JPS58164777A - Formation of metallic compound film - Google Patents

Abstract

PURPOSE:To form uniform and beautiful decorative films on a large number of substrates by disposing plural pieces of anode plates and cathode plates spacially so as to face each other. CONSTITUTION:Plural pieces of cathode plates 5 are disposed below and anode plates 6 above spacially so as to face each other in a vacuum vessel 2 provided with a gas supply port 3, an evacuating port 1 and heating means 8 for the walls of the vessel. Substrates 4 to be treated are placed on the respective plates 5 and the inside of the vessel 2 is evacuated. A reacting gas contg. gaseous metallic compds. is introduced therein to 0.1-10Torr, and 2,000-8,000V DC voltage is applied between both electrodes 5, 6 to form electric discharge spaces near the substrates 4; at the same time, the inside of the vessel 2 is heated to 200- 1,000 deg.C whereby films of metallic compds. are formed on the surfaces of the substrates 4.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention 1] The present invention relates to a method for forming a metal compound film that can form a uniform and beautiful film on a large amount of substrates.

[Technical background of the invention and its problems] Conventionally, on the surface of a substrate made of metal, ceramics, etc.
□It is a method for forming coatings of high melting point compounds such as titanium nitride and titanium carbide, which have excellent wear resistance!
Vapor deposition methods are known. In this method, the shape and formation of the high melting point compound coating is carried out at 900 to 1200°C, so there is a limitation that it cannot be applied to substrates that are thin or thin, easily deformed, or made of materials with a single point. there were.

Another disadvantage is that the surface of the resulting coating is rough, making it unsuitable for decorative purposes.

For this reason, when used as the outside of a wristwatch, etc., a glow discharge space is formed near the base when coating with the above-mentioned metal compound in order to improve wear resistance and add decorative properties. A glow discharge chemical vapor deposition method is being considered in which the reaction is caused and the heating temperature required for coating is as low as 400 to 600°C.

This method will be explained with reference to FIG. 1 when, for example, the surface of a substrate is coated with a metal nitride. First, the inside of the vacuum chamber 2 is evacuated from the exhaust port 1 connected to a vacuum pump to a pressure below 1O-sTorr. After evacuating to a degree of vacuum, a mixed gas of metal halide, nitrogen, and hydrogen is introduced into the vacuum container 2 from the gas supply port 3 so that the pressure in the vacuum volume I2 becomes 0.1 to 10 Torr. Inside the vacuum container 2, there is a cathode plate 5 that can be placed in an electrically conductive state with the substrate 4 to be processed.
and an anode plate 6 supported above the cathode plate 5 at a predetermined distance. 200~8QO between this electrode
A DC voltage of OV is applied and the heating plate 7 provided on the back surface of the cathode plate 5 is heated to heat the substrate to a temperature of 200 to 1,000.
℃, preferably 400 to 600℃, the temperature can be reduced! A glow discharge space is formed near the substrate, and the mixed gas reacts on the surface of the substrate to form a metal nitride film.

However, in this method, the amount of material that can be treated is limited. 6I
! Since the number of substrates is limited to the number that can be placed on the cathode plate, it has been difficult to process a large number of substrates at the same time.

[Object of the invention] The present invention provides uniform processing even when processing a large number of substrates.
The object of the present invention is to provide a method for forming a metal compound film that can form an attractive decorative film.

[Summary of the Invention] The present invention provides a vacuum vessel 2 equipped with a gas supply port 3, an exhaust row, and a vessel wall heating means 8 as shown in No. 2@l, with a cathode plate 5 placed downward and an anode plate 6 placed upward. A plurality of substrates 4 to be treated are placed on each cathode plate 5 and the inside of the vacuum container 2 is evacuated, and then a reaction gas containing a gaseous metal compound is applied at a rate of 0.1 to 0. 10 Torr, and apply a DC voltage of 200 to 8000 V between the two poles]! ! A discharge space is formed in the vicinity of the substrate 4, and the inside of the vacuum container 2 is heated to about 200 to 1000°C to form a metal compound coating on the surface of the substrate 4 to be processed. be.

Metal compounds that can be applied to the present invention include N8, Va, Vla group compounds, nitrides, carbides, borides, or combinations thereof, and raw material gases include ,child
) Use a halide of the a, va, or group a, hydrogen, and nitrogen (or ammonia gas instead of nitrogen). The mixing specific gravity of these gases is metal halide:
The hydrogen:nitrogen molar ratio is preferably 1:12 to 100:1 to 100, preferably 1:12 to 5°:1 to 3°. The reason for this is that if it deviates from this value, it is difficult to obtain a uniform decorative film.

The method of the present invention can form a uniform decorative metal compound coating on any electrically conductive material substrate, including metals, semiconductors, and conductive ceramics. can.

[Embodiments of the invention] Next, an implementation example of the present invention will be described.

Example A treatment @ stomach was used in which three disk-shaped cathode plates were placed in a cylindrical vacuum container, and an anode plate was placed above each of the cathode plates. %, 813
．． 25 pieces x 25+s consisting of an alloy with a composition of 8% and the remainder N1
900 X4+n metal plates were placed as substrates to be processed and processed under the following conditions.

A uniform and beautiful TIN film with a thickness of 1 μm was formed on each substrate.

Reaction gas composition TI CJ24:H2:N2-1:
19:6 (molar ratio) Pressure 2T0rr Voltage 500v Current density W1 0.11A101 Substrate concentration 550°C 11#fl 30 minutes [Effect 1 of the invention] As is clear from the above examples, the method of the present invention According to this method, it is possible to obtain a uniform, beautiful coating without uneven color on a large number of substrates.

[Brief explanation of drawings]

1st! 11 is a sectional view schematically showing the apparatus used in the conventional method, and FIG. 2 is a sectional view schematically showing the apparatus used in the method of the present invention. 2......Vacuum vessel 4...Substrate to be processed 5...Cathode plate 6...・・・・・・・・・Anode plate 8・・・・・・・・・Heating means (7317) Representative patent attorney Kensuke Norichika (and 1 other person)

Claims (1)

[Claims] In a vacuum container equipped with a gas supply port, an exhaust port, and means for heating the container wall, a plurality of cathode plates and monopolar plates are arranged facing each other at four intervals, and each cathode plate is covered with a coating. A substrate to be treated is placed, the vacuum container is evacuated, and then a reaction gas containing a gaseous metal compound is supplied at 0.1 to 10 To. r, and apply 200 to 8゜00V between the two poles.
A DC voltage of 1! is applied to form a discharge space in the vicinity of the MW body, and the wall of the vacuum vessel is heated to generate the MW body. A method for forming a metal compound film, the method comprising forming a metal compound film on the surface of a substrate.