds 4.75 g/cm3.
Although the second layer 22 to the fifth layer 25 may be low-density layers or high-density layers, in this embodiment, it is necessary that at least one of the third layer 23 and the fifth layer 25 other than the outermost layer 2S is a high-density layer. For example, the fifth layer 25 may be a high-density layer and other layers may be low-density layers.
The total thickness of the anti-reflection film 2 including the first layer 21 to the fifth layer 25 is equal to or smaller than 500 nm, and preferably, equal to or smaller than 400 nm.
Next, a method of manufacturing the dust-proof glass 10 will be described.
FIG. 3 is a schematic view of an apparatus for forming a film on a substrate.
In FIG. 3, a film formation apparatus includes a grounded chamber 50, and a dome 51 which is rotatably supported at the ceiling of the chamber 50. The dome 51 is rotated by a motor 52 through a rotary shaft 51A provided at the central part thereof. A plurality of substrates 1 which are subjected to film formation are attached to the dome 51. A first deposition source 53 and a second deposition source 54 are provided at the lower part of the chamber 50 so as to be opposite the substrates 1. Silicon oxide is stored in the first deposition source 53, and metal oxide, such as zirconium oxide, tantalum oxide, or titanium oxide, is stored in the second deposition source 54.
An ion source 55 and an electron gun 56 are arranged between the first deposition source 53 and the second deposition source 54. Silicon oxide and zirconium oxide, tantalum oxide, or titanium oxide respectively stored in the first deposition source 53 and the second deposition source 54 are dissolved by irradiating electron beams.
The ion source 55 discharges ions for assistance. The electron gun 56 irradiates electron beams.
A monitoring device 57 is provided at the central part of the dome 51. The monitoring device 57 includes an optical monitor which manages the thickness of the film formed on the substrate 1, and a crystal monitor which performs rate management.
In forming the five-layer anti-reflection film 2 on the substrate 1 by using the film formation apparatus configured as above, the substrate 1 is set in the dome 51. Thereafter, the electron beams are irradiated from the electron gun 56 while rotating the dome 51 to deposit silicon oxide stored in the first deposition source 53 or zirconium oxide, tantalum oxide, or titanium oxide stored in the second deposition source 54. At this time, ionized oxygen is accelerated and irradiated from the ion source 55 to alternately form the silicon oxide layer 2A and the metal oxide layer 2B made of zirconium oxide, tantalum oxide, or titanium oxide on the substrate 1.
Assist power for forming the outermost layer 2S to the fourth layer 24 is low assist power with an acceleration voltage equal to or greater than 300 V and equal to or smaller than 450 V (acceleration current equal to or greater than 450 mA and equal to or smaller than 550 mA), regardless of the silicon oxide layer 2A and the metal oxide layer 2B. Assist power for forming the fifth layer 25 is high assist power with an acceleration voltage greater than 450 V, for example, 1000 V (acceleration current of 1200 my).
After the anti-reflection film 2 is formed on the substrate 1, the fluorine-containing organic silicon compound film 3 is formed on the anti-reflection film 2 as necessary.
In forming the fluorine-containing organic silicon compound film 3, the substrate 1 on which the anti-reflection film 2 is formed and the deposition sources are set inside a vacuum apparatus, and reduced-pressure evacuation is performed. Then, in a state where the temperature of the substrate 1 is maintained at 60° C., the deposition sources are heated to about 600° C., and a fluorine-containing organic silicon compound is evaporated and formed as a film on the anti-reflection film 2.
Second Embodiment
Next, a second embodiment will be described with reference to FIGS. 4 and 5.
In the second embodiment, an example will be described where an electronic apparatus is an imaging apparatus, such as a digital still camera, and an optical component which is incorporated into the imaging apparatus is an optical multilayer filter.
FIG. 4 is a schematic configuration diagram of an imaging apparatus.
In FIG. 4, an imaging apparatus 200 includes an imaging module 210, a lens 220 which is arranged on the light incidence side, and a main body 230 which performs recording/reproduction of an imaging signal output from the imaging module 210. The main body 230 includes a signal processing section which performs correction or the like of the imaging signal, a recording section which records the imaging signal onto a recording medium, such as a magnetic tape, a reproducing section which reproduces the imaging signal, a display section which displays a video being reproduced, and the like.
The imaging module 210 includes an optical multilayer filter 20, an optical low-pass filter 211, a CCD (Charge Coupled Device) 212 serving as an imaging element which electrically converts an optical image, and a driving section 213 which drives the imaging element 212.
The optical multilayer filter 20 is combined with the CCD 212 as a single body at the front surface of the CCD 212 by a fixture 214. The optical multilayer filter 20 has a function of cutting IR and UV and a function as dust-proof glass for the CCD 212.
The fixture 214 is made of metal and electrically connected to the optical multilayer filter 20. The fixture 214 is grounded by a ground wire 215.
FIG. 5 shows the schematic configuration of the optical multilayer filter 20.
In FIG. 5, the optical multilayer filter 20 is structured such that an IR-UV cut film 4 is provided on the light incidence surface of the substrate 1, and a fluorine-containing organic silicon compound film 3 is provided on the surface of the IR-UV cut film 4 as necessary. That is, the fluorine-containing organic silicon compound film 3 may or may not be provided on the surface of the IR-UV cut film 4.
The IR-UV cut film 4 has a 39-layer structure in which a low-refractive-index silicon oxide (SiO2) layer 2A and a high-refractive-index metal oxide layer 2B are alternately laminated.
A first layer which is the furthest away from the substrate 1 is an outermost layer 2S, and the outermost layer 2S is constituted by the low-refractive-index silicon oxide layer 2A. The metal oxide layer 2B serving as a second layer 22 is provided to be in contact with the outermost layer 2S, and the silicon oxide layer serving as a third layer is provided near the second layer 22. A fourth layer constituted by the metal oxide layer is provided near the third layer. A fifth layer constituted by the silicon oxide layer is provided near the fourth layer. Finally, the metal oxide layer 2B constituting a 38th layer 238 is provided near the silicon oxide layer constituting a 37th layer. The silicon oxide layer 2A constituting a 39th layer 239 is provided near the 38th layer 238. The 39th layer 239 is in contact with the substrate 1.
The silicon oxide layer 2A is constituted by any one of a low-density layer and a high-density layer having a density higher than the low-density layer. At least the silicon oxide layer 2A of the outermost layer 2S is a low-density layer. The metal oxide layer 2B is constituted by any one of a low-density layer and a high-density layer having a density higher than the low-density layer.
Although in this embodiment, the sixth layer 26 to the 39th layer 239 may be low-density layers or high-density layers, it is necessary that at least one of the third layer 23 and the fifth layer 25 other than the outermost layer 2S is a low-density layer. For example, the fifth layer 25 may be a high-density layer and other layers may be low-density layers.
The total thickness of the IR-UV cut film 4 including the outermost layer 2S to the fifth layer is equal to or smaller than 500 nm, and preferably, equal to or smaller than 400 nm. In the second embodiment, an IR cut film, instead of the IR-UV cut film 4, may be provided on the substrate 1.
The density of the silicon oxide layer 2A and the surface roughness of the outermost layer differ depending on the material of the metal oxide layer 2B.
When the metal oxide is zirconium oxide, the low-density silicon oxide layer 2A has a density equal to or higher than 2.00 g/cm3 and equal to or lower than 2.20 g/cm3. It will suffice that the density of the high-density silicon oxide layer 2A exceeds 2.20 g/cm3.
In this embodiment, the outermost layer 2S is the low-density silicon oxide layer 2A, and the surface roughness thereof is equal to or greater than 0.65 nm and equal to or smaller than 0.80 nm.
The metal oxide layer 2B made of low-density zirconium oxide has a density equal to or higher than 4.80 g/cm3 and equal to or lower than 5.4 g/cm3. It will suffice that the density of the metal oxide layer 2B made of high-density titanium oxide exceeds 5.4 g/cm3.
When the metal oxide is tantalum oxide, the low-density silicon oxide layer 2A has a density equal to or higher than 2.00 g/cm3 and equal to or lower than 2.15 g/cm3. It will suffice that the density of the high-density silicon oxide layer 2A exceeds 2.15 g/cm3.
In this embodiment, the outermost layer 2S is the low-density silicon oxide layer 2A, and the surface roughness thereof is equal to or greater than 0.55 nm and equal to or smaller than 0.65 nm.
The metal oxide layer 2B made of low-density tantalum oxide has a density equal to or higher than 7.70 g/cm3 and equal to or lower than 8.00 g/cm3. It will suffice that the density of the metal oxide layer 2B made of high-density titanium oxide exceeds 8.00 g/cm3.
When the metal oxide is titanium oxide, the low-density silicon oxide layer 2A has a density equal to or higher than 2.00 g/cm3 and equal to or lower than 2.15 g/cm3. It will suffice that the density of the high-density silicon oxide layer 2A exceeds 2.15 g/cm3.
In this embodiment, the outermost layer 2S is the low-density silicon oxide layer 2A, and the surface roughness thereof is equal to or greater than 0.6 nm and equal to or smaller than 0.7 nm.
The metal oxide layer 2B made of low-density titanium oxide has a density equal to or higher than 4.50 g/cm3 and equal to or lower than 4.75 g/cm3. It will suffice that the density of the metal oxide layer 2B made of high-density titanium oxide exceeds 4.75 g/cm3.
Next, a method of manufacturing the optical multilayer filter 20 will be described.
In manufacturing the optical multilayer filter 20, the IR-UV cut film 4 is formed on the substrate 1 by using the apparatus shown in FIG. 3.
In forming the 39-layer IR-UV cut film 4 on the substrate 1, the substrate 1 is set in the dome 51, and then the electron beams are irradiated from the electron gun 56 while rotating the dome 51 to deposit silicon oxide stored in the first deposition source 53 and zirconium oxide, tantalum oxide, or titanium oxide stored in the second deposition source 54. At this time, ionized oxygen is accelerated and irradiated from the ion source 55 to alternately form the silicon oxide layer 2A and the metal oxide layer 2B made of zirconium oxide, tantalum oxide, or titanium oxide on the substrate 1.
In the second embodiment, assist power for forming the fourth layer at the fourth from the outermost layer 2S is low assist power with an acceleration voltage equal to or greater than 300 V and equal to or smaller than 450 V (acceleration current equal to or greater than 450 mA and equal to or smaller than 550 mA), regardless of the silicon oxide layer 2A and the metal oxide layer 2B made of zirconium oxide, tantalum oxide, or titanium oxide. The fifth layer to the 39th layer 239 are formed with high assist power with an acceleration voltage greater than 450 V, for example, 1000 V (acceleration current of 1200 mV). In this embodiment, the fifth layer from the outermost layer 2S and subsequent layers, for example, the outermost layer 2S to the 39th layer 239 may be formed with low assist power.
In the second embodiment, the fluorine-containing organic silicon compound film 3 may be provided on the IR-UV cut film 4 formed on the substrate 1 as necessary. In this case, the same method as in the first embodiment is used.
Third Embodiment
Next, a third embodiment will be described with reference to FIG. 6.
In the third embodiment, an example will be described where an electronic apparatus is an optical pickup apparatus, and an optical component which is incorporated into the optical pickup apparatus is a beam splitter.
FIG. 6 is a schematic configuration diagram of a recording and reproducing apparatus.
In FIG. 6, an optical pickup 300 is configured so as to irradiate three kinds of laser beams having different wavelengths onto three kinds of optical disks (CD 301, DVD 302, and BD 303) having different focal positions and to detect predetermined signals.
Specifically, the optical pickup 300 includes, as an optical system in relation to the CD 301, a laser diode 310 which generates a laser beam, a collimator lens 311, a polarization beam splitter 30, a lens 313, a dichroic prism 314, a quarter-wave plate 315, an opening filter 316, an objective lens 317, and a signal detection system 318 which detects a signal read from the CD 301 by a laser beam.
The optical pickup 300 includes, as an optical system in relation to the DVD 302, an LD 321 which generates a laser beam, a lens 322, a polarization beam splitter 30, and a signal detection system 323 which detects a signal read from the DVD 302 by a laser beam.
The optical pickup 300 includes, as an optical system in relation to the BD 303, an LD 331 which generates a laser beam, a lens 332, a polarization beam splitter 30, a lens 333, a dichroic prism 334, and a signal detection system 335 which detects a signal read from the BD 303 by a laser beam.
The schematic configuration of the polarization beam splitter 30 is the same as the dust-proof glass 10 shown in FIG. 2, except for the shape of the substrate 1. That is, the polarization beam splitter 30 is structured such that an anti-reflection film 2 is provided on the substrate 1, and a fluorine-containing organic silicon compound film 3 is provided on the surface of the anti-reflection film 2 as necessary. The method of forming the anti-reflection film 2 on the substrate 1 and forming the fluorine-containing organic silicon compound film 3 on the anti-reflection film 2 is the same as in the first embodiment.
EXAMPLES
Examples of this embodiment will be described. First, examples of an optical component having a zirconium oxide layer and a silicon oxide layer will be described.
Optical Component Having Zirconium Oxide Layer and Silicon Oxide Layer
Examples 1 to 4, Comparative Examples 1 to 10, and Reference Examples 1 and 2 corresponding to the optical component according to the first embodiment of the invention will be described. With regard to a deposition experiment, a deposition instrument (product name: SID-1350) manufactured by SHINCRON Co., Ltd. was used. In the experiment, an anti-reflection film was manufactured on the surface of a sample having a predetermined shape, for example, white plate glass (refractive index n=1.52) having a diameter of 30 mm and a thickness of 0.3 mm under the conditions of Examples and Comparative Examples.
Example 1
In Example 1, the anti-reflection film 2 is formed on the substrate 1, and no fluorine-containing organic silicon compound film 3 is provided.
The layer configuration of the anti-reflection film 2 of Example 1 is shown in Tables 1 to 3. In Tables, the outermost layer 2S is the silicon oxide layer 2A which is a low-density layer having a density of 2.069 g/cm3 and a refractive index n of 1.449. The thickness of the outermost layer 2S is 84.5 nm, and the optical film thickness is 1.449×84.5 nm=122.1105 nm. The relative value 4nd of the optical film thickness to a design wavelength (in Example 1, 510 nm) (hereinafter, simply referred to as the relative value to the design wavelength) is 0.977. That is, in design for an optical thin-film, since 1⁄4 of the design wavelength is used as a basis, the value of the optical thin-film nd to the relevant value becomes 0.963. The second layer 22 is the metal oxide layer 2B which is a low-density layer having a density of 5.17 g/cm3 and made of zirconium oxide having a refractive index n of 1.977. The thickness of the second layer 22 is 98.8 nm, and the relative value 4nd to the design wavelength is 1.534. The third layer 23 is the silicon oxide layer 2A which is a low-density layer having a density of 2.069 g/cm3 and a refractive index n of 1.449. The thickness of the third layer is 18.4 nm, and the relative value 4nd to the design wavelength is 0.210. The fourth layer 24 is the metal oxide layer 2B which is a low-density layer having a density of 5.17 g/cm3 and made of zirconium oxide having a refractive index n of 1.977. The thickness of the fourth layer 24 is 20.2 nm, and the relative value 4nd to the design wavelength is 0.313. The fifth layer 25 is the silicon oxide layer 2A which is a high-density layer having a density of 2.213 g/cm3 and a refractive index n of 1.481. The thickness of the fifth layer 25 is 172.5 nm, and the relative value 4nd to the design wavelength is 1.985. The total thickness of the outermost layer 2S to the fifth layer 25 is 394.3 nm.
In forming the anti-reflection film 2 configured as above on the substrate 1, in Example 1, the outermost layer 2S to the fourth layer 24 are formed through ion-assisted electron beam deposition (IAD) with low assist power. The film formation temperature is 150° C. When a low-density layer is formed as the silicon oxide layer 2A, the vacuum pressure is 1.8×10−2 Pa, and assist power has an acceleration voltage of 300 V and an acceleration current 450 mA. When the metal oxide layer 2B is formed of zirconium oxide, the vacuum pressure is 1.8×10−2 Pa, and assist power has an acceleration voltage of 300 V and an acceleration current of 450 mA. Thus, the surface roughness of the outermost layer 2S is in a range of 0.65 nm to 0.75 nm. The fifth layer 25 is formed through ion-assisted electron beam deposition (IAD) with high assist power. In this case, assist power has an acceleration voltage of 1000 Vm and an acceleration current of 1200 mA.
Example 2
Example 2 is different from Example 1 in that the fluorine-containing organic silicon compound film 3 is formed on the anti-reflection film 2.
With regard to the fluorine-containing organic silicon compound film 3, for example, as a deposition source, a material is used which is obtained by diluting a fluorine-containing organic silicon compound (product name: KY-130) manufactured by Shin-Etsu Chemical Co., Ltd. with a fluorine-based solvent (manufactured by Sumitomo 3M Ltd.: Novec HFE-7200) to prepare a solution having a solid content concentration of 3%, impregnating 1 g of the solution into a porous ceramic pellet, and performing drying.
Example 3
Example 3 is different from Example 1 in terms of assist power for forming a low-density layer. That is, in Example 3, assist power is low assist power with an acceleration voltage of 400 V and an acceleration current of 500 mA. For this reason, the low-density layers constituting the silicon oxide layer 2A serving as the outermost layer 2S and the third layer 23 have a density of 2.086 g/cm3. The low-density layers constituting the second layer 22 and the fourth layer 24, that is, the metal oxide layers 2B made of zirconium oxide have a density of 5.23 g/cm3. The density of the fifth layer 25 is the same as in Example 1.
Example 4
Example 4 is different from Example 3 in that the fluorine-containing organic silicon compound film 3 is provided on the anti-reflection film 2.
Comparative Example 1
Comparative Example 1 is different from Example 1 in terms of assist power for forming a low-density layer. That is, in Comparative Example 1, the outermost layer 2S to the fourth layer 24 are formed through ion-assisted electron beam deposition (IAD) with intermediate assist power having an acceleration voltage of 600 V and an acceleration current of 700 mA. For this reason, the low-density layers constituting the silicon oxide thin-film serving as the outermost layer and the third layer have a density of 2.172 g/cm3, and the low-density layers constituting the second layer and the fourth layer, that is, the metal oxide layers 2B made of zirconium oxide have a density of 5.36 g/cm3. In Comparative Example 1, the surface roughness of the outermost layer is 0.77 nm to 0.85 nm, which is greater than in Examples 1 to 4.
Comparative Example 2
Comparative Example 2 is different from Comparative Example 1 in that a fluorine-containing organic silicon compound film is provided on an anti-reflection film.
Comparative Example 3
Comparative Example 3 is different from Example 1 in terms of assist power for forming a low-density layer. That is, in Comparative Example 3, the outermost layer 2S to the fourth layer 24 are formed through ion-assisted electron beam deposition (IAD) with intermediate assist power having an acceleration voltage of 800 V and an acceleration current of 900 mA. For this reason, the low-density layers constituting the silicon oxide thin-film serving as the outermost layer and the third layer have a density of 2.201 g/cm3, and the low-density layers constituting the second layer and the fourth layer, that is, the metal oxide layers 2B made of zirconium oxide have a density of 5.41 g/cm3. In Comparative Example 3, the surface roughness of the outermost layer is 0.77 nm to 0.85 nm, which is greater than in Examples 1 to 4.
Comparative Example 4
Comparative Example 4 is different from Comparative Example 3 in that a fluorine-containing organic silicon compound film is formed on an anti-reflection film.
Comparative Example 5
Comparative Example 5 is different from Example 1 in terms of assist power for forming a low-density layer. That is, in Comparative Example 5, all layers are formed through ion-assisted electron beam deposition (IAD) with high assist power having an acceleration voltage of 1000 V and an acceleration current of 1200 mA. For this reason, the low-density layers constituting the silicon oxide thin-film serving as the outermost layer and the third layer have a density of 2.213 g/cm3, and the low-density layers constituting the second layer and the fourth layer, that is, the metal oxide layers 2B made of zirconium oxide have a density of 5.45 g/cm3. In Comparative Example 5, the surface roughness of the outermost layer is 0.80 nm to 0.90 nm, which is greater than in Examples 1 to 4.
Comparative Example 6
Comparative Example 6 is different from Comparative Example 5 in that a fluorine-containing organic silicon compound film is provided on an anti-reflection film.
Comparative Example 7
Comparative Example 7 has the same layer configuration as in Example 1, but electron deposition (EB) is used as the method of forming the outermost layer. The film formation temperature is 200° C. The vacuum pressure at the time of forming silicon oxide is 8.0×10−3 Pa, and the vacuum pressure at the time of forming zirconium oxide is 5.0×10−3 Pa. For this reason, the density of the silicon oxide layer is 2.037 g/cm3, and the density of the metal oxide layer made of zirconium oxide is 7.52 g/cm3. In Comparative Example 7, the surface roughness of the outermost layer is 0.95 nm to 1.200 nm, which is greater than in Examples 1 to 4.
Comparative Example 8
Comparative Example 8 is different from Comparative Example 7 in that a fluorine-containing organic silicon compound film is provided on an anti-reflection film.
Comparative Example 9
In Comparative Example 9, an anti-reflection film includes an outermost layer constituted by a silicon oxide layer having a thickness of 86.0 nm, a second layer constituted by a titanium oxide thin-film having a thickness of 102.7 nm, a third layer constituted by a silicon oxide thin-film having a thickness of 30.6 nm, a fourth layer constituted by a titanium oxide thin-film having a thickness of 12.1 nm, and a fifth layer constituted by a silicon oxide thin-film having a thickness of 136.6 nm. The layer configuration of Comparative Example 9 is shown in Table 4. In Comparative Example 9 having this layer configuration, film formation was performed by the same method as described in Japanese Patent No. 4207083. That is, in Comparative Example 9, the outermost layer is formed by electron deposition (EB) without using ion assist, and the layers other than the outermost layer are formed by the same film formation method as in Comparative Example 5. The second layer to the fifth layer were formed through ion-assisted electron beam deposition (IAD) with high assist power having an acceleration voltage of 1000 V and an acceleration current of 1200 mA. The film formation temperature is 200° C. The vacuum pressure at the time of forming silicon oxide is 8.0×10−3 Pa, and the vacuum pressure at the time of forming titanium oxide is 1.5×10−2 Pa. For this reason, the density of the silicon oxide thin-film is 2.037 g/cm3, and the density of the titanium oxide thin-film is 4.87 g/cm3. In Comparative Example 9, the surface roughness of the outermost layer is 0.80 nm to 0.95 nm, which is greater than in Examples 1 to 4.
Comparative Example 10
Comparative Example 10 is different from Comparative Example 9 in that a fluorine-containing organic silicon compound film is provided on an anti-reflection film.
Reference examples related to the invention will be described.
Reference Example 1
Reference Example 1 is different from Example 1 in that the layer configuration is as shown in Table 4, similarly to Comparative Example 9. Meanwhile, with regard to the film formation method, similarly to Example 1, the outermost layer to the fourth layer were formed through ion-assisted electron beam deposition (IAD) with low assist power, and the fifth layer was formed through ion-assisted electron beam deposition (IAD) with high assist power. In Reference Example 1, the surface roughness of the outermost layer is 0.6 nm to 0.7 nm, which is smaller than in Examples 1 to 4.
Reference Example 2
Reference Example 2 is different from Reference Example 1 in that a fluorine-containing organic silicon compound film is provided on an anti-reflection film.
With the above, it can be seen that the surface roughness of the outermost layer corresponds to assist power at the time of forming the outermost layer. That is, in Examples 1 to 4, the outermost layer is formed with low assist power having an acceleration voltage of 300 V to 400 V (acceleration current of 450 mA to 500 mA), such that the surface roughness of the outermost layer becomes 0.55 nm to 0.65 nm. Meanwhile, in Comparative Examples 1 to 4, the outermost layer is formed with intermediate assist power having an acceleration voltage of 600 V to 800 V (acceleration current of 700 mA to 900 mA), such that the surface roughness of the outermost layer becomes 0.6 nm to 0.7 nm or 0.62 nm to 0.75 nm. In Comparative Examples 5 and 6, the outermost layer is formed with high assist power having an acceleration voltage of 1000 V (acceleration current of 1200 mA), such that the surface roughness of the outermost layer becomes 0.65 nm to 0.75 nm. In Reference Examples 1 and 2, while film formation is performed with the same assist power as in Examples 1 and 2, unlike Examples 1 and 2, since an even-numbered layer is a titanium oxide thin-film, the surface roughness becomes 0.6 nm to 0.7 nm. In Examples 1 and 2, the good surface roughness is obtained because of the properties of the materials, such as atomic weight compared to Reference Examples 1 and 2.












