JPH10301499A - Blanks or black matrix and their production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a black matrix which less affects the environment, has chemical resistance and heat resistance, allow the pattern formation by a conventional Cr wet etching soln., provides excellent productivity and has high light shieldability and excellent low reflectiveness. SOLUTION: The light shielding films 2 or antireflection films 3a, 3b of the black matrix consisting of the light shielding films 2 or the light shielding films 2 and antireflection films 3a, 3b formed in direct or indirect adhesion onto the surface of a transparent substrate 1 are formed as thin films consisting of essentially metal components of Mo and Ni. The transparent substrate 1 is installed in a vacuum chamber and the light shielding films 2 are formed thereon by a sputtering method by using a sputter target consisting of the Mo and Ni as the essential components of the metallic components and using a gaseous mixture formed by adding gaseous Ar to an atmosphere gas or adding at least one reactive gas among O2 , N2 , NO, CO2 and CH4 to this gaseous Ar.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flat panel display (FPD) such as a liquid crystal color display device.
The present invention relates to a blank or black matrix which is a light-shielding material and a method for producing the blank or black matrix.

[0002]

2. Description of the Related Art Here, a blank refers to a light-shielding layer composed of a thin film layer uniformly formed on the surface of a transparent substrate, and a predetermined portion of the blank is subjected to an etching process or the like to remove the thin film layer. A pattern formed by forming the formed opening portion and a light-shielding layer complementary to the opening portion is called a black matrix. Therefore, blanks and black matrices differ only in the presence or absence of a pattern.
Since the functions are the same, they will be treated as equivalents unless specifically distinguished below.

In order to improve the visibility of a liquid crystal display, the black matrix needs to have a light shielding property of 3.5 or more (transmittance of 0.03% or less) in optical density (OD) of transmitted light. Conventionally, a black matrix in which a light-shielding layer made of a single-layer thin film of Cr (chromium) metal having high light-shielding properties is formed on the surface of a transparent substrate has been used. Cr
The surface of the metal film has high reflectivity, and the reflectance of the black matrix on the transparent substrate side in the visible light wavelength range is about 50%. A black matrix is used in which a light-shielding layer made of Cr metal is laminated on an anti-reflection layer made of, for example, chromium. For example, Japanese Patent Application Laid-Open No. HEI 8-29768 discloses a two-layer black structure in which an antireflection film made of a Cr oxide or the like is formed on the surface of a transparent substrate, and a light-shielding film made of Cr metal is laminated on the surface. A matrix is described. Also, JP-A-8-179301 discloses that a first layer of an antireflection film made of oxide of Cr is formed on a surface of a transparent substrate,
Next, a three-layer black matrix is described in which a second layer of an antireflection film is formed on the surface, and a light shielding film made of Cr metal is sequentially laminated on the surface.

On the other hand, from the viewpoint of productivity and environmental pollution, a resin black matrix has been proposed and its development has been advanced. In this method, a resin solution in which a pigment is dispersed is applied to a substrate, and a pattern is formed by photolithography.

[0005]

The black matrix containing Cr is wet-etched in a pattern forming process by photolithography, and the Cr is contained in an etching solution.
Elutes. Since hexavalent Cr affects the environment,
There is a problem that not only a lot of labor is required for maintaining and managing the solution, but also a great deal of cost is required for treating the waste liquid.

On the other hand, it is difficult to increase the pigment concentration of a resin black matrix, a film thickness of 1 μm is required to obtain an optical density of 3.5, and a level difference occurs in a color filter, impairing flatness. There are drawbacks such as lower resolution.

Further, even if a light-shielding material made of a metal material other than Cr is used, a light-shielding property and low reflectivity equivalent to or higher than that of a black matrix made of Cr cannot be obtained, or pattern processing using a conventional Cr wet etching solution is performed. There is a problem that the black matrix cannot be obtained or does not have chemical resistance such as acid resistance and alkali resistance required for the black matrix. For example, a light-shielding material containing only Mo as a metal component has low alkali resistance, and therefore has no resistance to an alkali solution used for developing and peeling a resist material in a lithography process, and cannot be used in a pattern manufacturing process. Further, a light-shielding material containing only Ni as a metal component is inferior in acid resistance and furthermore, since Ni is a ferromagnetic material,
Even when used as a sputter target material, the thin film formation rate is low, and the sputter input power for obtaining the film thickness needs to be extremely large, which has the effect of lowering the yield, etc., and is not suitable for DC magnetron sputtering. However, the black matrix manufacturing method has a problem that it is not practical.

