JP2000193801A - Light absorbing reflection preventing film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To satisfy low surface resistance and proper visible ray absorbtance and obtain light absorbing reflection preventing film whose reflectance is low against incidental light from the film surface and the reflection side by forming on a base plate in order from the base plate side a first light absorbing film, minute absorbing high refractive index film, a second light absorbing film, and a transparent low refractive index film. SOLUTION: On a base plate 10, in the order from the base plate 10 side, a first light absorbing film 11, a minute absorbing high refractive index film 12, a second light absorbing film 13, and a transparent low refractive index film 14 are formed, and hence a light absorbing reflection preventing film is formed. At this time, for the geometrical film thickness of the first light absorbing film 11, it is desirable to be in the range of 10-30 nm for realizing low reflection. Further, the film thickness of the minute absorbing high refractive index film 12 on the upper layer is desirable to be between 5 and 20 nm. Meanwhile for the film thickness of the second light absorbing film 13, it is desirable to be 1-8 nm. Further for the film thickness of the transparent low refractive index film 14 is desirable to be in the range of 50-90 nm in a viewpoint of preventing reflection.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light absorbing antireflection film.

[0002]

2. Description of the Related Art In recent years, with the rapid spread of computers, in order to improve the working environment of terminal operators, it has been required to reduce the reflection on the display surface and to prevent the surface of a CRT (cathode ray tube) from being charged. In recent years, it has been required to further reduce the transmittance of panel glass or to shield extremely low frequency electromagnetic waves that affect the human body in order to improve contrast.

One of the methods for meeting these requirements is to provide a conductive anti-reflection film on the panel surface. There are two methods of providing an anti-reflection film: (a) a method of coating a panel and then molding it into a cathode ray tube; and (b) a method of forming a cathode ray tube and then performing surface coating. At present, they use the so-called wet method.
This is because in a so-called dry method such as a vacuum evaporation method, (a)
In the case of (1), there is a problem that the film properties change due to the heat treatment in the cathode ray tube molding process after the film formation, and the desired performance cannot be obtained. In the case of (b), the entire CRT is installed in a vacuum chamber. This is because there is a problem that the volume and weight are limited due to the necessity of handling, and the handling is difficult. Further, in the sputtering method, which is a typical film forming method of a dry method, there is a problem in high-speed stable film formation of SiO ₂ as a low-refractive-index film which is essential for forming an antireflection film. At present, the technology for industrially producing antireflection films has not been established.

However, with the advancement of required characteristics, the following problems have begun to occur in the surface treatment by the wet method. (1) In the wet method, it is more difficult to control the film thickness than in the dry method, and when a multilayer structure having three or more layers having good antireflection performance is formed, reproducibility and uniformity become problems. (2) The sheet resistance value realized by the wet method is up to about 10 ⁶ Ω / □ so far, which is sufficient for antistatic, but the 10 ³ Ω / □ required for electromagnetic wave shielding is difficult. is there. (3) It is difficult to impart light absorbency without impairing the antireflection performance. On the other hand, the vapor deposition method has a problem that, besides the above-mentioned thermal stability of the film characteristics, the film formation cost is considerably higher than that of the wet method, and the realization of a cheaper film formation method has been demanded. Recently, a method for forming SiO ₂ stably and at high speed by a sputtering method has been actively developed, and several methods are being realized. For example, MMRS (metal mode r) found in U.S. Pat.
eactive sputtering) and the CM of US Pat. No. 4,851,095.
ag (cylindrical magnetron) and the like. As a result,
Although the antireflection film formed by the sputtering method is becoming a reality, the configuration of the antireflection film is conventionally similar to the film configuration formed by the vacuum deposition method in many cases.
In fact, a film configuration particularly effective in the sputtering method has not been known so far.

Further, the inventors of the present invention disclosed in JP-A-09-156964 and JP-A-10-230558 that the productivity was high, the antireflection performance was excellent, and the low surface capable of coping with electromagnetic wave shielding was disclosed. We have proposed light-absorbing anti-reflection coatings that have a resistance value and an appropriate light absorption rate to ensure high contrast. The present invention relates to a protective film.

In recent years, flattening of CRT displays has progressed, and a difference in wall thickness between the central portion and the peripheral portion of the panel glass is indispensable for strength design as compared with a conventional curved tube. Means for increasing the contrast by using a glass substrate having a low transmittance has the disadvantage that the brightness of the central portion of the screen differs from that of the peripheral portion.

[0007] Therefore, a new antireflection film for a CRT having a considerably lower transmittance has been required. As a means for achieving this requirement, for example, an ARAS (conductive anti-reflection) coat is applied on a film, and a dye or the like is mixed into an adhesive used when the film is attached to a CRT surface, so that the transmittance is reduced. There is a method of dropping (for example, Japanese Patent Application Laid-Open No. 09-156964). However, this method is based on the use of a film, and the film has a lower surface hardness than glass, uneven appearance due to uneven thickness of the hard coat, and concerns about the durability of coloring materials such as dyes. It has been pointed out that there is a problem that it cannot cope with the case where the durability obtained by directly forming an inorganic substance on glass is important.

US Pat. No. 5,091,244 discloses glass / glass.
Transition metal nitride / transparent film / transition metal nitride / transparent film 4
The layer configuration is illustrated. However, there is no description about the so-called double image problem caused by the reflection of the signal light from the display on the inner surface. Therefore, the inventor of the present invention has excellent anti-reflection performance for incident light from the film surface side, has a low surface resistance value that can cope with electromagnetic wave shielding, and furthermore has an appropriate light absorption rate to secure a high contrast. We are dedicated to the development of a light-absorbing anti-reflective coating that has a low reflectance to incident light from the side opposite to the film surface and improves the degree of double image. As a result, the present invention has been achieved.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to eliminate the above-mentioned disadvantages of the prior art. That is, a light that satisfies a sufficiently low reflection performance, a sufficiently low surface resistance value and an appropriate absorptivity of visible light at the same time, and does not have a high reflectance even for incident light from the side opposite to the film surface. It is an object of the present invention to provide an absorptive antireflection film.

[0010]

