JP3190240B2 - Light-absorbing antireflective body and method for producing the same - Google Patents

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 body and a method for producing the same.

[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, there has been a demand for further reducing the transmittance of panel glass or shielding extremely low frequency electromagnetic waves that affect the human body in order to improve contrast.

[0003] As a method for meeting these demands,
(1) providing a conductive anti-reflection film on the panel surface;
(2) A conductive anti-reflection film is provided on the surface of a display screen face plate such as a CRT and the resin is adhered to the panel surface. (3) A filter glass provided with a conductive anti-reflection film on both sides is a front surface of a cathode ray tube. To be installed in the office.

In the cases of (2) and (3), an antireflection film is generally formed in multiple layers by a vacuum evaporation method. Examples of specific film configurations include, for example,
-168102. This publication describes that an antireflection film is formed by combining a low refractive index dielectric film, a high refractive index dielectric film, and a high refractive index conductive film. By coating the surface with a multilayer antireflection film having such a film configuration, the luminous reflectance of the surface is 0.3% or less and the sheet resistance of the surface is 1 k.
Ω / □ or less, and the above-mentioned electromagnetic wave shielding effect can be imparted.

As a method for increasing the contrast, it is known that it is effective to use an absorbing film as a part of the structure. For example, JP-A-64-707
No. 01 discloses an example in which a stainless film having a thickness of 4 nm, a titanium oxide film having a thickness of 29 nm, and a silica film having a thickness of 95 nm are sequentially formed on a glass substrate by a vacuum evaporation method. By coating the surface with a multilayer absorptive antireflection film, the luminous reflectance of the surface can be 0.3% or less and the sheet resistance of the surface can be 1 kΩ / □ or less.
At the same time, the visible light transmittance is reduced by several tens of percent, and high contrast can be achieved.

On the other hand, the method (1) includes (a) a method of forming a CRT after coating a panel and a method of (b) performing a surface coating after forming a CRT. At the present time, the so-called wet method such as spin coating is used at present.

In the case of the so-called dry method such as the above-mentioned vacuum evaporation method, in the case of (a), the film properties change due to the heat treatment in the cathode ray tube forming step after film formation, and the expected performance cannot be obtained. In addition, in the case of (b), there is a problem that it is necessary to install the entire cathode ray tube in a vacuum chamber, which limits the volume and weight and also makes it difficult to handle.

Also, in the sputtering method, which is a typical film forming method of the dry method, there is a difficulty in high-speed stable film formation of SiO ₂ , which is a low-refractive-index material essential for forming an antireflection film. At present, the technology for industrially producing an antireflection film having an area has not been established.

However, recently, with the advancement of the required characteristics as described above, the following problems have begun to occur in the surface treatment by the wet method. That is, (1) the wet method is more difficult to control the film thickness than the dry method, and if a multilayer structure having three or more layers having good antireflection performance is formed, reproducibility and uniformity become problems. The lower limit of the sheet resistance value so far is up to about 10 ³ kΩ / □, which is sufficient for antistatic, but 1 kΩ / □ required for electromagnetic wave shielding is difficult. (3) Antireflection It is difficult to impart absorptivity without impairing the 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 it has been required to realize a cheaper film formation method.

[0011] From these backgrounds, as a result of the recent active development of a method for forming SiO ₂ by a sputtering method stably and at high speed, several methods are being realized. For example, MMRS (metal mode reactive sputtering) found in US Pat. No. 4,445,997.
And C-Mag (cyl) of U.S. Pat.
indrical magnetron).

As a result, an antireflection film formed by a sputtering method is becoming a reality. However, the structure of the antireflection film often conforms to a film structure conventionally formed by a vacuum deposition method. Particularly effective film configurations have not been known so far.

The following is known as a conventional example of an antireflection film. For example, JDRancourt's "Optical
On page 128 of "Thin Films User's Handbook" (McGRAW-HILL, 1987), a complex refractive index (n
-Ik) = 2-i2 and a transparent film with n = 1.65 are formed in order of 3 nm and 75.8 nm, respectively.

However, in this case, what is presented is a theoretical calculation value, and the reflection characteristics are such that the reflection is made zero only at a single wavelength, which is indicated by a transparent two-layer film which is a basic structure of antireflection. Described as corresponding to a so-called “V coat”, and has a wide wavelength range (for example, 5
(00-650 nm).

US Pat. No. 5,091,244 discloses a structure for reducing the reflection of incident light from the substrate side (incident light from the side opposite to the film surface side) as a transition metal nitride in order from the substrate side. Material film and transparent film
It is described that the film is formed with a thickness of 9 nm and a thickness of 2 to 15 nm.

When the absorption film having an appropriate optical constant is formed thinly, the reflectance from the substrate side decreases, for example, as described in "Thin-Film Optical Filters", HAMacleod, McGRAW-H.
ILL, 2nd Ed., Pp. 65-66 (1989), and U.S. Pat.
O ₂ is laminated thinly ( ₂ to 15 nm).

However, this configuration is a configuration with a film thickness designed for the purpose of reducing the reflection from the substrate side. In the case of a multilayer film including an absorption film, the reflection on the front and back surfaces is completely different, and thus, in this configuration invented for reducing the reflection from the substrate side, the reflectance from the film surface side is about 10% over the visible light region. Yes, no low reflection performance can be obtained.

US Pat. No. 5,091,244 exemplifies a four-layer structure of glass / transition metal nitride / transparent film / transition metal nitride / transparent film as a structure for reducing the reflection on the film surface side. I have.

However, the purpose is to reduce the visible light transmittance to 50% or less. This is realized by dividing the absorption layer into two layers and increasing the number of layers to four or more. However, there is a practical problem in terms of manufacturing cost.

As described above, a film that includes an absorbing film as a constituent element, is basically a two-layer structure, has low manufacturing cost, and has low reflectivity over a wide wavelength range with respect to incident light from the film surface side. The composition was previously unknown.

[0021]

SUMMARY OF THE INVENTION The present invention is intended to solve the above-mentioned disadvantages of the prior art, and has a sufficient low reflection performance in a wide wavelength range and a sufficient electromagnetic shielding property. It is an object of the present invention to provide an inexpensive light-absorbing antireflective body having a low surface resistance value and an appropriate absorptivity of visible light for ensuring a high contrast, and having excellent productivity and a method for manufacturing the same.