TABLE 1







Layer
Material
d (nm)
4nd





















Incidence Medium
Air





Outermost Layer
SiO2
84.5
0.963



Second Layer
ZrO2
98.8
1.534



Third Layer
SiO2
18.4
0.210



Fourth Layer
ZrO2
20.2
0.313



Fifth Layer
SiO2
172.5
1.985



Emergence Medium
Glass







n is a refractive index



total film thickness: 394.33 nm



design wavelength: 510 nm





















TABLE 2







Film





Odd-Numbered



Formation


Odd-Numbered

Odd-Numbered
Layer (SiO2)



Method of 
Film
Odd-Numbered
Layer (SiO2)
Odd-Numbered
Layer (SiO2)
Refractive



First to
Formation
Layer (SiO2)
Vacuum
Layer (SiO2)
Density
Index



Fourth Layers
Temperature
Rate (Å/sec)
Pressure (O2)
Assist Power
(g/cm3)
(at 550 nm)
























Example 1, 2
IAD
150° C.
7
1.8E−2 Pa
300
V
2.069
1.449







450
mA


Example 3, 4
IAD
150° C.
7
1.8E−2 Pa
400
V
2.086
1.453







500
mA


Comparative
IAD
150° C.
7
1.8E−2 Pa
600
V
2.172
1.461


Example 1, 2




700
mA


Comparative
IAD
150° C.
7
1.8E−2 Pa
800
V
2.201
1.473


Example 3, 4




900
mA


Comparative
IAD
150° C.
7
1.8E−2 Pa
1000
V
2.213
1.481


Example 5, 6




1200
mA














Comparative
EB
200° C.
7
8.0E−3 Pa
—
2.037
1.44


Example 7, 8


Comparative
EB
200° C.
7
8.0E−3 Pa
—
2.037
1.44


Example 9, 10















Reference
IAD
150° C.
7
1.8E−2 Pa
300
V
2.069
1.449


Example 1, 2




450
mA


























TABLE 3







Film


Even-


Even-





Formation

Even-
Numbered
Even-
Even-
Numbered



Method of

Numbered
Layer
Numbered
Numbered
Layer



First to
Film
Layer
Vacuum
Layer
Layer
Refractive
Surface
Surface



Fourth
Formation
Rate
Pressure
Assist
Density
Index
Roughness
Resistance



Layers
Temperature
(Å/sec)
(O2)
Power
(g/cm3)
(at 550 nm)
(nm)
(Ω/□)


























Example 1, 2
IAD
150° C.
3
1.8E−2 Pa
300
V
5.17
1.977
0.6 to 0.7
9.12E+09







450
mA


Example 3, 4
IAD
150° C.
3
1.8E−2 Pa
400
V
5.23
1.985
0.6 to 0.7
1.77E+10







500
mA


Comparative
IAD
150° C.
3
1.8E−2 Pa
600
V
5.36
2.009
0.62 to 0.72
8.58E+10


Example 1, 2




700
mA


Comparative
IAD
150° C.
3
1.8E−2 Pa
800
V
5.41
2.026
0.68 to 0.78
2.12E+12


Example 3, 4




900
mA


Comparative
IAD
150° C.
3
1.8E−2 Pa
1000
V
5.45
2.042
0.7 to 0.8
1.00E+15


Example 5, 6




1200
mA
















Comparative
EB
200° C.
3
5.0E−3 Pa
—
4.98
1.942
0.85 to 1.0 
6.32E+11


Example 7, 8

















Comparative
IAD
200° C.
3
2.1E−2 Pa
1000
V
4.87
2.489
 0.8 to 0.95
8.16E+12


Example 9, 10




1200
mA


Reference
IAD
150° C.
3
2.1E−2 Pa
300
V
4.65
2.466
0.6 to 0.7
5.77E+10


Example 1, 2




450
mA





















TABLE 4







Layer
Material
d (nm)
4nd





















Incidence Medium
Air





Outermost Layer
SiO2
86.0
0.979



Second Layer
TiO2
102.7
2.014



Third Layer
SiO2
30.6
0.349



Fourth Layer
TiO2
12.1
0.237



Fifth Layer
SiO2
136.6
1.573



Emergence Medium
Glass







n is a refractive index



total film thickness: 367.9 nm



design wavelength: 510 nm






Experiment Result

1 Measurement of Surface Resistance (Sheet Resistance)

In measuring the surface resistance, a surface resistance measurement instrument 504 shown in FIG. 7A is used. The surface resistance measurement instrument 504 is Hiresta UP MCP-HT45 manufactured by Mitsubishi Chemical Corporation. The surface resistance measurement instrument 504 is configured such that a probe 501 comes into contact with the surface of a sample 502 of a filter. A stage 506 on which the sample 502 is placed is made of Teflon (Registered Trademark). The measurement condition is 1000 V and 30 sec. In the measurement environment, the moisture is 55%±15%, and the temperature is 25° C.±3° C.
With regard to Examples, Comparative Examples, and Reference Examples, the surface resistance of the sample was measured. The results are shown in Table 3. As shown in Table 3, it can be seen that, in Examples 1 to 4, the surface resistance is low compared to Comparative Examples 5 to 8. The low surface resistance means that adhesion of dust or grit to the surface due to static electricity is reduced.
2 Relationship Between Surface Resistance and Total Thickness
FIG. 8 shows the relationship between a film thickness and surface resistance in Example 1.
In FIG. 8, X0 is surface resistance (1.0×1015Ω/□) when all layers are formed through electron beam deposition with high assist power. X1 is surface resistance (3.17×1012Ω/□) when only the outermost layer having a thickness of 84.5 nm is formed through electron beam deposition with low assist power (an acceleration voltage is 300 V and an acceleration current is 450 mV). X2 is surface resistance (3.13×1010Ω/□) when the outermost layer and the second layer are formed through electron beam deposition with low assist power. X3 is surface resistance (1.11×1010Ω/□) when the outermost layer to the third layer are formed through electron beam deposition with low assist power. X4 is surface resistance (9.12×109Ω/□) when the outermost layer to the fourth layer are formed through electron beam deposition with low assist power. X5 is surface resistance (9.09×109Ω/□) when all layers are formed through electron beam deposition with low assist power. As shown in FIG. 8, it can be seen that, when two or more layers including the outermost layer are bonded to each other through electron beam deposition with low assist power, the value of surface resistance is reduced. It can also be seen that, when the outermost layer to the fourth layer are formed through electron beam deposition with low assist power and when all layers (five layers) including the outermost layer are formed through electron beam deposition with low assist power, the value of surface resistance is not changed so much. For this reason, in this example, it will suffice that the outermost layer to the fourth layer (film thickness 221.9 nm) are formed through electron beam deposition with low assist power.
3 Charge-Through
With regard to charge-through, the outermost layer of the sample is frictionally charged, and the residual charge quantity (relative value) in the outermost layer is displayed over time. The charge-through is shown in FIG. 9. In FIG. 9, a graph A shows Comparative Example 5, a graph B shows Comparative Example 7, and a graph C shows Example 1. For the measurement of surface charges, a surface electrometer 500 shown in FIG. 7B is used. The surface electrometer 500 is Model 341 manufactured by TREK JAPAN Co., Ltd. The surface electrometer 500 is configured such that the distance between a probe 501 and the surface of a sample 502 of a filter is 10 mm. A stage 503 on which the sample 502 is placed is made of metal. The measurement is performed in a state of being grounded. In the measurement environment, the moisture is 55%±5%, and the temperature is 25° C.±3° C.
As shown in FIG. 9, in the graph C of Example 1, the residual charge quantity over time is small compared to the graph A of Comparative Example 5 or the graph B of Comparative Example 7. As a result, it can be seen that, in Example 1, dust or grit is less likely to adhere to the surface compared to Comparative Example 5 or Comparative Example 7.
4 Dust-Proof Performance
A dust-proof performance test was performed by 4-1 polyethylene powder method, 4-2 Kanto loam method, and 4-3 cotton linter method.
4-1 Polyethylene Powder Method
In the case of the polyethylene powder method, a sample is dropped onto polyethylene powder (manufactured by SEISHIN Co., Ltd: SK-PE-20L) on a tray from above 1 cm and is then gradually moved up, and the adhered dust quantity and the residual quantity of powder adhered to the sample are measured. The adhered dust quantity is obtained by simply wiping the sample with powder adhered, imaging the surface of the sample, and calculating the dust area through image analysis. The residual quantity is obtained by removing dust from the surface of the sample with powder adhered through air blow (the distance from the sample is 3 cm, pressure is about 50 KPa, and the number of blows is three), imaging the surface of the sample, and calculating the dust area through image analysis.
4-2 Kanto Loam Method
In the case of the Kanto loam method, powder (JIS test powder 1, seven types) which is standardized by JIS assuming dust on road and in the field is used for a test. In this case, a sample is dropped onto powder covered on a tray, dust is dropped, the sample is turned over and flicked twice, and the adhered dust quantity and the residual quantity of powder adhered to the sample are measured. The methods of obtaining the adhered dust quantity and the residual quantity are the same as in the polyethylene powder method.
4-3 Cotton Linter Method
In the case of the cotton linter method, textile dust called cotton linter on a tray is used for a test. In this case, a sample is dropped onto powder covered on the tray, dust is dropped, the sample is turned over and flickered twice, and the adhered dust quantity and the residual quantity of powder adhered to the sample are measured. The methods of obtaining the adhered dust quantity and the residual quantity are the same as in the polyethylene powder method.
The results of dust-proof performance by these methods are shown in Table 5.
Table 5 shows the results of the methods of 4-1 polyethylene powder method, 4-2 Kanto loam method, and 4-3 cotton linter method.
As shown in Table 5, it can be seen that, when the polyethylene powder method is used, the adhered dust quantity and the residual quantity in Examples 1 and 3 are small compared to Comparative Examples 1, 3, 5, 7, and 9 or Reference Example 1. It can also be seen that, in Examples 2 and 4, the adhered dust quantity and the residual quantity are small compared to Comparative Examples 2, 4, 6, 8, and 10 or Reference Example 2. As described above, it is thought that the adhered dust quantity and the residual quantity in Examples 1 and 3 are small compared to Reference Example 1, and the adhered dust quantity and the residual quantity in Examples 2 and 4 are small compared to Reference Example 2 because Zr has small electronegativity compared to Ti.
The electronegativity numerically indicates the ability that the bonded atoms in the molecules attract electrons. Although any method is used to obtain the numerical value, the numerical value is in general obtained by a Pauling's method. With regard to the electronegativity by the Pauling's method, Zr has a value of 1.33 smaller than 1.54 of Ti. The electronegativity can be interpreted as minimum energy necessary for separating foreign particles from the surface. For this reason, the use of oxide containing an element having small electronegativity enables improvement in dust-proof performance.
With regard to Examples and Comparative Examples, it can be seen that the adhered dust quantity and the residual quantity in Examples 2 and 4, Comparative Examples 2, 4, 6, 8, and 10, and Reference Example 2 where the fluorine-containing organic silicon compound film 3 is provided are small compared to Examples 1 and 3, Comparative Examples 1, 3, 5, 7, and 9, and Reference Example 1 where no fluorine-containing organic silicon compound film 3 is provided. In the case of the Kanto loam method and the cotton linter method, similarly to the polyethylene powder method, with regard to Examples, Comparative Examples, and Reference Examples, it can be seen that the adhered dust quantity and the residual quantity in Examples 1 and 2 are small compared to Comparative Examples 1 to 10 or Reference Examples 1 and 2. It can also be seen that the adhered dust quantity and the residual quantity in Examples 2 and 4, Comparative Examples 2, 4, 6, 8, and 10, and Reference Example 2 where fluorine-containing organic silicon compound film 3 is provided are small compared to Examples 1 and 3, Comparative Examples 1, 3, 5, 7, and 9, and Reference Example 1 where no fluorine-containing organic silicon compound film 3 is provided. The above results are obtained because the fluorine-containing organic silicon compound film reduces surface energy, and dust or grit is less likely to adhere to the surface.













TABLE 5









Film
Fluorine-






Formation
containing
Polyethylene



Method of
Organic
Powder
Kanto Loam
Cotton Linter


















Outermost
Acceleration
Acceleration
Silicon
Adhered dust
Residual
Adhered dust
Residual
Adhered dust
Residual



Layer
Voltage (V)
Current (mA)
Compound
quantity
Quantity
quantity
Quantity
quantity
Quantity





















