JPH06322517A - Wear resistant amorphous hard film and its production - Google Patents

Abstract

(57) [Summary] [Objective] An abrasion-resistant amorphous hard film that is dense, has excellent adhesion to a substrate, is resistant to bending, and has high hardness is formed by a relatively simple process. [Structure] General formula: Al _a M _b (where M is Ti, T
a, V, Cr, Zr, Nb, Mo, Hf, W, Fe, C
at least one element selected from the group consisting of o, Ni, Cu, and Mn, a and b each represent atomic%;
0 at% ≦ a ≦ 98.5 at%, 1.5 at% ≦ b ≦ 4
0 at%, where a + b = 100 at%) is used, and a physical vapor deposition method such as a sputtering method or an ion plating method is used while supplying a nitrogen, oxygen or carbon-based reaction gas using an evaporation source material. Thus, an amorphous film is formed on the base material in an inert gas atmosphere containing a predetermined amount of reaction gas.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an abrasion-resistant amorphous hard film and a method for producing the same, and more specifically, it has good adhesion to a base material and high hardness without preheating the base material. The present invention relates to a method for obtaining a dense wear-resistant amorphous hard film and its composition.

[0002]

2. Description of the Related Art TiN, TiC, WC, and Al-Ti are wear resistant coating materials for preventing wear and abrasion of machine parts and tools.
-N-based material or the like is used. And, these films are generally formed by a physical vapor deposition method such as a reactive sputtering method or an ion plating method and are used as abrasion resistant films, but in order to obtain high hardness, It is necessary to increase the nitrogen concentration or carbon concentration to some extent. However, this can cause residual stresses in the film after processing. Further, the formed film must be dense and have excellent adhesion to the substrate. Therefore, generally, a method of preheating a base material and then forming a film is adopted. However, even if such a treatment is performed, the film has a columnar structure, and there is a problem that the film becomes mechanically brittle. Further, at this time, since preheating is performed at least at 200 ° C. or higher, there is a limitation on the material that can be used as the base material, and a material such as an aluminum alloy whose mechanical properties are remarkably deteriorated by preheating is used. It could not be used as a material.

Further, conventionally, an amorphous alloy material having excellent characteristics such as high strength and high heat resistance has been manufactured by a liquid quenching method or the like. In particular, the aluminum-based amorphous alloy material obtained by the liquid quenching method disclosed in JP-A-1-275732 is an alloy excellent in high strength, high heat resistance and corrosion resistance. However, the amorphous alloy material obtained by the liquid quenching method has characteristics such as excellent strength among metal materials, but it is lower than materials such as ceramics and leaves room for improvement. On the other hand, ceramic materials show excellent characteristics in terms of strength and hardness,
It is difficult to use as a material that requires high toughness. In particular,
When used as a thin film, the above high toughness is required.

The present invention has been made in order to solve the above-mentioned problems of the prior art, has an amorphous structure, is excellent in adhesion to a substrate, and has drawbacks of a ceramic material as a whole film. The present invention is intended to provide a dense wear-resistant amorphous hard film having a high hardness with reduced brittleness. Further, the object of the present invention is to provide a dense film that adheres well without causing cracks or peeling at their interfaces even if a film is formed without preheating the substrate prior to coating. Another object of the present invention is to provide a method capable of inexpensively producing a stable amorphous hard film by a simple process.

[0005]

In order to achieve the above object, according to the present invention, the general formula: (Al _a M _b ) _100-c X _c
(Where M is Ti, Ta, V, Cr, Zr, Nb,
At least one element selected from the group consisting of Mo, Hf, W, Fe, Co, Ni, Cu and Mn, X is N,
One element selected from the group consisting of O and C, a, b and c each represent atomic%, and 60 at% ≦ a ≦ 98.5.
at%, 1.5 at% ≦ b ≦ 40 at%, 0 at% <c
There is provided a wear-resistant amorphous hard film having a composition represented by ≦ 65 at%, where a + b = 100 at%), showing an amorphous structure, and having high hardness. Further, according to the present invention, in order to provide the amorphous thin film, it is represented by the general formula: Al _a M _b (where M, a and b have the same meanings as described above) by physical vapor deposition. It is possible to form an amorphous film on a substrate in an inert gas atmosphere containing a predetermined amount of a reaction gas while supplying a reaction gas containing nitrogen, oxygen or carbon by using an evaporation source material having a composition described below. A method of making a featured wear resistant amorphous hard film is provided.