[0022]

Means for Solving the Problems The present invention is, from the substrate side on the substrate, by forming a light absorbing film and sheet silica film in this order, the light absorption to reduce the reflection of incident light from the silica film side In the reflective antireflective body, the light absorbing film is made of titanium or zirconium.
At least selected from the group consisting of
The one metal nitrides a film mainly geometric thickness of that is 5 to 25 nm, and the geometrical film thickness of the silica film light absorption I 70~110nm der Membrane and silica
Geometry between the film and the optically insignificant layer
Or silicon nitride with a target thickness of 1-20 nm
Things to provide light-absorptive antireflection member, wherein Rukoto layer mainly has been formed and its manufacturing method.

[0023]

In the present invention, the geometric thickness of the light absorbing film (hereinafter, “geometric thickness” is simply referred to as “film thickness”) is
In order to realize low reflection, the thickness is 5 to 25 nm, and the thickness of the silica film is also 70 to 110 from the viewpoint of antireflection.
It is important that it is nm. If the thickness of any of the layers deviates from this range, sufficient antireflection performance in the visible light region cannot be obtained. In particular, the thickness range of the light absorbing film is preferably from 7 to 20 nm because low reflectivity over the visible light region can be realized.

A silica film (preferably having a refractive index of 1.4)
The thickness range of the silica film of 6 to 1.47) is 80 to
It is preferable that the wavelength is 100 nm because the low reflection wavelength region can be adjusted to the center of the visible light region.

It is particularly preferable that the thickness of the silica is more than 80 nm and 85 nm or less. When the thickness of silica is 80 nm or less, the reflectance on the long wavelength side tends to increase,
If it exceeds m, the rise of the reflectance on the short wavelength side shifts to the long wavelength side.

Further, from the viewpoint of heat resistance, the thickness of the light absorbing film in the present invention is desirably 10 to 20 nm. When the film thickness is less than 10 nm, the low reflection performance and the deterioration of the surface resistance value during the heat treatment become large.
If it exceeds nm, the heat resistance is improved, but the antireflection region is narrowed.

On the other hand, from the viewpoint of low reflection performance after film formation,
The thickness of the light absorbing film in the present invention is desirably 7 to 15 nm. When the film thickness is less than 7 nm, the reflectance on the long wavelength side tends to increase, and when the film thickness is 15 n
When m exceeds m, the low reflection wavelength region becomes narrow.

The thickness of the light absorbing film is more than 8 nm and 13 nm.
It is preferable that the thickness be less than 8 nm, especially 10 nm or less. When the thickness of the light absorbing film is 8 nm or less, the reflectance on the long wavelength side tends to increase. When the thickness is 13 nm or more, the rise of the reflectance on the short wavelength side shifts to the long wavelength side, and the reflectance on the long wavelength side increases. The rise tends to shift to the short wavelength side, and the low reflection region tends to be narrow.

Although the light-absorbing antireflection body of the present invention exhibits excellent antireflection properties, the properties may be deteriorated in the heat treatment step in the process of forming a cathode ray tube as described above. This characteristic change is mainly caused by oxidation of the light absorbing film.

Further, after forming the light absorbing film as the first layer, the light absorbing film may be oxidized when the second layer silica film is formed, and desired characteristics may not be obtained.

Therefore, between the light absorbing film and the silica film,
Inserting a layer that prevents oxidation of the light absorbing film (hereinafter referred to as an oxidation barrier layer) prevents oxidation during film formation,
Heat resistance can be improved.

This kind of oxidation barrier layer is widely used in a so-called Low-E glass using a silver film, and is disclosed in, for example, US Pat. No. 4,546,691 and JP-A-59-165001. Discloses that a barrier layer is formed for the purpose of preventing the silver film from being oxidized at the time of forming an oxide film subsequently formed on the silver film. As described above, this barrier layer is a thin film formed to prevent oxidation of another layer formed thereunder, and has no optical significance.

The thickness of the oxidation barrier layer is a 20nm or less in order not to impair the inherent antireflective performance. Also,
If the thickness of the oxidation barrier layer is less than 1 nm, the improvement in heat resistance will be insufficient. Therefore, when an oxidation barrier layer having a thickness of 1 to 20 nm is inserted, heat resistance is effectively improved.
Can be

As described above, the oxidation barrier layer has no optical significance and is an optically unnecessary layer.
The insertion of this layer may degrade the antireflection performance. In particular, when the oxidation barrier layer is light-absorbing (for example, light-absorbing silicon nitride), the antireflection performance is significantly deteriorated unless the thickness of the oxidation barrier layer is approximately 5 nm or less.

When a transparent oxidation barrier layer is used, the allowable thickness varies depending on the refractive index of this layer. The most acceptable thickness increases when the refractive index is used approximately 2.0 material (eg nitride silicon down), a barrier layer of up to about 20nm between the lower nitride layer and an upper silica layer, Insertion can be performed while maintaining low reflection characteristics.

Examples of the oxidation barrier layer, since there use <br/> a film mainly made of nitride film or silicon as a main component shea Rico emissions, the improvement sufficient antioxidant properties, excellent reflection maintenance of inhibition characteristics are compatible.

The film mainly made of nitride film or silicon as a main component divorced, after having excellent oxidation barrier performance, if formed by using a Si target conductive silica film, the target material In that there is no need to increase
It is advantageous in production.

The light absorptivity of the light-absorbing antireflection body in the present invention is 10 to 10 with respect to visible light incident from the silica film side.
Desirably, it is 35%. If the light absorption rate deviates from this range, the thickness range of the light absorption film is inappropriate, or the optical constant of the light absorption film is inappropriate,
Sufficient antireflection performance in the visible light region cannot be obtained.

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

Glass or plastic can be used as the substrate in the present invention. In particular, a glass substrate, a plastic substrate, or a plastic film constituting the front surface of the display surface for a display is preferable since the effects of the present invention can be sufficiently exerted.

Examples of the glass used as a substrate used on the front surface of the display include a panel glass itself constituting a cathode ray tube, a face plate glass used by attaching a resin to the cathode ray tube, and a glass placed between the cathode ray tube and an operator. And the like. Other examples include front glass of flat displays such as liquid crystal display panels and plasma display panels.

Examples of the plastic as a substrate or a film used on the front surface of the display include: 1) a transparent material such as PET (polyethylene terephthalate) which is used by adhering to a front glass of a cathode ray tube or the flat display with a resin. Examples include a film-like plastic, 2) a transparent plastic as a filter base provided between a cathode ray tube and an operator, and 3) a transparent plastic plate forming a front surface of a flat display.

FIG. 17 shows an example in which the light-absorbing antireflection member of the present invention is used. FIGS. 17A to 17C show examples in which the light-absorbing antireflection body of the present invention is applied to a CRT, a panel glass, and a plastic film attached to the front surface of the CRT, respectively.