SUMMARY OF THE INVENTION The above-mentioned object of the present invention is as follows.
On a substrate, at least one light-absorbing film, at least one transparent high-refractive-index film or finely-absorbing high-refractive-index film, at least one transparent low-refractive-index film or a transparent medium-refractive-index film,
Achieved by a light-absorbing antioxidant film having a specific structure formed by forming an absorptive oxide film in some cases, specifically,
The invention has been solved by the following first invention, second invention, third invention, fourth invention, fifth invention, and sixth invention. 1. A light-absorptive antireflection film (hereinafter, referred to as a first light-absorptive film) formed by forming a first light-absorbing film, a slightly absorbing high-refractive-index film, a second light-absorbing film, and a transparent low-refractive-index film on a substrate in this order from the substrate side. Of the invention). 2. Light absorbing antireflection formed by forming a first light absorbing film, a transparent high refractive index film or a slightly absorbing high refractive index film, a second light absorbing film, and a transparent medium refractive index film on a substrate in this order from the substrate side. A film (hereinafter, referred to as a second invention). 3. A first light absorbing film, a first transparent high refractive index film or a slightly absorbing high refractive index film, a second light absorbing film, a second transparent high refractive index film or a slightly absorbing High refractive index film,
3. a light absorbing antireflection film formed by forming a third light absorbing film and a transparent low refractive index film (hereinafter, referred to as a third invention); A light-absorbing anti-reflection coating comprising a first light-absorbing film, a transparent high-refractive-index film or a finely-absorbing high-refractive-index film, a second light-absorbing film, and a transparent low-refractive-index film formed on a substrate in this order from the substrate side. A film (hereinafter, referred to as a fourth invention). 5. Forming a light-absorbing film, a transparent high-refractive-index film or a slightly absorbing high-refractive-index film, a first transparent low-refractive-index film, an absorbing oxide film, and a second transparent low-refractive-index film on a substrate in this order from the substrate side A light-absorbing antireflection film (hereinafter referred to as a fifth invention). 6. On the substrate, in order from the substrate side, a light absorbing film, a transparent high refractive index film or a slightly absorbing high refractive index film, a first transparent low refractive index film, a first absorbing oxide film, and a second transparent low refractive index film A light-absorbing anti-reflection film (hereinafter referred to as a sixth invention) formed by forming a film, a second absorbing oxide film, and a third transparent low-refractive-index film.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION As a substrate in the present invention, glass or transparent plastic can be used.
In particular, it is preferable to apply the present invention using glass used for the front surface of the display as a substrate, since the effects of the present invention are sufficiently exhibited. Examples of these glasses include a panel glass itself constituting a cathode ray tube, a tele panel (face plate glass) used by sticking the cathode ray tube with a resin, and a filter glass installed between the cathode ray tube and an operator.

The first to third and fifth and sixth aspects of the present invention
The light absorbing film used in the invention of the fourth aspect, or the light absorbing film used in
Has a complex optical constant of n−ik (refractive index n, extinction coefficient k), k at a wavelength of 400 nm is k ₄₀₀ , k at a wavelength of 700 nm is k ₇₀₀ , and n at a wavelength of 400 nm is n
₄₀₀ , n at a wavelength of 700 nm is n _700, and n _dif = n
When the _{400 -n 700, k dif = k} 700 -k 400,
The optical constant of the light absorbing film satisfies all of the following expressions.

N _dif > 0.5 k _dif > 0.5

As the material of the above-mentioned light absorbing film, a material capable of substantially reducing the surface reflectance by the light interference effect with another layer formed at the same time can be used. The light absorbing film is preferably a film mainly containing at least one kind of metal selected from the group consisting of titanium, zirconium, and hafnium or a nitride of a mixture thereof. Above all, a titanium nitride film shows a value of an optical constant in a visible light region close to an ideal wavelength dependence in optical design, and is most excellent in terms of durability and ease of fabrication. Note that a film containing titanium nitride as a main component includes a titanium nitride film containing no other component. In the following, the term “main component” is used in a similar meaning.
Further, it is known that a small amount of oxygen is mixed in the nitride film to make the optical constant closer to an ideal. In the case of a titanium nitride film, titanium, It is preferable that the ratio of nitrogen and oxygen is in the range of 1: 0.5: 0.01 to 1: 1.5: 0.5. It is particularly preferable that the ratio of titanium to oxygen is between 1: 0.06 and 1: 0.33.

In the light absorbing film containing titanium nitride as a main component in the present invention, the ratio of nitrogen to titanium in the film is preferably in the range of 0.5 to 1.5 from the viewpoint of optical constant and specific resistance. If this ratio is less than 0.5,
The film becomes a slightly metallic titanium nitride film, and although the specific resistance is lowered, the optical constant becomes inappropriate and the antireflection effect becomes insufficient. On the other hand, when this ratio is larger than 1.5, the titanium nitride film becomes excessive in nitrogen, and the optical constant changes,
Since the specific resistance increases, both the reflectance and the surface resistance become insufficient. In the light absorbing film containing titanium nitride as a main component in the present invention, the ratio of oxygen to titanium in the film is preferably in the range of 0.5 or less from the viewpoint of optical constant and specific resistance. If this ratio is larger than 0.5, the film becomes a titanium oxynitride film, the specific resistance increases, the optical constant becomes inappropriate, and both the surface resistance and the antireflection effect become insufficient.

In the fourth invention, the first light absorbing film is a film mainly composed of at least one metal selected from the group consisting of chromium, nickel, titanium and zirconium or a mixture thereof. Preferably, the light-absorbing film 2 is a film mainly composed of at least one metal selected from the group consisting of titanium, zirconium and hafnium or a nitride of a mixture thereof. By using the above-mentioned film, it is possible to effectively suppress the reflectance with respect to the incident light from the side opposite to the film surface, as compared with the case where another material is used as the first light absorbing film.

In the present invention, the slightly absorbing high refractive index film is
It is made of a material which has a small absorption in the visible region and whose extinction coefficient is larger on the shorter wavelength side. In particular, the extinction coefficient of the slightly absorbing film is 400 to 700 nm (hereinafter also referred to as a visible region).
From 0.05 to 0.6, preferably from 0.05 to
It is a slightly absorbent film in the range of 0.4. Further, the refractive index in the visible region is preferably a high refractive index in the range of about 1.9 to 2.7. As a specific material, for example, a material mainly containing any of silicon nitride, bismuth oxide, and chromium oxide, or a mixture thereof can be given. Above all, it is preferable to use a material containing silicon nitride as a main component. In particular, it is preferable to use silicon nitride containing a small amount of oxygen from the viewpoints of refractive index, durability, and the like. As a film formation method, DC sputtering of a conductive silicon target in the presence of nitrogen gas is preferable from the viewpoint of productivity. At this time, a small amount of impurities will be mixed in order to impart conductivity to the target.However, silicon nitride referred to here is generally the same as silicon nitride containing no impurities, even if it contains a small amount of impurities. It should be considered that the film has a refractive index and an extinction coefficient. Alternatively, RF sputtering may be used.
Further, it may be formed by a technique such as CVD, spin coating or dip coating.

The transparent low refractive index film of the present invention is preferably a material having a low refractive index of about 1.35 to 1.6 in the visible region, and has an extinction coefficient of, for example, 0 over the entire visible region. Those having excellent transparency of not more than 0.03 are preferred. As a specific material, a film containing silicon oxide as a main component is preferable from the viewpoint of refractive index, durability, and the like.
As a film formation method, DC sputtering of a conductive silicon target in the presence of oxygen gas is preferable from the viewpoint of productivity. At this time, a small amount of impurities will be mixed in order to impart conductivity to the target.However, the silicon oxide film referred to here generally contains substantially the same amount of impurities as silicon oxide containing no impurities. It should be considered a film with a refractive index. Further, recently, as described above, various methods for forming silicon oxide at a high speed have been devised, and a silicon oxide film formed by using these methods may be used. Alternatively, RF sputtering may be used. Further, it may be formed by a technique such as CVD, spin coating or dip coating.