The present invention solves the above-mentioned drawbacks and problems, has a small effect on the environment, has chemical resistance and heat resistance, and is capable of producing a pattern by a conventional Cr wet etching solution, thereby increasing productivity. An object of the present invention is to provide a blank or black matrix having excellent, high light-shielding properties, and excellent low reflectivity, and a method for producing these blanks or black matrices.

[0009]

According to the present invention, in order to achieve the above object, a light-shielding film formed directly or indirectly on a surface of a transparent substrate or a blank or black comprising a light-shielding film and an antireflection film is provided. In the matrix, the light-shielding film or the antireflection film was a thin film containing Mo and Ni as main components of a metal component. Further, the above object is achieved by forming the light-shielding film or the antireflection film by forming at least one of an oxide, a nitride, an oxynitride, and a carbide having Mo and Ni as main components of a metal component.
And at least one of an oxide, a nitride, and an oxynitride containing Mo and Ni as main components of a metal component directly or indirectly on the surface of the transparent substrate. This can also be achieved by providing a thin antireflection film made of and forming a thin light shielding film containing Mo and Ni as main components of the metal component on the surface of the antireflection film. If necessary, the anti-reflection film is composed of upper and lower two layers, and the first anti-reflection film on the transparent substrate side is formed of at least one of oxides and oxynitrides containing Mo and Ni as main components of a metal component. A second anti-reflection film directly attached to the first anti-reflection film surface, wherein at least one of an oxide, a nitride, and an oxynitride containing Mo and Ni as main components of a metal component; A thin film having a larger extinction coefficient than that of the first anti-reflection film, and a light-shielding film made of a thin film containing Mo and Ni as main components as a main component by directly adhering to the second anti-reflection film surface. You.

The light-shielding film is formed by using a sputtering target containing Mo and Ni as main components of a metal component, and using Ar gas as an atmospheric gas or O ₂ , N ₂ , NO, CO ₂ ,
When a single- or multi-layer anti-reflection film is formed on a transparent substrate by a sputtering method using a mixed gas to which a small amount of a reaction gas of at least one of CH ₄ is added. Is a single layer, a sputter target containing Mo and Ni as main components of the metal is used for the one layer, and a mixed gas containing Ar gas and at least one of O ₂ or CO ₂ is used as an atmosphere gas. Sputtering method or this mixed gas is further added with N ₂ , N
It is formed by a sputtering method using a mixed gas to which at least one reaction gas of O and CH ₄ is added.
When the antireflection film has two layers, a sputtering target composed of Mo and Ni is used, and Ar gas, O
₂ , a sputtering method using a mixed gas containing at least one of CO ₂ , or N ₂ , NO
After the first layer of the antireflection film is formed on the transparent substrate surface by a sputtering method using a mixed gas to which at least one reactive gas is added, the atmosphere gas is Ar gas, N gas
₂ , a sputtering method using a mixed gas containing at least one of NO, or O ₂ , C
A second layer of an anti-reflection film is formed on the first layer by a sputtering method using a mixed gas to which at least one of O ₂ and CH ₄ is added.

As the sputter target, for example, M
An alloy or sintered body of o and Ni is used, and the elemental component ratio of Mo to Ni is 6 depending on the composition of the atmosphere gas.
Atomic% or more or Mo: Ni = 75: 2
Mo: Ni = 15: 8 even when the Ni ratio is high from 5 atomic%
Those having a content of 5 atomic% are used, and the light shielding film and the antireflection film are formed by magnetron sputtering.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described with reference to the drawings. FIGS. 1 to 3 schematically show the structure of a black matrix according to the present invention. A light-shielding film 2 in which a thin film containing Mo and Ni as main components is directly formed in a pattern on the surface of a transparent substrate 1.
The light incident from below the transparent substrate 1 is partially blocked by the light-shielding film 2, and the remaining light is emitted from the opening between the light-shielding films 2. FIG. 2 shows a black matrix in which a light-shielding film 2 is formed via an anti-reflection film 3 formed directly on the surface of a transparent substrate 1. FIG. 3 shows two layers of anti-reflection films 3a and 3b.
The light-shielding film 2 and each of the anti-reflection films 3, 3a, 3b are also made of Mo.
And an anti-reflection film having a higher content of the constituent elements of the reactive gas than the light-shielding film, and thus a thin film having a smaller value of the extinction coefficient k. Is formed. The light shielding film 2 and the antireflection films 3, 3a,
3b may be a thin film made of at least one of oxide, nitride, oxynitride, and carbide obtained by oxidizing, nitriding, oxynitriding, and carbonizing Mo and Ni. 2 anti-reflective coatings
When formed in a layer, the extinction coefficient k of the upper antireflection film
2 is formed of a film adjusted so as to be larger than the extinction coefficient k3 of the lower antireflection film.