As shown in FIG. 17, the light-absorbing antireflection body of the present invention in which the antireflection film is formed only on the surface of the substrate on the observer side has extremely excellent antireflection characteristics.
Further, since the antireflection film is formed directly on the surface of the substrate that generates the electromagnetic waves, the electromagnetic waves can be shielded very effectively.

When the light-absorptive antireflection body of the present invention is applied to the filter glass, an antireflection film may be formed on the surface of the substrate opposite to the observer.

As the light absorbing film in the present invention, a material is used which substantially reduces the surface reflectivity due to the light interference effect with the silica layer formed thereon.

[0053] As the light absorbing film, titanium, is used as a main component a nitride of at least one metallic selected from the group consisting of zirconium <br/> U beam Contact and hafnium
You. Titanium as a main component at least one metal nitride selected from the group consisting of zirconium beam contact and hafnium, preferably from the refractive index and dispersion relation extinction coefficient in the visible light region, the values of the optical constants Accordingly, there is a feature that a low reflection region in a visible light region is widened.

When two or more materials are used for the light absorbing film,
1) It may be used as a composite material, or 2) A film made of a different material may be laminated so as to have a total thickness of 5 to 25 nm.

Further, the film containing titanium nitride as the main component has a value in the visible light region of the optical constant that matches well with the silica film to reduce the reflectance, and has a suitable absorption coefficient. Since the film thickness for obtaining a good light absorption is in the range of several nm to several tens nm, it is particularly preferable from the viewpoint of productivity and reproducibility.

[0056] With the film mainly containing nitride as oxidation barrier layer, the first layer (light absorbing film) and in the same gas atmosphere oxide barrier layer can be formed by sputtering.
This is a great advantage when an actual film forming facility by sputtering is assumed.

That is, when a so-called in-line type sputtering apparatus excellent in mass productivity is considered, the light absorbing film and the oxidation barrier layer can be formed in the same chamber (referred to as chamber A). Therefore, the chamber for gas separation only needs to be provided between the chamber A and the chamber for forming a silica film which is subsequently formed on the upper layer, which is extremely efficient.

In particular, when a film containing titanium nitride as a main component is used as the first layer and silicon nitride is used as the oxidation barrier layer, the effect of improving the adhesion between the titanium nitride film and the outermost silica film can be obtained. . In this case, when both are formed by an in-line sputtering method in which they are formed in the same chamber, the silicon nitride film of the oxidation barrier layer becomes light-absorbing under suitable sputtering gas conditions for obtaining titanium nitride. In addition, the effect of improving the adhesive force can be obtained similarly.

[0059] As a forming method of the light absorbing film Contact and silica film in the present invention can adopt a general thin film forming means. For example, sputtering, vacuum deposition, CVD
And sol-gel methods.

In particular, the DC sputtering method is relatively easy to control the film thickness, obtains practical film strength even when formed on a low-temperature substrate, and is easy to increase the area.
The use of a so-called in-line facility is preferable in that the formation of a laminated film is easy. Moreover, titanium, zirconium, nitrides of hafnium, it is also an advantage that is relatively easy to adjust the film formation conditions to have a good <br/> preferable optical constant as the light absorbing layer .

When an in-line type sputtering apparatus is used, the film thickness distribution in the width direction of the transfer can be adjusted to some extent by setting a mask plate, a magnetic field intensity distribution of a cathode magnet, and the like. For this reason, when a substrate used on the front surface of the display is used as the substrate, it is possible to set the thickness of the peripheral portion of the substrate to be slightly thicker than that of the central portion. By providing such a film thickness distribution on the substrate, when the peripheral portion of the screen is viewed from the center, the phenomenon that the reflected color shifts to yellow or red due to the oblique incidence effect of light can be mitigated. preferable.

[0062] The vacuum deposition method requires that the substrate be heated.
The drawbacks are that it is difficult to increase the area and it is relatively difficult to obtain a good nitride.However, if the base material is relatively small and can withstand high temperatures, the process is the most completed than before. Is advantageous.

The CVD method requires a higher temperature, and it is difficult to increase the area from the viewpoint of the film thickness distribution. However, the CVD method is an excellent method for obtaining a good nitride.

The sol-gel method is a wet method described in the section of the prior art, and has a track record as a surface treatment technique for a cathode ray tube. It is relatively difficult to obtain good nitrides, and batch processing is performed one by one. However, since equipment investment is small, there is a possibility that it is advantageous in terms of cost during small-scale production.

The light absorbing antireflection film of the present invention can be formed by combining these methods. For example, a light absorbing layer of the first layer, after forming a relatively preferred are easy sputtering obtained optical constants, by silica film can be formed by spin coating of a wet method with excellent film-forming cost. Similarly, after the light absorption layer of the first layer is formed by CVD, by silica film can be formed by spin coating of a wet method with excellent film-forming cost.

In this case, depending on the spin coating liquid, the light absorbing film already formed as the first layer may be eroded, and as a result, desired characteristics may not be obtained.
For example, when using a spin coat solution composed of 0.1 N hydrochloric acid, tetraethoxysilane and ethyl alcohol, a durable oxide film or nitride film is formed as a protective film of the first layer before the spin coat. Preferably.

[0067] As described above, as the method of forming the light-absorptive antireflection film of the present invention, various techniques and combinations thereof are contemplated, the present invention is not limited thereto.

As a light absorbing film containing titanium nitride as a main component (referred to as a TiN light absorbing film), a metal titanium target obtained by DC sputtering in the presence of nitrogen gas is most preferably used from the viewpoint of productivity. preferable.

At this time, in order to keep the optical constant of the TiN light absorbing film in a preferable range, the sputtering gas contains nitrogen and a rare gas as main components, and the proportion of nitrogen is 3%.
It is preferable that the content be from 50 to 50% by volume, especially from 5 to 20% by volume. If the proportion of nitrogen is smaller than this, the TiN light absorbing film becomes excessive in titanium, and the low reflection wavelength region is narrowed. On the other hand, if the proportion of nitrogen is larger than this, the TiN light absorbing film becomes excessive in nitrogen, the low reflection wavelength region is narrowed, and the specific resistance of the TiN light absorbing film is increased to increase the surface resistance.

The power applied to the target is 1 W / cm
Preferably, the power density is ² or more. This is because the film formation speed is kept fast enough for industrial production and the amount of impurities taken into the TiN light absorbing film during film formation is kept low. In particular, as described later, the effect of suppressing the amount of oxygen taken into the film is great.