The transparent high-refractive-index film of the present invention is preferably a high-refractive-index film having a refractive index of about 1.9 to 2.7 in the visible region, and has an extinction coefficient of, for example, 0 over the entire visible region. Those having excellent transparency of not more than 0.03 are preferred. Specifically, for example, a film mainly containing at least one selected from the group consisting of silicon nitride, aluminum nitride, tin oxide, zinc oxide, zirconium oxide, indium oxide, tantalum oxide, niobium oxide, and titanium oxide is preferable. . Among them, a film containing silicon nitride as a main component is preferable from the viewpoints of refractive index, durability, and the like. As a film formation method, DC sputtering of a conductive silicon target in the presence of nitrogen gas is preferable from the viewpoint of productivity. At this time, a small amount of impurities are mixed in order to impart conductivity to the target, but the silicon nitride film referred to here generally contains substantially the same amount of impurities as silicon nitride containing no impurities. It should be considered a film with a refractive index. Further, oxygen may be contained. Alternatively, RF sputtering may be used. Also,
It may be formed by a technique such as CVD, spin coating or dip coating.

In the second to sixth inventions, either a transparent high refractive index film or a slightly absorbing high refractive index film may be used. Even if a transparent high-refractive-index film is used, sufficient low-reflection characteristics can be obtained, but it is more preferable to use a slightly-absorbing high-refractive-index film to simultaneously improve the reflection characteristics on the film surface and the non-film surface side. Can be.

The transparent medium refractive index film of the present invention is preferably a medium refractive index film having a refractive index in the visible range of 1.6 to 1.9, and the extinction coefficient is, for example, in the entire visible range. It is preferable that the composition has excellent transparency of not more than 0.03. As a specific material, aluminum oxide which is a transparent medium refractive index material is used alone, or silicon oxide which is a transparent low refractive index material and niobium oxide which is a transparent high refractive index material, tantalum oxide, titanium oxide, What mixed zirconium oxide etc. is preferable from a viewpoint of a refractive index, durability, etc. As the film forming method, 1) DC sputtering of a conductive metal aluminum target in the presence of oxygen gas, 2) DC sputtering of a target of a mixture of silicon and niobium or titanium in the presence of oxygen gas, or 3) A target of a mixture of silicon oxide and niobium oxide or titanium oxide is subjected to DC under an inert gas such as Ar or in the presence of a trace amount of oxygen.
Sputtering is preferable in terms of productivity.
An aluminum oxide film or a mixture film of silicon oxide and niobium oxide or titanium oxide here is generally considered to be a film having substantially the same refractive index as a film containing no impurities, even if it contains a small amount of impurities. Should. Alternatively, RF sputtering may be used. Further, it may be formed by a technique such as CVD, spin coating or dip coating.

In the present invention, the absorptive oxide film is an oxide film having a light absorbing property in a visible region,
The film preferably has an extinction coefficient in the visible region in the range of 0.05 to 2.5. By incorporating the absorptive oxide into the film configuration, it is possible to suppress the reflectance for the incident light from the side opposite to the film surface while maintaining the low reflection characteristics for the incident light from the film surface side. As a specific absorbent oxide film, a film mainly containing an oxide of at least one metal selected from the group consisting of cobalt, nickel, manganese, and iron is preferable. As the film forming method, 1)
DC sputtering of conductive metal targets in the presence of oxygen gas, or 2) DC sputtering of these metal oxide targets under an inert gas such as argon, or in the presence of trace amounts of oxygen It is preferable from the viewpoint of properties.

Also, at the interface between each layer or the interface with the substrate,
A transparent nitride film having a thickness that does not substantially change optical characteristics may be formed. Heat resistance and adhesion,
Scratch resistance characteristics can be improved.

Each layer of the present invention can be formed by various conventionally known film forming methods,
For example, it is formed by a sputtering method, a vacuum evaporation method, a CVD method, a sol-gel method, or the like.

The light-absorbing anti-reflection film according to the present invention preferably has a light absorptivity of 10 to 65% for incident light from the film surface, and more preferably 30 to 65%. More preferred. Outside this range, the effect of improving the contrast in the display is often lost, or the luminance of the display is often insufficient because the transmittance is too low.

FIG. 1 is a schematic sectional view of the first invention.
In the first invention, a first electrode formed on the substrate (10) is provided.
The light absorbing film (11) has a geometric film thickness (hereinafter simply referred to as a film thickness) of 10 to 30 n in order to realize low reflection.
m is desirable. Further, in this case, it is preferable that the film thickness of the upper microabsorptive high refractive index film (12) is between 5 and 20 nm. In addition, the second light absorbing film (1
The thickness 3) is preferably 1 to 8 nm. The thickness of the transparent low refractive index film (14) is 50
It is also desirable to be within the range of 90 nm from the viewpoint of antireflection. If the thickness of any of the layers deviates from this range, sufficient antireflection performance in the visible light region cannot be obtained.

According to another aspect of the first invention, the thickness of the light absorbing film is 5 to 2 in order to realize low reflection.
It is desirable to be in the range of 0 nm. Also, in this case,
The thickness of the upper microabsorptive high refractive index film is preferably between 10 and 40 nm. The thickness of the second light absorbing film is preferably 5 to 20 nm. Also, the thickness of the transparent low refractive index film is preferably in the range of 60 to 100 nm from the viewpoint of preventing reflection. If the thickness of any of the layers deviates from this range, sufficient antireflection performance in the visible light region cannot be obtained.

FIG. 4 is a schematic sectional view of the second invention.
In the second aspect, the thickness of the light absorbing film (21) formed on the substrate (20) is desirably in the range of 3 to 20 nm in order to realize low reflection. In this case, it is preferable that the thickness of the upper transparent high refractive index film or the slightly absorbing high refractive index film (22) is between 15 and 45 nm. The thickness of the second light absorbing film (23) is 5 to 3
It is preferably 0 nm. Also, the thickness of the transparent medium refractive index film (24) is preferably in the range of 40 to 100 nm from the viewpoint of preventing reflection. If the thickness of any of the layers deviates from this range, sufficient antireflection performance in the visible light region cannot be obtained.

FIG. 6 is a schematic sectional view of the third invention.
In the third aspect, the thickness of the light absorbing film (31) formed on the substrate (30) is desirably in the range of 2 to 10 nm in order to realize low reflection. In this case, the thickness of the upper transparent first high refractive index film (32) is 3
It is preferably between 0 and 60 nm. The thickness of the second light absorbing film (33) is preferably 5 to 15 nm. In addition, (3) of the second transparent high refractive index film
4) The thickness is preferably between 20 and 60 nm.
The thickness of the third light absorbing film (35) is 5 to 2
It is preferably 0 nm. Also, the thickness of the transparent low refractive index film (36) is preferably in the range of 50 to 100 nm from the viewpoint of preventing reflection. If the thickness of any of the layers deviates from this range, sufficient antireflection performance in the visible light region cannot be obtained.

FIG. 8 is a schematic sectional view of the fourth invention.
In the fourth aspect, the thickness of the light absorbing film (41) formed on the substrate (40) is desirably in the range of 1 to 10 nm in order to realize low reflection. In this case, it is preferable that the thickness of the upper transparent high-refractive-index film or the slightly-absorbing high-refractive-index film (42) is between 40 and 80 nm. The thickness of the second light absorbing film (43) is as follows.
It is preferably from 5 to 15 nm. Also, the thickness of the transparent low refractive index film (44) is preferably in the range of 50 to 110 nm from the viewpoint of preventing reflection. If the thickness of any of the layers deviates from this range, sufficient antireflection performance in the visible light region cannot be obtained.