Example 1
IAD
300
450
None
0.11%
0.01%
0.12%
0.01%
1.87%
0.23%


Example 2
IAD
300
450
Provided
0.01%
0.00%
0.01%
0.00%
0.54%
0.01%


Example 3
IAD
400
500
None
0.12%
0.00%
0.14%
0.01%
1.94%
0.27%


Example 4
IAD
400
500
Provided
0.05%
0.01%
0.02%
0.00%
0.68%
0.02%


Comparative
IAD
600
700
None
0.34%
0.05%
0.38%
0.11%
2.12%
0.36%


Example 1


Comparative
IAD
600
700
Provided
0.06%
0.01%
0.09%
0.02%
0.85%
0.03%


Example 2


Comparative
IAD
800
900
None
1.15%
0.22%
0.81%
0.15%
2.95%
0.65%


Example 3


Comparative
IAD
800
900
Provided
0.11%
0.02%
0.58%
0.09%
1.77%
0.11%


Example 4


Comparative
IAD
1000
1200
None
2.15%
0.31%
0.98%
0.22%
4.41%
0.78%


Example 5


Comparative
IAD
1000
1200
Provided
0.47%
0.11%
0.67%
0.15%
2.12%
0.19%


Example 6


Comparative
EB
0
0
None
0.33%
0.05%
0.52%
0.07%
2.43%
0.40%


Example 7


Comparative
EB
0
0
Provided
0.11%
0.02%
0.34%
0.03%
0.98%
0.05%


Example 8


Comparative
EB
0
0
None
7.74%
1.34%
1.06%
0.09%
3.82%
0.81%


Example 9


Comparative
EB
0
0
Provided
0.93%
0.12%
12.90%
5.92%
4.58%
0.35%


Example 10


Reference
IAD
300
450
None
3.78%
0.59%
0.29%
0.02%
2.87%
0.63%


Example 1


Reference
IAD
300
450
Provided
0.16%
0.01%
0.19%
0.01%
1.84%
0.14%


Example 2









Next, Examples 5 to 8, Comparative Examples 11 to 20, and Reference Examples 3 and 4 corresponding to the optical component according to the second embodiment of the invention will be described. With regard to the deposition experiment, similarly to the experiment of Examples 1 to 4, Comparative Examples 1 to 10, and Reference Examples 1 and 2, the deposition instrument manufactured by SHINCRON Co., Ltd. was used to manufacture an anti-reflection film on the surface of white plate glass having a predetermined shaped under the conditions of Examples and Comparative Examples.
Example 5
In Example 5, the IR-UV cut film 4 is formed on the substrate 1, and no fluorine-containing organic silicon compound film 3 is provided.
The layer configuration of the IR-UV cut film 4 of Example 5 is shown in Tables 6 to 10. Table 6 shows the relationship between the material of each layer and the film thickness. Tables 7 and 8 show the film formation condition of the outermost layer, and the like. Tables 9 and 10 show the film formation conditions of the fifth layer to the 39th layer, and the like.
In Tables 6 to 8, the outermost layer 2S is the silicon oxide layer 2A which is a low-density layer having a density of 2.069 g/cm3 and a refractive index n of 1.449. The thickness of the outermost layer 2S is 72.9 nm, and the relative value 4nd to the design wavelength is 0.435. The second layer 22 is the metal oxide layer 2B which is a low-density layer having a density of 5.17 g/cm3 and made of zirconium oxide having a refractive index n of 1.977. The thickness of the second layer is 81.4 nm, and the relative value 4nd to the design wavelength is 0.660. The third layer is the silicon oxide layer 2A which is a low-density layer having a density of 2.069 g/cm3 and a refractive index n of 1.449. The thickness of the third layer is 148.9 nm, and the relative value 4nd to the design wavelength is 0.887. The fourth layer is the metal oxide layer 2B which is a low-density layer having a density of 5.17 g/cm3 and made of zirconium oxide having a refractive index n of 1.977. The thickness of the fourth layer is 85.9 nm, and the relative value 4nd to the design wavelength is 0.697.
In Tables 6, 9, and 10, the fifth layer is the silicon oxide layer 2A which is a high-density layer having a density of 2.213 g/cm3 and a refractive index n of 1.481. The thickness of the fifth layer is 143.6 nm, and the relative value 4nd to the design wavelength is 0.866. The sixth layer is the metal oxide layer 2B which is a high-density layer having a density of 4.87 g/cm3 and made of titanium oxide having a refractive index n of 2.489. The thickness of the sixth layer is 85.2 nm, and the relative value 4nd to the design wavelength is 0.791. Subsequently, the seventh layer to the 39th layer have the layer configuration described in Tables 1, 9, and 10, and the total film thickness of the outermost layer 2S to the 39th layer is 4735.45 nm.
In forming the IR-UV cut film 4 configured as above on the substrate 1, in Example 5, the outermost layer 2S to the fourth layer are formed through ion-assisted electron beam deposition (IAD) with low assist power. The film formation temperature is 150° C. When a low-density layer is formed as the silicon oxide layer 2A, the vacuum pressure is 1.8×10−2 Pa. Assist power has an acceleration voltage of 300 V and an acceleration current of 450 mA. When the metal oxide layer 2B is formed of zirconium oxide, the vacuum pressure is 1.8×10−2 Pa, and assist power has an acceleration voltage of 300 V and an acceleration current of 450 mA. The fifth layer to the 39th layer are formed through ion-assisted electron beam deposition (IAD) with high assist power. In this case, in the same manner as when the silicon oxide layer 2A is formed and when the metal oxide layer 2B is formed of titanium oxide, assist power has an acceleration voltage of 1000 Vm and an acceleration current of 1200 mA. The surface roughness of the outermost layer 2S is 0.65 nm to 0.75 nm.
Example 6
Example 6 is different from Example 5 in that the fluorine-containing organic silicon compound film 3 is provided on the IR-UV cut film 4.
The fluorine-containing organic silicon compound film 3 is the same as in Example 1.
Example 7
Example 7 is different from Example 5 in terms of assist power for forming a low-density layer. That is, in Example 7, assist power is low assist power with an acceleration voltage of 400 V and an acceleration current of 500 mA. For this reason, the low-density layers constituting the silicon oxide layer 2A serving as the outermost layer 2S and the third layer have a density of 2.086 g/cm3, and the low-density layers constituting the second layer 22 and the fourth layer, that is, the metal oxide layers 2B made of zirconium oxide have a density of 5.23 g/cm3. The fifth layer 25 to the 39th layer have the same density as in Example 1.
Example 8
Example 8 is different from Example 7 in that the fluorine-containing organic silicon compound film 3 is provided on the IR-UV cut film 4.
Comparative Example 11
Comparative Example 11 is different from Example 5 in terms of assist power for forming a low-density layer. That is, in Comparative Example 9, the outermost layer 2S to the fourth layer 24 are formed through ion-assisted electron beam deposition (LAD) with intermediate assist power having an acceleration voltage of 600 V and an acceleration current of 700 mA. For this reason, the low-density layers constituting the silicon oxide thin-film serving as the outermost layer and the third layer have a density of 2.172 g/cm3, and the low-density layers constituting the second layer and the fourth layer, that is, the metal oxide layers 2B made of zirconium oxide have a density of 5.36 g/cm3.
In Comparative Example 9, the surface roughness of the outermost layer is 0.77 nm to 0.85 nm, which is greater than in Examples 5 to 8.
Comparative Example 12
Comparative Example 12 is different from Comparative Example 10 in that the fluorine-containing organic silicon compound film 3 is provided on the IR-UV cut film 4.
Comparative Example 13
Comparative Example 13 is different from Example 5 in terms of assist power for forming a low-density layer. That is, in Comparative Example 13, the outermost layer 2S to the fourth layer 24 are formed through ion-assisted electron beam deposition (IAD) with intermediate assist power having an acceleration voltage of 800 V and an acceleration current of 900 mA. For this reason, the low-density layers constituting the silicon oxide thin-film serving as the outermost layer and the third layer have a density of 2.201 g/cm3, and the low-density layers constituting the second layer and the fourth layer, that is, the metal oxide layers 2B made of zirconium oxide have a density of 5.41 g/cm3.
In Comparative Example 13, the surface roughness of the outermost layer is 0.77 nm to 0.85 nm, which is greater than in Examples 5 to 8.
Comparative Example 14
Comparative Example 14 is different from Comparative Example 13 in that the fluorine-containing organic silicon compound film is provided on the IR-UV cut film.
Comparative Example 15
Comparative Example 15 is different from Example 1 in terms of assist power for forming a low-density layer. That is, in Comparative Example 15, all layers are formed through ion-assisted electron beam deposition (IAD) with high assist power having an acceleration voltage of 1000 V and an acceleration current of 1200 mA. For this reason, the low-density layers constituting the silicon oxide thin-film serving as the outermost layer and the third layer have a density of 2.213 g/cm3, and the low-density layers constituting the second layer and the fourth layer, that is, the metal oxide layers 2B made of zirconium oxide have a density of 5.45 g/cm3.
In Comparative Example 15, the surface roughness of the outermost layer is 0.80 nm to 0.90 nm, which is greater than in Examples 5 to
Comparative Example 16
Comparative Example 16 is different from Comparative Example 15 in that the fluorine-containing organic silicon compound film is provided on the IR-UV cut film.
Comparative Example 17
Comparative Example 17 has the same layer configuration as in Example 5, but, unlike Example 5, the film formation method for the outermost layer to the fourth layer is electron deposition (EB) without using ion assist. The fifth layer to the 39th layer were formed through ion-assisted electron beam deposition (IAD) with high assist power having an acceleration voltage of 1000 V and an acceleration current of 1200 mA. The vacuum pressure at the time of forming silicon oxide for the outermost layer to the fourth layer is 8.0×10−3 Pa, and the vacuum pressure at the time of forming zirconium oxide is 5.0×10−3 Pa. For this reason, for the outermost layer to the fourth layer, the metal oxide layer made of silicon oxide has a density of 2.037 g/cm3, and the metal oxide layer made of zirconium oxide has a density of 7.52 g/cm3. In Comparative Example 17, the surface roughness of the outermost layer is 0.95 nm to 1.20 nm, which is greater than in Examples 5 to 8.
Comparative Example 18
Comparative Example 18 is different from Comparative Example 17 in that the fluorine-containing organic silicon compound film is provided on the IR-UV cut film.
Comparative Example 19
In Comparative Example 19, an IR-UV cut film has an outermost layer constituted by a silicon oxide layer having a thickness of 71.8 nm, a second layer constituted by a metal oxide layer made of titanium oxide having a thickness of 84.2 nm, a third layer constituted by a silicon oxide layer having a thickness of 147.2 nm, a fourth layer constituted by a metal oxide layer made of titanium oxide having a thickness of 83.6 nm, a fifth layer constituted by a silicon oxide layer having a thickness of 140.2 nm, and a sixth layer constituted by a metal oxide layer made of titanium oxide having a thickness of 83.1 nm. The number of layers is 39 in total, and the total film thickness is 4726.25 nm. The layer configuration of Comparative Example 19 is shown in Table 11. In Comparative Example 19 having this layer configuration, film formation was performed in the same method as in the related art described in Japanese Patent No. 4207083. That is, in Comparative Example 19, the outermost layer is formed through electron deposition (EB) without using ion assist, and the layers other than the outermost layer are formed in the same manner as in Comparative Example 5. The second layer to the fifth layer were formed through ion-assisted electron beam deposition (IAD) with high assist power having an acceleration voltage of 1000 V and an acceleration current of 1200 mA. The film formation temperature is 150° C. The vacuum pressure at the time of forming silicon oxide for the outermost layer is 8.0×10−3 Pa, and the silicon oxide thin-film of the outermost layer has a density of 2.037 g/cm3. In Comparative Example 19, the surface roughness of the outermost layer is 0.80 nm to 0.95 nm, which is greater than in Examples 1 to 4.
Comparative Example 20
Comparative Example 20 is different from Comparative Example 19 in that the fluorine-containing organic silicon compound film is provided on the IR-UV cut film.
Reference Example 3
Reference Example 3 is different from Example 1 in that the layer configuration is as shown in Table 11, similarly to Comparative Example 19. Meanwhile, with regard to the film formation method, similarly to Example 1, the outermost layer to the fourth layer were formed through ion-assisted electron beam deposition (IAD) with low assist power, and the fifth layer and subsequent layers were formed through ion-assisted electron beam deposition (IAD) with high assist power. In Reference Example 3, the surface roughness of the outermost layer is 0.55 nm to 0.65 nm, which is greater than in Examples 1 to 4.
Reference Example 4
Reference Example 4 is different from Reference Example 3 in that the fluorine-containing organic silicon compound film is provided on the IR-UV cut film.











TABLE 6





Layer
Material
d (nm)
4nd
Film Formation Condition



















Incidence
Air





Medium


Outermost
SiO2
72.9
0.435
Low Assist Power


Layer


Second Layer
ZrO2
81.4
0.660
Low Assist Power


Third Layer
SiO2
148.9
0.887
Low Assist Power


Fourth Layer
ZrO2
85.9
0.697
Low Assist Power


Fifth Layer
SiO2
143.6
0.866
High Assist Power


Sixth Layer
TiO2
85.2
0.791
High Assist Power


Seventh Layer
SiO2
139.2
0.839
High Assist Power


Eighth Layer
TiO2
81.4
0.756
High Assist Power


Ninth Layer
SiO2
139.8
0.843
High Assist Power


Tenth Layer
TiO2
81.1
0.753
High Assist Power


11th Layer
SiO2
139.4
0.841
High Assist Power


12th Layer
TiO2
81.0
0.752
High Assist Power


13th Layer
SiO2
139.4
0.841
High Assist Power


14th Layer
TiO2
82.0
0.761
High Assist Power


15th Layer
SiO2
140.8
0.849
High Assist Power


16th Layer
TiO2
83.3
0.773
High Assist Power


17th Layer
SiO2
143.2
0.863
High Assist Power


18th Layer
TiO2
86.7
0.805
High Assist Power


19th Layer
SiO2
150.6
0.908
High Assist Power


20th Layer
TiO2
100.4
0.932
High Assist Power


21st Layer
SiO2
179.7
1.083
High Assist Power


22nd Layer
TiO2
110.0
1.021
High Assist Power


23rd Layer
SiO2
169.7
1.023
High Assist Power


24th Layer
TiO2
101.5
0.942
High Assist Power


25th Layer
SiO2
175.7
1.059
High Assist Power


26th Layer
TiO2
115.0
1.067
High Assist Power


27th Layer
SiO2
189.1
1.140
High Assist Power


28th Layer
TiO2
116.5
1.081
High Assist Power


29th Layer
SiO2
191.2
1.153
High Assist Power


30th Layer
TiO2
119.4
1.108
High Assist Power


31st Layer
SiO2
189.9
1.145
High Assist Power


32nd Layer
TiO2
117.5
1.091
High Assist Power


33rd Layer
SiO2
193.2
1.165
High Assist Power


34th Layer
TiO2
116.7
1.083
High Assist Power


35th Layer
SiO2
184.2
1.110
High Assist Power


36th Layer
TiO2
119.1
1.105
High Assist Power


37th Layer
SiO2
46.2
0.278
High Assist Power


38th Layer
TiO2
11.8
0.109
High Assist Power


39th Layer
SiO2
82.9
0.500
High Assist Power


Emergence
Glass


Medium





n is a refractive index


total film thickness: 4735.45 nm


design wavelength: 967 nm





















TABLE 7







Film









Formation


Odd-Numbered

Odd-Numbered
Odd-Numbered



Method of
Film
Odd-Numbered
Layer (SiO2)
Odd-Numbered
Layer (SiO2)
Layer (SiO2)



First to
Formation
Layer (SiO2)
Vacuum
Layer (SiO2)
Density
Refractive



Fourth Layers
Temperature
Rate (Å/sec)
Pressure (O2)
Assist Power
(g/cm3)
Index (at 550 nm)
























Example 5, 6
IAD
150° C.
7
1.8E−2 Pa
300
V
2.069
1.449







450
mA


Example 7, 8
IAD
150° C.
7
1.8E−2 Pa
400
V
2.086
1.453







500
mA


Comparative
IAD
150° C.
7
1.8E−2 Pa
600
V
2.172
1.461


Example 11, 12




700
mA


Comparative
IAD
150° C.
7
1.8E−2 Pa
800
V
2.201
1.473


Example 13, 14




900
mA


Comparative
IAD
150° C.
7
1.8E−2 Pa
1000
V
2.213
1.481


Example 15, 16




1200
mA














Comparative
EB
150° C.
7
8.0E−3 Pa
—
2.037
1.44


Example 17, 18


Comparative
EB
150° C.
7
8.0E−3 Pa
—
2.037
1.44


Example 19, 20















Reference
IAD
150° C.
7
1.8E−2 Pa
300
V
2.069
1.449


Example 3, 4




450
mA
























TABLE 8







Film Formation
Film
Even-Numbered
Even-Numbered
Even-Numbered
Even-Numbered
Even-Numbered



Method of
Formation
Layer Rate
Layer Vacuum
Layer Assist
Layer Density
Layer Refractive



First to Fourth Layers
Temperature
(Å/sec)
Pressure (O2)
Power
(g/cm3)
Index (at 550 nm)
























Example 5, 6
IAD
150° C.
4
1.8E−2 Pa
300
V
5.17
1.977







450
mA


Example 7, 8
IAD
150° C.
4
1.8E−2 Pa
400
V
5.23
1.985







500
mA


Comparative
IAD
150° C.
4
1.8E−2 Pa
600
V
5.36
2.009


Example 11, 12




700
mA


Comparative
IAD
150° C.
4
1.8E−2 Pa
800
V
5.41
2.026


Example 13, 14




900
mA


Comparative
IAD
150° C.
4
1.8E−2 Pa
1000
V
5.45
2.042


Example 15, 16




1200
mA














Comparative
EB
150° C.
7
5.0E−3 Pa
—
4.98
1.942


Example 17, 18















Comparative
IAD
150° C.
3
2.1E−2 Pa
1000
V
4.87
2.489


Example 19, 20




1200
mA


Reference
IAD
150° C.
3
2.1E−2 Pa
300
V
4.65
2.466


Example 3, 4




450
mA
























TABLE 9







Film









Formation



Method of



Fifth Layer


Odd-Numbered

Odd-Numbered
Odd-Numbered



and
Film
Odd-Numbered
Layer (SiO2)
Odd-Numbered
Layer (SiO2)
Layer (SiO2)



Subsequent
Formation
Layer (SiO2)
Vacuum
Layer (SiO2)
Density
Refractive



Layers
Temperature
Rate (Å/sec)
Pressure (O2)
Assist Power
(g/cm3)
Index (at 550 nm)























Example 5, 6
IAD
150° C.
7
1.8E−2 Pa
1000 V
2.213
1.481







1200 mA


Example 7, 8
IAD
150° C.
7
1.8E−2 Pa
1000 V
2.213
1.481







1200 mA


Comparative
IAD
150° C.
7
1.8E−2 Pa
1000 V
2.213
1.481


Example 11, 12




1200 mA


Comparative
IAD
150° C.
7
1.8E−2 Pa
1000 V
2.213
1.481


Example 13, 14




1200 mA


Comparative
IAD
150° C.
7
1.8E−2 Pa
1000 V
2.213
1.481


Example 15, 16




1200 mA


Comparative
IAD
150° C.
7
1.8E−2 Pa
1000 V
2.213
1.481


Example 17, 18




1200 mA


Comparative
IAD
150° C.
7
1.8E−2 Pa
1000 V
2.213
1.481


Example 19, 20




1200 mA


Reference
IAD
150° C.
7
1.8E−2 Pa
1000 V
2.213
1.481


Example 3, 4




1200 mA


























TABLE 10







Film











Formation


Even-


Even-



Method of


Numbered
Even-
Even-
Numbered



Fifth

Even-
Layer
Numbered
Numbered
Layer



Layer and
Film
Numbered
Vacuum
Layer
Layer
Refractive
Surface
Surface



Subsequent
Formation
Layer Rate
Pressure
Assist
Density
Index
Roughness
Resistance



Layer
Temperature
(Å/sec)
(O2)
Power
(g/cm3)
(at 550 nm)
(nm)
(Ω/□)

