It is preferable that the power applied to the target at this time has a power density of 10 W / cm ² or less. This is to obtain a TiN light-absorbing film having an appropriate optical constant and to avoid frequent dissolution of the target or the cathode and frequent occurrence of abnormal discharge due to excessive power supply to the target. That is, when more power is applied, a Ti-rich TiN light-absorbing film is formed even in a pure nitrogen atmosphere, and a desired composition cannot be obtained. In addition, the target and its peripheral components are heated, and arcing occurs and in some cases, There is a risk of melting of the heated area.

The inclusion of a small amount of impurities in the composition of the target or the sputtering gas poses no problem as long as the finally formed thin film has substantially the optical constant of the TiN light absorbing film. Also, using a material containing titanium nitride as a main component as a target,
An N light absorbing film may be formed.

The TiN light absorbing film preferably has an atomic ratio of nitrogen to titanium in the film of 0.5 to 1.5 from the viewpoint of optical constant and specific resistance. If it is smaller than 0.5, the titanium nitride film becomes a little excessively titanium and the specific resistance is lowered, but the optical constant becomes inappropriate and the antireflection effect becomes insufficient. On the other hand, if it is larger than 1.5, the film becomes a titanium nitride film having an excessive amount of nitrogen.
Since the specific resistance increases, both the reflectance and the surface resistance become insufficient.

In particular, from the viewpoint of preventing reflection, the atomic ratio of nitrogen to titanium in the film is preferably 0.75 to 1.30.

On the other hand, it has been found that the presence of oxygen has the effect of improving the adhesion to the oxide substrate and the upper silica film. Therefore, as long as the optical constant of the TiN light absorbing film is kept in a preferable range, it may be preferable that oxygen is contained in the TiN light absorbing film.

In this case, the atomic ratio of oxygen to titanium in the TiN light absorbing film is preferably 0.5 or less from the viewpoint of optical constant and specific resistance. When this ratio is larger than 0.5, a titanium oxynitride film is formed,
As the specific resistance increases, the optical constant becomes inappropriate,
Both the surface resistance and the antireflection effect become insufficient.

When a TiN light absorbing film is formed by a normal sputtering method, it is inevitable that oxygen is mixed into the film due to residual gas in a vacuum chamber. The effect of oxygen in the film on the optical properties of the TiN light absorbing film has not been known so far. In particular, the effect on the performance as a light absorbing layer in the present invention was not known at all.

The present inventors have conducted intensive studies on the relationship between the film forming conditions of the TiN light absorbing film and the amount of oxygen in the TiN light absorbing film, and the relationship with the performance as a light absorbing layer in the present invention. It has been found that, from the viewpoint of optical constants, the atomic ratio of oxygen to titanium in the film is preferably 0.4 or less from the viewpoint of optical constants.

When this ratio exceeds 0.4, the wavelength dependence of the optical constant of TiN deviates from a preferable range, and as a result, the low reflection characteristic tends to decrease. Further, since the oxynitride film is formed, the specific resistance also increases, and the surface resistance tends to exceed 1 kΩ / □ necessary for shielding electromagnetic waves.

The present inventors have made T based on the above findings.
By selecting the film forming method and film forming conditions of iN,
As shown in the examples described later, when the silica film is formed on the upper layer with an optimum film thickness, a low reflectance of 0.1 as a low reflection characteristic.
The wavelength region satisfying 6% or less is at least 500 to 650.
Ti that realizes a laminate having a wide range of nm
An N light absorbing film was formed.

As described above, in the present invention, by keeping the optical constant of the used TiN light absorbing film within a certain preferable range, a laminate having extremely excellent low reflection characteristics can be obtained.

The optical constants will be described in more detail below.

Conventionally, in the case of a two-layer antireflection film using a transparent film, the reflectance at the design wavelength is made completely zero by selecting the refractive index and the film thickness of each layer according to the refractive index of the substrate. sell. However, at wavelengths other than the design wavelength, the antireflection conditions are degraded, so that the reflectance rises significantly before and after the so-called “V-coat”, and the low reflectivity in the wide wavelength range that the present inventors aim for cannot be obtained.

On the other hand, if the absorbing film is used as a component,
The parameters of the single film are (n, d) (n:
Refractive index, d: geometric film thickness) from (n, k, d)
Since (k: extinction coefficient) is increased to three, and the wavelength dependence (dispersion) of (n, k) is large in the absorption film, the absorption film having an ideal (n, k) wavelength dispersion. Is formed to a predetermined film thickness, it can be theoretically possible to make the reflectance completely zero at all wavelengths when combined with a transparent film laminated thereon.

Here, as an example of the theoretical calculation performed by the present inventors, a 15 nm absorption film was formed in the lower layer, and SiO ₂ was formed in the upper layer.
FIG. 16 shows the dispersion relationship of (n, k) necessary to make the reflectance zero over the entire visible region when the layers are stacked to a thickness of 00 nm. FIGS. 16A and 16B show the relationship between n and wavelength and the relationship between k and wavelength, respectively.
Find a material with (n, k) as shown in this figure or
If combined, a complete anti-reflection film can be realized with a two-layer configuration. However, as can be seen from this figure, there is a wavelength range in which k must take a negative value.
Such materials cannot be realized.

The present inventors searched for a material having an optical constant close to the ideal (n, k), and found that titanium nitride,
Zirconium nitride and hafnium nitride were found to be candidates.

In addition, as a result of conducting various experiments using the sputtering method, it was found that by selecting a specific material, a specific film forming condition, or a film thickness, a very excellent low reflection characteristic could be obtained in a wide wavelength range. It has been found that a two-layer film configuration can be obtained.

As the silica film used in the present invention, it is preferable from the viewpoint of productivity that a conductive silicon target is subjected to DC sputtering in the presence of oxygen gas. At this time, a small amount of impurities are mixed in order to impart conductivity to the target.In this case, the silica film includes, in these cases, generally includes a small amount of impurities, and substantially contains silica. It should be considered to indicate a film with approximately the same refractive index.

In DC sputtering of silicon, arcing is induced by the charging of the insulating silica film attached to the peripheral portion of the erosion (erosion) region of the target, so that the discharge becomes unstable or the silicon emitted from the arc spot becomes unstable. Alternatively, silica particles may adhere to the substrate to cause defects. In order to prevent this, a method of neutralizing the charge by periodically applying a positive voltage to the cathode is often adopted, and the use of a silica film formed by these methods is not suitable for process stability. Very preferred from the point of view. As a method for forming a silica film, RF sputtering may be used.

The light-absorbing anti-reflective body of the present invention exhibits excellent anti-reflection properties, but has a particularly low reflectance at the center of the visible region, and therefore has a reflection color from blue to purple. The thicker the silica, the more bluish, and the thinner the silica, the more reddish. Further, when the thickness of the light absorbing film is increased, the color becomes darker, and conversely, when the thickness of the light absorbing film is decreased, the color becomes colorless. Therefore, the film thickness may be appropriately adjusted according to the application.