FIG. 10 is a schematic sectional view of the fifth invention. In the fifth invention, the thickness of the light absorbing film (51) formed on the substrate (50) is desirably in the range of 2 to 20 nm in order to realize low reflection. Also,
In this case, it is preferable that the thickness of the upper transparent high-refractive-index film or the slightly absorbing high-refractive-index film (52) is between 3 and 50 nm. The thickness of the first transparent low refractive index film (53) is preferably 10 to 70 nm. Also,
The thickness of the absorbing oxide film (54) is preferably between 2 and 20 nm. In addition, the second transparent low refractive index film (5
The thickness 5) is preferably in the range of 50 to 110 nm from the viewpoint of preventing reflection. If the thickness of any of the layers deviates from this range, sufficient antireflection performance in the visible light region cannot be obtained.

FIG. 12 is a schematic sectional view of the sixth invention. In the sixth invention, the thickness of the light absorbing film (61) formed on the substrate (60) is desirably in the range of 1 to 20 nm in order to realize low reflection. Also,
In this case, it is preferable that the thickness of the upper transparent high-refractive-index film or the slightly-absorbing high-refractive-index film (62) is between 3 and 50 nm. The first transparent low refractive index film (63) preferably has a thickness of 10 to 50 nm. Also,
The thickness of the first absorbing oxide film (64) is preferably between 2 and 20 nm. The thickness of the second transparent low refractive index film (65) is preferably 10 to 50 nm. The thickness of the second absorbent oxide film (66) is preferably between 2 and 20 nm. Also, the third
The thickness of the transparent low refractive index film (67) is 50 to 110.
The range of nm is also desirable from the viewpoint of antireflection. If the thickness of any of the layers deviates from this range, sufficient antireflection performance in the visible light region cannot be obtained.

The light absorbing film of the present invention absorbs a part of the incident light and reduces the transmittance. When the present invention is applied to the front glass of a display, this reduces the intensity of light rays incident from the surface and reflected on the display element side surface, thereby increasing the ratio between display light and this background light. The contrast can be increased. In the present invention, the substrate, light absorbing film, transparent high refractive index film or finely absorbing high refractive index film, transparent medium refractive index film, and transparent low refractive index film have a reflection Fresnel coefficient at each interface and a phase change between the interfaces. The total reflectance determined by the amount and the amount of amplitude attenuation in each layer is set to be sufficiently low in the visible light region. In particular, the optical constant of the light-absorbing film shows a dependence different from the dispersion relationship (wavelength dependence) in the visible light region of a normal transparent film, and thus the optical constant in the visible light region is higher than that in the case where the transparent film is composed of only the transparent film. It works to widen the low reflection area. This effect is remarkable when a nitride of titanium, zirconium, or hafnium is used as the light absorbing film. In addition, in the film configuration of the present invention, the total reflection determined by the reflection Fresnel coefficient of each interface, the phase change amount of each interface, and the amplitude attenuation amount in each layer also with respect to the incidence of light from the side opposite to the film surface. The Fresnel coefficient is set to be low in the visible region to a level at which there is no practical problem.

[0034]

[Example 1] (First invention) In a vacuum chamber, metal titanium and a specific resistance of 2.8 × 10 ^-2 Ω ·
cm of sprayed silicon was set on the cathode as a target (6 inch φ), and the vacuum chamber was set to 1 × 10 ⁻⁵ T
evacuated to orr. A four-layer film shown in FIG. 1 was formed on a soda lime glass substrate (10) set in a vacuum chamber as follows. (1) First, a mixed gas of argon and nitrogen (20% nitrogen) was introduced as a discharge gas, and the conductance was adjusted so that the pressure became 2 × 10 ⁻³ Torr. Then, using a MDX-10K (manufactured by Advanced Energy) as a power source for the titanium cathode, a 20 nm titanium nitride film (11) was formed by DC sputtering of a titanium target with an input power of 0.8 kW. (2) After stopping the gas introduction and making the vacuum chamber high vacuum,
Mixed gas of argon and nitrogen as discharge gas (20% nitrogen)
Was introduced, and the conductance was adjusted so that the pressure became 2 × 10 ⁻³ Torr. Then SP on the silicon cathode
MD via ARCLE-V (by Advanced Energy)
A power of 0.2 kW was applied from X-10K, and 11.5 n was obtained by intermittent DC sputtering of a silicon target.
Then, a silicon nitride film (12) having a small absorption of m was formed. This film has a refractive index of about 2.21 at 550 nm and an extinction coefficient of 400.
It was about 0.19 in nm. (3) After stopping the gas introduction and making the vacuum chamber high vacuum,
In the same manner as in the above (1), a mixed gas of argon and nitrogen (20% nitrogen) was introduced as a discharge gas, and the pressure was 2 × 10 ^−3.
The conductance was adjusted to be Torr. Then, using MDX-10K as a power source for the titanium cathode,
With a power input of 0.8 kW, a 3 nm titanium nitride film (13) was formed by DC sputtering of a titanium target. (4) After stopping the gas introduction and making the vacuum chamber high vacuum,
Oxygen is introduced as a discharge gas, and the pressure is 2 × 10 ⁻³ Torr.
The conductance was adjusted to be r. Then, MDX-1 was connected to the silicon cathode via SPARCLE-V.
A power of 0.75 kW was applied from 0 K, and a 73.5 nm transparent silicon oxide film (14) was formed by intermittent DC sputtering of a silicon target. The refractive index of this film was about 1.47 at 550 nm, and the extinction coefficient was 0.01 or less. The spectral transmittance of the obtained glass with a four-layer film was measured. Further, the spectral reflectance of this sample was measured in a state where black lacquer was applied to the back surface of the glass substrate to eliminate the back surface reflection. The obtained spectral reflectance curve 15 and spectral transmittance curve 16 are shown in FIG. When the titanium nitride film taken out after the film formation of (1) was analyzed by ESCA, it was found that Ti: N: O = 1: 0.95: 0.08.

[Example 2] (Another embodiment of the first invention) In a vacuum chamber, metallic titanium and a specific resistance of 2.8 × 10 ^-2 Ω ·
cm of sprayed silicon was set on the cathode as a target (6 inch φ), and the vacuum chamber was set to 1 × 10 ⁻⁵ T
evacuated to orr. A four-layer film shown in FIG. 1 was formed on a soda lime glass substrate (10) set in a vacuum chamber as follows. (1) First, a mixed gas of argon and nitrogen (20% nitrogen) was introduced as a discharge gas, and the conductance was adjusted so that the pressure became 2 × 10 ⁻³ Torr. Then, using a MDX-10K (manufactured by Advanced Energy) as a power source for the titanium cathode, a 12 nm titanium nitride film (11) was formed by DC sputtering of a titanium target at an input power of 0.8 kW. (2) After stopping the gas introduction and making the vacuum chamber high vacuum,
Mixed gas of argon and nitrogen as discharge gas (20% nitrogen)
Was introduced, and the conductance was adjusted so that the pressure became 2 × 10 ⁻³ Torr. Then SP on the silicon cathode
MD via ARCLE-V (by Advanced Energy)
A power of 0.2 kW was applied from X-10K, and 22.5 n was obtained by intermittent DC sputtering of a silicon target.
Then, a silicon nitride film (12) having a small absorption of m was formed. (3) After stopping the gas introduction and making the vacuum chamber high vacuum,
As in the above (1), a mixed gas of argon and nitrogen (20% nitrogen) is introduced as a discharge gas, and the pressure is 2 × 10 ⁻³ T.
The conductance was adjusted to be orr. Then, using MDX-10K as a power source for the titanium cathode,
With a power input of 0.8 kW, a 10 nm titanium nitride film (13) was formed by DC sputtering of a titanium target. (4) After stopping the gas introduction and making the vacuum chamber high vacuum,
Oxygen is introduced as a discharge gas, and the pressure is 2 × 10 ⁻³ Torr.
The conductance was adjusted to be r. Then, MDX-1 was connected to the silicon cathode via SPARCLE-V.
A power of 0.75 kW was applied from 0 K, and a transparent silicon oxide film (14) of 80.5 nm was formed by intermittent DC sputtering of a silicon target.