Example 5, 6
IAD
150° C.
3
2.1E−2 Pa
1000 V
4.87
2.489
0.65 to 0.75
3.54E+09







1200 mA


Example 7, 8
IAD
150° C.
3
2.1E−2 Pa
1000 V
4.87
2.489
0.65 to 0.75
1.13E+10







1200 mA


Comparative
IAD
150° C.
3
2.1E−2 Pa
1000 V
4.87
2.489
0.77 to 0.85
1.89E+11


Example 11, 12




1200 mA


Comparative
IAD
150° C.
3
2.1E−2 Pa
1000 V
4.87
2.489
0.77 to 0.85
2.68E+12


Example 13, 14




1200 mA


Comparative
IAD
150° C.
3
2.1E−2 Pa
1000 V
4.87
2.489
0.8 to 0.9
5.21E+13


Example 15, 16




1200 mA


Comparative
IAD
150° C.
3
2.1E−2 Pa
1000 V
4.87
2.489
0.95 to 1.2 
7.91E+11


Example 17, 18




1200 mA


Comparative
IAD
150° C.
3
2.1E−2 Pa
1000 V
4.87
2.489
0.80 to 0.95
7.26E+12


Example 19, 20




1200 mA


Reference
IAD
150° C.
3
2.1E−2 Pa
1000 V
4.87
2.489
0.55 to 0.65
6.87E+10


Example 3, 4




1200 mA




















TABLE 11





Layer
Material
d (nm)
4nd
Film Formation Condition



















Incidence
Air





Medium


Outermost
SiO2
71.8
0.433
Low Assist Power


Layer


Second Layer
TiO2
84.2
0.782
Low Assist Power


Third Layer
SiO2
147.2
0.887
Low Assist Power


Fourth Layer
TiO2
83.6
0.776
Low Assist Power


Fifth Layer
SiO2
140.2
0.845
High Assist Power


Sixth Layer
TiO2
83.1
0.772
High Assist Power


Seventh Layer
SiO2
139.2
0.839
High Assist Power


Eighth Layer
TiO2
81.4
0.756
High Assist Power


Ninth Layer
SiO2
139.8
0.843
High Assist Power


Tenth Layer
TiO2
81.1
0.753
High Assist Power


11th Layer
SiO2
139.4
0.841
High Assist Power


12th Layer
TiO2
81.0.
0.752
High Assist Power


13th Layer
SiO2
139.4
0.841
High Assist Power


14th Layer
TiO2
82.0
0.761
High Assist Power


15th Layer
SiO2
140.8
0.849
High Assist Power


16th Layer
TiO2
83.3
0.773
High Assist Power


17th Layer
SiO2
143.2
0.863
High Assist Power


18th Layer
TiO2
86.7
0.805
High Assist Power


19th Layer
SiO2
150.6
0.908
High Assist Power


20th Layer
TiO2
100.4
0.932
High Assist Power


21st Layer
SiO2
179.7
1.083
High Assist Power


22nd Layer
TiO2
110.0
1.021
High Assist Power


23rd Layer
SiO2
169.7
1.023
High Assist Power


24th Layer
TiO2
101.5
0.942
High Assist Power


25th Layer
SiO2
175.7
1.059
High Assist Power


26th Layer
TiO2
115.0
1.067
High Assist Power


27th Layer
SiO2
189.1
1.140
High Assist Power


28th Layer
TiO2
116.5
1.081
High Assist Power


29th Layer
SiO2
191.2
1.153
High Assist Power


30th Layer
TiO2
119.4
1.108
High Assist Power


31st Layer
SiO2
189.9
1.145
High Assist Power


32nd Layer
TiO2
117.5
1.091
High Assist Power


33rd Layer
SiO2
193.2
1.165
High Assist Power


34th Layer
TiO2
116.7
1.083
High Assist Power


35th Layer
SiO2
184.2
1.110
High Assist Power


36th Layer
TiO2
119.1
1.105
High Assist Power


37th Layer
SiO2
44.8
0.270
High Assist Power


38th Layer
TiO2
11.8
0.110
High Assist Power


39th Layer
SiO2
82.9
0.500
High Assist Power


Emergence
Glass


Medium





n is a refractive index


total film thickness: 4726.25 nm


design wavelength: 967 nm






Experiment Result

1 Measurement of Surface Resistance (Sheet Resistance)

In measuring the surface resistance, the same apparatus as in Examples 1 to 4, Comparative Examples 1 to 8, and Reference Examples 1 and 2 was used to measure the surface resistance. The result is shown in Table 10.
As shown in Table 10, it can be seen that the surface resistance in Examples 5 to 8 is low compared to Comparative Examples 11 to 20 or Reference Examples 3 and 4. The low surface resistance means that dust or grit is less likely to adhere to the surface.
2 Relationship Between Surface Resistance and Total Film Thickness
FIG. 10 shows the relationship between a film thickness and surface resistance in Example 5.
In FIG. 10, Y0 is surface resistance (1.0×1015Ω/□) when all layers are formed through electron beam deposition with high assist power. Y1 is surface resistance (3.12×1012Ω/□) when only the outermost layer having a thickness of 72.94 nm is formed through electron beam deposition with low assist power (an acceleration voltage is 300 V and an acceleration current is 450 mV). Y2 is surface resistance (1.46×1011Ω/□) when the outermost layer and the second layer are formed through electron beam deposition with low assist power. Y3 is surface resistance (5.61×109Ω/□) when the outermost layer to the third layer are formed through electron beam deposition with low assist power. Y4 is surface resistance (3.54×109Ω/□) when the outermost layer to the fourth layer are formed through electron beam deposition with low assist power. Y5 is surface resistance (3.51×109Ω/□) when the outermost layer to the fifth layer are formed through electron beam deposition with low assist power. Y6 is surface resistance (3.49×109Ω/□) when the outermost layer to the sixth layer are formed through electron beam deposition with low assist power. Y39 is surface resistance (3.48×109Ω/□) when all layers of the outermost layer to the 39th layer are formed through electron beam deposition with low assist power.
As shown in FIG. 10, it can be seen that, if the number of bonded layers including the outermost layer is great, the value of surface resistance is reduced. Meanwhile, it can be seen that, when the outermost layer to the fourth layer are formed through electron beam deposition with low assist power and when all layers (39 layers) including the outermost layer are formed through electron beam deposition with low assist power, the value of surface resistance is not changed so much. For this reason, in this example, it will suffice that the outermost layer to the fourth layer (film thickness 389.1 nm) are formed through electron beam deposition with low assist power.
Table 12 shows the results of dust-proof performance by the polyethylene powder method, the Kanto loam method, and the cotton linter method.
As shown in Table 12, it can be seen that, in the case of the polyethylene powder method, the adhered dust quantity and the residual quantity in Examples 5 and 7 are small compared to Comparative Examples 11, 13, 15, 17, and 19 or Reference Example 1. It can also been seen that the adhered dust quantity and the residual quantity in Examples 6 and 8 are small compared to Comparative Examples 12, 14, 16, 18, and 20 or Reference Example 4. As described above, it is thought that the adhered dust quantity and the residual quantity in Examples 5 and 7 are small compared to Reference Example 3, and the adhered dust quantity and the residual quantity in Examples 6 and 8 are small compared to Reference Example 4 because Zr has small electronegativity compared to Ti.
The electronegativity can be interpreted as minimum energy necessary for separating foreign particles from the surface. If the value is small, foreign particles are easily separated from the surface. For this reason, the use of oxide containing an element having small electronegativity enables improvement in dust-proof performance.
With regard to Examples, Comparative Examples, and Reference Examples, it can be seen that the adhered dust quantity and the residual quantity in Examples 6 and 8, Comparative Examples 12, 14, 16, 18, and 20, and Reference Example 4 where the fluorine-containing organic silicon compound film 3 is provided are small compared to Examples 5 and 7, Comparative Examples 11, 13, 15, 17, and 19, and Reference Example 3 where no fluorine-containing organic silicon compound film 3 is provided. In the case of the Kanto loam method and the cotton linter method, similarly to the polyethylene powder method, with regard to Examples, Comparative Examples, and Reference Examples, it can be seen that the adhered dust quantity and the residual quantity in Examples 5 to 8 are small compared to Comparative Examples 11 to 20 or Reference Examples 3 and 4. The above results are obtained because the surface roughness is improved and dust or grit is less likely to adhere to the surface.













TABLE 12










Fluorine-
Polyethylene





Film
containing
Powder
Kanto Loam
Cotton Linter


















Formation


Organic
Adhered

Adhered

Adhered




Method of
Acceleration
Acceleration
Silicon
dust
Residual
dust
Residual
dust
Residual



Outermost Layer
Voltage (V)
Current (mA)
Compound
quantity
Quantity
quantity
Quantity
quantity
Quantity





















Example 5
IAD
300
450
None
0.09%
0.01%
0.10%
0.01%
1.77%
0.22%


Example 6
IAD
300
450
Provided
0.01%
0.00%
0.01%
0.00%
0.52%
0.01%


Example 7
IAD
400
500
None
0.10%
0.01%
0.13%
0.01%
1.92%
0.28%


Example 8
IAD
400
500
Provided
0.04%
0.00%
0.02%
0.01%
0.67%
0.02%


Comparative
IAD
600
700
None
0.31%
0.04%
0.36%
0.10%
2.03%
0.33%


Example 11


Comparative
IAD
600
700
Provided
0.05%
0.01%
0.07%
0.02%
0.84%
0.04%


Example 12


Comparative
IAD
800
900
None
1.08%
0.20%
0.82%
0.16%
3.23%
0.70%


Example 13


Comparative
IAD
800
900
Provided
0.12%
0.03%
0.77%
0.12%
2.34%
0.10%


Example 14


Comparative
IAD
1000
1200
None
3.98%
0.61%
1.24%
0.27%
5.67%
1.23%


Example 15


Comparative
IAD
1000
1200
Provided
0.58%
0.14%
0.69%
0.16%
3.08%
0.25%


Example 16


Comparative
EB
0
0
None
0.28%
0.04%
0.47%
0.06%
1.98%
0.33%


Example 17


Comparative
EB
0
0
Provided
0.09%
0.02%
0.32%
0.03%
0.89%
0.06%


Example 18


Comparative
EB
0
0
None
8.94%
1.87%
1.03%
0.27%
5.89%
1.76%


Example 19


Comparative
EB
0
0
Provided
0.77%
0.10%
15.66%
7.14%
4.78%
0.54%


Example 20


Reference
IAD
300
450
None
21.18%
3.98%
3.47%
1.23%
15.67%
2.98%


Example 3


Reference
IAD
300
450
Provided
4.92%
1.73%
31.56%
15.46%
14.73%
2.63%


Example 4









Next, examples of an optical component having a tantalum oxide layer and a silicon oxide layer will be described.
Optical Component Having Tantalum Oxide Layer and Silicon Oxide Layer
Examples 9 to 12, Comparative Examples 21 to 26, and Reference Examples 5 and 6 corresponding to the optical component according to the first embodiment of the invention will be described.
Example 9
In Example 9, the anti-reflection film 2 is formed on the substrate 1, and no fluorine-containing organic silicon compound film 3 is provided.
The layer configuration of the anti-reflection film 2 of Example 9 is shown in Tables 13 to 15. In these tables, the outermost layer 2S is the silicon oxide layer 2A which is a low-density layer having a density of 2.069 g/cm3 and a refractive index n of 1.449. The thickness of the outermost layer 2S is 85.7 nm, and the optical film thickness is 1.449×85.7 nm=124.1793 nm. The relative value 4nd of the optical film thickness to the design wavelength (in Example 1, 510 nm) (hereinafter, simply referred to as the relative value to the design wavelength) is 0.977. That is, in design of the optical thin-film, since 1⁄4 of the design wavelength is used as a basis, the value of an optical thin-film nd to the relevant value becomes 0.977. The second layer 22 is the metal oxide layer 2B which is a low-density layer having a density of 7.91 g/cm3 and made of tantalum oxide having a refractive index n of 2.144. The thickness of the second layer 22 is 115.6 nm, and the relative value 4nd to the design wavelength is 1.958. The third layer 23 is the silicon oxide layer 2A which is a low-density layer having a density of 2.069 g/cm3 and a refractive index n of 1.449. The thickness of the third layer 23 is 30.5 nm, and the relative value 4nd to the design wavelength is 0.348. The fourth layer 24 is the metal oxide layer 2B which is a low-density layer having a density of 7.91 g/cm3 and made of a tantalum oxide having a refractive index n of 2.144. The thickness of the fourth layer 24 is 12.1 nm, and the relative value 4nd to the design wavelength is 0.206. The fifth layer 25 is the silicon oxide layer 2A which is a high-density layer having a density of 2.213 g/cm3 and a refractive index n of 1.481. The thickness of the fifth layer 25 is 151.3 nm, and the relative value 4nd to the design wavelength is 1.742. The total thickness of the outermost layer 2S to the fifth layer 25 is 395.3 nm.
In forming the anti-reflection film 2 configured as above on the substrate 1, in Example 9, the outermost layer 2S to the fourth layer 24 are formed through ion-assisted electron beam deposition (IAD) with low assist power. The film formation temperature is 150° C. When a low-density layer is formed as the silicon oxide layer 2A, the vacuum pressure is 1.8×10−2 Pa. Assist power has an acceleration voltage of 300 V and an acceleration current of 450 mA. When the metal oxide layer 22 is formed of tantalum oxide, the vacuum pressure is 1.8×10−2 Pa, and assist power has an acceleration voltage of 300 V and an acceleration current of 450 mA. Thus, the surface roughness of the outermost layer 2S becomes 0.55 nm to 0.65 nm. The fifth layer 25 is formed through ion-assisted electron beam deposition (IAD) with high assist power. In this case, assist power has an acceleration voltage of 1000 Vm and an acceleration current of 1200 mA.
Example 10
Example 10 is different from Example 9 in that the fluorine-containing organic silicon compound film 3 is provided on the anti-reflection film 2.
With regard to the fluorine-containing organic silicon compound film 3, for example, as a deposition source, a material is used which is obtained by diluting fluorine-containing organic silicon compound (product name: KY-130) manufactured by Shin-Etsu Chemical Co., Ltd. with a fluorine-based solvent (manufactured by Sumitomo 3M Ltd.: Novec HFE-7200) to prepare a solution having a solid content concentration of 3%, impregnating 1 g of the solution into a porous ceramic pellet, and performing drying.
Example 11
Example 11 is different from Example 9 in terms of assist power for forming a low-density layer. That is, in Example 11, assist power is low assist power having an acceleration voltage of 400 V and an acceleration current of 500 mA. For this reason, the low-density layer constituting the silicon oxide layer 2A serving as the outermost layer 2S and the third layer 23 have a density of 2.086 g/cm3, and the low-density layers constituting the second layer 22 and the fourth layer 24, that is, the metal oxide layers 2B made of tantalum oxide have a density of 7.98 g/cm3. The density of the fifth layer 25 is the same as in Example 9.
Example 12
Example 12 is different from Example 11 in that the fluorine-containing organic silicon compound film 3 is provided on the anti-reflection film 2.
Comparative Example 21
Comparative Example 21 is different from Example 9 in terms of assist power for forming a low-density layer. That is, in Comparative Example 21, the outermost layer 2S to the fourth layer 24 are formed through ion-assisted electron beam deposition (IAD) with intermediate assist power having an acceleration voltage of 600 V and an acceleration current of 700 mA. For this reason, the low-density layers constituting the silicon oxide layer serving as the outermost layer and the third layer have a density of 2.172 g/cm3, and the low-density layers constituting the second layer and the fourth layer, that is, the metal oxide layers 2B made of tantalum oxide have a density of 8.09 g/cm3. In Comparative Example 21, the surface roughness of the outermost layer is 0.57 nm to 0.67 nm, which is greater than in Examples 9 to 12.
Comparative Example 22
Comparative Example 22 is different from Comparative Example 21 in that the fluorine-containing organic silicon compound film is provided on the anti-reflection film.
Comparative Example 23
Comparative Example 23 is different from Example 9 in terms of assist power for forming a low-density layer. That is, in Comparative Example 23, the outermost layer 2S to the fourth layer 24 are formed through ion-assisted electron beam deposition (IAD) with intermediate assist power having an acceleration voltage of 800 V and an acceleration current of 900 mA. For this reason, the low-density layers constituting the silicon oxide layer serving as the outermost layer and the third layer have a density of 2.201 g/cm3, and the low-density layers constituting the second layer and the fourth layer, that is, the metal oxide layers 2B made of tantalum oxide have a density of 8.15 g/cm3. In Comparative Example 23, the surface roughness of the outermost layer is 0.6 nm to 0.7 nm, which is greater than in Examples 9 to 12.
Comparative Example 24
Comparative Example 24 is different from Comparative Example 23 in that the fluorine-containing organic silicon compound film is provided on the anti-reflection film.
Comparative Example 25
Comparative Example 25 is different from Example 9 in terms of assist power for forming a low-density layer. That is, in Comparative Example 25, all layers are formed through ion-assisted electron beam deposition (IAD) with high assist power having an acceleration voltage of 1000 V and an acceleration current of 1200 mA. For this reason, the low-density layers constituting the silicon oxide layer serving as the outermost layer and the third layer have a density of 2.213 g/cm3, and the low-density layers constituting the second layer and the fourth layer, that is, the metal oxide layers 2B made of tantalum oxide have a density of 8.19 g/cm3. In Comparative Example 25, the surface roughness of the outermost layer is 0.62 nm to 0.72 nm, which is greater than in Examples 9 to 13.
Comparative Example 26
Comparative Example 26 is different from Comparative Example 25 in that the fluorine-containing organic silicon compound film is provided on the anti-reflection film.
Reference Example 5
In Reference Example 5, an anti-reflection film has an outermost layer constituted by a silicon oxide thin-film having a thickness of 86.0 nm, a second layer constituted by a titanium oxide thin-film having a thickness of 102.7 nm, a third layer constituted by a silicon oxide thin-film having a thickness of 30.6 nm, a fourth layer constituted by a titanium oxide thin-film having a thickness of 12.1 nm, and a fifth layer constituted by a silicon oxide layer having a thickness of 136.6 nm. Reference Example 5 is different from Example 9 in terms of the vacuum pressure and the refractive index of the even-numbered layer. Table 16 shows the layer configuration of Reference Example 5. In Reference Example 5, the surface roughness of the outermost layer is 0.6 nm to 0.7 nm, which is greater than in Examples 9 to 12. In Reference Example 5, film formation is performed with the same assist power as in Example 9.
Reference Example 6
Reference Example 6 is different from Reference Example 5 in that the fluorine-containing organic silicon compound film is provided on the anti-reflection film.
With the above, it can be seen that the surface roughness of the outermost layer corresponds to assist power when the outermost layer is formed. That is, in Examples 9 to 12, the outermost layer is formed with low assist power having an acceleration voltage of 300 V to 400 V (acceleration current of 450 mA to 500 mA), such that the surface roughness of the outermost layer becomes 0.55 nm to 0.65 nm. Meanwhile, in Comparative Examples 21 to 24, the outermost layer is formed with intermediate assist power having an acceleration voltage of 600 V to 800 V (acceleration current of 700 mA to 900 mA), such that the surface roughness of the outermost layer becomes 0.6 nm to 0.7 nm or 0.62 nm to 0.75 nm. In Comparative Examples 25 and 26, the outermost layer is formed with high assist power having an acceleration voltage of 1000 V (acceleration current of 1200 mA), such that the surface roughness of the outermost layer becomes 0.62 nm to 0.72 nm. In Reference Examples 5 and 6, while film formation is performed with the same assist power as in Examples 9 and 10, unlike Examples 9 and 10, since the even-numbered layer is constituted by a titanium oxide thin-film, the surface roughness becomes 0.6 nm to 0.7 nm.