In the present invention, an additional thin film layer for improving the adhesion at the interface and adjusting the color tone may be provided as appropriate.

Further, an oil-repellent organic film containing fluorocarbon can be formed on the outermost layer to facilitate wiping when a fingerprint is attached to the outermost surface. As a forming method, there are a vapor deposition method, a coating drying method, and the like, all of which form an extremely thin film to such an extent that optically is not affected. By performing these treatments, the surface of the antireflection film is less likely to be stained, and even if it is stained, it can be easily wiped off.

In the light-absorbing antireflection body of the present invention,
In a wide wavelength range of 500 to 650 nm, it is preferable to form the film by appropriately determining the film forming conditions and the film thickness of each layer so that the reflectance does not exceed 0.6%. In particular, 45
It is preferable that each layer is formed so that the reflectance at 0 to 650 nm does not exceed 1.0%. further,
Each layer is preferably formed so that the reflectance does not exceed 0.6% at 450 to 650 nm.

[0094]

The light-absorbing anti-reflective body of the present invention absorbs a part of incident light and reduces the transmittance. Therefore, when applied to the front glass of a display, the light enters from the surface and is reflected on the display element side surface. The intensity of the incoming light beam is reduced, and the contrast can be increased by increasing the ratio between the display light and the background light.

[0095] substrate in the present invention, the light absorbing film, and a sheet silica film reflection Fresnel coefficient of each interface, total reflectivity determined by the amplitude attenuation of the phase variation and the layers between each interface, visible light It is set to be sufficiently low in the region.

In particular, the optical constant of the light absorbing film exhibits a dependency different from the dispersion relationship (wavelength dependency) in the visible light region of a normal transparent film. Therefore, when an absorbing film material having an appropriate dispersion relation is used as the first layer, the low reflection region in the visible light region is widened as compared with a case where the material is composed of only the transparent film. This effect is titanium, is remarkable in the case of using at least one metal nitride selected from the group consisting of zirconium beam Contact and hafnium as the light absorbing film.

Although the principle of realizing low-reflection characteristics in a wide wavelength range by the film configuration of the present invention, as shown in Examples described later, has not yet been elucidated in many parts, the optical constants of the absorbing thin film of the present invention are unclear. Is closer to the ideal value than expected. The possible causes are as follows.

1) Since the film thickness is small, the film is actually not a uniform film, but has a distribution of optical constants in a plane or in a thickness direction, and shows an optical constant equivalent to an ideal.

2) A film having a dispersion of optical constants (nearly ideal) which has not been known until now can be obtained under specific film forming conditions.

3) In the process of forming the upper silica film, the upper part of the lower absorption film is partially oxidized, so that the substantial optical constant changes (to a more ideal value).

According to [0102] the present invention, by forming a TiN light absorbing film having optical constants of a preferred range, has an effect as described above, substantially two-layer or Ranaru, very good low reflection characteristic Can be realized.

[0102]

EXAMPLES [Example 1 (Comparative Example) ] In a vacuum chamber, metal titanium and N having a specific resistance of 1.2 Ω · cm
The vacuum chamber was evacuated to 1 × 10 ⁻⁵ Torr by setting the mold silicon (phosphorus-doped single crystal) as a target on the cathode. A two-layer film was formed on a soda lime glass substrate 10 placed in a vacuum chamber as follows, to obtain a light-absorbing antireflective member as shown in FIG.

As a discharge gas, a mixed gas of argon and nitrogen (20% by volume of nitrogen) was introduced, and the pressure was 2 × 10 ⁻³ To.
The conductance was adjusted to be rr. Next, a negative DC voltage (input power density of about 2.0
W / cm ² ) and a titanium nitride film 11 having a thickness of 14 nm (geometric film thickness, the same applies to the following film thickness) was formed by DC sputtering of a titanium target (step 1).

Next, the gas introduction was stopped, the inside of the vacuum chamber was made high vacuum, and a mixed gas of argon and oxygen (50% by volume of oxygen) was introduced as a discharge gas, and the pressure was 2 × 10 ⁻³ To.
The conductance was adjusted to be rr. Then, a voltage having the waveform shown in FIG. 3 was applied to the silicon cathode, and 1
A 00 nm silica film 13 (refractive index: 1.46) was formed (Step 2).

The spectral transmittance of the obtained light-absorbing anti-reflection glass was measured. Also, the spectral reflectance of this sample is
The measurement was performed from the film surface side in a state where black lacquer was applied to the back surface of the glass substrate to eliminate reflection on the back surface. FIG. 4 shows the obtained spectral transmittance curve 42 and spectral reflectance curve 41.

After the step 1, the glass substrate with the titanium nitride film was taken out, and the titanium nitride film was analyzed by ESCA. The atomic ratio was Ti: N: O = 1: 0.86: 0.
It was 16.

[Example 2 (Comparative Example) ] Using the same apparatus and target as in Example 1, and using one vacuum chamber
Evacuation was performed to × 10 ⁻⁵ Torr. A two-layer film was formed on a soda lime glass substrate set in a vacuum chamber as follows. The discharge gas of step 1 in Example 1 except the E-varying nitrogen gas (100% nitrogen) in the same manner as Example 1, was deposited 14nm of titanium nitride film. Next, a silica film having a thickness of 100 nm was formed in the same manner as in Step 2 of Example 1.

After the formation of the titanium nitride film, the substrate was taken out in the same manner as in Example 1, and the titanium nitride film was analyzed by ESCA. The atomic ratio was Ti: N: O = 1: 0.92: 0.20. .

Example 3 (Comparative Example) Using the same apparatus and target as in Example 1, and using a vacuum chamber
Evacuation was performed to × 10 ⁻⁵ Torr. A two-layer film was formed on a soda lime glass substrate set in a vacuum chamber as follows. The discharge gas of step 1 example 1 example varying a mixed gas of nitrogen 10% by volume of argon and nitrogen, in the same manner as in Example 1 12n
m of titanium nitride film was formed. Next, a silica film having a thickness of 85 nm was formed in the same manner as in Step 2 of Example 1.

With respect to the obtained light-absorbing anti-reflection glass, a spectral reflectance curve 61 was measured in the same manner as in Example 1. FIG. 6 shows the results.

After forming the titanium nitride film, the substrate was taken out in the same manner as in Example 1, and the titanium nitride film was analyzed by ESCA. The atomic ratio was Ti: N: O = 1: 0.95: 0.08. In addition, about the obtained light absorption anti-reflection glass,
FIG. 14 shows a curve of the spectral reflectance after heat treatment at 450 ° C. for 30 minutes three times.