When the anti-reflection film 3 is composed of upper and lower two layers, the first anti-reflection film 3a on the transparent substrate 1 side is made of at least one of an oxide and an oxynitride containing Mo and Ni as metal components. The second antireflection film 3b formed of a single thin film and directly adhered thereto is formed of at least one of an oxide, a nitride, and an oxynitride containing Mo and Ni as main components of a metal component.
It is preferable that the light-shielding film 2 is made of a thin film having a larger extinction coefficient than that of the first antireflection film 3a, and the light-shielding film 2 thereon is formed of a thin film containing Mo and Ni as main components of a metal component.

These light shielding films and antireflection films are made of Mo and Ni.
As a main component of the metal component, it has chemical resistance and heat resistance, can be mass-produced practically using the current Cr etching solution, and is as high as or higher than the black matrix made of Cr. It has a light-shielding property and excellent low reflectivity, and has little effect on the environment.

That is, as for chemical resistance, it is excellent in acid resistance and alkali resistance, has heat resistance to withstand 250 ° C., can be rapidly etched with an ordinary etching solution for Cr, and has good optical density and reflectance. It has good light-shielding properties and low reflectivity, and does not use Cr, so that there is no need to control the etching waste liquid and there is little effect on the environment.

The blank or black matrix of the present invention is produced by sputtering using a sputtering target of an alloy or sintered body containing Mo and Ni as main components of a metal component and a sputtering gas having a specific component. In the sputtering apparatus, for example, as shown in FIG. 4, a sputtering target 12 having a cathode potential is provided in a vacuum chamber 10 so as to face a transparent substrate 1 which is mounted on a carrier 11 and conveyed. Gas is introduced from the provided gas introduction system 13, the pressure in the room is adjusted by the exhaust system 14, power is supplied from the DC power supply 15, and plasma is restrained by the magnetic field of the magnet 16 provided behind the target 12. A DC magnetron sputtering device for sputtering the target 12 is used.

The composition ratio of Mo and Ni of the sputtering target 12 has a close relationship with the gas atmosphere in the vacuum chamber 10, and the light shielding film is formed in an atmosphere containing only Ar gas.
When sputtering is performed, a sputtering target 12 containing at least 6 atomic% of Mo with respect to Ni is used.
By using, a light-shielding film satisfying the object of the present invention can be easily obtained with good controllability. When the single-layer or multi-layer anti-reflection film 3 for the purpose of the present invention is formed using the target 12 in which Mo and Ni are the main components of the metal component, in the case of a single-layer anti-reflection film, Ar gas as atmosphere gas
A gas, at least one of O ₂ or CO ₂ , N ₂ ,
Sputtering is performed using a mixed gas to which at least one reaction gas of NO and CH ₄ is added. Further, M
When the two-layer antireflection film 3 is formed using the target 12 in which o and Ni are the main components of the metal component, the atmosphere gas for forming the first layer is Ar gas, O ₂ , C
By using a mixed gas containing at least one O ₂ gas, low reflectivity is enhanced, and Ar 2 is used for forming the second layer.
Sputtering is performed using a gas and a mixed gas containing at least one of N ₂ and NO gases.

By mixing such reaction gases, the sputtered Mo and Ni become oxides, nitrides, oxynitrides, and carbides to form a light-shielding film and an anti-reflection film. It is excellent in heat resistance, can be etched with a commercially available Cr etching solution, does not cause environmental problems unlike Cr, and can provide blanks or black matrices having a light-shielding property and anti-reflection property equal to or higher than that of a Cr black matrix. In the blanks or black matrix of the present invention, the presence of a carbide is optional, and is added as a constituent component as necessary for light-shielding properties and consistency of the pattern of the black matrix. When a light-shielding film is formed, oxides, nitrides, and oxynitrides are arbitrarily added as film components within a range that does not hinder the light-shielding properties.

When a gas obtained by mixing a reactant gas with an Ar gas is used, the ratio of Mo to Ni, which is the main component of the metal component of the sputtering target 12, is set to Mo: Ni = 7.
5:25 atomic% to Mo: Ni = 15: 85 atomic%
When it is in the range, the blanks or black matrix of the present invention can be formed by a DC magnetron sputtering method,
The constituent materials of the light-shielding film and the antireflection film can be selected from Mo, Ni, and oxides, nitrides, oxynitrides, and carbides of Mo and Ni, and the optical characteristics of the thin film system can be easily designed.