The spectral transmittance of the obtained glass with a four-layer film was measured. Further, the spectral reflectance of this sample was measured in a state where black lacquer was applied to the back surface of the glass substrate to eliminate the back surface reflection. The obtained spectral reflectance curve 17 and spectral transmittance curve 18 are shown in FIG.

Example 3 (Second Invention) In a vacuum chamber, metal titanium and a specific resistance of 2.8 × 10 ^-2 Ω ·
cm of sprayed silicon and NbSix with a specific resistance of 0.4Ωcm
Oy and Oy were respectively set on the cathode as targets (6 inches φ), and the vacuum chamber was evacuated to 1 × 10 ⁻⁵ Torr. A four-layer film shown in FIG. 4 was formed on a soda lime glass substrate (20) set in a vacuum chamber as follows. (1) First, a mixed gas of argon and nitrogen (20% nitrogen) was introduced as a discharge gas, and the conductance was adjusted so that the pressure became 2 × 10 ⁻³ Torr. Then, using a MDX-10K (manufactured by Advanced Energy) as a power source for the titanium cathode, a 12-nm titanium nitride film (21) was formed by a DC sputtering of a titanium target with an input power of 0.8 kW. (2) After stopping the gas introduction and making the vacuum chamber high vacuum,
Mixed gas of argon and nitrogen as discharge gas (20% nitrogen)
Was introduced, and the conductance was adjusted so that the pressure became 2 × 10 ⁻³ Torr. Then SP on the silicon cathode
MD via ARCLE-V (by Advanced Energy)
A power of 0.2 kW was applied from X-10K, and a silicon nitride film (22) having a small absorption of 26 nm was formed by intermittent DC sputtering of a silicon target. (3) After stopping the gas introduction and making the vacuum chamber high vacuum,
As in the above (1), a mixed gas of argon and nitrogen (20% nitrogen) is introduced as a discharge gas, and the pressure is 2 × 10 ⁻³ T.
The conductance was adjusted to be orr. Then, using MDX-10K as a power source for the titanium cathode,
With a power input of 0.8 kW, a 10 nm titanium nitride film (23) was formed by DC sputtering of a titanium target. (4) After stopping the gas introduction and making the vacuum chamber high vacuum,
Argon is introduced as a discharge gas and the pressure is 2 × 10 ⁻³ T
The conductance was adjusted to be orr. Then N
A power of 0.25 kW is applied to the cathode of bSixOy from MDX-10K via SPARCLE-V, and Nb
A 74 nm transparent NbSixOy film (24) was formed by intermittent DC sputtering of a SixOy target. The refractive index of this film is about 1.6 at 550 nm.
8. The extinction coefficient was 0.01 or less.

The spectral transmittance of the obtained glass with a four-layer film was measured. Further, the spectral reflectance of this sample was measured in a state where black lacquer was applied to the back surface of the glass substrate to eliminate the back surface reflection. The obtained spectral reflectance curve 25 and spectral transmittance curve 26 are shown in FIG.

[Example 4] (Third invention) Metallic titanium and a specific resistance of 2.8 × 10 ^-2 Ω ·
cm of sprayed silicon was set on the cathode as a target (6 inch φ), and the vacuum chamber was set to 1 × 10 ⁻⁵ T
evacuated to orr. A six-layer film shown in FIG. 6 was formed on a soda lime glass substrate (30) set in a vacuum chamber as follows. (1) First, a mixed gas of argon and nitrogen (20% nitrogen) was introduced as a discharge gas, and the conductance was adjusted so that the pressure became 2 × 10 ⁻³ Torr. Next, a titanium nitride film (31) having a thickness of 4.5 nm was formed by DC sputtering of a titanium target using MDX-10K (manufactured by Advanced Energy) as a power source for the titanium cathode at a power supply of 0.8 kW. (2) After stopping the gas introduction and making the vacuum chamber high vacuum,
Mixed gas of argon and nitrogen (30% nitrogen) as discharge gas
Was introduced, and the conductance was adjusted so that the pressure became 2 × 10 ⁻³ Torr. Then SP on the silicon cathode
MD via ARCLE-V (by Advanced Energy)
A power of 0.75 kW was applied from X-10K, and 42 nm was obtained by intermittent DC sputtering of a silicon target.
A transparent silicon nitride film (32) was formed. The refractive index of this film was about 2.05 at 550 nm, and the extinction coefficient was 0.01 or less. (3) After stopping the gas introduction and making the vacuum chamber high vacuum,
As in the above (1), a mixed gas of argon and nitrogen (20% nitrogen) is introduced as a discharge gas, and the pressure is 2 × 10 ⁻³ T.
The conductance was adjusted to be orr. Then, using MDX-10K as a power source for the titanium cathode,
With a power input of 0.8 kW, a 9 nm titanium nitride film (33) was formed by DC sputtering of a titanium target. (4) After stopping the gas introduction and making the vacuum chamber high vacuum,
As in the above (2), a mixed gas of argon and nitrogen (30% nitrogen) was introduced as a discharge gas, and the pressure was 2 × 10 ⁻³ T.
The conductance was adjusted to be orr. Next, SPARCLE-V (advanced en
Power of 0.75 kW from MDX-10K is supplied to the device through the intermittent DC sputtering of a silicon target through a 38 nm transparent silicon nitride film (34).
Was formed. (5) After stopping the gas introduction and making the vacuum chamber high vacuum,
As in the above (1), a mixed gas of argon and nitrogen (20% nitrogen) is introduced as a discharge gas, and the pressure is 2 × 10 ⁻³ T.
The conductance was adjusted to be orr. Then, using MDX-10K as a power source for the titanium cathode,
With a power input of 0.8 kW, a 10 nm titanium nitride film (35) was formed by DC sputtering of a titanium target. (6) After stopping the gas introduction and making the inside of the vacuum chamber a high vacuum,
Oxygen is introduced as a discharge gas, and the pressure is 2 × 10 ⁻³ Torr.
The conductance was adjusted to be r. Then, MDX-1 was connected to the silicon cathode via SPARCLE-V.
A power of 0.75 kW was applied from 0K, and a 73 nm transparent silicon oxide film (36) was formed by intermittent DC sputtering of a silicon target.