Example 4 (Comparative Example) Using the same apparatus and target as in Example 1, and using a vacuum chamber
Evacuation was performed to × 10 ⁻⁵ Torr. A two-layer film was formed on a soda lime glass substrate set in a vacuum chamber as follows. A titanium nitride film of 7 nm and 85
nm of silica film was sequentially formed.

With respect to the obtained light-absorbing anti-reflection glass, a curve of spectral reflectance was measured in the same manner as in Example 1.
The results are shown in FIG. After forming the titanium nitride film, the substrate was taken out in the same manner as in Example 1 and the titanium nitride film was analyzed by ESCA. The atomic ratio was Ti: N: O = 1: 0.95: 0.09.
Met.

Example 5 (Comparative Example) Using the same apparatus and target as in Example 1, and using a vacuum chamber
Evacuation was performed to × 10 ⁻⁵ Torr. A two-layer film was formed on a soda lime glass substrate set in a vacuum chamber as follows. A titanium nitride film having a thickness of 20 nm was formed in the same manner as in Step 1 of Example 1. Next, in the same manner as in Step 2 of Example 1, 10
A 0 nm silica film was formed.

With respect to the obtained light-absorbing anti-reflection glass, the curve of the spectral reflectance was measured in the same manner as in Example 1.
The results are shown in FIG. After forming the titanium nitride film, the substrate was taken out in the same manner as in Example 1, and the titanium nitride film was analyzed by ESCA. The atomic ratio was Ti: N: O = 1: 0.84: 0.17.
Met.

Example 6 Using the same apparatus and target as in Example 1, and using a vacuum chamber
Evacuation was performed to × 10 ⁻⁵ Torr. A multilayer film was formed on a soda lime glass substrate set in a vacuum chamber as follows. A 14 nm titanium nitride film was formed in the same manner as in Step 1 of Example 1.

Next, the discharge gas was switched to 100% argon, the pressure was adjusted to 2 × 10 ⁻³ Torr, a negative DC voltage was applied to the silicon cathode, and the oxide barrier film was formed by DC sputtering of a silicon target. A 2 nm silicon film was formed. Next, a silica film having a thickness of 100 nm was formed in the same manner as in Step 2 of Example 1.

After forming the titanium nitride film, the substrate was taken out in the same manner as in Example 1, and the titanium nitride film was analyzed by ESCA. As a result, the atomic ratio was Ti: N: O = 1: 0.88: 0.14.

Example 7 Using the same apparatus and target as in Example 1, and using a vacuum chamber
Evacuation was performed to × 10 ⁻⁵ Torr. A multilayer film was formed on a soda lime glass substrate set in a vacuum chamber as follows.

First, a titanium nitride film having a thickness of 12 nm was formed in the same manner as in Example 3. Next, the discharge gas was 30% by volume of nitrogen.
Switch to a mixed gas of argon and nitrogen at a pressure of 2 × 1
After adjusting to 0 ⁻³ Torr, a negative DC voltage was applied to the silicon cathode, and a 5 nm light-absorbing silicon nitride film was formed as an oxidation barrier film by DC sputtering of a silicon target. Next, in the same manner as in Example 3, an 85 nm silica film was formed thereon.

After forming the titanium nitride film, the substrate was taken out in the same manner as in Example 1, and the titanium nitride was analyzed by ESCA. As a result, the atomic ratio was Ti: N: O = 1: 0.97: 0.06.
In addition, about the obtained light-absorbing antireflection glass, 45
FIG. 15 shows a curve of the spectral reflectance after heat treatment at 0 ° C. for 30 minutes three times.

Example 8 (Comparative Example) Using the same apparatus and target as in Example 1, and using one vacuum chamber
Evacuation was performed to × 10 ⁻⁵ Torr. After introducing oxygen gas as a discharge gas and adjusting the pressure to 2 × 10 ⁻³ Torr,
A negative DC voltage was applied to the titanium cathode, and an underlayer of a 3 nm titanium oxide film was formed on a soda lime glass substrate set in a vacuum chamber by DC sputtering of a titanium target. Next, a titanium nitride film of 12 nm and a silica film of 85 nm were formed on the titanium oxide film in the same manner as in Example 3.

With respect to the obtained light-absorbing anti-reflection glass, the spectral reflectance curve 71 was measured in the same manner as in Example 1. FIG. 7 shows the results. After forming the titanium nitride film, the substrate was taken out in the same manner as in Example 1, and the titanium nitride film was analyzed by ESCA. The atomic ratio was Ti: N: O = 1: 0.93: 0.0.
It was 7.

Example 9 (Comparative Example) Using the same apparatus and target as in Example 1, and using a vacuum chamber
Evacuation was performed to × 10 ⁻⁵ Torr. P installed in a vacuum chamber
A two-layer film was formed on an ET substrate (having a hard coat and having a thickness of 150 μm) as follows. 12n as in Example 3
A titanium nitride film of m and a silica film of 85 nm were formed.

With respect to the obtained PET with the light-absorbing anti-reflection film, the spectral reflectance curve 81 was measured in the same manner as in Example 1. FIG. 8 shows the results. After forming the titanium nitride film, the substrate was taken out in the same manner as in Example 1, and the titanium nitride film was analyzed by ESCA. The atomic ratio was Ti: N: O = 1: 0.91:
0.11.

Example 10 (Comparative Example) Using the same apparatus and target as in Example 1, and using a vacuum chamber
Evacuation was performed to × 10 ⁻⁵ Torr. A three-layer film was formed on a soda-lime glass substrate 20 placed in a vacuum chamber as follows, to obtain a light-absorbing antireflective member as shown in FIG.

Using the same gas and pressure as in Step 1 of Example 1, a negative DC voltage was applied to the titanium cathode, and a 30 nm titanium nitride film 21 was formed by DC sputtering of a titanium target.

Next, after the gas introduction was stopped and the inside of the vacuum chamber was set to a high vacuum, a negative DC voltage was applied to the titanium cathode using the same gas and pressure as in step 1 of Example 1 to obtain a titanium target. The titanium oxide film 22 (refractive index: about 2.2) of 18 nm was formed by DC sputtering.

Next, a voltage having a waveform shown in FIG. 3 was applied to the silicon cathode while the introduced gas was kept as it was, and the silicon target was subjected to intermittent DC sputtering to produce a 63 nm
Was formed.

After forming the titanium nitride film, the substrate was taken out in the same manner as in Example 1, and the titanium nitride film was analyzed by ESCA. As a result, the atomic ratio was Ti: N: O = 1: 0.87: 0.14. .