[0006]

The present invention relates to a physical vapor deposition method,
In particular, when a film is formed on a substrate by a sputtering method or an ion plating method, a composition that becomes amorphous when a film is formed while supplying a reaction gas in an inert gas atmosphere as a target (evaporating material) It is characterized by using a material. That is, the general formula: Al _a M _b (where M
Is Ti, Ta, V, Cr, Zr, Nb, Mo, Hf,
At least one element selected from the group consisting of W, Fe, Co, Ni, Cu and Mn, a and b each represent atomic%, and 60 at% ≦ a ≦ 98.5 at%, 1.5a
t% ≦ b ≦ 40 at%, where a + b = 100 at%)
An evaporation source material having a composition represented by the following formula can be used to supply an amount of a reaction gas containing nitrogen, oxygen or carbon, and a partial pressure of the reaction gas in the atmosphere depending on the evaporation source material used to form an amorphous film. An inert gas containing a predetermined amount of reaction gas by physical vapor deposition method, particularly sputtering method or ion plating method while controlling the partial pressure to be constant within the range or to change continuously or stepwise. An amorphous film is formed by forming a film on a base material in an atmosphere. In such a method of the present invention, a crystalline film is generally formed at a reaction gas partial pressure of 0 Pa, but it has been found that as the reaction gas partial pressure increases, it becomes an amorphous film and the hardness also increases. .
Therefore, by forming the film in an atmosphere of a partial pressure of a reaction gas capable of forming an amorphous film, it has an amorphous structure, is extremely dense, and has excellent adhesion to a substrate. A film with high hardness that does not exhibit a certain brittleness can be produced. Therefore, the defect of breakage at the grain boundary occurring in the crystalline high hardness film can also be improved.

The other component of the evaporation source material used in the present invention,
That is, Ti, Ta, V, Cr, Zr, Nb, Mo, H
Transition metals such as f, W, Fe, Co, Ni, Cu, and Mn are elements having a small diffusivity in the Al matrix, form various metastable or stable intermetallic compounds, and have a high temperature of a fine crystal structure. Contribute to stabilization in. These metals are also known to have conductivity as a nitride or the like, or a material having excellent corrosion resistance. Examples of the vapor deposition means include a sputtering method and an ion plating method. Further, the evaporation source may be a compound or mixture containing the necessary composition in one evaporation source, or when using a plurality of evaporation sources at the same time,
Each evaporation source may have a single composition, or a combination of the above evaporation sources.

The reaction gas concentration in the gas introduced into the processing apparatus during vapor deposition is preferably such that the ratio of the reaction gas to the inert gas is in the range of 2 to 35% by volume. Outside this range, crystalline particles precipitate. It is not preferable because it becomes easy. Further, the film to be formed may have a composition in which the concentration of the reaction gas component in the amorphous film is uniform throughout, or there is a difference in the composition of the film in contact with the substrate and the composition of the film surface, It may change continuously or stepwise in the film thickness direction. That is,
An inert gas (Ar, He, Ne, Xe, Kr, etc.) was introduced to keep the gas pressure (total pressure) at a low pressure of 0.6 to 1.2 Pa. By controlling the supply amount of gas, methane gas, etc.) at a constant partial pressure to form a film, an amorphous hard film having a composition in which the concentration of the reaction gas component in the film is substantially uniform throughout is obtained, Also, by controlling the supply amount of the reaction gas so that the partial pressure thereof changes continuously or stepwise, the concentration of the reaction gas component in the amorphous film increases toward the film surface. It is also possible to obtain an amorphous hard film having a higher part hardness. The method of the present invention is particularly useful when coating a substrate such as a polymeric material or aluminum whose material temperature cannot exceed 200 ° C., but is not applicable to substrates of other materials. Of course.