The blank or black matrix of the present invention can be used as is in a flat panel display (FPD).
Light shielding materials, for example, mask blanks, electrode materials, and photomasks. Further, in the blanks or black matrix of the present invention, an anti-reflection film can be formed directly on the light-shielding film.
, That is, a high light-shielding black matrix in which both upper and lower surfaces of the light-shielding film have low reflectivity.

In addition, other than Mo and Ni, the film material may be Fe or Cu of several tens atomic% or less, or Si or Z of ten or more atomic% or less.
When r and W were added, the environmental resistance such as moisture resistance and water resistance was further improved. Other metals to improve environmental resistance,
For example, Al, V, Nb, Hf, Ta, etc.
The following ratio may be added to the film material.

[0022]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Using the in-line type DC magnetron sputtering apparatus shown in FIG. 4, each layer of a light shielding film and an anti-reflection film constituting a blank or a black matrix, a black matrix having a film constitution shown in FIGS. Black matrices having the film configurations shown in FIGS. 5 to 7 were produced. The transparent substrate 1 is made of Corning 7059 having a thickness of 1.1.
After washing and drying, the glass was mounted on the carrier 11 and was conveyed over the target 12 in the vacuum chamber 10 at a constant speed to form a film by a passing method. As shown in Table 1, the ratio of Ni to Mo in the sputter target 12 ranges from Mo: Ni = 75: 25 atomic% to Mo: Ni = 15: 85 atomic% even at a high Ni ratio. , Mo: Ni = 3: 1, M
o: Ni = 2: 1, Mo: Ni = 1: 1, Mo: Ni =
A sintered sputter target having a thickness of 4 mm with 1: 2 and Mo: Ni = 1: 3 was typically used.

[0023]

[Table 1]

The transport speed of the transparent substrate 1 is 224 mm / mi
n, the distance (T / S distance) between the target 12 and the substrate 1 was 70 mm, and the speed and distance were constant. The substrate 1 and the carrier 11 are heated by a quartz heater provided in the vacuum chamber 10 and its front chamber (not shown), and the temperature in the vacuum chamber 10 is controlled by the heater. 115
C. to 125.degree. Atmosphere gas is A
At least one of r, O ₂ , CO ₂ , N ₂ , NO, and CH ₄ was used and introduced through an opening of a gas introduction system 13 provided near the target 12. The pressure in the vacuum chamber 10 is measured by a diaphragm type vacuum gauge, and is from 1 × 10 ⁻³ Torr to 4 × 10 ⁻³ Torr.
It was fixed at a predetermined value in the range of Torr. The film thickness was controlled to a predetermined value by controlling the applied power.

The single films of the light-shielding film and the antireflection film were prepared for confirming the relationship between the flow rate of the atmosphere gas at the time of sputtering, the change in the flow rate ratio, and the film characteristics (film composition, optical constant). Evaluation of film conditions and film characteristics will be described in detail below.

A. Light Shielding Film (Film Formation Conditions) Using the Mo—Ni sintered target shown in Table 1, a light shielding film 2 was formed on a glass substrate 1 by sputtering using the apparatus shown in FIG. Table 2 shows the gas flow rates and the gas flow ratios introduced into the vacuum chamber 10 at the time of film formation corresponding to various light-shielding film numbers L1 to L7, L15, L22, and L24 to L34. The film number is common to the used targets m = 1 to 5. In addition, samples having one or more film thicknesses were prepared for evaluating the characteristics of each film number. The operating pressure during sputter deposition is 0.8 × 10 ^{-3 to} 1.0 × 10 ^-3 To
rr, the sputtering power is 2.0 to 2.3 KW, the sputtering voltage is 400 to 520 V, and the sputtering current is 4 to 5 A. Substrate temperature is 115-125 ° C, transfer speed is about 22
4 mm / min.

[0027]

[Table 2]

(Analysis of film composition) Light shielding films L1 to L
Table 3 shows the analysis results of the film composition by Auger analysis (AES) and emission analysis (ICP) for the target composition m = 5 of 7, L15, and L22. The film composition analysis was also performed on the examples of the black matrix having two or more layers described in the section c and the section d described later, and the analysis result almost coincided with the result of the corresponding single layer film.

[0029]

[Table 3]

(Optical constants) Table 4 shows the light shielding films L1 to L
7, wavelength 550 nm of L15, L22, L24 to L34
Are shown for each target composition. The optical constant n-ik (n is the refractive index and k is the extinction coefficient) of the light-shielding film is defined as the spectral reflectance (R), the spectral transmittance (T), and the film thickness (d) for the vertically incident light from the film surface. It was determined by the so-called R, T method using the measured values. The film thickness is S
It was measured by a stylus type film thickness meter DEKTAK3030 manufactured by Loan. The spectral reflectance and the spectral transmittance were measured using a Hitachi U-4000 spectrophotometer in the visible light wavelength range, and the absolute values were determined.