The spectral transmittance of the obtained glass with a six-layer film was measured. Further, the spectral reflectance of this sample was measured in a state where black lacquer was applied to the back surface of the glass substrate to eliminate the back surface reflection. The resulting spectral reflectance curve 37 and spectral transmittance curve 38 are shown in FIG.

[Example 5] (Fourth invention) Metal chromium, metal titanium, and specific resistance
8 × 10 ⁻² Ω · cm sprayed silicon was set on the cathode as a target (6 inch φ), and the vacuum chamber was evacuated to 1 × 10 ⁻⁵ Torr. A four-layer film shown in FIG. 8 was formed on a soda lime glass substrate (40) placed in a vacuum chamber as follows. (1) First, argon is introduced as a discharge gas and the pressure is 2
The conductance was adjusted to be × 10 ⁻³ Torr. Next, MDX-10 was used as a power source for the chromium cathode.
Using K (manufactured by Advanced Energy), a 3 nm chromium film (41) was formed by DC sputtering of a chromium target at an input power of 0.25 kW. (2) After stopping the gas introduction and making the vacuum chamber high vacuum,
Mixed gas of argon and nitrogen (30% nitrogen) as discharge gas
Was introduced, and the conductance was adjusted so that the pressure became 2 × 10 ⁻³ Torr. Then SP on the silicon cathode
MD via ARCLE-V (by Advanced Energy)
A power of 0.75 kW was applied from X-10K, and 63 nm was obtained by intermittent DC sputtering of a silicon target.
A transparent silicon nitride film (42) was formed. (3) After stopping the gas introduction and making the vacuum chamber high vacuum,
Mixed gas of argon and nitrogen as discharge gas (20% nitrogen)
Was introduced, and the conductance was adjusted so that the pressure became 2 × 10 ⁻³ Torr. Then, using MDX-10K as a power source for the titanium cathode, with a power input of 0.8 kW,
10n by DC sputtering of titanium target
m titanium nitride film (43) was formed. (4) After stopping the gas introduction and making the vacuum chamber high vacuum,
Oxygen is introduced as a discharge gas, and the pressure is 2 × 10 ⁻³ Torr.
The conductance was adjusted to be r. Then, MDX-1 was connected to the silicon cathode via SPARCLE-V.
A power of 0.75 kW was applied from 0 K, and a 86 nm transparent silicon oxide film (44) was formed by intermittent DC sputtering of a silicon target.

The spectral transmittance of the obtained glass with a four-layer film was measured. Further, the spectral reflectance of this sample was measured in a state where black lacquer was applied to the back surface of the glass substrate to eliminate the back surface reflection. The obtained spectral reflectance curve 45 and spectral transmittance curve 46 are shown in FIG.

Example 6 (Fifth Invention) Metallic titanium, metallic cobalt, and sprayed silicon having a specific resistance of 2.8 × 10 ⁻² Ω · cm were each placed in a vacuum chamber as targets (6 inch φ). ), And the vacuum chamber was evacuated to 1 × 10 ⁻⁵ Torr. A five-layer film shown in FIG. 10 was formed on a soda lime glass substrate (50) set in a vacuum chamber as follows. (1) First, a mixed gas of argon and nitrogen (20% nitrogen) was introduced as a discharge gas, and the conductance was adjusted so that the pressure became 2 × 10 ⁻³ Torr. Then, using an MDX-10K (manufactured by Advanced Energy) as a power source for the titanium cathode, an 8 nm titanium nitride film (51) was formed by DC sputtering of a titanium target at an input power of 0.8 kW. (2) After stopping the gas introduction and making the vacuum chamber high vacuum,
Mixed gas of argon and nitrogen (30% nitrogen) as discharge gas
Was introduced, and the conductance was adjusted so that the pressure became 2 × 10 ⁻³ Torr. Then SP on the silicon cathode
MD via ARCLE-V (by Advanced Energy)
A power of 0.75 kW was applied from X-10K, and 25 nm was obtained by intermittent DC sputtering of a silicon target.
A transparent silicon nitride film (52) was formed. (3) After stopping the gas introduction and making the vacuum chamber high vacuum,
Oxygen is introduced as a discharge gas, and the pressure is 2 × 10 ⁻³ Torr.
The conductance was adjusted to be r. Then, MDX-1 was connected to the silicon cathode via SPARCLE-V.
A power of 0.75 kW was applied from 0K, and a 46 nm transparent silicon oxide film (53) was formed by DC sputtering of a silicon target. (4) After stopping the gas introduction and making the vacuum chamber high vacuum,
Mixed gas of argon and oxygen as discharge gas (10% oxygen)
Was introduced, and the conductance was adjusted so that the pressure became 2 × 10 ⁻³ Torr. Then MD on the cobalt cathode
A power of 0.5 kW was applied from X-10K, and a 4 nm-absorbent cobalt oxide film (54) was formed by DC sputtering of a cobalt target. This film has a refractive index of about 2.79 at 550 nm and an extinction coefficient of 550.
It was about 2.09 in nm. (5) After stopping the gas introduction and making the vacuum chamber high vacuum,
Oxygen is introduced as a discharge gas, and the pressure is 2 × 10 ⁻³ Torr.
The conductance was adjusted to be r. Then, MDX-1 was connected to the silicon cathode via SPARCLE-V.
A power of 0.75 kW was applied from 0 K, and a 70 nm transparent silicon oxide film (55) was formed by intermittent DC sputtering of a silicon target.

The spectral transmittance of the obtained glass with a five-layer film was measured. Further, the spectral reflectance of this sample was measured in a state where black lacquer was applied to the back surface of the glass substrate to eliminate the back surface reflection. The obtained spectral reflectance curve 56 and spectral transmittance curve 57 are shown in FIG.