Example 11 (Comparative Example) Instead of the titanium oxide film in Example 10, an ITO (tin-doped indium oxide) target was used to form an ITO film (refractive index: about 2.0). A light-absorbing antireflective body with a three-layer film was obtained in the same manner as in Example 10, except that the thicknesses of the titanium film and the silica film were changed.

That is, as in Example 10, first, 2
A titanium nitride film having a thickness of 3 nm was formed, and then an ITO cathode was used in place of the titanium cathode of Example 10, and a mixed gas of argon and oxygen (1% by volume of oxygen) was used as a discharge gas. To perform DC sputtering,
A 22 nm ITO film was formed, and finally a 59 nm silica film was formed.

After forming the titanium nitride film, the substrate was taken out in the same manner as in Example 1, and the titanium nitride film was analyzed by ESCA. The atomic ratio was Ti: N: O = 1: 0.86: 0.18. .

Example 12 (Comparative Example) Using the same apparatus and target as in Example 10, the vacuum chamber was evacuated to 1 × 10 ⁻⁵ Torr. After introducing oxygen gas as a discharge gas and adjusting the pressure to 2 × 10 ⁻³ Torr, a negative DC voltage is applied to the titanium cathode, and DC sputtering of a titanium target is performed, soda lime glass placed in a vacuum chamber. 3 nm as an underlayer on the substrate
Was formed.

Next, Example 10 was formed on a 3 nm titanium oxide film.
A titanium nitride film having a thickness of 30 nm, a titanium oxide film having a thickness of 18 nm, and a silica film having a thickness of 63 nm were formed in this order.

After forming the titanium nitride film, the substrate was taken out in the same manner as in Example 1, and the titanium nitride film was analyzed by ESCA. The atomic ratio was Ti: N: O = 1: 0.85: 0.17.

Example 13 (Comparative Example) Using the same apparatus and target as in Example 10, the vacuum chamber was evacuated to 1 × 10 ⁻⁵ Torr. A three-layer film was formed on a soda lime glass substrate set in a vacuum chamber as follows.

First, a 30 nm titanium nitride film was formed in the same manner as in Example 10. Next, the discharge gas was changed to argon 10
After switching to 0% and adjusting the pressure to 2 × 10 ⁻³ Torr, a negative DC voltage was applied to the silicon cathode, and a 3 nm silicon film was formed as an oxidation barrier film by DC sputtering of a silicon target. Next, Example 1
0, a titanium oxide film of 18 nm and 6
A 3 nm silica film was formed.

After forming the titanium nitride film, the substrate was taken out in the same manner as in Example 1, and the titanium nitride was analyzed by ESCA. The atomic ratio was Ti: N: O = 1: 0.88: 0.16.

[Example 14 (Comparative Example) ] Using the same apparatus and target as in Example 1, and using one vacuum chamber
Evacuation was performed to × 10 ⁻⁵ Torr. On a soda lime glass substrate set in a vacuum chamber, a two-layer film composed of a 9 nm titanium nitride film and an 85 nm silica film was formed in this order in the same manner as in Example 3. After forming the titanium nitride film, the substrate was taken out in the same manner as in Example 1, and the titanium nitride film was analyzed by ESCA. The atomic ratio was Ti: N: O = 1: 0.94: 0.11.
Met. The spectral reflectance of the obtained sample was measured in the same manner as in Example 1. The result is shown in FIG.

[Example 15 (Comparative Example) ] Using the same apparatus and target as in Example 1, and using one vacuum chamber
Evacuation was performed to × 10 ⁻⁵ Torr. A two-layer film was formed on a soda lime glass substrate set in a vacuum chamber as follows.

First, a titanium nitride film of 12 nm was formed in a mixed gas atmosphere of 10% by volume of nitrogen and argon in the same manner as in Example 3; , Ie, the input power density was about 0.5 W / cm ² . Next, a silica film having a thickness of 102 nm was formed in the same manner as in Example 3.

After forming the titanium nitride film, the substrate was taken out in the same manner as in Example 1, and the titanium nitride film was analyzed by ESCA. The atomic ratio was Ti: N: O = 1: 0.70: 0.65.

The spectral reflectance of the obtained sample was measured in the same manner as in Example 1. FIG. 13 shows the results.

Example 16 (Comparative Example) An ITO film was formed by using an ITO target instead of the titanium nitride film in Example 1, and the thickness of the silica film was changed. Thus, an antireflection body with a two-layer film was obtained.

That is, DC sputtering was performed in the same manner as in Example 1 except that an ITO cathode was used instead of the titanium cathode, and a mixed gas of argon and oxygen (oxygen was 1% by volume) was used as a discharge gas. ITO
Was formed, and then a 110 nm silica film was formed in the same manner as in Example 1.

With respect to the obtained sample, the curve 52 of the spectral transmittance and the curve 5 of the spectral reflectance were obtained in the same manner as in Example 1.
1 was measured. The results are shown in FIG.

Example 17 (Comparative Example) Using the same apparatus and target as in Example 1, and using a vacuum chamber
Evacuation was performed to × 10 ⁻⁵ Torr. A two-layer film was formed on a soda lime glass substrate set in a vacuum chamber as follows. A 30 nm titanium nitride film and 1
A silica film having a thickness of 00 nm was formed.

With respect to the obtained sample, a curve 92 of spectral transmittance and a curve 9 of spectral reflectance were obtained in the same manner as in Example 1.
1 was measured. FIG. 9 shows the results. After forming the titanium nitride film, the substrate was taken out in the same manner as in Example 1, and the titanium nitride film was
When analyzed by SCA, the atomic ratio was Ti: N: O = 1:
0.87: 0.15.

The antireflection glass obtained in each of Examples 1 to 17 was cut into a 3 cm square, and electrodes were formed at four corners of the film surface with glass solder. Surface resistance measured by Van der Pauw method, luminous reflectance and luminous transmittance obtained from spectral curves, and light absorption for incident light from the silica film side (hereinafter simply referred to as light absorption) Are summarized in Table 1.

The same light-absorbing anti-reflection glass has 45
Surface resistance measured in the same manner after the heat treatment for 30 minutes at 0 ° C. for 30 minutes, and a wavelength range where the luminous reflectance, luminous transmittance, light absorption and reflectance are 0.6% or less. Are shown in Table 1. Note that “before” and “after” in Table 1 mean before and after heat treatment, respectively.

As can be seen from Table 1 and FIGS.
According to the present invention, a light-absorptive anti-reflection glass having excellent heat resistance can be realized with a simple film configuration.