[0031]

[Table 4]

B. Antireflection film (Film forming conditions) An antireflection film was formed on the glass substrate 1 using the Mo-Ni sintered targets shown in Table 1. In Table 5,
The gas flow rate and the gas flow ratio introduced into the vacuum chamber 10 at the time of film formation are adjusted to various antireflection film numbers L8 to L14, L16 to L21,
It described corresponding to L23 and L35-L47. The film number is common to the used targets m = 1 to 5. In addition, samples having one or more film thicknesses were prepared for evaluating the characteristics of each film number. Operating pressure during sputter deposition is 1 × 1
0 ^{-3 to} 3 × 10 ^-3 Torr, and the sputtering power is 2-3K.
W, the sputtering voltage is 400 to 500 V, and the sputtering current is 4 to 6 A. The substrate temperature is 115 to 125 ° C., and the transfer speed is about 224 mm / min.

[0033]

[Table 5]

(Analysis of Film Composition) Table 6 shows that the antireflection films L8 to
Target composition m of L14, L16 to L21, L23 =
Analysis (AES) and luminescence analysis (I
3 shows the results of film composition analysis by CP).

[0035]

[Table 6]

(Optical constants) Table 7 shows that these antireflection films L8 to L14, L16 to L21, L23, L35 to L4
7 shows the measured values of the optical constants at a wavelength of 550 nm for each target composition. Optical constant of antireflection film n-
ik was determined by the R and T methods in the same manner as in the case of the light shielding film.

[0037]

[Table 7]

C. Two-layer film 1 A black matrix having the film configuration shown in FIG. 2, wherein an antireflection film 3 made of a Mo—Ni oxide film and a light-shielding film 2 made of a Mo—Ni film were sequentially formed on a glass substrate 1. Specifically, an anti-reflection film L23 having a thickness of d ₂ is formed on a glass substrate under the same conditions as those for forming the anti-reflection film of b, and the film formation conditions of a are formed on this L23. With light shielding film L22
Was formed to a thickness of d ₁ to form a two-layer film having a film configuration of L22 / L23 / glass substrate. Table 8 shows the values of the film thicknesses d ₁ and d ₂ for each target composition (m = 1 to 5) and the wavelengths 400, 550, and 700 nm with respect to the vertically incident light from the glass surface (back surface) for each of the target compositions (m = 1 to 5). And the optical density at a wavelength of 550 nm. D. Are shown together with the values of the optical constants. FIG. 8 shows the spectral reflectance curves of the two-layer films for target numbers m = 1, 3, and 5. From Table 7 and FIG. 8, it can be seen that these samples optically have practical optical characteristics.

[0039]

[Table 8]

D. Two-layer film No. 2 A black matrix having the film configuration shown in FIG. 2, wherein an antireflection film made of an oxide film containing O, N, C and the like of Mo—Ni and an O, N , C, etc. were sequentially formed. Specifically, 2 of the above c
As in the case of the layer film 1, the reaction gas CH ₄ , N ₂ , CO
_{A two-} layer film was formed using one or more of ₂ , NO and O ₂ . Specific examples are shown in Table 9 as sample Nos. S1 to S13.
It was shown to. The reflectance RB% of the incident light from the back surface of the substrate at the wavelengths of 400, 550 and 700 nm, and the wavelength of 550 n
m. D. Is shown for each sample. FIG. 9 shows the spectral reflectance curves of Sample Nos. S11 to S13. For samples S1 to S14 in Table 9, the optical constants of the respective films are given in Tables 4 and 7, and therefore, the optical constants are omitted for samples other than samples S11 to S14. It can be seen from Table 9 and FIG. 9 that the samples other than the sample S9 have practical optical characteristics.

[0041]

[Table 9]

E. Three-layer film A black matrix having a film configuration of a light-shielding film / anti-reflection film / anti-reflection film / glass substrate shown in FIG. 3 was prepared. First, an anti-reflection film L9 is formed on the glass substrate 1 under the film formation condition b, then an anti-reflection film L14 is formed thereon, and a light-shielding film L13 is formed thereon further under the film formation condition a. did.
The details are shown in Table 9 in Sample No. S14.
L14 / L9 / G (glass substrate)
Optical constant, film thickness, wavelength 400, 5
The reflectance RB of the incident light from the back surface of the substrate at 50 and 700 nm and the optical density O.D. D. showed that. FIG. 10 shows a spectral reflectance curve of the sample S14. From Table 9 and FIG. 10, this sample S14
Has practical optical characteristics. In this three-layer film, the antireflection film 3 was selected from those shown in Table 7, but instead of the light shielding films shown in Table 4, those having a relatively small extinction coefficient k (k <2.0) were selected. May be.