[0009]

EXAMPLES The present invention will be specifically described below with reference to examples of the present invention, but it goes without saying that the present invention is not limited to the following examples.

A target made of Example 1 (80 at% Al-20 at% Ti) is arranged facing an electrode (ground potential) in a magnetron sputter vapor deposition apparatus, and a glass plate or an aluminum plate is covered between the electrode and the target. It was arranged as a vapor deposition substrate. After exhausting the inside of the sputtering apparatus with a vacuum pump, argon gas was supplied, and the gas pressure (total pressure) inside the apparatus was set to 1 Pa.
Prior to coating, a high frequency power source was connected to a jig fixing a glass substrate or an aluminum substrate, and the glass substrate or the aluminum substrate was sputter-etched, respectively. Then, a direct current power supply was connected to the target to carry out preliminary discharge. At this time, the glass substrate or the aluminum substrate was not coated by the preliminary discharge. The purpose of this preliminary discharge is to remove the gas and moisture adsorbed on the target surface. After the preliminary discharge, the shutter was moved to start coating on the glass substrate or the aluminum substrate. However, the substrate was not preheated prior to coating. During the coating, the nitrogen gas which is a reaction gas has a nitrogen partial pressure within the apparatus from 0 Pa to 0.
The pressure was controlled so as to be a predetermined partial pressure within the range of 129 Pa. The pressure change in the device was adjusted so that the pressure was 1 Pa by the valve provided between the exhaust pump and the device.

FIG. 1 shows the results of X-ray diffraction analysis of each thin film produced with the nitrogen partial pressure kept constant. The X-ray diffraction patterns of the respective films are collectively shown by shifting in the direction of partial pressure in the strength direction of the ordinate axis for easy understanding. As is clear from FIG. 1, the film obtained without introducing nitrogen gas became crystalline, but the nitrogen partial pressure was 0.021 Pa, 0.038 Pa,
An amorphous film could be obtained at 0.055 Pa, 0.072 Pa, and 0.087 Pa. This nitrogen partial pressure 0.021P
The nitrogen concentration in the film produced at a-0.102 Pa was 12 at% to 38 at%. That is, the formula (Al
₈₀ Ti ₂₀ ) _{100- c Nc} 12 at% ≤ c ≤ 38a
t% and 12 at% are nitrogen partial pressure 0.021 Pa, 3
8 at% represents the nitrogen concentration in the film produced at a nitrogen partial pressure of 0.102 Pa (hereinafter the same). In addition, the nitrogen ratio is obtained by obtaining the weight of the film used for the measurement,
Using the total weight of i and N, the amount at% of Al and Ti was determined by EPMA, and then the amount of N in the film at% was obtained by calculation. The Knoop hardness of these amorphous films measured by a micro hardness meter is shown in FIG. The hardness increased with an increase in the nitrogen partial pressure, and became 911 Hk when the nitrogen partial pressure was 0.072 Pa.

Example 2 A film was formed on a substrate in the same manner as in Example 1 except that a target made of 89 at% Al-11 at% Ti was used. FIG. 3 shows the analysis result by X-ray diffraction of each thin film produced by keeping the nitrogen partial pressure constant. As is clear from FIG. 3, the film obtained without introducing nitrogen gas became crystalline, but an amorphous film could be obtained at a nitrogen partial pressure of 0.028 Pa or higher. Nitrogen partial pressure 0.028Pa-0.109Pa
The nitrogen concentration in the film produced in
It was at%.

Example 3 A film was formed on a substrate in the same manner as in Example 1 except that a target made of (98.5 at% Al-1.5 at% Ti) was used. FIG. 4 shows the analysis result by X-ray diffraction of each thin film produced by keeping the nitrogen partial pressure constant. As is clear from FIG. 4, the film obtained without introducing nitrogen gas became crystalline, but the nitrogen partial pressures were 0.042 Pa and 0.060 P.
An amorphous film could be obtained with a. Nitrogen partial pressure 0.042
The nitrogen concentration in the film produced at Pa to 0.060 Pa was 17 at% to 25 at%.