TABLE 13







Layer
Material
d (nm)
4nd





















Incidence Medium
Air





Outermost Layer
SiO2
85.7
0.977



Second Layer
Ta2O5
115.6
1.958



Third Layer
SiO2
30.5
0.348



Fourth Layer
Ta2O5
12.1
0.206



Fifth Layer
SiO2
151.3
1.742



Emergence Medium
Glass







n is a refractive index



total film thickness: 395.3 nm



design wavelength: 510 nm





















TABLE 14







Film





Odd-Numbered



Formation


Odd-Numbered

Odd-Numbered
Layer (SiO2)



Method of
Film
Odd-Numbered
Layer (SiO2)
Odd-Numbered
Layer (SiO2)
Refractive



First to
Formation
Layer (SiO2)
Vacuum
Layer (SiO2)
Density
Index



Fourth Layers
Temperature
Rate (Å/sec)
Pressure (O2)
Assist Power
(g/cm3)
(at 550 nm)
























Example 9, 10
IAD
150° C.
7
1.8E−2 Pa
300
V
2.069
1.449







450
mA


Example 11, 12
IAD
150° C.
7
1.8E−2 Pa
400
V
2.086
1.453







500
mA


Comparative
IAD
150° C.
7
1.8E−2 Pa
600
V
2.172
1.461


Example 21, 22




700
mA


Comparative
IAD
150° C.
7
1.8E−2 Pa
800
V
2.201
1.473


Example 23, 24




900
mA


Comparative
IAD
150° C.
7
1.8E−2 Pa
1000
V
2.213
1.481


Example 25, 26




1200
mA


Reference
IAD
150° C.
7
1.8E−2 Pa
300
V
2.069
1.449


Example 5, 6




450
mA


























TABLE 15







Film


Even-


Even-





Formation


Numbered
Even-
Even-
Numbered



Method of

Even-
Layer
Numbered
Numbered
Layer



First to
Film
Numbered
Vacuum
Layer
Layer
Refractive
Surface
Surface



Fourth
Formation
Layer Rate
Pressure
Assist
Density
Index
Roughness
Resistance



Layers
Temperature
(Å/sec)
(O2)
Power
(g/cm3)
(at 550 nm)
(nm)
(Ω/□)


























Example 9, 10
IAD
150° C.
3
1.8E−2 Pa
300
V
7.91
2.144
0.55 to 0.65
8.50E+10







450
mA


Example 11, 12
IAD
150° C.
3
1.8E−2 Pa
400
V
7.98
2.167
0.55 to 0.65
3.10E+11







500
mA


Comparative
IAD
150° C.
3
1.8E−2 Pa
600
V
8.09
2.201
0.57 to 0.67
9.85E+12


Example 21, 22




700
mA


Comparative
IAD
150° C.
3
1.8E−2 Pa
800
V
8.15
2.217
0.6 to 0.7
1.00E+15


Example 23, 24




900
mA


Comparative
IAD
150° C.
3
1.8E−2 Pa
1000
V
8.19
2.221
0.62 to 0.72
1.00E+15


Example 25, 26




1200
mA


Reference
IAD
150° C.
3
2.1E−2 Pa
300
V
4.65
2.466
0.6 to 0.7
5.77E+10


Example 5, 6




450
mA





















TABLE 16







Layer
Material
d (nm)
4nd





















Incidence Medium
Air





Outermost Layer
SiO2
86.0
0.979



Second Layer
TiO2
102.7
2.014



Third Layer
SiO2
30.6
0.349



Fourth Layer
TiO2
12.1
0.237



Fifth Layer
SiO2
136.6
1.573



Emergence Medium
Glass







n is a refractive index



total film thickness: 367.9 nm



design wavelength: 510 nm






Experiment Result

1 Measurement of Surface Resistance (Sheet Resistance)

In measuring the surface resistance, the surface resistance measurement instrument 504 shown in FIG. 7A is used. The surface resistance measurement instrument 504 and the stage 506 are configured as above, and the measurement condition and the measurement environment are the same as in the above-described experiment.
With regard to Examples, Comparative Examples, and Reference Examples, the surface resistance of the sample was measured. The results are shown in Table 15. As shown in Table 15, it can be seen that the surface resistance in Examples 9 to 12 is low compared to Comparative Examples 25 to 28. The low surface resistance means that dust or grit is less likely to adhere to the surface.
2 Relationship Between Surface Resistance and Total Film Thickness
FIG. 11 shows the relationship between a film thickness and surface resistance in Example 9.
In FIG. 11, X0 is surface resistance (1.5×1015Ω/□) when all layers are formed through electron beam deposition with high assist power. X1 is surface resistance (3.17×1012Ω/□) when only the outermost layer having a thickness of 85.74 nm is formed through electron beam deposition with low assist power (an acceleration voltage is 300 V and an acceleration current is 450 mV). X2 is surface resistance (1.47×1011Ω/□) when the outermost layer and the second layer are formed through electron beam deposition with low assist power. X3 is surface resistance (1.01×1011Ω/□) when the outermost layer to the third layer are formed through electron beam deposition with low assist power. X4 is surface resistance (8.88×1010Ω/□) when the outermost layer to the fourth layer are formed through electron beam deposition with low assist power. X5 is surface resistance (8.50×1010Ω/□) when all layers are formed through electron beam deposition with low assist power.
As shown in FIG. 11, it can be seen that, if a large number of bonded layers including the outermost layer are formed through electron beam deposition with low assist power, the value of surface resistance is reduced. Meanwhile, it can be seen that, when the outermost layer to the fourth layer are formed through electron beam deposition with low assist power and when all layers (five layers) including the outermost layer are formed through electron beam deposition with low assist power, the value of surface resistance is not changed so much. For this reason, in this example, it will suffice that the outermost layer to the fourth layer (film thickness 244.0 nm) are formed through electron beam deposition with low assist power.
3 Charge-Through
With regard to charge-through, the outermost layer of the sample is frictionally charged, and the residual charge quantity (relative value) in the outermost layer is displayed over time. The charge-through is shown in FIG. 12. In FIG. 12, a graph A shows Comparative Example 25, and a graph B shows Example 9. For the measurement of surface charges, the surface electrometer 500 shown in FIG. 7B is used. The surface electrometer 500 is the same as that used in the above-described experiment, and the distance between the probe 501 and the surface of the sample 502 of a filter is 10 mm. The stage 503 on which the sample 502 is placed is made of metal, and measurement is performed in a state of being grounded. The measurement environment is the same as in the above-described experiment.
As shown in FIG. 12, in the graph B of Example 9, the residual charge quantity over time is small compared to the graph A of Comparative Example 25. As a result, it can be seen that, in Example 9, adhesion of dust or grit to the surface due to static electricity is reduced compared to Comparative Example 25.
4 Dust-Proof Performance
A dust-proof performance test was performed by 4-1 polyethylene powder method, 4-2 Kanto loam method, and 4-3 cotton linter method. The detailed specification of these methods is as described above.
Table 17 shows the results of 4-1 polyethylene powder method, 4-2 Kanto loam method, and 4-3 cotton linter method.
As shown in Table 17, in the case of the polyethylene powder method, it can be seen that the adhered dust quantity and the residual quantity in Examples 9 and 10 are small compared to Comparative Examples 21 to 24 or Reference Examples 5 and 6. As described above, it is thought that the adhered dust quantity and the residual quantity in Examples 9 and 11 are small compared to Reference Example 5, and the adhered dust quantity and the residual quantity in Examples 10 and 12 are small compared to Reference Example 6 because Ta has small electronegativity compared to Ti. With regard to Examples and Comparative Examples, it can be seen that the adhered dust quantity and the residual quantity in Examples 10 and 12, Comparative Examples 22, 24, and 26, and Reference Example 6 where the fluorine-containing organic silicon compound film 3 is provided are small compared to Examples 9 and 11, Comparative Examples 21, 23, and 25, and Reference Example 5 where no fluorine-containing organic silicon compound film 3 is provided. In the case of the Kanto loam method and the cotton linter method, similarly to the polyethylene powder method, with regard to Examples, Comparative Examples, and Reference Examples, it can be seen that the adhered dust quantity and the residual quantity in Examples 9 and 10 are small compared to Comparative Examples 21 to 24 or Reference Examples 5 and 6.
The electronegativity numerically indicates the ability that the bonded atoms in the molecules attract electrons. Although any method is used to obtain the numerical value, the numerical value is in general obtained by a Pauling's method. With regard to the electronegativity by the Pauling's method, Ti has 1.54 smaller than 1.50 of Ta. The electronegativity can be interpreted as minimum energy necessary for separating foreign particles from the surface. For this reason, the use of oxide containing an element having small electronegativity enables improvement in dust-proof performance.
It can be seen that the adhered dust quantity and the residual quantity in Examples 10 and 12, Comparative Examples 22, 24, and 26, and Reference Example 6 where the fluorine-containing organic silicon compound film 3 is provided are great compared to Examples 9 and 11, Comparative Examples 21, 23, and 25, and Reference Example 5 where no fluorine-containing organic silicon compound film 3 is provided. The above results are obtained because the fluorine-containing organic silicon compound film reduces surface energy, and dust or grit is less likely to adhere to the surface.













TABLE 17










Fluorine-
Polyethylene





Film
containing
Powder
Kanto Loam
Cotton Linter


















Formation


Organic
Adhered

Adhered

Adhered




Method of
Acceleration
Acceleration
Silicon
dust
Residual
dust
Residual
dust
Residual



Outermost Layer
Voltage (V)
Current (mA)
Compound
quantity
Quantity
quantity
Quantity
quantity
Quantity





















Example 9
IAD
300
450
None
2.72%
0.49%
0.17%
0.01%
3.13%
0.65%


Example 10
IAD
300
450
Provided
0.07%
0.01%
0.23%
0.01%
2.25%
0.19%


Example 11
IAD
400
500
None
3.13%
0.55%
0.21%
0.01%
3.26%
0.65%


Example 12
IAD
400
500
Provided
0.10%
0.01%
0.27%
0.01%
2.47%
0.22%


Comparative
IAD
600
700
None
8.98%
1.24%
0.92%
0.09%
4.19%
0.78%


Example 21


Comparative
IAD
600
700
Provided
0.91%
0.16%
1.12%
0.11%
3.97%
0.38%


Example 22


Comparative
IAD
800
900
None
11.02%
2.78%
2.10%
0.52%
8.63%
1.52%


Example 23


Comparative
IAD
800
900
Provided
3.52%
0.99%
1.95%
0.48%
9.71%
0.55%


Example 24


Comparative
IAD
1000
1200
None
19.20%
3.84%
3.15%
0.81%
12.54%
1.95%


Example 25


Comparative
IAD
1000
1200
Provided
3.81%
1.02%
5.23%
1.25%
11.78%
0.63%


Example 26


Reference
IAD
300
450
None
3.78%
0.59%
0.29%
0.02%
2.87%
0.63%


Example 5


Reference
IAD
300
450
Provided
0.16%
0.01%
0.19%
0.01%
1.84%
0.14%


Example 6









Next, Examples 13 to 16, Comparative Examples 27 to 32, and Reference Examples 7 and 8 corresponding to the optical component according to the second embodiment of the invention will be described. With regard to the deposition experiment, similarly to the experiment of Examples 9 to 12, Comparative Examples 21 to 26, and Reference Examples 5 and 6, the deposition instrument manufactured by SHINCRON Co., Ltd. was used to manufacture an anti-reflection film on the surface of white plate glass having a predetermined shape under the conditions of Examples and Comparative Examples.
Example 13
In Example 13, the IR-UV cut film 4 is formed on the substrate 1, and no fluorine-containing organic silicon compound film 3 is provided.
The layer configuration of the IR-UV cut film 4 of Example 13 is shown in Tables 18 to 22. Table 18 shows the relationship between the material of each layer and the film thickness. Tables 19 and 20 show the film formation condition of the outermost layer, and the like. Tables 21 and 22 show the film formation condition for the fifth layer to the 39th layer, and the like.
In Tables 18 to 20, the outermost layer 2S is the silicon oxide layer 2A which is a low-density layer having a density of 2.069 g/cm3 and a refractive index n of 1.449. The thickness of the outermost layer 2S is 70.3 nm, and the relative value 4nd to the design wavelength is 0.419. The second layer 22 is the metal oxide layer 2B which is a low-density layer having a density of 7.91 g/cm3 and made of tantalum oxide having a refractive index n of 2.144. The thickness of the second layer 22 is 86.3 nm, and the relative value 4nd to the design wavelength is 0.745. The third layer is the silicon oxide layer 2A which is a low-density layer having a density of 2.069 g/cm3 and a refractive index n of 1.449. The thickness of the third layer is 146.6 nm, and the relative value 4nd to the design wavelength is 0.874. The fourth layer is metal oxide layer 2B which is a low-density layer having a density of 7.91 g/cm3 and made of tantalum oxide having a refractive index n of 2.144. The thickness of the fourth layer is 88.6 nm, and the relative value 4nd to the design wavelength is 0.765.
In Tables 18, 21, and 22, the fifth layer is the silicon oxide layer 2A which is a high-density layer having a density of 2.213 g/cm3 and a refractive index n of 1.481. The thickness of the fifth layer is 140.2 nm, and the relative value 4nd to the design wavelength is 0.845. The sixth layer is the metal oxide layer 2B which is a high-density layer having a density of 4.87 g/cm3 and made of titanium oxide having a refractive index n of 2.489. The thickness of the sixth layer is 83.1 nm, and the relative value 4nd to the design wavelength is 0.772. Subsequently, the seventh layer to the 39th layer have the layer configuration described in Tables 18, 21, and 22. The total film thickness of the outermost layer 2S to the 39th layer is 4731.39 nm.
In forming the IR-UV cut film 4 configured as above on the substrate 1, in Example 13, the outermost layer 2S to the fourth layer are formed through ion-assisted electron beam deposition (IAD) with low assist power. The film formation temperature is 150° C. When a low-density layer is formed as the silicon oxide layer 2A, the vacuum pressure is 1.8×10−2 Pa. Assist power has an acceleration voltage of 300 V and an acceleration current of 450 mA. When the metal oxide layer 2B is formed of tantalum oxide, the vacuum pressure is 1.8×10−2 Pa. Assist power has an acceleration voltage of 300 V and an acceleration current of 450 mA. The fifth layer to the 39th layer are formed through ion-assisted electron beam deposition (IAD) with high assist power. In this case, in the same manner as when the silicon oxide layer 2A is formed and when the metal oxide layer 2B is formed of titanium oxide, assist power has an acceleration voltage of 1000 Vm and an acceleration current of 1200 mA. The surface roughness of the outermost layer 2S is 0.55 nm to 0.65 nm.
Example 14
Example 14 is different from Example 13 in that the fluorine-containing organic silicon compound film 3 is provided on the IR-UV cut film 4.
The fluorine-containing organic silicon compound film 3 is the same as in Example 9.
Example 15
Example 15 is different from Example 13 in terms of assist power for forming a low-density layer. That is, in Example 15, assist power is low assist power having an acceleration voltage of 400 V and an acceleration current of 500 mA. For this reason, the low-density layers constituting the silicon oxide layer 2A serving as the outermost layer 2S and the third layer have a density of 2.086 g/cm3, and the low-density layers constituting the second layer 22 and the fourth layer, that is, the metal oxide layers 2B made of tantalum oxide have a density of 7.98 g/cm3.
Example 16
Example 16 is different from Example 15 in that the fluorine-containing organic silicon compound film 3 is provided on the IR-UV cut film 4.
Comparative Example 27
Comparative Example 27 is different from Example 13 in terms of assist power for forming a low-density layer. That is, in Comparative Example 27, the outermost layer 2S to the fourth layer 24 are formed through ion-assisted electron beam deposition (IAD) with intermediate assist power having an acceleration voltage of 600 V and an acceleration current of 700 mA. For this reason, the low-density layers constituting the silicon oxide thin-film serving as the outermost layer and the third layer have a density of 2.172 g/cm3, and the low-density layers constituting the second layer and the fourth layer, that is, the metal oxide layers 2B made of tantalum oxide have a density of 8.09 g/cm3.
In Comparative Example 27, the surface roughness of the outermost layer is 0.57 nm to 0.67 nm, which is greater than in Examples 13 to 16.
Comparative Example 28
Comparative Example 28 is different from Comparative Example 27 in that the fluorine-containing organic silicon compound film 3 is provided on the IR-UV cut film 4.
Comparative Example 29
Comparative Example 29 is different from Example 13 in terms of assist power for forming a low-density layer. That is, in Comparative Example 29, the outermost layer 2S to the fourth layer 24 are formed through ion-assisted electron beam deposition (IAD) with intermediate assist power having an acceleration voltage of 800 V and an acceleration current of 900 mA. For this reason, the low-density layers constituting the silicon oxide layer serving as the outermost layer and the third layer have a density of 2.201 g/cm3, and the low-density layers constituting the second layer and the fourth layer, that is, the metal oxide layers 2B made of tantalum oxide have a density of 8.15 g/cm3.
In Comparative Example 29, the surface roughness of the outermost layer is 0.6 nm to 0.7 nm, which is greater than in Examples 13 to 16.
Comparative Example 30
Comparative Example 30 is different from Comparative Example 29 in that the fluorine-containing organic silicon compound film 3 is provided on the IR-UV cut film 4.
Comparative Example 31
Comparative Example 31 is different from Example 13 in terms of assist power for forming a low-density layer. That is, in Comparative Example 31, all layers are formed through ion-assisted electron beam deposition (IAD) with high assist power having an acceleration voltage of 1000 V and an acceleration current of 1200 mA. For this reason, the low-density layers constituting the silicon oxide layer serving as the outermost layer and the third layer have a density of 2.213 g/cm3, and the low-density layers constituting the second layer and the fourth layer, that is, the metal oxide layers 2B made of tantalum oxide have a density of 8.19 g/cm3.
In Comparative Example 31, the surface roughness of the outermost layer is 0.62 nm to 0.72 nm, which is greater than in Examples 13 to 16.
Comparative Example 32
Comparative Example 32 is different from Comparative Example 31 in that the fluorine-containing organic silicon compound film 3 is provided on the IR-UV cut film 4.
Reference Example 7
In Reference Example 7, an IR-UV cut film has an outermost layer constituted by a silicon oxide thin-film having a thickness of 71.8 nm, a second layer constituted by the metal oxide layer 2B made of titanium oxide having a thickness of 84.2 nm, a third layer constituted by a silicon oxide layer having a thickness of 147.2 nm, a fourth layer constituted by the metal oxide layer 2B made of titanium oxide having a thickness of 83.6 nm, a fifth layer constituted by the silicon oxide layer having a thickness of 140.2 nm, and a sixth layer constituted by the metal oxide layer 2B made of titanium oxide having a thickness of 83.1 nm. The total film thickness of the 39 layers is 4726.25 nm. The layer configuration of Reference Example 7 is shown in Table 23. In Reference Example 7, the surface roughness of the outermost layer is 0.55 nm to 0.65 nm, which is greater than in Examples 13 to 16. In Reference Example 7, film formation is performed by the same method as in Example 13. The design wavelength is 967 nm.
Reference Example 8
Reference Example 8 is different from Reference Example 7 in that the fluorine-containing organic silicon compound film is provided on the IR-UV cut film.











TABLE 18





Layer
Material
d (nm)
4nd
Film Formation Condition



















Incidence
Air





Medium


Outermost
SiO2
70.3
0.419
Low Assist Power


Layer


Second Layer
Ta2O5
86.3
0.745
Low Assist Power


Third Layer
SiO2
146.6
0.874
Low Assist Power


Fourth Layer
Ta2O5
88.6
0.765
Low Assist Power


Fifth Layer
SiO2
140.2
0.845
High Assist Power


Sixth Layer
TiO2
83.1
0.772
High Assist Power


Seventh Layer
SiO2
139.2
0.839
High Assist Power


Eighth Layer
TiO2
81.4
0.756
High Assist Power


Ninth Layer
SiO2
139.8
0.843
High Assist Power


Tenth Layer
TiO2
81.1
0.753
High Assist Power


11th Layer
SiO2
139.4
0.841
High Assist Power


12th Layer
TiO2
81.0
0.752
High Assist Power


13th Layer
SiO2
139.4
0.841
High Assist Power


14th Layer
TiO2
82.0
0.761
High Assist Power


15th Layer
SiO2
140.8
0.849
High Assist Power


16th Layer
TiO2
83.3
0.773
High Assist Power


17th Layer
SiO2
143.2
0.863
High Assist Power


18th Layer
TiO2
86.7
0.805
High Assist Power


19th Layer
SiO2
150.6
0.908
High Assist Power


20th Layer
TiO2
100.4
0.932
High Assist Power


21st Layer
SiO2
179.7
1.083
High Assist Power


22nd Layer
TiO2
110.0
1.021
High Assist Power


23rd Layer
SiO2
169.7
1.023
High Assist Power


24th Layer
TiO2
101.5
0.942
High Assist Power


25th Layer
SiO2
175.7
1.059
High Assist Power


26th Layer
TiO2
115.0
1.067
High Assist Power


27th Layer
SiO2
189.1
1.140
High Assist Power


28th Layer
TiO2
116.5
1.081
High Assist Power


29th Layer
SiO2
191.2
1.153
High Assist Power


30th Layer
TiO2
119.4
1.108
High Assist Power


31st Layer
SiO2
189.9
1.145
High Assist Power


32nd Layer
TiO2
117.5
1.091
High Assist Power


33rd Layer
SiO2
193.2
1.165
High Assist Power


34th Layer
TiO2
116.7
1.083
High Assist Power


35th Layer
SiO2
184.2
1.110
High Assist Power


36th Layer
TiO2
119.1
1.105
High Assist Power


37th Layer
SiO2
44.8
0.270
High Assist Power


38th Layer
TiO2
11.8
0.110
High Assist Power


39th Layer
SiO2
82.9
0.500
High Assist Power


Emergence
Glass


Medium





n is a refractive index


total film thickness: 4731.39 nm


design wavelength: 967 nm





















TABLE 19







Film





Odd-Numbered



Formation


Odd-Numbered
Odd-
Odd-Numbered
Layer (SiO2)



Method of
Film
Odd-Numbered
Layer (SiO2)
Numbered
Layer (SiO2)
Refractive



First to
Formation
Layer (SiO2)
Vacuum
Layer (SiO2)
Density
Index



Fourth Layers
Temperature
Rate (Å/sec)
Pressure (O2)
Assist Power
(g/cm3)
(at 550 nm)
