F. FIG. 11 shows an arbitrary optical constant n ₂ −ik ₂ on the glass substrate 1.
Film configuration antireflection film thickness d ₂ is formed to have a 350~450Å thickness, the light-shielding film 2 of No.L3 Table 2 thereon thickness d ₁ was formed to a 1300Å thick For the two-layer film, a contour line of the back surface reflectivity RB of light vertically incident on the back surface of the substrate is drawn on the optical constants n ₂ and k _{2 of the} antireflection film. In the figure, the antireflection films L8 to L14, L23, L29, L35, L38,
The values of the optical constants n ₂ and k ₂ of the antireflection film when L43 is combined for those having various target numbers m are plotted. The wavelength is 550 nm. From FIG. 11, L8 to L21, L23, L3 shown in Table 7 including these films
It is understood that practical optical constants are satisfied when 5 to L47 are used as the antireflection film.

G. 2-layer film that 4 12 and 13, the antireflection film L8 on the glass substrate 1 thickness d2 is formed to be 450 Å, any of the light-shielding film of the optical constants n ₁ -ik ₁ thereon To the film thickness d ₁ = 130
0 °, the substrate back surface reflectivity RB and the optical density O.D. on the n ₁ and k ₁ planes, respectively. D. The contour lines are drawn. The wavelength is 550 nm. FIG.
And FIG. 13 shows that the anti-reflection film L18 has light shielding films L1 to L
5, L7, L22, L24, L26, L28, L30, and L34 have various target numbers m, and the optical constant n of the light-shielding film when combined at a film thickness of 1300 °
1, where k1 values are plotted. From FIG. 12 and FIG. 13, L1 to L7 shown in Table 2 including these films,
When used as the light-shielding films of L15, L22, and L24 to L34, it can be seen that most of them satisfy practical optical constants. The optical densities of the light-shielding films L34 and L30 in FIG. 13 are small and insufficient as they are, but the optical density is almost proportional to the thickness of the light-shielding film. Can make up for the minute.

H. Evaluation of Film The following measurements and evaluations were performed on various samples. The optical density was measured using an optical densitometer TD-904 manufactured by Macbeth. The etching rate was determined by dissolving 165 g of ceric ammonium nitrate and 42 ml of 70% perchloric acid in pure water to make a 1000 ml solution (ordinary etching solution for Cr) as an etching solution. After keeping the temperature constant at a predetermined temperature, the time from immersion of the sample to dissolution (peeling) of the thin film was measured by monitoring the change in the transmittance of laser light. Acid resistance is determined by conc. The container containing the H ₂ SO ₄ solution (95% by weight or more) was kept at a constant temperature of 50 ° C. in a constant temperature bath, and the sample was immersed for 30 minutes so that the O.S. D.
The change in value was measured. Alkali resistance is 5wt% NaO
The H. solution was placed in a thermostatic bath at a constant temperature of 50 ° C., and the sample was immersed for 10 or 30 minutes, so that the O.H. The change in D value was measured. Heat resistance was measured using a constant temperature heating device in the air at 250
C. for 30 minutes by heating the sample before and after treatment. D. The change in value was measured.

FIG. 14 shows the measurement results of the relationship between the Mo and Ni component ratios with respect to the etching rates at 20 ° C. and 40 ° C. Each of them can be etched within a few minutes and has an etching rate that can correspond to a mass production patterning process. In particular, when the elemental component of the thin film is Mo: Ni = 75: 25 atomic%, N
A light-shielding film having a high i-ratio and in the range of Mo: Ni = 15: 85 atomic% has a higher etching rate than a Cr film, and thus has excellent productivity.

FIG. 15 shows the measurement results of acid resistance and alkali resistance.
Shown in The components of Mo and Ni in the thin film are Mo: Ni = 7
Ni ratio is higher than 5:25 atomic%, and Mo: Ni = 1
5: Up to 85 atomic%, excellent in acid resistance and alkali resistance.

From the above results, when the Mo and Ni components in the thin film have a higher Ni ratio than Mo: Ni = 75: 25 atomic%, and excellent chemical resistance in the range of Mo: Ni = 15: 85 atomic%. The film has a light-shielding property and can be wet-etched in a short time with an etching solution currently used.