Example 4 A target made of (64 at% Al-36 at% Ti) was placed facing the electrode (+ pole) in the magnetron sputtering deposition apparatus, and a glass plate or an aluminum plate was placed between the electrode and the target. It was arranged as a deposition target substrate. After exhausting the inside of the sputtering apparatus with a vacuum pump, argon gas was supplied, and the gas pressure (total pressure) inside the apparatus was set to 1 Pa. Prior to coating, a high frequency power source was connected to a jig fixing a glass substrate or an aluminum substrate, and the glass substrate or the aluminum substrate was sputter-etched. Then, a direct current power supply was connected to the target to carry out preliminary discharge. At this time, the glass substrate or the aluminum substrate was not coated by the preliminary discharge. After the above preliminary discharge,
The shutter was moved to start coating on the glass substrate or aluminum substrate. However, the substrate was not preheated prior to coating. During the coating, the reaction gas, nitrogen gas, continuously changed the partial pressure of nitrogen gas from 0 Pa to 0.074 Pa by an electrically controllable flow rate controller.

FIGS. 5 to 9 show the results of X-ray diffraction analysis of each thin film produced with the nitrogen partial pressure kept constant. As is clear from these X-ray diffraction patterns, the nitrogen partial pressure is 0.0
An amorphous film was obtained at 285 to 0.0406 Pa. The nitrogen concentration in the film produced at a nitrogen partial pressure of 0.0285 Pa to 0.0406 Pa was 18 at% to 35 at%. FIG. 10 shows the results of measuring the hardness of a film formed with a predetermined nitrogen partial pressure. The hardness was measured by a micro hardness meter. As is clear from FIG. 10, the hardness increased as the nitrogen partial pressure increased.

Example 5 A target made of (80 at% Al-20 at% Zr) was placed facing the electrode (ground potential) in the magnetron sputtering deposition apparatus, and a glass plate or an aluminum plate was placed between the electrode and the target. It was arranged as a deposition target substrate. After exhausting the inside of the sputtering apparatus with a vacuum pump, argon gas was supplied, and the gas pressure (total pressure) inside the apparatus was set to 1 Pa. Prior to coating, a high frequency power source was connected to a jig fixing a glass substrate or an aluminum substrate, and the glass substrate or the aluminum substrate was sputter-etched, respectively. Then, a direct current power supply was connected to the target to carry out preliminary discharge. At this time, the glass substrate or the aluminum substrate was not coated by the preliminary discharge. After the preliminary discharge, the shutter was moved to start coating on the glass substrate or the aluminum substrate. However, the substrate was not preheated prior to coating. During coating, the reaction gas, nitrogen gas,
An electrically controllable flow controller kept the amount introduced into the device at a predetermined constant flow rate or continuously increased it. The nitrogen partial pressure at this time is 0 Pa to 0.129 Pa.
Became. The pressure change in the device due to the difference in the amount of introduced nitrogen gas was adjusted so that the pressure was 1 Pa by the valve arranged between the exhaust pump and the device.

FIG. 11 shows the result of analysis by X-ray diffraction of each thin film produced by keeping the nitrogen partial pressure constant on the glass substrate. As is clear from FIG. 11, there was a peak showing a crystalline phase of Al and Al ₃ Zr at a nitrogen partial pressure of 0 Pa without introducing nitrogen gas, but an amorphous phase was obtained at a nitrogen partial pressure of 0.028 Pa. Further, even if the nitrogen partial pressure was further increased, a peak showing a crystalline phase did not appear. Nitrogen partial pressure 0.028P
The nitrogen concentration in the film produced at a-0.109 Pa was 15 at% to 62 at%. FIG. 12 shows the Knoop hardness of each thin film produced by keeping a nitrogen partial pressure constant on an aluminum substrate. The Knoop hardness of the film was 400 Hk at a nitrogen partial pressure of 0 Pa, but the hardness gradually increased with an increase in the nitrogen partial pressure, and reached 2100 Hk at 0.129 Pa. FIG. 13 shows the electric resistance of each thin film formed on the glass substrate while keeping the nitrogen partial pressure constant. The resistance value of the film increased as the nitrogen partial pressure increased, and no conductivity was exhibited at a nitrogen partial pressure of 0.129 Pa. Further, the nitrogen partial pressure is changed from 0 Pa to 0.
The graded film in which the nitrogen concentration in the film produced by continuously increasing it to 129 Pa increased toward the film surface was dense over the entire thickness range and had good adhesion to the substrate.