Example 13, 14
IAD
150° C.
7
1.8E−2 Pa
300
V
2.069
1.449







450
mA


Example 15, 16
IAD
150° C.
7
1.8E−2 Pa
400
V
2.086
1.453







500
mA


Comparative
IAD
150° C.
7
1.8E−2 Pa
600
V
2.172
1.461


Example 27, 28




700
mA


Comparative
IAD
150° C.
7
1.8E−2 Pa
800
V
2.201
1.473


Example 29, 30




900
mA


Comparative
IAD
150° C.
7
1.8E−2 Pa
1000
V
2.213
1.481


Example 31, 32




1200
mA


Reference
IAD
150° C.
7
1.8E−2 Pa
300
V
2.069
1.449


Example 7, 8




450
mA
























TABLE 20







Film





Even-Numbered



Formation

Even-
Even-
Even-

Layer



Method of
Film
Numbered
Numbered
Numbered
Even-Numbered
Refractive



First to
Formation
Layer Rate
Layer Vacuum
Layer Assist
Layer Density
Index



Fourth Layers
Temperature
(Å/sec)
Pressure (O2)
Power
(g/cm3)
(at 550 nm)
























Example 13, 14
IAD
150° C.
3
1.8E−2 Pa
300
V
7.91
2.144







450
mA


Example 15, 16
IAD
150° C.
3
1.8E−2 Pa
400
V
7.98
2.167







500
mA


Comparative
IAD
150° C.
3
1.8E−2 Pa
600
V
8.09
2.201


Example 27, 28




700
mA


Comparative
IAD
150° C.
3
1.8E−2 Pa
800
V
8.15
2.217


Example 29, 30




900
mA


Comparative
IAD
150° C.
3
1.8E−2 Pa
1000
V
8.19
2.221


Example 31, 32




1200
mA


Reference
IAD
150° C.
3
1.8E−2 Pa
300
V
4.65
2.466


Example 7, 8




450
mA
























TABLE 21







Film









Formation



Method of





Odd-Numbered



Fifth Layer


Odd-Numbered

Odd-Numbered
Layer (SiO2)



and
Film
Odd-Numbered
Layer (SiO2)
Odd-Numbered
Layer (SiO2)
Refractive



Subsequent
Formation
Layer (SiO2)
Vacuum
Layer (SiO2)
Density
Index



Layers
Temperature
Rate (Å/sec)
Pressure (O2)
Assist Power
(g/cm3)
(at 550 nm)























Example 13, 14
IAD
150° C.
7
1.8E−2 Pa
1000 V
2.213
1.481







1200 mA


Example 15, 16
IAD
150° C.
7
1.8E−2 Pa
1000 V
2.213
1.481







1200 mA


Comparative
IAD
150° C.
7
1.8E−2 Pa
1000 V
2.213
1.481


Example 27, 28




1200 mA


Comparative
IAD
150° C.
7
1.8E−2 Pa
1000 V
2.213
1.481


Example 29, 30




1200 mA


Comparative
IAD
150° C.
7
1.8E−2 Pa
1000 V
2.213
1.481


Example 31, 32




1200 mA


Reference
IAD
150° C.
7
1.8E−2 Pa
1000 V
2.213
1.481


Example 7, 8




1200 mA


























TABLE 22







Film











Formation


Even-


Even-



Method of


Numbered
Even-
Even-
Numbered



Fifth

Even-
Layer
Numbered
Numbered
Layer



Layer and
Film
Numbered
Vacuum
Layer
Layer
Refractive
Surface
Surface



Subsequent
Formation
Layer Rate
Pressure
Assist
Density
Index
Roughness
Resistance



Layers
Temperature
(Å/sec)
(O2)
Power
(g/cm3)
(at 550 nm)
(nm)
(Ω/□)

























Example 13, 14
IAD
150° C.
3
2.1E−2 Pa
1000 V
4.87
2.489
0.55 to 0.65
7.71E+10







1200 mA


Example 15, 16
IAD
150° C.
3
2.1E−2 Pa
1000 V
4.87
2.489
0.55 to 0.65
2.93E+11







1200 mA


Comparative
IAD
150° C.
3
2.1E−2 Pa
1000 V
4.87
2.489
0.57 to 0.67
2.46E+13


Example 27, 28




1200 mA


Comparative
IAD
150° C.
3
2.1E−2 Pa
1000 V
4.87
2.489
0.6 to 0.7
7.80E+14


Example 29, 30




1200 mA


Comparative
IAD
150° C.
3
2.1E−2 Pa
1000 V
4.87
2.489
0.62 to 0.72
1.00E+15


Example 31, 32




1200 mA


Reference
IAD
150° C.
3
2.1E−2 Pa
1000 V
4.87
2.489
0.6 to 0.7
6.87E+10


Example 7, 8




1200 mA




















TABLE 23





Layer
Material
d (nm)
4nd
Film Formation Condition



















Incidence
Air





Medium


Outermost
SiO2
71.8
0.433
Low Assist Power


Layer


Second Layer
TiO2
84.2
0.782
Low Assist Power


Third Layer
SiO2
147.2
0.887
Low Assist Power


Fourth Layer
TiO2
83.6
0.776
Low Assist Power


Fifth Layer
SiO2
140.2
0.845
High Assist Power


Sixth Layer
TiO2
83.1
0.772
High Assist Power


Seventh Layer
SiO2
139.2
0.839
High Assist Power


Eighth Layer
TiO2
81.4
0.756
High Assist Power


Ninth Layer
SiO2
139.8
0.843
High Assist Power


Tenth Layer
TiO2
81.1
0.753
High Assist Power


11th Layer
SiO2
139.4
0.841
High Assist Power


12th Layer
TiO2
81.0
0.752
High Assist Power


13th Layer
SiO2
139.4
0.841
High Assist Power


14th Layer
TiO2
82.0
0.761
High Assist Power


15th Layer
SiO2
140.8
0.849
High Assist Power


16th Layer
TiO2
83.3
0.773
High Assist Power


17th Layer
SiO2
143.2
0.863
High Assist Power


18th Layer
TiO2
86.7
0.805
High Assist Power


19th Layer
SiO2
150.6
0.908
High Assist Power


20th Layer
TiO2
100.4
0.932
High Assist Power


21st Layer
SiO2
179.7
1.083
High Assist Power


22nd Layer
TiO2
110.0
1.021
High Assist Power


23rd Layer
SiO2
169.7
1.023
High Assist Power


24th Layer
TiO2
101.5
0.942
High Assist Power


25th Layer
SiO2
175.7
1.059
High Assist Power


26th Layer
TiO2
115.0
1.067
High Assist Power


27th Layer
SiO2
189.1
1.140
High Assist Power


28th Layer
TiO2
116.5
1.081
High Assist Power


29th Layer
SiO2
191.2
1.153
High Assist Power


30th Layer
TiO2
119.4
1.108
High Assist Power


31st Layer
SiO2
189.9
1.145
High Assist Power


32nd Layer
TiO2
117.5
1.091
High Assist Power


33rd Layer
SiO2
193.2
1.165
High Assist Power


34th Layer
TiO2
116.7
1.083
High Assist Power


35th Layer
SiO2
184.2
1.110
High Assist Power


36th Layer
TiO2
119.1
1.105
High Assist Power


37th Layer
SiO2
44.8
0.270
High Assist Power


38th Layer
TiO2
11.8
0.110
High Assist Power


39th Layer
SiO2
82.9
0.500
High Assist Power


Emergence
Glass


Medium





n is a refractive index


total film thickness: 4726.25 nm


design wavelength: 967 nm






Experiment Result

1 Measurement of Surface Resistance (Sheet Resistance)

In measuring the surface resistance, the same apparatus as in Examples 9 to 12, Comparative Examples 21 to 26, and Comparative Examples 5 and 6 was used to measure the surface resistance. The result is shown in Table 22.
As shown in Table 22, it can be seen that the surface resistance in Examples 13 to 16 is low compared to Comparative Examples 27 to 32 or Reference Examples 7 and 8. The low surface resistance means that adhesion of dust or grit to the surface due to static electricity is reduced.
2 Relationship Between Surface Resistance and Total Film Thickness
FIG. 13 shows the relationship between a film thickness and surface resistance in Example 13.
In FIG. 13, Y0 is surface resistance (1.0×1015Ω/□) when all layers are formed through electron beam deposition with high assist power. Y1 is surface resistance (3.17×1012Ω/□) when only the outermost layer having a thickness of 70.29 nm is formed through electron beam deposition with low assist power (an acceleration voltage is 300 V and an acceleration current is 450 mV). Y2 is surface resistance (1.46×1011Ω/□) when the outermost layer and the second layer are formed through electron beam deposition with low assist power. Y3 is surface resistance (7.95×1010Ω/□) when the outermost layer to the third layer are formed through electron beam deposition with low assist power. Y4 is surface resistance (7.71×1010Ω/□) when the outermost layer to the fourth layer are formed through electron beam deposition with low assist power. Y5 is surface resistance (7.67×1010Ω/□) when the outermost layer to the fifth layer are formed through electron beam deposition with low assist power. Y6 is surface resistance (7.61×1010Ω/□) when the outermost layer to the sixth layer are formed through electron beam deposition with low assist power. Y39 is surface resistance (7.59×1010Ω/□) when all layers of the outermost layer to the 39th layer are formed through electron beam deposition with low assist power.
As shown in FIG. 13, it can be seen that, if the number of bonded layers including the outermost layer is large, the value of surface resistance is reduced. Meanwhile, it can be seen that, when the outermost layer to the fourth layer are formed through electron beam deposition with low assist power and when all layers (39 layers) including the outermost layer are formed through electron beam deposition with low assist power, the value of surface resistance is not changed so much. For this reason, in this example, it will suffice that the outermost layer to the fourth layer (film thickness 391.86 nm) are formed through electron beam deposition with low assist power.
Table 24 shows the results of dust-proof performance by the polyethylene powder method, the Kanto loam method, and the cotton linter method.
As shown in Table 24, in the case of the polyethylene powder method, it can be seen that the adhered dust quantity and the residual quantity in Examples 13 and 15 are small compared to Comparative Examples 27, 29, and 31 or Reference Example 7, and the adhered dust quantity and the residual quantity in Examples 14 and 16 are small compared to Comparative Examples 28 and 30 or Reference Example 8. As described above, the adhered dust quantity and the residual quantity in Examples 13 and 15 are small compared to Reference Example 7, and the adhered dust quantity and the residual quantity in Examples 14 and 16 are small compared to Reference Example 8 because Ta has small electronegativity compared to Ti.
The electronegativity can be interpreted as minimum energy necessary for separating foreign particles from the surface. If the value is small, foreign particles are easily separated from the surface. For this reason, the use of oxide containing an element having small electronegativity enables improvement in dust-proof performance.
With regard to Examples, Comparative Examples, and Reference Examples, it can be seen that the adhered dust quantity and the residual quantity in Examples 14 and 16, Comparative Examples 28, 30, and 32, and Reference Example 8 where the fluorine-containing organic silicon compound film 3 is provided are small compared to Examples 13 and 15, Comparative Examples 27, 29, and 31, and Reference Example 7 where no fluorine-containing organic silicon compound film 3 is provided. In the case of the Kanto loam method and the cotton linter method, similarly to the polyethylene powder method, with regard to Examples, Comparative Examples, and Reference Examples, it can be seen that the adhered dust quantity and the residual quantity in Examples 13 to 16 are small compared to Comparative Examples 27 to 32 or Reference Examples 7 and 8. The above results are obtained because the surface roughness is improved, and dust or grit is less likely to adhere to the surface.













TABLE 24










Fluorine-
Polyethylene





Film
containing
Powder
Kanto Loam
Cotton Linter


















Formation


Organic
Adhered

Adhered

Adhered




Method of
Acceleration
Acceleration
Silicon
dust
Residual
dust
Residual
dust
Residual



Outermost Layer
Voltage (V)
Current (mA)
Compound
quantity
Quantity
quantity
Quantity
quantity
Quantity





















Example 13
IAD
300
450
None
2.23%
0.38%
0.15%
0.01%
2.98%
0.58%


Example 14
IAD
300
450
Provided
0.05%
0.01%
0.17%
0.01%
1.97%
0.17%


Example 15
IAD
400
500
None
2.98%
0.51%
0.21%
0.01%
3.11%
0.63%


Example 16
IAD
400
500
Provided
0.08%
0.01%
0.22%
0.01%
2.29%
0.20%


Comparative
IAD
600
700
None
7.67%
1.05%
0.91%
0.10%
4.23%
0.89%


Example 27


Comparative
IAD
600
700
Provided
0.87%
0.17%
1.03%
0.10%
3.76%
0.36%


Example 28


Comparative
IAD
800
900
None
10.95%
2.68%
1.95%
0.41%
7.97%
1.32%


Example 29


Comparative
IAD
800
900
Provided
3.21%
0.96%
2.61%
0.87%
8.15%
0.67%


Example 30


Comparative
IAD
1000
1200
None
20.12%
4.11%
3.02%
0.79%
13.86%
2.34%


Example 31


Comparative
IAD
1000
1200
Provided
4.33%
1.49%
5.89%
1.30%
11.92%
1.08%


Example 32


Reference
IAD
300
450
None
3.01%
0.45%
0.27%
0.02%
2.58%
0.52%


Example 7


Reference
IAD
300
450
Provided
0.12%
0.01%
0.15%
0.01%
1.55%
0.12%


Example 8









Next, examples of an optical component having a titanium oxide layer and a silicon oxide layer will be described.
Optical Component having Titanium Oxide Layer and Silicon Oxide Layer
Examples 17 to 20 and Comparative Examples 33 to 40 corresponding to the optical component according to the first embodiment of the invention will be described.
With regard to a deposition experiment, a deposition instrument (product name: SID-1350) manufactured by SHINCRON Co., Ltd. was used. In the experiment, an anti-reflection film was manufactured on the surface of a sample having a predetermined shape, for example, white plate glass (refractive index n=1.52) having a diameter of 30 mm and a thickness of 0.3 mm under the conditions of Examples and Comparative Examples.
Example 17
In Example 17, the anti-reflection film 2 is formed on the substrate 1, and no fluorine-containing organic silicon compound film 3 is provided.
The layer configuration of the anti-reflection film 2 of Example 17 is shown in Tables 25 to 27. In these tables, the outermost layer 2S is the silicon oxide layer 2A which is a low-density layer having a density of 2.069 g/cm3 and a refractive index n of 1.449. The thickness of the outermost layer 2S is 86.0 nm, and the optical film thickness is 1.449×86.0 nm=124.614 nm. The relative value 4nd of the optical film thickness to the design wavelength (in Example 1, 510 nm) (hereinafter, simply referred to as the relative value to the design wavelength) is 0.979. That is, in design of the optical thin-film, since 1⁄4 of the design wavelength is used as a basis, the value of the optical thin-film nd (1.449×86.0) to the relevant value (127.5) becomes 0.979. The second layer 22 is the metal oxide layer 2B which is a low-density layer having a density of 4.65 g/cm3 and made of titanium oxide having a refractive index n of 2.466. The thickness of the second layer 22 is 102.7 nm, and the relative value 4nd to the design wavelength is 2.014. The third layer 23 is the silicon oxide layer 2A which is a low-density layer having a density of 2.069 g/cm3 and a refractive index n of 1.449. The thickness of the third layer 23 is 30.6 nm, and the relative value 4nd, to the design wavelength is 0.349. The fourth layer 24 is the metal oxide layer 2B which is a low-density layer having a density of 4.65 g/cm3 and made of titanium oxide having a refractive index n of 2.466. The thickness of the fourth layer 24 is 12.1 nm, and the relative value 4nd to the design wavelength is 0.237. The fifth layer 25 is the silicon oxide layer 2A which is a high-density layer having a density of 2.213 g/cm3 and a refractive index n of 1.481. The thickness of the fifth layer 25 is 136.6 nm, and the relative value 4nd to the design wavelength is 1.573. The total thickness of the outermost layer 2S to the fifth layer 25 is 367.9 nm.
In forming the anti-reflection film 2 configured as above on the substrate 1, in Example 17, the outermost layer 2S to the fourth layer 24 are formed through ion-assisted electron beam deposition (IAD) with low assist power. The film formation temperature is 150° C. When a low-density layer is formed as the silicon oxide layer 2A, the vacuum pressure is 1.8×10−2 Pa. Assist power has an acceleration voltage of 300 V and an acceleration current of 450 mA. When a titanium oxide is formed as the metal oxide layer 2B, the vacuum pressure is 2.1×10−2 Pa. Assist power has an acceleration voltage of 300 V and an acceleration current of 450 mA. Thus, the surface roughness of the outermost layer 2S becomes 0.6 nm to 0.7 nm. The fifth layer 25 is formed through ion-assisted electron beam deposition (IAD) with high assist power. In this case, assist power has an acceleration voltage of 1000 Vm and an acceleration current of 1200 mA.
Example 18
Example 18 is different from Example 17 in that the fluorine-containing organic silicon compound film 3 is provided on the anti-reflection film 2.
With regard to the fluorine-containing organic silicon compound film 3, for example, as a deposition source, a material is used which is obtained by diluting a fluorine-containing organic silicon compound (product name: KY-130) manufactured by Shin-Etsu Chemical Co., Ltd. with a fluorine-based solvent (manufactured by Sumitomo 3M Ltd.: Novec HFE-7200) to prepare a solution having a solid content concentration of 3%, impregnating 1 g of the solution into a porous ceramic pellet, and performing drying.
Example 19
Example 19 is different from Example 17 in terms of assist power for forming a low-density layer. That is, in Example 19, assist power is low assist power having an acceleration voltage of 400 V and an acceleration current of 500 mA. For this reason, the low-density layers constituting the silicon oxide layer 2A serving as the outermost layer 2S and the third layer 23 have a density of 2.086 g/cm3, and the low-density layers constituting the second layer 22 and the fourth layer 24, that is, the metal oxide layers 2B made of titanium oxide have a density of 4.69 g/cm3. The density of the fifth layer 25 is the same as in Example 17.
Example 20
Example 20 is different from Example 19 in that the fluorine-containing organic silicon compound film 3 is provided on the anti-reflection film 2.
Comparative Example 33
Comparative Example 33 is different from Example 17 in terms of assist power for forming a low-density layer. That is, in Comparative Example 33, the outermost layer 2S to the fourth layer 24 are formed through ion-assisted electron beam deposition (IAD) with intermediate assist power having an acceleration voltage of 600 V and an acceleration current of 700 mA. For this reason, the low-density layers constituting the silicon oxide layer serving as the outermost layer and the third layer have a density of 2.172 g/cm3, and the low-density layers constituting the second layer and the fourth layer, that is, the metal oxide layers 2B made of titanium oxide have a density of 4.79 g/cm3. In Comparative Example 33, the surface roughness of the outermost layer is 0.62 nm to 0.72 nm, which is greater than in Examples 17 to 20.
Comparative Example 34
Comparative Example 34 is different from Comparative Example 33 in that the fluorine-containing organic silicon compound film is provided on the anti-reflection film.
Comparative Example 35
Comparative Example 35 is different from Example 17 in terms of assist power for forming a low-density layer. That is, in Comparative Example 35, the outermost layer 2S to the fourth layer 24 are formed through ion-assisted electron beam deposition (IAD) with intermediate assist power having an acceleration voltage of 800 V and an acceleration current of 900 mA. For this reason, the low-density layers constituting the silicon oxide layer serving as the outermost layer and the third layer have a density of 2.201 g/cm3, and the low-density layers constituting the second layer and the fourth layer, that is, the metal oxide layers 2B made of titanium oxide have a density of 4.89 g/cm3. In Comparative Example 35, the surface roughness of the outermost layer is 0.65 nm to 0.75 nm, which is greater than in Examples 17 to 20.
Comparative Example 36
Comparative Example 36 is different from Comparative Example 35 in that the fluorine-containing organic silicon compound film is provided on the anti-reflection film.
Comparative Example 37
Comparative Example 37 is different from Example 17 in terms of assist power for forming a low-density layer. That is, in Comparative Example 37, all layers are formed through ion-assisted electron beam deposition (IAD) with high assist power having an acceleration voltage of 1000 V and an acceleration current of 1200 mA. For this reason, the low-density layers constituting the silicon oxide layer serving as the outermost layer and the third layer have a density of 2.213 g/cm3, and the low-density layers constituting the second layer and the fourth layer, that is, the metal oxide layers 2B made of titanium oxide have a density of 4.87 g/cm3. In Comparative Example 37, the surface roughness of the outermost layer is 0.67 nm to 0.77 nm, which is greater than in Examples 17 to 20.
Comparative Example 38
Comparative Example 38 is different from Comparative Example 37 in that the fluorine-containing organic silicon compound film is provided on the anti-reflection film.
Comparative Example 39
Comparative Example 39 has the same layer configuration as in Example 17, but, unlike Example 17, the film formation method is the same as in the related art described in Japanese Patent No. 4207083. That is, in Comparative Example 39, the outermost layer is formed through electron deposition (EB) without using ion assist, and the film formation method for the layers other than the outermost layer is the same as in Comparative Example 37. The second layer to the fifth layer were formed through ion-assisted electron beam deposition (IAD) with high assist power having an acceleration voltage of 1000 V and an acceleration current of 1200 mA. The vacuum pressured at the time of forming silicon oxide for the outermost layer is 8.0×10−3 Pa. For this reason, the silicon oxide layer of the outermost layer has a density of 2.037 g/cm3. In Comparative Example 39, the surface roughness of the outermost layer is 0.8 nm to 0.95 nm, which is greater than in Examples 17 to 20.
Comparative Example 40
Comparative Example 40 is different from Comparative Example 39 in that the fluorine-containing organic silicon compound film is provided on the anti-reflection film.
With the above, it can be seen that the surface roughness of the outermost layer corresponds to assist power when the outermost layer is formed. That is, in Examples 17 to 20, the outermost layer is formed with low assist power having an acceleration voltage of 300 V to 400 V (an acceleration current of 450 mA to 500 mA), such that the surface roughness of the outermost layer becomes 0.60 nm to 0.70 nm. Meanwhile, in Comparative Examples 33 to 36, the outermost layer is formed with intermediate assist power having an acceleration voltage of 600 V to 800 V (an acceleration current of 700 mA to 900 mA), such that the surface roughness of the outermost layer becomes 0.62 nm to 0.75 nm. In Comparative Examples 37 and 38, the outermost layer is formed with high assist power having an acceleration voltage of 1000 V (an acceleration current of 1200 mA), such that the surface roughness of the outermost layer becomes 0.67 nm to 0.77 nm.