Example 7 (Sixth Invention) Metallic titanium, metallic cobalt, and sprayed silicon having a specific resistance of 2.8 × 10 ⁻² Ω · cm were each set in a vacuum chamber as a target (6 inch φ). ), And the vacuum chamber was evacuated to 1 × 10 ⁻⁵ Torr. A seven-layer film shown in FIG. 12 was formed on a soda lime glass substrate (60) set in a vacuum chamber as follows. (1) First, a mixed gas of argon and nitrogen (20% nitrogen) was introduced as a discharge gas, and the conductance was adjusted so that the pressure became 2 × 10 ⁻³ Torr. Then, using a MDX-10K (manufactured by Advanced Energy) as a power source for the titanium cathode, a 2 nm-thick titanium nitride film (61) was formed by DC sputtering of a titanium target with an input power of 0.8 kW. (2) After stopping the gas introduction and making the vacuum chamber high vacuum,
Mixed gas of argon and nitrogen (30% nitrogen) as discharge gas
Was introduced, and the conductance was adjusted so that the pressure became 2 × 10 ⁻³ Torr. Then SP on the silicon cathode
MD via ARCLE-V (by Advanced Energy)
A power of 0.75 kW was applied from X-10K, and 33 nm was obtained by intermittent DC sputtering of a silicon target.
A transparent silicon nitride film (62) was formed. (3) After stopping the gas introduction and making the vacuum chamber high vacuum,
Oxygen is introduced as a discharge gas, and the pressure is 2 × 10 ⁻³ Torr.
The conductance was adjusted to be r. Then, MDX-1 was connected to the silicon cathode via SPARCLE-V.
A power of 0.75 kW was applied from 0K, and a 15 nm transparent silicon oxide film (63) was formed by intermittent DC sputtering of a silicon target. (4) After stopping the gas introduction and making the vacuum chamber high vacuum,
Mixed gas of argon and oxygen as discharge gas (20% oxygen)
Was introduced, and the conductance was adjusted so that the pressure became 2 × 10 ⁻³ Torr. Then MD on the cobalt cathode
A power of 0.5 kW was applied from X-10K, and a 10 nm-absorptive cobalt oxide film (64) was formed by DC sputtering of a cobalt target. The refractive index of this film is about 2.85 at 550 nm, and the extinction coefficient is 55
It was about 0.92 at 0 nm. (5) After stopping the gas introduction and making the vacuum chamber high vacuum,
Oxygen is introduced as a discharge gas, and the pressure is 2 × 10 ⁻³ Torr.
The conductance was adjusted to be r. Then, MDX-1 was connected to the silicon cathode via SPARCLE-V.
A power of 0.75 kW was applied from 0K, and a 30.5 nm transparent silicon oxide film (65) was formed by intermittent DC sputtering of a silicon target. (6) After stopping the gas introduction and making the inside of the vacuum chamber a high vacuum,
Mixed gas of argon and oxygen as discharge gas (20% oxygen)
Was introduced, and the conductance was adjusted so that the pressure became 2 × 10 ⁻³ Torr. Then MD on the cobalt cathode
A power of 0.5 kW was applied from X-10K, and a 10 nm-absorptive cobalt oxide film (66) was formed by intermittent DC sputtering of a cobalt target. (7) After stopping the gas introduction and making the inside of the vacuum chamber a high vacuum,
Oxygen is introduced as a discharge gas, and the pressure is 2 × 10 ⁻³ Torr.
The conductance was adjusted to be r. Then, MDX-1 was connected to the silicon cathode via SPARCLE-V.
A power of 0.75 kW was applied from 0 K, and a transparent silicon oxide film (67) of 80 nm was formed by intermittent DC sputtering of a silicon target.

The spectral transmittance of the obtained glass with a seven-layer film was measured. Further, the spectral reflectance of this sample was measured in a state where black lacquer was applied to the back surface of the glass substrate to eliminate the back surface reflection. The obtained spectral reflectance curve 68 and spectral transmittance curve 69 are shown in FIG.

The glass with an antireflection film obtained in each of Examples 1 to 7 was cut out into a square of about 5 cm, and the sheet resistance was measured with a non-contact conductivity meter. Table 1 summarizes the sheet resistance value thus obtained, the luminous reflectance on the film surface side (only on the film surface), the luminous transmittance, and the luminous reflectance on the glass surface side (including glass) obtained from the spectral curve. Indicated. Further, the sheet resistance, luminous reflectance and luminous transmittance measured in the same manner after the same glass having an antireflection film subjected to heat treatment twice at 450 ° C. for 30 minutes are also shown. Example 1 above
7 to 7, it is considered that films having the same film forming conditions have the same refractive index, extinction coefficient, and composition.

[0048]

[Table 1]

This table and FIGS. 2, 3, 5, 7, 9, 1
As can be seen from FIGS. 1 and 13, according to the present invention, a light-absorbing antireflection film having a relatively low reflectance from a glass surface can be realized with a relatively simple film configuration. Moreover, as can be seen from the spectral transmittance curve and the luminous transmittance shown in Table 1, the transmittance can be reduced by the light absorbing film used in the present invention. Therefore, when the present invention is applied to a panel glass, a face plate, a filter glass, or the like installed on the front of a display screen such as a CRT, the effect of improving the contrast of the display screen becomes more remarkable than that of the transparent anti-reflection film. . Further, when the present invention is applied to a plastic film such as PET or a substrate, a cylindrical C
The same effect as described above can be obtained by attaching to a surface of a display such as an RT, a flat CRT, a PDP, and an LCD.

[0050]

As is clear from the above examples, according to the present invention, it is possible to realize an antireflection film having an appropriate light absorptance with a simple film configuration and without increasing the total film thickness too much. it can. Further, if sputtering is used as a film formation method, there are advantages such as easy process stability and large area, and in combination with the above-described features, a light-absorbing anti-reflection film can be produced at low cost. It is. Further, as is apparent from the examples, the light-absorbing anti-reflection film according to the present invention has a relatively low reflectance with respect to the incident light from the back surface, and the signal light from the display is reflected on the inner surface. That is, the degree of a so-called double image is reduced, and the level can be suppressed to a level having no practical problem. Therefore, by coating the present invention directly on a CRT or by coating it on a plastic film and then affixing it to the surface of the CRT, a good contrast and a flat CRT can be obtained.
Also in the RT, it is possible to realize a CRT in which there is no difference in luminance between the central portion and the peripheral portion, and the visibility is not reduced by the double image. Further, in some configurations of the present invention, since it has excellent heat resistance and can sufficiently withstand the heat treatment required for the panel glass of a cathode ray tube, it is necessary to coat the panel glass and then mold it into a CRT. Thus, a similar CRT can be realized. When the heat resistance, adhesive strength, and scratch resistance are insufficient, a transparent nitride film having a thickness that does not substantially change the optical characteristics is inserted into each interface or the interface with the substrate as necessary. Thereby, these characteristics can be improved. Also, C
It can be expected to be applied not only to RT but also to applications requiring heat resistance.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing an example of the first invention.

FIG. 2 is a diagram showing a spectral reflectance and a spectral transmittance of Example 1.

FIG. 3 is a diagram showing a spectral reflectance and a spectral transmittance of Example 2.

FIG. 4 is a schematic sectional view showing an example of the second invention.

FIG. 5 is a diagram showing a spectral reflectance and a spectral transmittance of Example 3.

FIG. 6 is a schematic sectional view showing an example of the third invention.

FIG. 7 is a view showing a spectral reflectance and a spectral transmittance of Example 4.

FIG. 8 is a schematic sectional view showing an example of the fourth invention.

FIG. 9 is a diagram showing a spectral reflectance and a spectral transmittance of Example 5.

FIG. 10 is a schematic sectional view showing an example of the fifth invention.

FIG. 11 is a view showing a spectral reflectance and a spectral transmittance of Example 6.

FIG. 12 is a schematic sectional view showing an example of the sixth invention.

FIG. 13 is a view showing the spectral reflectance and the spectral transmittance of Example 7.