Example 6 A target made of (80 at% Al-20 at% Cr) was placed facing an electrode (ground potential) in a magnetron sputtering vapor deposition apparatus, and a glass plate or an aluminum plate was placed between the electrode and the target. It was arranged as a deposition target substrate. After exhausting the inside of the sputtering apparatus with a vacuum pump, argon gas was supplied, and the gas pressure (total pressure) inside the apparatus was set to 1 Pa. Prior to coating, a high frequency power source was connected to a jig fixing a glass substrate or an aluminum substrate, and the glass substrate or the aluminum substrate was sputter-etched, respectively. Then, a direct current power supply was connected to the target to carry out preliminary discharge. At this time, the glass substrate or the aluminum substrate was not coated by the preliminary discharge. After the preliminary discharge, the shutter was moved to start coating on the glass substrate or the aluminum substrate. However, the substrate was not preheated prior to coating. During coating, the reaction gas, nitrogen gas,
An electrically controllable flow controller kept the amount introduced into the device at a predetermined constant flow rate or continuously increased it. The nitrogen partial pressure at this time is 0 Pa to 0.108 Pa
Became. The pressure change in the device due to the difference in the amount of introduced nitrogen gas was adjusted so that the pressure was 1 Pa by the valve arranged between the exhaust pump and the device.

FIG. 14 shows the result of analysis by X-ray diffraction of each thin film produced by keeping the nitrogen partial pressure constant on the glass substrate. As is clear from FIG. 14, there is a peak showing a crystalline phase of Al at a nitrogen partial pressure of 0 Pa without introduction of nitrogen gas, but at a nitrogen partial pressure of 0.020 Pa or more, an amorphous phase was formed. The nitrogen concentration in the film produced at a nitrogen partial pressure of 0.020 Pa to 0.11 Pa was 8 at% to 45 at%. FIG. 15 shows a micro hardness tester (load 20 gf, time 2) for each thin film produced by keeping a nitrogen partial pressure constant on an aluminum substrate.
The Knoop hardness measured by 0 second) is shown. The Knoop hardness of the film was 235 Hk at a nitrogen partial pressure of 0 Pa, but the hardness gradually increased as the nitrogen partial pressure increased to 0.108 P.
It was 963 Hk for a. Moreover, the graded film in which the nitrogen concentration in the film produced by continuously increasing the nitrogen partial pressure from 0 Pa to 0.108 Pa increases toward the film surface is dense over the entire thickness range and adheres well to the substrate. The sex was also good.

Example 7 An apparatus having an inclined electrode system as shown in FIG. 16 was used for film formation on the substrate 2. Two targets, that is, disc-shaped high-purity aluminum and high-purity manganese targets 5 and 6 are used, and the alloy composition is adjusted by sputtering at the same time.
10 was used. The two targets 5 and 6 attached to the support bases 7 and 8 are the holders 3 whose normals passing through the centers of these two targets are rotated by the motor 4.
So that they intersect at the surface of the substrate 2 attached to
It was installed so as to be inclined in the sputtering chamber 1. In addition,
The alloy composition ratio of each is controlled by adjusting the amount of electric power applied to the target, and the relative ratio of aluminum and manganese is 80 at% Al-20 at% Mn.
And The amount of nitrogen, which is a modulation component in the formed film, was controlled by adjusting the amount of nitrogen gas introduced into the chamber with a mass flow controller. At this time, the partial pressure of nitrogen gas in the chamber is 0 Pa to 0.06.
It changed in the range of 5 Pa. Coating is performed after pre-exhaust in the chamber and pre-sputtering for cleaning the target surface, and after the coating process, the temperature of the target and substrate is lowered to introduce air to bring the chamber to atmospheric pressure and take out the sample. It was

FIG. 17 shows the result of X-ray diffraction of a uniform composition film produced by keeping each nitrogen partial pressure constant. As is clear from FIG. 17, an amorphous film was obtained at a nitrogen partial pressure of 0 to 0.051 Pa. FIG. 18 shows the result of the hardness test conducted on a 33 μm thick film formed by continuously increasing the nitrogen partial pressure on an aluminum substrate. As is clear from FIG. 18, the Knoop hardness inside the film increased in the film thickness direction. This is because the nitrogen concentration in the film increased toward the film surface.