When comparing the spectral reflectance curves of Example 16 (Comparative Example) composed of only the transparent film and Example 1, the spectral reflectance curve of Example 1 has a wider low-reflection region and shows excellent antireflection characteristics. .

[0154] Also, as can be seen from the spectral transmittance curve and the luminous transmittance in Table 1, towards the light absorption film used in this onset Ming, compared with the antireflection film of the transparent, can reduce the transmittance. Therefore, the present invention can be applied to a panel glass, a face plate,
When applied to a filter glass or the like, the effect of improving the contrast of the display screen becomes more remarkable than in the case of a transparent antireflection film.

Also, as can be seen from these examples,
According to the present invention, by selecting the thickness of the light-absorbing film within a preferred range, the light-absorbing antireflective body of the present invention can have a light absorption rate of 10 to 35% with respect to incident light from the silica film side. Can be adjusted. As can be seen from the graph of the spectral reflectance of the embodiment, if the thickness of the light absorbing film is increased, the low reflection wavelength region is narrowed, and thus the thickness may be selected according to the purpose.

Examples 1 to 5, 14, FIG. 4, FIG. 6, FIG.
As can be seen from a comparison between Example No. 0 and FIG. 11, and Example 17 (Comparative Example) and FIG. It can be done. However, when the antireflection performance is improved by thinning the titanium nitride, the heat resistance is slightly reduced, and the change in characteristics after the heat treatment is slightly increased.

As can be seen from Example 5, when the thickness of titanium nitride is increased, the change in characteristics due to the heat treatment is alleviated as compared with the case where the thickness is small. However, in this case, the luminous reflectance before the heat treatment is as low as 0.12%, but the reflectance in the wavelength region at both ends of the visible light is remarkably increased, and the reflected color is light blue-violet.

As can be seen from Examples 6 and 7, even when the thickness of titanium nitride is reduced, the heat resistance can be remarkably improved by forming the oxidation barrier layer on the titanium nitride film.

As can be seen from Example 8 and FIG. 7, the reflection color tone can be made more colorless by inserting the reflection color adjusting layer into the film structure.

[0160] As can be seen from Examples 9 and 8, in the case of using a plastic as a substrate, a light absorptive antireflection member showing a good good low reflection characteristic is obtained.

Before and after the heat treatment of the samples of Examples 1 to 15, a scratch resistance test (500
(g load, 20 reciprocations), no scratches that would cause a practical problem were found in any case. In particular, Examples 1 to
No damage was observed when the samples of Examples 9 and 14 and 15 were subjected to heat treatment before and after the heat treatment.

[0162]

[Table 1]

[0163]

The multilayer film used in the light-absorbing anti-reflective body of the present invention has an appropriate light absorption and anti-reflection performance,
This can be realized with a simple film configuration and without increasing the total film thickness too much.

The contrast can be increased by lowering the transmittance, and a light-absorbing antireflective body having a resistance value of 1 kΩ / □ or less and having electromagnetic wave shielding performance can be provided.

[0165] Further, since the present invention is substantially 2 So構 formed, compared to the anti-reflection film of a conventional multi-layer structure, and mechanical strength such as the small number scratch resistance of the membrane surface, heat resistance Are better. Also, in the present invention, when using a DC sputtering as a film forming method, there are advantages such that stability and a large area of the process is easy, together with the feature, preventing light absorbing reflected at a low cost Can produce the body.

The light-absorptive antireflection body according to the present invention has excellent heat resistance and can sufficiently withstand the heat treatment required for CRT panel glass. It can be expected to be applied to applications.

[Brief description of the drawings]

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

FIG. 2 is a schematic sectional view of another example of the present invention.

FIG. 3 is a graph showing a time variation of a voltage applied to a silicon target used in Examples and Comparative Examples.

FIG. 4 is a graph showing the spectral reflectance and the spectral transmittance of Example 1.

FIG. 5 is a graph showing the spectral reflectance and the spectral transmittance of Example 16.

FIG. 6 is a graph showing the spectral reflectance of Example 3.

FIG. 7 is a graph showing the spectral reflectance of Example 8.

FIG. 8 is a graph showing the spectral reflectance of Example 9.

FIG. 9 is a graph showing a spectral reflectance and a spectral transmittance of Example 17.

FIG. 10 is a graph showing the spectral reflectance of Example 4.

FIG. 11 is a graph showing the spectral reflectance of Example 5.

FIG. 12 is a graph showing the spectral reflectance of Example 14.

FIG. 13 is a graph showing the spectral reflectance of Example 15.

FIG. 14 is a graph showing the spectral reflectance after heat treatment of Example 3.

FIG. 15 is a graph showing the spectral reflectance after heat treatment of Example 7.

FIG. 16 is a graph showing a dispersion relationship of optical constants of an ideal absorption film obtained by calculation.

FIG. 17 is a diagram showing an example using the light-absorbing anti-reflection body of the present invention.

[Explanation of symbols]

V _N : negative voltage applied to the silicon target in Examples and Comparative Examples

Claims (5)

(57) [Claims] From 1. A base body on a substrate, by forming a light absorbing film and sheet silica film in this order, the light absorptive antireflection member for reducing the reflection of incident light from the silica film side, the light absorption Group consisting of titanium, zirconium and hafnium
A nitride of at least one metal selected from the group consisting of
A film that geometrically thickness of that is 5 to 25 nm, and the geometrical film thickness of the silica film is 70~110nm
Between the light absorbing film and the silica film I der, meaning optically
Layer with a geometric thickness of 1 to 20 nm
A layer mainly composed of silicon or silicon nitride is formed.
Light absorptive antireflection member, wherein that you have been. 2. The light-absorbing anti-reflective body according to claim 1, wherein said light-absorbing film is a film containing titanium nitride as a main component. Wherein said substrate constitutes the front surface of the display surface of displays, glass substrates, the light absorptive antireflection body according to claim 1 or 2 is a plastic substrate or a plastic film. 4. The light-absorbing anti-reflective body has a reflectance of 50%.
The light-absorbing anti-reflective body according to claim 1 , 2 or 3, which does not exceed 0.6% in a wavelength range of 0 to 650 nm. 5. Titanium and zircon are sequentially arranged on a substrate from the substrate side.
At least one selected from the group consisting of
Both form a light-absorbing film composed mainly of one metal nitride geometric thickness 5 ~25nm, silicon or silicon
A layer mainly composed of a nitride of
formed by m, and the geometrical film thickness of the silica film 7 0-11
Formed at 0 nm to reduce reflection of incident light from the silica film side
Method for producing a light-absorptive antireflection member, wherein Rukoto obtain a light absorptive antireflection stop member to.