By optimizing the target composition, film forming conditions and film thickness, the reflectance at the bottom wavelength on the glass substrate side is not more than 6.0% and the reflectance at the visible light wavelength region is 400% or less.
reflectivity over the range from 10 nm to 700 nm.
% Or less, and excellent low reflectivity can be obtained.
When the film thickness is designed so that the bottom wavelength is between 500 nm and 600 nm, the film thickness of the antireflection film is 400 ° to 500 °. The thickness of the light-shielding film of 1300 ° was sufficient. Also. O. D. Are not less than 4.2,
If a light-shielding film having a thickness of 1300 ° or more is formed, O.D. D. It was found that 4.2 or more was obtained.

From the above results, the light-shielding film and the anti-reflection film containing Mo and Ni as the main components of the metal component, and the black matrix composed of the laminated two-layered and three-layered thin-films are excellent in light-shielding properties and excellent. It has low reflectivity, has little effect on the environment, has chemical resistance and heat resistance, and is capable of pattern production with conventional wet etching solutions, has excellent productivity, high light shielding properties, and excellent low reflectivity. Have.

I. Production of Black Matrix A production example of the black matrix of the present invention is as shown in FIG. 16, in which an antireflection film 3 and a light shielding film 2 are sequentially formed by sputtering on a glass transparent substrate 1 shown in FIG. Then, a black matrix blank is prepared (FIG. (B)), and a resist material 4 is applied to the thin film surface of the blank (FIG. (C)). Then, the resist material is exposed, the exposed portion 5 is developed in a lithography process as shown in FIG. 7E, and a part of the antireflection film 3 and a part of the light shielding film 2 as shown in FIG. Then, the resist material 4 is removed to obtain a black matrix pattern.

[0052]

As described above, according to the present invention, since the light shielding film or the antireflection film of the black matrix is a thin film containing Mo and Ni as the main components of the metal component, it has excellent chemical resistance and heat resistance. It has the same light-shielding properties and low reflectivity as Cr
An effect is obtained such that a black matrix which can be etched using an etching solution for r and has less influence on the environment is obtained, and the light-shielding film or the antireflection film is formed of an oxide containing Mo and Ni as main components of a metal component, A thin film made of at least one of a nitride, an oxynitride and a carbide;
A thin film made of at least one of an oxide, a nitride, an oxynitride, and a carbide containing o and Ni as main components of a metal component, and a light-shielding film made of a thin film containing Mo and Ni as main components of a metal component The above effects can be obtained even by combining films. In addition, the above-described effects can be accurately achieved also by adopting the configuration described in claims 5 and 6, and sputtering is performed by using a sputter target having a composition as described in claims 6 to 10 and adjusting the type of atmospheric gas. This has the effect that the black matrix of the present invention can be easily manufactured.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating a film configuration of a black matrix of the present invention.

FIG. 2 is a cross-sectional view illustrating a film configuration of a black matrix of the present invention.

FIG. 3 is a cross-sectional view illustrating a film configuration of a black matrix of the present invention.

FIG. 4 is a cut-away side view of the apparatus used for producing the black matrix of the present invention.

FIG. 5 is a cross-sectional view of a modified example of the film configuration of the black matrix of the present invention.

FIG. 6 is a sectional view of a modification of the film configuration of the black matrix of the present invention.

FIG. 7 is a cross-sectional view of a modification of the film configuration of the black matrix of the present invention.

FIG. 8 shows a spectral reflectance curve of a black matrix having a two-layer structure according to the present invention.

FIG. 9 shows a spectral reflectance curve of a two-layer black matrix of the present invention.

FIG. 10 shows a spectral reflectance curve of a black matrix having a three-layer structure according to the present invention.

FIG. 11 is a diagram showing the relationship between the optical constants of the black matrix of the present invention and the backside reflectance RB.

FIG. 12 is a diagram showing the relationship between the optical constants of the black matrix of the present invention and the backside reflectance RB.

FIG. 13 shows the optical constants and optical densities of the black matrix of the present invention. D. Diagram showing the relationship

FIG. 14 is a diagram showing wet etching characteristics of the black matrix of the present invention.

FIG. 15 is a diagram showing the chemical resistance of the black matrix of the present invention.