[0022]

As described in detail above, according to the method of the present invention, a dense wear-resistant amorphous film having good adhesion to a substrate and high hardness can be obtained without preheating the substrate. It can be manufactured without adding a special process to the processing process. In addition, the film obtained by the present invention is a high hardness film having an amorphous structure, and defects such as breakage at grain boundaries occurring in a crystalline high hardness film are improved, and excellent adhesion to a substrate is obtained. It has excellent properties such as strong bending resistance and high hardness, and can be used as a wear resistant film. In addition, it has high hardness and conductivity, so it can be applied to electrical contacts with wear resistance. . In addition, the amorphous hard film of the present invention has excellent mechanically and electrically properties, and since brittleness, which is a defect of the ceramic material, is mitigated, an electric / electronic material, a high strength material, an abrasion resistant material, It can be used as a high temperature resistant material and can be used for various industrial applications.

[Brief description of drawings]

[1] Example Each (Al ₈₀ Ti ₂₀₎ was prepared by holding the nitrogen partial pressure constant at 1 is an X-ray diffraction diagram of _{100- c} N _c composition film, for each X-ray diffraction pattern the vertical axis It is shown by shifting in the order of partial pressure of nitrogen in the strength direction.

Is a graph showing the relationship between the _{(Al 80 Ti 20) 100- c} N c composition amorphous film Knoop hardness and nitrogen partial pressure which is manufactured by holding the nitrogen partial pressure constant in Figure 2 EXAMPLE 1 .

FIG. 3 is a X-ray diffraction pattern of the _{(Al 89 Ti 11) 100- c} N c composition thin film prepared by holding the nitrogen partial pressure constant in the second embodiment, the respective X-ray diffraction pattern the vertical axis It is shown by shifting in the order of partial pressure of nitrogen in the strength direction.

FIG. 4 is an X of each (Al _98.5 Ti _1.5 ) _100-c N _c composition thin film prepared in Example 3 while keeping the nitrogen partial pressure constant.
It is a line diffraction diagram, and shows each X-ray diffraction diagram shifted in the direction of the nitrogen partial pressure in the strength direction of the ordinate axis.

5 is a X-ray diffraction diagram of nitrogen partial pressure 0.0285Pa prepared in _{(Al 64 Ti 36) 100- c} N c composition film in Example 4.

6 is a X-ray diffraction diagram of nitrogen partial pressure 0.0333Pa prepared in _{(Al 64 Ti 36) 100- c} N c composition film in Example 4.

7 is a X-ray diffraction diagram of nitrogen partial pressure 0.0378Pa prepared in _{(Al 64 Ti 36) 100- c} N c composition film in Example 4.

8 is a X-ray diffraction diagram of nitrogen partial pressure 0.0406Pa prepared in _{(Al 64 Ti 36) 100- c} N c composition film in Example 4.

9 is a X-ray diffraction diagram of nitrogen partial pressure 0.0415Pa prepared in _{(Al 64 Ti 36) 100- c} N c composition film in Example 4.

Is a graph showing the relationship between the _{(Al 64 Ti 36) 100- c} N c composition amorphous film Knoop hardness and nitrogen partial pressure which is manufactured by holding the nitrogen partial pressure constant in [10] Example 4 .

[11] Example Each was prepared to hold the nitrogen partial pressure constant at 5 (Al ₈₀ Zr ₂₀₎ an X-ray diffraction diagram of _{100- c} N _c composition film, for each X-ray diffraction pattern the vertical axis It is shown by shifting in the order of partial pressure of nitrogen in the strength direction.