TABLE 25







Layer
Material
d (nm)
4nd





















Incidence Medium
Air





Outermost Layer
SiO2
86.0
0.979



Second Layer
TiO2
102.7
2.014



Third Layer
SiO2
30.6
0.349



Fourth Layer
TiO2
12.1
0.237



Fifth Layer
SiO2
136.6
1.573



Emergence Medium
Glass







n is a refractive index



total film thickness: 367.9 nm



design wavelength: 510 nm





















TABLE 26







Film









Formation





SiO2



Method of
Film




Refractive



First to
Formation
SiO2 Rate
SiO2 Vaccum
SiO2 Assist
SiO2 Density
Index



Fourth Layers
Temperature
(Å/sec)
Pressure (O2)
Power
(g/cm3)
(at 550 nm)
























Example 17, 18
IAD
150° C.
7
1.8E−2 Pa
300
V
2.069
1.449







450
mA


Example 19, 20
IAD
150° C.
7
1.8E−2 Pa
400
V
2.086
1.453







500
mA


Comparative
IAD
150° C.
7
1.8E−2 Pa
600
V
2.172
1.461


Example 33, 34




700
mA


Comparative
IAD
150° C.
7
1.8E−2 Pa
800
V
2.201
1.473


Example 35, 36




900
mA


Comparative
IAD
150° C.
7
1.8E−2 Pa
1000
V
2.213
1.481


Example 37, 38




1200
mA














Comparative
EB
150° C.
7
8.0E−3 Pa
—
2.037
1.44


Example 39, 40


























TABLE 27







Film











Formation



Method of





TiO2



First to
Film

TiO2 Vaccum
TiO2
TiO2
Refractive
Surface
Surface



Fourth
Formation
TiO2 Rate
Pressure
Assist
Density
Index
Roughness
Resistance



Layers
Temperature
(Å/sec)
(O2)
Power
(g/cm3)
(at 550 nm)
(nm)
(Ω/□)


























Example 17, 18
IAD
150° C.
3
2.1E−2 Pa
300
V
4.65
2.466
0.6 to 0.7
5.77E+10







450
mA


Example 19, 20
IAD
150° C.
3
2.1E−2 Pa
400
V
4.69
2.473
0.6 to 0.7
2.23E+11







500
mA


Comparative
IAD
150° C.
3
2.1E−2 Pa
600
V
4.79
2.487
0.62 to 0.72
4.85E+12


Example 33, 34




700
mA


Comparative
IAD
150° C.
3
2.1E−2 Pa
800
V
4.89
2.497
0.65 to 0.75
1.00E+15


Example 35, 36




900
mA


Comparative
IAD
150° C.
3
2.1E−2 Pa
1000
V
4.87
2.489
0.67 to 0.77
1.00E+15


Example 37, 38




1200
mA


Comparative
IAD
150° C.
3
2.1E−2 Pa
1000
V
4.87
2.489
 0.8 to 0.95
8.16E+12


Example 39, 40




1200
mA









Experiment Result

1 Measurement of surface resistance (sheet resistance)

In measuring the surface resistance, the surface resistance measurement instrument 504 shown in FIG. 7A is used. The surface resistance measurement instrument 504 and the stage 506 are configured as above, and the measurement condition and the measurement environment are the same as in the above-described experiment.
With regard to Examples and Comparative Examples, the surface resistance of the sample was measured. The results are shown in Table 27. A representative example from among the experiment results is shown in FIG. 14 as a graph.
FIG. 14 shows Example 17 where deposition is performed with low assist power, Comparative Example 37 where deposition is performed with high assist power, and Comparative Example 39 corresponding to the related art in Example 17 and Comparative Examples 37 and 39, no fluorine-containing organic silicon compound film is provided on the surface.
As shown in FIG. 14, it can be seen that the surface resistance in Example 17 is low compared to Comparative Examples 37 and 39. Even with reference to Table 27 for other Examples and Comparative Examples, it can be seen that the surface resistance in Examples 17 to 20 is low compared to Comparative Examples 37 to 40. The low surface resistance means that adhesion of dust or grit due to static electricity is reduced.
2 Relationship Between Surface Resistance and Total Film Thickness
FIG. 15 shows the relationship between a film thickness and surface resistance in Example 1.
In FIG. 15, X0 is surface resistance (1.0×1015Ω/□) when all layers are formed through electron beam deposition with high assist power. X1 is surface resistance (3.17×1012Ω/□) when only the outermost layer having a thickness of 86.0 nm is formed through electron beam deposition with low assist power (an acceleration voltage is 300 V and an acceleration current is 450 mV). X2 is surface resistance (1.44×1011Ω/□) when the outermost layer and the second layer are formed through electron beam deposition with low assist power. X3 is surface resistance (7.28×1010Ω/□) when the outermost layer to the third layer are formed through electron beam deposition with low assist power. X4 is surface resistance (5.77×1010Ω/□) when the outermost layer to the fourth layer are formed through electron beam deposition with low assist power. X5 is surface resistance (5.74×1010Ω/□) when all layers are formed through electron beam deposition with low assist power. As shown in FIG. 15, it can be seen that, if a large number of bonded layers including the outermost layer are formed through electron beam deposition with low assist power, the value of surface resistance is reduced. Meanwhile, it can be seen that, when the outermost layer to the fourth layer are formed through electron beam deposition with low assist power and when all layers (five layers) including the outermost layer are formed through electron beam deposition with low assist power, the value of surface resistance is not changed so much. For this reason, in this example, it will suffice that the outermost layer to the fourth layer (film thickness 240 nm) are formed through electron beam deposition with low assist power.
3 Charge-Through
With regard to charge-through, the outermost layer of the sample is frictionally charged, and the residual charge quantity (relative value) in the outermost layer is displayed over time. The charge-through is shown in FIG. 16. In FIG. 16, a graph A shows Comparative Example 37, a graph B shows Comparative Example 39, and a graph C shows Example 17. For the measurement of surface charges, the surface electrometer 500 shown in FIG. 7B is used. The surface electrometer 500 is the same as that used in the above-described experiment, and the distance between the probe 501 and the surface of the sample 502 of a filter is 10 mm. The stage 503 on which the sample 502 is placed is made of metal, and measurement is performed in a state of being grounded. The measurement environment is the same as in the above-described experiment.
As shown in FIG. 16, in the graph C of Example 17, the residual charge quantity over time is small compared to the graph A of Comparative Example 37 or the graph B of Comparative Example 39. As a result, it can be seen that, in Example 17, adhesion of dust or grit due to static electricity is reduced compared to Comparative Example 37 or Comparative Example 39.
4 Dust-Proof Performance
A dust-proof performance test was performed by 4-1 polyethylene powder method, 4-2 Kanto loam method, and 4-3 cotton linter method. The detailed specification of these methods is as described above.
The results of dust-proof performance by these methods are shown in Table 28.
Table 28 shows the results of 4-1 polyethylene powder method, 4-2 Kanto loam method, and 4-3 cotton linter method.
As shown in Table 28, in the case of the polyethylene powder method, it can be seen that the adhered dust quantity and the residual quantity in Examples 17 and 18 are small compared to Comparative Examples 33 to 36. With regard to Examples and Comparative Examples, it can also be seen that the adhered dust quantity and the residual quantity in Examples 18 and 20 and Comparative Examples 34, 36, 38, and 40 where the fluorine-containing organic silicon compound film 3 is provided are small compared to Examples 17 and 19 and Comparative Examples 33, 35, 37, and 39 where no fluorine-containing organic silicon compound film 3 is provided. In the case of the Kanto loam method and the cotton linter method, similarly to the polyethylene powder method, with regard to Examples and Comparative Examples, it can be seen that the adhered dust quantity and the residual quantity in Examples 17 and 18 are small compared to Comparative Examples 33 to 36. It can also be seen that the adhered dust quantity and the residual quantity in Examples 18 and 20 and Comparative Examples 34, 36, 38, and 40 where the fluorine-containing organic silicon compound film 3 is provided are small compared to Examples 17 and 19 and Comparative Examples 33, 35, 37, and 39 where no fluorine-containing organic silicon compound film 3 is provided. The above results are obtained because the surface roughness is improved, and dust or grit is less likely to adhere to the surface.













TABLE 28










Fluorine-
Polyethylene





Film
containing
Powder
Kanto Loam
Cotton Linter


















Formation


Organic
Adhered

Adhered

Adhered




Method of
Acceleration
Acceleration
Silicon
dust
Residual
dust
Residual
dust
Residual



Outermost Layer
Voltage (V)
Current (mA)
Compound
quantity
Quantity
quantity
Quantity
quantity
Quantity





















Example 17
IAD
300
450
None
3.78%
0.59%
0.29%
0.02%
2.87%
0.63%


Example 18
IAD
300
450
Provided
0.16%
0.01%
0.19%
0.01%
1.84%
0.14%


Example 19
IAD
400
500
None
3.94%
0.65%
0.35%
0.03%
3.12%
0.65%


Example 20
IAD
400
500
Provided
0.17%
0.02%
0.31%
0.02%
1.97%
0.16%


Comparative
IAD
600
700
None
8.95%
1.78%
1.04%
0.09%
4.58%
0.97%


Example 33


Comparative
IAD
600
700
Provided
1.02%
0.19%
8.97%
2.45%
4.47%
0.41%


Example 34


Comparative
IAD
800
900
None
15.20%
3.02%
2.20%
0.49%
9.93%
1.89%


Example 35


Comparative
IAD
800
900
Provided
3.23%
0.98%
13.45%
6.28%
10.50%
0.65%


Example 36


Comparative
IAD
1000
1200
None
17.01%
3.50%
2.73%
0.54%
10.83%
2.13%


Example 37


Comparative
IAD
1000
1200
Provided
3.78%
1.08%
14.40%
7.01%
11.20%
0.71%


Example 38


Comparative
EB
0
0
None
7.74%
1.34%
1.06%
0.09%
3.82%
0.81%


Example 39


Comparative
EB
0
0
Provided
0.93%
0.12%
12.90%
5.92%
4.58%
0.35%


Example 40









Next, Examples 21 to 24 and Comparative Examples 41 to 48 corresponding to the optical component according to the second embodiment of the invention will be described. With regard to the deposition experiment, similarly to the experiment of Examples 17 to 20 and Comparative Examples 33 to 40, the deposition instrument manufactured by SHINCRON Co., Ltd. was used to manufacture an anti-reflection film on the surface of white plate glass having a predetermined shape under the conditions of Examples and Comparative Examples.
Example 21
In Example 21, the IR-UV cut film 4 is formed on the substrate 1, and no fluorine-containing organic silicon compound film 3 is provided.
The layer configuration of the IR-UV cut film 4 of Example 21 is shown in Tables 29 to 33. Table 29 shows the relationship between the material of each layer and the film thickness. Tables 30 and 31 show the film formation condition of the outermost layer, and the like. Tables 32 and 33 show the film formation condition of the fifth layer to the 39th layer, and the like. In Example 21, the design wavelength is 967 nm.
In Tables 29 to 31, the outermost layer 2S is the silicon oxide layer 2A which is a low-density layer having a density of 2.069 g/cm3 and a refractive index n of 1.449. The thickness of the outermost layer 2S is 71.8 nm, and the relative value 4nd to the design wavelength is 0.433. The second layer 22 is the metal oxide layer 2B which is a low-density layer having a density of 4.65 g/cm3 and made of titanium oxide having a refractive index n of 2.466. The thickness of the second layer 22 is 84.2 nm, and the relative value 4nd to the design wavelength is 0.782. The third layer is the silicon oxide layer 2A which is a low-density layer having a density of 2.069 g/cm3 and a refractive index n of 1.449. The thickness of the third layer is 147.2 nm, and the relative value 4nd to the design wavelength is 0.887. The fourth layer is the metal oxide layer 2B which is a low-density layer having a density of 4.65 g/cm3 and made of titanium oxide having a refractive index n of 2.466. The thickness of the fourth layer is 83.6 nm, and the relative value 4nd to the design wavelength is 0.776.
In Tables 29, 32, and 33, the fifth layer is the silicon oxide layer 2A which is a high-density layer having a density of 2.213 g/cm3 and a refractive index n of 1.481. The thickness of the fifth layer is 140.2 nm, and the relative value 4nd to the design wavelength is 0.845. The sixth layer is the metal oxide layer 2B which is a high-density layer having a density of 4.87 g/cm3 and made of titanium oxide having a refractive index n of 2.489. The thickness of the sixth layer is 83.1 nm, and the relative value 4nd to the design wavelength is 0.772. Subsequently, the seventh layer to the 39th layer have the same configuration as described in Tables 1, 9, and 10. The total thickness of the outermost layer 2S to the 39th layer is 4726.25 nm.
In forming the IR-UV cut film 4 configured as above on the substrate 1, in Example 21, the outermost layer 2S to the fourth layer are formed through ion-assisted electron beam deposition (IAD) with low assist power. The film formation temperature is 150° C. When a low-density layer is formed as the silicon oxide layer 2A, the vacuum pressure is 1.8×10−2 Pa. Assist power has an acceleration voltage of 300 V and an acceleration current of 450 mA. When the metal oxide layer 2B is formed of titanium oxide, the vacuum pressure is 2.1×10−2 Pa. Assist power has an acceleration voltage of 300 V and an acceleration current of 450 mA. The fifth layer to the 39th layer are formed through ion-assisted electron beam deposition (IAD) with high assist power. In this case, in the same manner as when the silicon oxide layer 2A is formed and when the metal oxide layer 2B is formed of titanium oxide, assist power has an acceleration voltage of 1000 Vm and an acceleration current of 1200 mA. The surface roughness of the outermost layer 2S is 0.6 nm to 0.7 nm.
Example 22
Example 22 is different from Example 21 in that the fluorine-containing organic silicon compound film 3 is provided on the IR-UV cut film 4.
The fluorine-containing organic silicon compound film 3 is the same as in Example 18.
Example 23
Example 23 is different from Example 21 in terms of assist power for forming a low-density layer. That is, in Example 23, assist power is low assist power having an acceleration voltage of 400 V and an acceleration current of 500 mA. For this reason, the low-density layers constituting the silicon oxide layer 2A serving as the outermost layer 2S and the third layer have a density of 2.086 g/cm3, and the low-density layers constituting the second layer 22 and the fourth layer, that is, the metal oxide layers 2B made of titanium oxide have a density of 4.69 g/cm3. The fifth layer 25 to the 39th layer have the same density as in Example 1.
Example 24
Example 24 is different from Example 23 in that the fluorine-containing organic silicon compound film 3 is provided on the IR-UV cut film 4.
The fluorine-containing organic silicon compound film 3 is the same as in Example 18.
Comparative Example 41
Comparative Example 41 is different from Example 21 in terms of assist power for forming a low-density layer. That is, in Comparative Example 41, the outermost layer 2S to the fourth layer 24 are formed through ion-assisted electron beam deposition (IAD) with intermediate assist power having an acceleration voltage of 600 V and an acceleration current of 700 mA. For this reason, the low-density layers constituting the silicon oxide thin-film serving as the outermost layer and the third layer have a density of 2.172 g/cm3, and the low-density layers constituting the second layer and the fourth layer, that is, the metal oxide layers 2E made of titanium oxide have a density of 4.79 g/cm3.
In Comparative Example 41, the surface roughness of the outermost layer is 0.62 nm to 0.72 nm, which is great compared to Examples 21 to 24.
Comparative Example 42
Comparative Example 42 is different from Comparative Example 41 in that the fluorine-containing organic silicon compound film 3 is provided on the IR-UV cut film 4.
Comparative Example 43
Comparative Example 43 is different from Example 21 in terms of assist power for forming a low-density layer. That is, in Comparative Example 43, the outermost layer 2S to the fourth layer 24 are formed through ion-assisted electron beam deposition (IAD) with intermediate assist power having an acceleration voltage of 800 V and an acceleration current of 900 mA. For this reason, the low-density layers constituting the silicon oxide layer serving as the outermost layer and the third layer have a density of 2.201 g/cm3, and the low-density layers constituting the second layer and the fourth layer, that is, the metal oxide layers 2B made of titanium oxide have a density of 4.89 g/cm3.
In Comparative Example 43, the surface roughness of the outermost layer is 0.65 nm to 0.75 nm, which is great compared to Examples 21 to 24.
Comparative Example 44
Comparative Example 44 is different from Comparative Example 43 in that the fluorine-containing organic silicon compound film is provided on the IR-UV cut film.
Comparative Example 45
Comparative Example 45 is different from Example 21 in terms of assist power for forming a low-density layer. That is, in Comparative Example 45, all layers are formed through ion-assisted electron beam deposition (IAD) with high assist power having an acceleration voltage of 1000 V and an acceleration current of 1200 mA. For this reason, the low-density layers constituting the silicon oxide thin-film serving as the outermost layer and the third layer have a density of 2.213 g/cm3, and the low-density layers constituting the second layer and the fourth layer, that is, the metal oxide layers 2B made of titanium oxide have a density of 4.87 g/cm3.
In Comparative Example 45, the surface roughness of the outermost layer is 0.67 nm to 0.77 nm, which is great compared to Examples 21 to 24.
Comparative Example 46
Comparative Example 46 is different from Comparative Example 45 in that the fluorine-containing organic silicon compound film is provided on the IR-UV cut film.
Comparative Example 47
Comparative Example 47 has the same configuration as in Example 21, but, unlike Example 21, the film formation method is the same as in the related art described in Japanese Patent No. 4207083. That is, in Comparative Example 47, the outermost layer is formed through electron deposition (EB) without using ion assist, and the film formation method of the layers other than the outermost layer is the same as in Comparative Example 37. The second layer to the 39th layer were formed through ion-assisted electron beam deposition (IAD) with high assist power having an acceleration voltage of 1000 V and an acceleration current of 1200 Tull. The vacuum pressure at the time of forming silicon oxide for the outermost layer is 8.0×10−3 Pa. For this reason, the density of the silicon oxide layer is 2.037 g/cm3. In Comparative Example 47, the surface roughness of the outermost layer is 0.8 nm to 0.95 nm, which is great compared to Examples 21 to 24.
Comparative Example 48
Comparative Example 48 is different from Comparative Example 47 in that the fluorine-containing organic silicon compound film is provided on the IR-UV cut film.