Continued on the front page F-term (reference) 2K009 AA07 AA08 AA09 AA12 CC02 CC03 CC14 DD04 4F100 AA12B AA12D AA20C AA20E AA22C AB12B AB12D AB13B AB16B AB40B AB40D AD04B AD04D AD04E AG00 AK01 BA00A00 BA00A00 BA00 AR00E AR00B AR00E JD20B JD20D JM02B JM02C JM02D JN01E JN18 JN18C JN18E YY00B YY00C YY00D YY00E 4G059 AA01 AC04 EA01 EA02 EA03 EA04 EA12 EA18 GA02 GA04 GA14

Claims (24)

[Claims] A first light absorbing film on a substrate in order from a substrate side;
A light-absorptive antireflection film formed by forming a micro-absorptive high-refractive-index film, a second light-absorbing film, and a transparent low-refractive-index film. 2. A first light absorbing film on a substrate in order from the substrate side,
A light-absorbing antireflection film formed by forming a transparent high-refractive-index film or a slightly absorbing high-refractive-index film, a second light-absorbing film, and a transparent medium-refractive-index film. 3. A first light absorbing film on a substrate in order from the substrate side,
A first transparent high refractive index film or a slightly absorbing high refractive index film,
A light absorbing film, a second transparent high refractive index film or a slightly absorbing high refractive index film, a third light absorbing film, and a transparent low refractive index film. 4. A first light absorbing film on a substrate in order from the substrate side,
A light-absorbing antireflection film formed by forming a transparent high-refractive-index film or a slightly absorbing high-refractive-index film, a second light-absorbing film, and a transparent low-refractive-index film. 5. A light-absorbing film, a transparent high-refractive-index film or a micro-absorbing high-refractive-index film, a first transparent low-refractive-index film, an absorptive oxide film, and a second transparent low-refractive-index film. A light-absorbing anti-reflection film formed by forming a refractive index film. 6. A light-absorbing film, a transparent high-refractive-index film or a slightly absorbing high-refractive-index film, a first transparent low-refractive-index film, a first absorptive oxide film, a second A transparent low refractive index film,
A light-absorbing anti-reflection film formed by forming a second absorbing oxide film and a third transparent low-refractive-index film. 7. The light absorption film according to claim 1, wherein said light absorption film is a film mainly composed of at least one metal selected from the group consisting of titanium, zirconium and hafnium or a nitride of a mixture thereof. The light-absorbing anti-reflection film according to claim 5. 8. The film according to claim 4, wherein said second light absorbing film is a film mainly containing at least one kind of metal selected from the group consisting of titanium, zirconium and hafnium or a nitride of a mixture thereof. Light absorbing anti-reflective coating. 9. The light-absorbing film is a film containing titanium nitride as a main component, and the ratio of titanium, nitrogen and oxygen in the film is in the range of 1: 0.5: 0.01 to 1: 1.5: 0.5. Certain claim 1
The light-absorbing antireflection film according to any one of claims 5 to 8. 10. The film according to claim 4, wherein said first light absorbing film is a film mainly composed of at least one metal selected from the group consisting of chromium, nickel, titanium and zirconium, or a mixture thereof. 9. The light-absorbing anti-reflection film according to 8. 11. The film according to claim 1, wherein said high-refractive-index film having a low absorbance is a film mainly composed of at least one selected from the group consisting of silicon oxynitride, bismuth oxide and chromium oxide.
11. The light-absorbing anti-reflection film according to any one of items 10 to 10. 12. The transparent high-refractive-index film is made of silicon nitride, aluminum nitride, tin oxide, zinc oxide, zirconium oxide,
The light-absorbing anti-reflection film according to any one of claims 2 to 11, which is a film containing at least one selected from the group consisting of indium oxide, tantalum oxide, niobium oxide, and titanium oxide as a main component. 13. The light-absorbing antireflection film according to claim 1, wherein the transparent low refractive index film is a film containing silicon oxide as a main component. 14. The transparent medium refractive index film is made of aluminum oxide or silicon oxide and two or more oxides having different refractive indexes selected from the group consisting of niobium oxide, tantalum oxide, titanium oxide and zirconium oxide. The light-absorbing antireflection film according to claim 2, which is a film containing a mixture as a main component. 15. The method according to claim 15, wherein the absorbing oxide film is at least one selected from the group consisting of cobalt, nickel, manganese, and iron.
A film mainly composed of an oxide of a kind of metal.
7. The light-absorptive anti-reflection film according to claim 9, or claim 11. 16. The first light-absorbing film having a geometric thickness of 10
-30 nm, the geometric thickness of the microabsorptive high refractive index film is 5-20 nm, the geometric thickness of the second light absorption film is 1-8 nm, and the transparent low refractive index film The light-absorbing anti-reflection film according to claim 1, wherein the geometric film thickness of the refractive index film is 50 to 90 nm. 17. The method according to claim 17, wherein the first light absorbing film has a geometric thickness of 5 to 5.
20 nm, wherein the geometrical thickness of the low absorption refractive index film is 10 to 40 nm, the geometrical thickness of the second light absorbing film is 5 to 20 nm, and the transparent low refractive index film is The light-absorbing antireflection film according to claim 1, wherein the film has a geometric thickness of 60 to 100 nm. 18. A geometric thickness of the first light absorbing film is 3 to 3.
20 nm, wherein the transparent high refractive index film or the slightly absorbing high refractive index film has a geometric thickness of 15 to 45 nm,
The light absorbing film has a geometric thickness of 5 to 30 nm, the transparent intermediate refractive index film has a refractive index of 1.6 to 1.9, and the geometric thickness is 40 to 100 nm. The light-absorbing anti-reflection film according to claim 2. 19. A geometric thickness of the first light absorbing film is 2 to 20.
10 nm, the first transparent high refractive index film or the micro-absorbent high refractive index film has a geometric thickness of 30 to 60 nm,
The second light-absorbing film has a geometric thickness of 5 to 15 nm, and the second transparent high-refractive-index film or the slightly absorbing high-refractive-index has a geometric thickness of 20 to 60 nm; The geometric thickness of the third light absorbing film is 5 to 20 nm, and the geometric thickness of the transparent low refractive index film is 50 to 100 nm.
3. The light-absorbing anti-reflection film according to item 1. 20. The first light-absorbing film having a geometric thickness of 1 to 20.
10 nm, the first transparent high refractive index film or the micro-absorbent high refractive index film has a geometric thickness of 40 to 80 nm,
The second light absorbing film has a geometric thickness of 5 to 15 nm, and the transparent low refractive index film has a geometric thickness of 50 to 110 n.
The light-absorbing anti-reflection film according to claim 4, wherein m is m. 21. The light-absorbing film has a geometric thickness of 2 to 20 n.
m, the transparent high-refractive-index film or the micro-absorbent high-refractive-index film has a geometric thickness of 3 to 50 nm, and the first transparent low-refractive-index film has a geometric thickness of 10 to 70 nm. The geometric thickness of the absorbing oxide film is 2 to 20 nm;
The light-absorbing anti-reflection film according to claim 5, wherein the low refractive index film has a geometric film thickness of 50 to 110 nm. 22. The light-absorbing film has a geometric thickness of 1 to 20 n.
m, the geometric thickness of the transparent high-refractive film or the microabsorptive high-refractive-index film is 3 to 50 nm, and the first transparent low-refractive-index geometric thickness is 10 to 50 nm. The first absorptive oxide film has a geometric thickness of 2 to 20 nm;
The second transparent low-refractive-index geometric film thickness is 10 to 50 nm.
Wherein the geometric thickness of the second absorbent oxide film is 2 to 2.
20 nm, and the geometric thickness of the third low refractive index film is 5
The light-absorbing anti-reflection film according to claim 6, which has a thickness of 0 to 110 nm. 23. The light-absorptive antireflection film according to claim 1, wherein the light absorptivity for incident light from the film surface side is 10 to 65%. 24. A transparent nitride film having a thickness that does not substantially change optical characteristics is formed at the interface between each layer or the interface with the substrate.
4. The light-absorptive anti-reflection film according to any one of the above items 3.