Is a graph showing FIG. 12 each were produced by holding the nitrogen partial pressure constant in Example 5 (Al ₈₀ Zr ₂₀₎ of _{100- c} N _c composition amorphous film Knoop hardness and the nitrogen partial pressure relationship .

[Figure 13] is a graph showing the relationship between Example each were produced by holding the nitrogen partial pressure constant at _{5 (Al 80 Zr 20) 100-} c N c composition amorphous film resistance and the nitrogen partial pressure .

[14] Example 6 each (Al ₈₀ Cr ₂₀₎ was prepared by holding the nitrogen partial pressure constant in a X-ray diffraction diagram of _{100- c} N _c composition film, for each X-ray diffraction pattern the vertical axis It is shown by shifting in the order of partial pressure of nitrogen in the strength direction.

Is a graph showing the relationship between FIG. 15 each were produced by holding the nitrogen partial pressure constant in Example _{6 (Al 80 Cr 20) 100-} c N c composition amorphous film Knoop hardness and the partial pressure of nitrogen .

16 is a schematic configuration diagram of a sputter deposition apparatus used in Example 7. FIG.

[17] Example Each was prepared to hold the nitrogen partial pressure constant at 7 (Al ₈₀ Mn ₂₀₎ an X-ray diffraction diagram of _{100- c} N _c composition film, for each X-ray diffraction pattern the vertical axis It is shown by shifting in the order of partial pressure of nitrogen in the strength direction.

FIG. 18: (Al ₈₀ Mn ₂₀ ) _100-c produced in Example 7
It is a graph which shows the Knoop hardness in the thickness direction of the structure gradient film of the composition of _Nc .

[Explanation of symbols]

1 sputter chamber, 2 substrate, 3 holder,
4 motors, 5 and 6 targets, 7 and 8 supports, 9 and 10 high frequency power supplies

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akihisa Inoue Kawauchi Muzenji, Aoba-ku, Sendai City, Miyagi 11-806 (72) Inventor Hiroshi Yamagata 1008 Dogenji, Tateyama-cho, Nakashinkawa-gun, Toyama Prefecture

Claims (6)

[Claims] 1. A general formula: (Al _a M _b ) _100-c X _c (where M is Ti, Ta, V, Cr, Zr, Nb, Mo,
At least one element selected from the group consisting of Hf, W, Fe, Co, Ni, Cu and Mn, X represents one element selected from the group consisting of N, O and C, a, b and c Represent atomic%, 60 at% ≦ a ≦ 98.5 at%,
1.5 at% ≦ b ≦ 40 at%, 0 at% <c ≦ 65a
A wear-resistant amorphous hard film having a composition represented by t%, where a + b = 100 at%), showing an amorphous structure, and having high hardness. 2. The physical formula: Al by a physical vapor deposition method.
_a M _b (where M is Ti, Ta, V, Cr, Zr, N
b, Mo, Hf, W, Fe, Co, Ni, Cu and Mn
At least one element selected from the group consisting of a and b each represents atomic% and 60 at% ≦ a ≦ 98.5.
at%, 1.5 at% ≦ b ≦ 40 at%, where a + b
= 100 at%), and an amorphous material on a substrate in an inert gas atmosphere containing a predetermined amount of a reaction gas while supplying a reaction gas containing nitrogen, oxygen or carbon using an evaporation source material. A method for producing an abrasion-resistant amorphous hard film, which comprises forming a film. 3. An amorphous structure in which the concentration of a reaction gas component in an amorphous film increases toward the film surface while controlling the supply amount of the reaction gas so that the partial pressure thereof changes continuously or stepwise. The method according to claim 2, wherein a quality film is formed. 4. At least one gas selected from nitrogen gas, ammonia gas and methane gas is used as a reaction gas, and the concentration of the reaction gas in the gas introduced into the processing apparatus during the vapor deposition is set to Ratio 2-35
The method according to claim 2 or 3, wherein the volume% is used. 5. The total pressure of the inert gas and the reaction gas is 0.6 to
The method according to claim 2, wherein the pressure is 1.2 Pa. 6. The method according to claim 2, wherein the physical vapor deposition method is a sputtering method or an ion plating method.