TABLE 29





Layer
Material
d (nm)
4nd
Film Formation Condition



















Incidence
Air





Medium


Outermost
SiO2
71.8
0.433
Low Assist Power


Layer


Second Layer
TiO2
84.2
0.782
Low Assist Power


Third Layer
SiO2
147.2
0.887
Low Assist Power


Fourth Layer
TiO2
83.6
0.776
Low Assist Power


Fifth Layer
SiO2
140.2
0.845
High Assist Power


Sixth Layer
TiO2
83.1
0.772
High Assist Power


Seventh Layer
SiO2
139.2
0.839
High Assist Power


Eighth Layer
TiO2
81.4
0.756
High Assist Power


Ninth Layer
SiO2
139.8
0.843
High Assist Power


Tenth Layer
TiO2
81.1
0.753
High Assist Power


11th Layer
SiO2
139.4
0.841
High Assist Power


12th Layer
TiO2
81.0
0.752
High Assist Power


13th Layer
SiO2
139.4
0.841
High Assist Power


14th Layer
TiO2
82.0
0.761
High Assist Power


15th Layer
SiO2
140.8
0.849
High Assist Power


16th Layer
TiO2
83.3
0.773
High Assist Power


17th Layer
SiO2
143.2
0.863
High Assist Power


18th Layer
TiO2
86.7
0.805
High Assist Power


19th Layer
SiO2
150.6
0.908
High Assist Power


20th Layer
TiO2
100.4
0.932
High Assist Power


21st Layer
SiO2
179.7
1.083
High Assist Power


22nd Layer
TiO2
110.0
1.021
High Assist Power


23rd Layer
SiO2
169.7
1.023
High Assist Power


24th Layer
TiO2
101.5
0.942
High Assist Power


25th Layer
SiO2
175.7
1.059
High Assist Power


26th Layer
TiO2
115.0
1.067
High Assist Power


27th Layer
SiO2
189.1
1.140
High Assist Power


28th Layer
TiO2
116.5
1.081
High Assist Power


29th Layer
SiO2
191.2
1.153
High Assist Power


30th Layer
TiO2
119.4
1.108
High Assist Power


31st Layer
SiO2
189.9
1.145
High Assist Power


32nd Layer
TiO2
117.5
1.091
High Assist Power


33rd Layer
SiO2
193.2
1.165
High Assist Power


34th Layer
TiO2
116.7
1.083
High Assist Power


35th Layer
SiO2
184.2
1.110
High Assist Power


36th Layer
TiO2
119.1
1.105
High Assist Power


37th Layer
SiO2
44.8
0.270
High Assist Power


38th Layer
TiO2
11.8
0.110
High Assist Power


39th Layer
SiO2
82.9
0.500
High Assist Power


Emergence
Glass


Medium





n is a refractive index


total film thickness: 4726.25 nm


design wavelength: 967 nm





















TABLE 30







Film









Formation





SiO2



Method of
Film




Refractive



First to
Formation
SiO2 Rate
SiO2 Vacuum
SiO2 Assist
SiO2 Density
Index



Fourth Layers
Temperature
(Å/sec)
Pressure (O2)
Power
(g/cm3)
(at 550 nm)
























Example 21, 22
IAD
150° C.
7
1.8E−2 Pa
300
V
2.069
1.449







450
mA


Example 23, 24
IAD
150° C.
7
1.8E−2 Pa
400
V
2.086
1.453







500
mA


Comparative
IAD
150° C.
7
1.8E−2 Pa
600
V
2.172
1.461


Example 41, 42




700
mA


Comparative
IAD
150° C.
7
1.8E−2 Pa
800
V
2.201
1.473


Example 43, 44




900
mA


Comparative
IAD
150° C.
7
1.8E−2 Pa
1000
V
2.213
1.481


Example 45, 46




1200
mA














Comparative
EB
150° C.
7
8.0E−3 Pa
—
2.037
1.44


Example 47, 48
























TABLE 31







Film









Formation





TiO2



Method of
Film




Refractive



First to
Formation
TiO2 Rate
TiO2 Vacuum
TiO2 Assist
TiO2 Density
Index



Fourth Layers
Temperature
(Å/sec)
Pressure (O2)
Power
(g/cm3)
(at 550 nm)
























Example 21, 22
IAD
150° C.
3
2.1E−2 Pa
300
V
4.65
2.466







450
mA


Example 23, 24
IAD
150° C.
3
2.1E−2 Pa
400
V
4.69
2.473







500
mA


Comparative
IAD
150° C.
3
2.1E−2 Pa
600
V
4.79
2.487


Example 41, 42




700
mA


Comparative
IAD
150° C.
3
2.1E−2 Pa
800
V
4.89
2.497


Example 43, 44




900
mA


Comparative
IAD
150° C.
3
2.1E−2 Pa
1000
V
4.87
2.489


Example 45, 46




1200
mA


Comparative
IAD
150° C.
3
2.1E−2 Pa
1000
V
4.87
2.489


Example 47, 48




1200
mA
























TABLE 32







Film









Formation



Method of



Fifth Layer





SiO2



and
Film




Refractive



Subsequent
Formation
SiO2 Rate
SiO2 Vacuum
SiO2 Assist
SiO2 Density
Index



Layers
Temperature
(Å/sec)
Pressure (O2)
Power
(g/cm3)
(at 550 nm)























Example 21, 22
IAD
150° C.
7
1.8E−2 Pa
1000 V
2.213
1.481







1200 mA


Example 23, 24
IAD
150° C.
7
1.8E−2 Pa
1000 V
2.213
1.481







1200 mA


Comparative
IAD
150° C.
7
1.8E−2 Pa
1000 V
2.213
1.481


Example 41, 42




1200 mA


Comparative
IAD
150° C.
7
1.8E−2 Pa
1000 V
2.213
1.481


Example 43, 44




1200 mA


Comparative
IAD
150° C.
7
1.8E−2 Pa
1000 V
2.213
1.481


Example 45, 46




1200 mA


Comparative
IAD
150° C.
7
1.8E−2 Pa
1000 V
2.213
1.481


Example 47, 48




1200 mA


























TABLE 33







Film











Formation



Method of



Fifth Layer


TiO2


TiO2



and
Film
TiO2
Vacuum

TiO2
Refractive
Surface
Surface



Subsequent
Formation
Rate
Pressure
TiO2 Assist
Density
Index
Roughness
Resistance



Layers
Temperature
(Å/sec)
(O2)
Power
(g/cm3)
(at 550 nm)
(nm)
(Ω/□)

























Example 21, 22
IAD
150° C.
3
2.1E−2 Pa
1000 V
4.87
2.489
0.6 to 0.7
6.87E+10







1200 mA


Example 23, 24
IAD
150° C.
3
2.1E−2 Pa
1000 V
4.87
2.489
0.6 to 0.7
2.87E+11







1200 mA


Comparative
IAD
150° C.
3
2.1E−2 Pa
1000 V
4.87
2.489
0.62 to 0.72
2.35E+13


Example 41, 42




1200 mA


Comparative
IAD
150° C.
3
2.1E−2 Pa
1000 V
4.87
2.489
0.65 to 0.75
1.00E+15


Example 43, 44




1200 mA


Comparative
IAD
150° C.
3
2.1E−2 Pa
1000 V
4.87
2.489
0.67 to 0.77
1.00E+15


Example 45, 46




1200 mA


Comparative
IAD
150° C.
3
2.1E−2 Pa
1000 V
4.87
2.489
 0.8 to 0.95
7.26E+12


Example 47, 48




1200 mA









Experiment Result

1 Measurement of Surface Resistance (Sheet Resistance)

In measuring the surface resistance, the same apparatus as in Examples 17 to 20 and Comparative Examples 33 to 40 was used to measure the surface resistance. The result is shown in Table 33.
As shown in Table 33, it can be seen that the surface resistance in Examples 21 to 24 is low compared to Comparative Examples 41 to 48. The low surface resistance means that adhesion of dust or grit due to static electricity is reduced.
2 Relationship Between Surface Resistance and Total Film Thickness
FIG. 17 shows the relationship between a film thickness and surface resistance in Example 21.
In FIG. 17, Y0 is surface resistance (1.0×1015Ω/□) when all layers are formed through electron beam deposition with high assist power. Y1 is surface resistance (3.17×1012Ω/□) when only the outermost layer having a thickness of 71.8 nm is formed through electron beam deposition with low assist power (an acceleration voltage is 300 V and an acceleration current is 450 mV). Y2 is surface resistance (1.44×1011Ω/□) when the outermost layer and the second layer are formed through electron beam deposition with low assist power. Y3 is surface resistance (7.28×1010Ω/□) when the outermost layer to the third layer are formed through electron beam deposition with low assist power. Y4 is surface resistance (6.87×1010Ω/□) when the outermost layer to the fourth layer are formed through electron beam deposition with low assist power. Y5 is surface resistance (6.85×1010Ω/□) when the outermost layer to the fifth layer are formed through electron beam deposition with low assist power. Y6 is surface resistance (6.81×1010Ω/□) when the outermost layer to the sixth layer are formed through electron beam deposition with low assist power. Y39 is surface resistance (6.75×1010Ω/□) when all layers of the outermost layer to the 39th layer are formed through electron beam deposition with low assist power.
As shown in FIG. 17, it can be seen that, if the number of bonded layers including the outermost layer is great, the value of surface resistance is reduced. Meanwhile, it can be seen that, when the outermost layer to the fourth layer are formed through electron beam deposition with low assist power and when all layers (39 layers) including the outermost layer are formed through electron beam deposition with low assist power, the value of surface resistance is not changed so much. For this reason, in this example, it will suffice that the outermost layer to the fourth layer (film thickness 386.8 nm) are formed through electron beam deposition with low assist power.
Table 34 shows the results of dust-proof performance by the polyethylene powder method, the Kanto loam method, and the cotton linter method.
As shown in Table 34, in the case of the polyethylene powder method, it can be seen that the adhered dust quantity and the residual quantity in Examples 21 and 23 are small compared to Comparative Examples 41, 43, 45, and 47, and the adhered dust quantity and the residual quantity in Examples 22 and 24 are small compared to Comparative Examples 42, 44, 46, and 48. With regard to Examples and Comparative Examples, it can be seen that the adhered dust quantity and the residual quantity in Examples 22 and 24 and Comparative Examples 42, 44, 46, and 48 where the fluorine-containing organic silicon compound film 3 is provided are small compared to Examples 21 and 23 and Comparative Examples 41, 43, 45, and 47 where no fluorine-containing organic silicon compound film 3 is provided. In the case of the Kanto loam method and the cotton linter method, similarly to the polyethylene powder method, with regard to Examples and Comparative Examples, it can be seen that the adhered dust quantity and the residual quantity in Examples 21 to 24 are small compared to Comparative Examples 41 to 48. The above results are obtained because the surface roughness is improved and dust or grit is less likely to adhere to the surface.













TABLE 34










Fluorine-
Polyethylene





Film
containing
Powder
Kanto Loam
Cotton Linter


















Formation


Organic
Adhered

Adhered

Adhered




Method of
Acceleration
Acceleration
Silicon
dust
Residual
dust
Residual
dust
Residual



Outermost Layer
Voltage (V)
Current (mA)
Compound
quantity
Quantity
quantity
Quantity
quantity
Quantity





















Example 21
IAD
300
450
None
3.01%
0.45%
0.27%
0.02%
2.58%
0.52%


Example 22
IAD
300
450
Provided
0.12%
0.01%
0.15%
0.01%
1.55%
0.12%


Example 23
IAD
400
500
None
3.88%
0.63%
0.38%
0.03%
3.43%
0.68%


Example 24
IAD
400
500
Provided
0.16%
0.02%
0.33%
0.02%
1.94%
0.17%


Comparative
IAD
600
700
None
8.12%
1.54%
1.23%
0.08%
4.67%
0.95%


Example 41


Comparative
IAD
600
700
Provided
0.98%
0.17%
6.78%
2.10%
4.93%
0.44%


Example 42


Comparative
IAD
800
900
None
17.50%
3.22%
2.76%
0.87%
10.98%
2.03%


Example 43


Comparative
IAD
800
900
Provided
4.02%
1.22%
20.97%
9.67%
11.23%
2.17%


Example 44


Comparative
IAD
1000
1200
None
21.18%
3.98%
3.47%
1.23%
15.67%
2.98%


Example 45


Comparative
IAD
1000
1200
Provided
4.92%
1.73%
31.56%
15.46%
14.73%
2.63%


Example 46


Comparative
EB
0
0
None
8.94%
1.87%
1.03%
0.27%
5.89%
1.76%


Example 47


Comparative
EB
0
0
Provided
0.77%
0.10%
15.66%
7.14%
4.78%
0.54%


Example 48









The invention is not limited to the above-described embodiments, and the following modifications within a range where the advantage of the invention can be achieved may be included in the invention.
For example, according to the invention, the optical component is not limited to the above-described configuration. For example, in the first embodiment, an optical component to which the invention is applied may be, for example, a polarization conversion element 114. In the second embodiment, an optical component to which the invention is applied may be, for example, an optical low-pass filter 211. In summary, the invention can be applied to any optical component insofar as the anti-reflection film 2 or an optical multilayer film including a UV-IR cut film is formed on the substrate 1.
The entire disclosure of Japanese Patent Application Nos: 2010-211690, filed Sep. 22, 2010 are expressly incorporated by reference herein.

## Claims

1. An optical component comprising:
a multilayer inorganic thin-film on a substrate,
wherein the inorganic thin-film is formed by laminating a plurality of layers made of silicon oxide and a plurality of layers made of metal oxide,
the metal oxide is metal oxide containing any one of zirconium, tantalum, and titanium,
the layers made of metal oxide include a low-density metal oxide layer and a high-density metal oxide layer having a density higher than the low-density metal oxide layer, at least one low-density metal oxide layer being between a high-density metal oxide layer and the substrate,
the high-density metal oxide layer being an outermost metal oxide layer and having the highest density of the metal oxide layers in the inorganic thin-film,
the layers made of silicon oxide include a low-density silicon oxide layer and a high-density silicon oxide layer having a density higher than the low-density silicon oxide layer,
the outermost layer of the inorganic thin-film is the low-density silicon oxide layer, and
the surface roughness of the outermost layer of the inorganic thin-film is equal to or greater than 0.55 nm and equal to or smaller than 0.7 nm.

2. The optical component according to claim 1,
wherein the layer of metal oxide near the outermost layer includes a layer of zirconium oxide, and
the surface roughness of the outermost layer of the inorganic thin-film is equal to or greater than 0.6 nm and equal to or smaller than 0.7 nm.

3. The optical component according to claim 2,
wherein the layers of zirconium oxide include a low-density zirconium oxide layer and a high-density zirconium oxide layer having a density higher than the low-density zirconium oxide layer, and at least a layer adjacent to the outermost layer of the inorganic thin-film is the high-density zirconium oxide layer.

4. The optical component according to claim 3,
wherein the low-density silicon oxide layer has a density equal to or higher than 2.00 g/cm3 and equal to or lower than 2.20 g/cm3, and the low-density zirconium oxide layer has a density equal to or higher than 4.8 g/cm3 and equal to or lower than 5.4 g/cm3.

5. The optical component according to claim 1,
wherein the layer of metal oxide near the outermost layer includes a layer of tantalum oxide, and
the surface roughness of the outermost layer of the inorganic thin-film is equal to or greater than 0.55 nm and equal to or smaller than 0.65 nm.

6. The optical component according to claim 5,
wherein the layers of tantalum oxide include a low-density tantalum oxide layer and a high-density tantalum oxide layer having a density higher than the low-density tantalum oxide layer, and at least a layer adjacent to the outermost layer of the inorganic thin-film is the high-density tantalum oxide layer.

7. The optical component according to claim 6,
wherein the low-density silicon oxide layer has a density equal to or higher than 2.00 g/cm3 and equal to or lower than 2.15 g/cm3, and the low-density tantalum oxide layer has a density equal to or higher than 7.7 g/cm3 and equal to or lower than 8.0 g/cm3.

8. The optical component according to claim 1,
wherein the layer of metal oxide near the outermost layer includes a layer of titanium oxide, and
the surface roughness of the outermost layer of the inorganic thin-film is equal to or greater than 0.6 nm and equal to or smaller than 0.7 nm.

9. The optical component according to claim 8,
wherein the layers of titanium oxide include a low-density titanium oxide layer and a high-density titanium oxide layer having a density higher than the low-density titanium oxide layer, and at least a layer adjacent to the outermost layer of the inorganic thin-film is the high-density titanium oxide layer.

10. The optical component according to claim 9,
wherein the low-density silicon oxide layer has a density equal to or higher than 2.00 g/cm3 and equal to or lower than 2.15 g/cm3, and the low-density titanium oxide layer has a density equal to or higher than 4.50 g/cm3 and equal to or lower than 4.75 g/cm3.

11. The optical component according to claim 1,
wherein the total thickness of the low-density silicon oxide layer and the low-density metal oxide layer is equal to or smaller than 500 nm.

12. The optical component according to claim 1,
wherein a fluorine-containing organic silicon compound film is formed on the surface of the outermost layer of the inorganic thin-film.

13. The optical component according to claim 2,
wherein the surface resistance of the inorganic thin-film is equal to or smaller than 3.1×1010Ω/and equal to or greater than 9.1×109Ω/.

14. The optical component according to claim 5,
wherein the surface resistance of the inorganic thin-film is equal to or smaller than 1.4×1011Ω/and equal to or greater than 7.7×109Ω/.

15. The optical component according to claim 8,
wherein the surface resistance of the inorganic thin-film is equal to or smaller than 1.4×1011Ω/and equal to or greater than 5.7×1010Ω/.

16. A method of manufacturing the optical component according to claim 1, the method comprising:
forming at least the outermost layer of the inorganic thin-film through ion-assisted electron beam deposition with assist power having an acceleration voltage equal to or greater than 300 V and equal to or smaller than 450 V.

17. The method according to claim 16,
wherein the plurality of layers are five or more layers, and at least four adjacent layers including the outermost layer from among the layers are formed through the ion-assisted electron beam deposition with assist power.

18. An electronic apparatus comprising:
the optical component according to claim 1; and
a case which accommodates the optical component,
wherein the optical component is an IR-UV cut filter, and an imaging element is arranged to be opposite the IR-UV cut filter.

19. An electronic apparatus comprising:
the optical component according to claim 1; and
a case which accommodates the optical component,
wherein the optical component has an anti-reflection film and is arranged in an optical path between a laser light source and an objective lens opposite an optical disk.

20. An electronic apparatus comprising:
the optical component according to claim 1; and
a case which accommodates the optical component,
wherein the optical component has an anti-reflection film and is arranged in an optical path between a light source and a dichroic prism.

21. The optical component according to claim 1, wherein the outermost layer of the inorganic thin-film is a layer of the inorganic thin-film that is farthest from the substrate.