FIG. 16 shows one of the steps of producing the black matrix of the present invention.
Schematic showing an example

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Transparent substrate, 2 Light-shielding film, 3 ・ 3a ・ 3b Antireflection film, 4 Resist material, 5 Exposure part, 10 Vacuum chamber, 1
2 sputter target, 13 gas introduction system, 14 exhaust system,

Continuation of the front page (72) Inventor Akihiko Shig 2804 Terao, Chiba, Saitama Prefecture Inside Alvac Film Co., Ltd. (72) Inventor Keiji Tanaka 1-1-1, Taito, Taito-ku, Tokyo Letterpress Printing Co., Ltd. (72) Inventor Kosuke Ueyama Inside Letterpress Printing Co., Ltd., 1-1-1, Taito, Taito-ku, Tokyo

Claims (12)

[Claims] In a blank or black matrix comprising a light-shielding film or a light-shielding film and an anti-reflection film formed by directly or indirectly adhering on the surface of a transparent substrate, the light-shielding film or the anti-reflection film is made of Mo and Ni. Blanks or black matrices, characterized in that: a thin film containing as a main component a metal component. 2. The method according to claim 1, wherein the light-shielding film or the antireflection film is made of Mo and Ni.
Oxides, nitrides, oxynitrides containing, as a main component of a metal component,
The blank or black matrix according to claim 1, wherein the blank or the black matrix is a thin film made of at least one of carbides. 3. A reflection of a thin film made of at least one of an oxide, a nitride, an oxynitride and a carbide containing Mo and Ni as main components of a metal component directly or indirectly on the surface of the transparent substrate. 2. The blank or black matrix according to claim 1, wherein an anti-reflection film is provided, and a light-shielding film made of a thin film containing Mo and Ni as main components of a metal component is formed on a surface of the anti-reflection film. 4. An anti-reflection film comprising upper and lower two layers, wherein the first anti-reflection film on the transparent substrate side comprises at least one of an oxide and an oxynitride containing Mo and Ni as main components of a metal component. A second anti-reflection film directly adhered to the surface of the first anti-reflection film, wherein at least one of an oxide, a nitride, and an oxynitride containing Mo and Ni as main components of a metal component; A thin film having a larger extinction coefficient than the first anti-reflection film, and directly attached to the second anti-reflection film surface,
4. The blank or black matrix according to claim 3, wherein a thin light-shielding film containing Mo and Ni as main components of a metal component is provided. 5. The light-shielding film according to claim 1, wherein the light-shielding film is a thin film made of at least one of an oxide, a nitride, an oxynitride, and a carbide containing Mo and Ni as main components of a metal component. 5. The blank or black matrix according to 3 or 4. 6. A method for forming a light-shielding film constituting a blank or a black matrix on a transparent substrate, wherein the transparent substrate is provided in a vacuum chamber and a sputter target containing Mo and Ni as main components of a metal component is used. A
O ₂ , N ₂ , NO, CO ₂ , C in r gas or Ar gas
A method for producing a blank or a black matrix, wherein the light-shielding film is formed by a sputtering method using a mixed gas to which at least one reactive gas of H ₄ is added. 7. When an atmosphere gas containing only Ar gas is used for forming the light shielding film, Mo is at least 6 atomic relative to Ni.
The method for producing a blank or black matrix according to claim 6, wherein a sputter target containing at least 0.1% is used. 8. A method for forming a single-layer or multi-layer antireflection film constituting a blank or a black matrix on a transparent substrate, wherein the transparent substrate is provided in a vacuum chamber.
And a sputtering target containing Ni as a main component of a metal component, and using an Ar gas, O ₂ or CO ₂ as an atmosphere gas.
Forming at least one layer of the antireflection film by a sputtering method using a mixed gas containing at least one of the following. 9. The method according to claim 8, wherein at least one of N ₂ , NO, and CH ₄ is added to the mixed gas. 10. A method for directly forming a two-layer antireflection film constituting a blank or a black matrix on a transparent substrate, wherein the transparent substrate is provided in a vacuum chamber, and Mo and N are provided.
Using a sputtering target containing i as a main component of a metal component, and using a mixed gas containing an Ar gas and O ₂ or CO ₂ gas as an atmospheric gas, a sputtering method using a sputtering method to form the first antireflection film on the transparent substrate surface. After forming one layer, the atmosphere gas always contains Ar gas and N ₂ or NO gas, and further contains O ₂ , CO 2
_2. A method for producing a blank or black matrix, comprising forming a second layer of an antireflection film on the first layer by a sputtering method using a mixed gas containing at least one of the following two. 11. A gas mixture for use in forming the first layer of the anti-reflection film, wherein at least one reaction gas of N ₂ and NO is added as necessary. The above-mentioned mixed gas used for forming the layer may be added with O
_{2. The} method for producing a blank or black matrix according to claim 10, wherein at least one of CO ₂ is included. 12. When an atmosphere gas of a mixed gas is used for forming the light-shielding film or the antireflection film, the sputter target has a Mo: Ni elemental component ratio of Mo: Ni = 7.
5:25 atomic% to Mo: Ni = 15: 85 atomic%
The method for producing a blank or a black matrix according to any one of claims 6 to 8, characterized in that: