JPS6016810A - Formation of surface coating film - Google Patents

Abstract

PURPOSE:To obtain a surface coating film having excellent durability, abrasion resistance, heat resistance, corrosion resistance, adhesivity, and gas barrier property, by decomposing a specific methyl hydrogen polysilane compound, and depositing silicon carbide to a substrate. CONSTITUTION:The reaction chamber containing the substrate such as glass, metal, ceramic, plastic, wood, etc. is evacuated to 0.01-5Torr, and charged with the methyl hydrogen polysilane compound of formula (1<b<4; 2b+1>=a>=1; 2b+1>=c>=1; a+c=2b+2) carried by a carrier gas. The substrate is heated at 100-700 deg.C and plasma is generated by the imposition of high frequency electrical power. The methyl hydrogen polysilane compound is decomposed and silicon carbide is deposited on the substrate by this procedure.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention (method for producing a silicon carbide coated film having excellent durability, abrasion resistance, heat resistance, corrosion resistance, adhesion, and gas impermeability) [This is related to two things.

In recent years, many glass materials have been used in housings and displays for various electrical devices, various functional films, building materials, cosmetics, toys, decorative items, etc.

Since the surface of this plastic material is made of a high molecular weight material with so-called organic bonds, it has the essential disadvantage of being inferior in durability, abrasion resistance, heat resistance, corrosion resistance, adhesiveness, and gas impermeability. there were. Also.

Glass materials used as protective materials for window glasses, various windows, glasses, and various electrical equipment have wear resistance (
Metal materials widely used in various fields such as iron, aluminum and copper have the disadvantages of poor hardness and limited strength. It has the disadvantage of being inferior to

Therefore, various methods of protection are used for these two materials, and for plastics, various additives are added to the film to form them.

The methods used include applying paint to molded products, gluing or sandwiching different types of films, and for glassy materials and ceramics, gluing or sandwiching glass films or applying paint. For the protection of metal, the methods of applying paint, chemically or physically treating the surface, or thermally spraying a protective material on the surface have been adopted, but these methods do not always give satisfactory results. It was not intended to give.

Therefore, the surface protection of these base materials is oxidation resistance, corrosion resistance,
A method has been proposed in which silicon carbide is coated with silicon carbide, which has heat resistance, thermal shock resistance, low thermal expansion, and is itself highly hard (high density). Sputtering method using hydrogen gas (Japanese Patent Publication No. 56-26.640, Japanese Unexamined Patent Publication No. 56-40
, No. 284), ■Ionize silicon vapor,
Ion grating method for forming a film on the surface of a carbon substrate C (see Japanese Patent Publication No. 55-18,678) - ■ Method for thermally decomposing a mixed gas of silane or halogenated i/ran gas and hydrocarbon gas 57-116.200
(Refer to Japanese Patent Application Laid-Open No. 118-082-1982), ■
A method of thermally decomposing the silane gas on a carbon surface (see Japanese Patent Publication No. 47-48-120), ■ A method of decomposing a hydrocarbon gas on a silicon substrate (Japanese Patent Publication No. 56-2
6,640), and furthermore, ■ a method of treating hydrogenated silane, alkylsilane, or halogenated silane with hydrocarbon gas by plasma vapor deposition method (hereinafter referred to as CVD method) (Japanese Patent Laid-Open No. 57-27, Publication No. 914, JP-A-57
22,112 (see Japanese Patent Publication No. 1983-200.215), and the like are known.

However, these methods (■ to ■) require high temperatures, tend to form glasters of each element, and are difficult to obtain a homogeneous film.
- In addition to the disadvantage that the film formation rate is slow, due to the difference in thermal expansion, there is a disadvantage that two films (= Bragg) are likely to occur when returned to room temperature, and the adhesive strength is poor. The law stipulates that if monosilane (5iH4) is used as the starting material, it is highly flammable and must be handled with great care.
It has the disadvantage of high cost, and the disadvantage of using halogenated silane is that the plasma generates hydrochloric acid and chlorine supply wells, which makes processing difficult, and the reaction rate is slow. If the deposition rate is accelerated due to the difference in reaction rate, glasters of 81 and O will occur, making it impossible to obtain a homogeneous film.

The present invention relates to a method for forming a secondary silicon film on a substrate surface which solves such disadvantages.
+1≧a≧1-2b+1≧C≧1, a+o=2b+2)
This method is characterized by depositing on a substrate a carbonized residue generated by the decomposition of at least one of the methylhydrodiene polysilanes shown in the following.

To explain this, the present inventors have previously discovered that a highly pure and uniform silicon carbide film can be obtained by treating a methylhydrogensilane compound as a starting material using a plasma OVD method. (2) It was confirmed that it is possible to obtain a homogeneous silicon carbide film at an extremely high growth rate by using methyl hydride-a-diene disilane or -trisilane (Patent Application No. 58-4, 69
(See No. 5). Based on this knowledge, the present invention uses methylhydrodiene polysilane as a starting material, processes it by plasma OVD method, and deposits the generated carbide on the substrate to improve durability and wear resistance. This was made based on the inventors' confirmation that a surface coating film with excellent properties, heat resistance, corrosion resistance, adhesiveness, and gas impermeability can be obtained.

The methylhydrodiene polysilane used in the present invention (2) is represented by the general formula (OH3)aSlbHo described above, and examples thereof include H-S i-81-81-R Il+ OH3HOH3. may be used alone or as a mixture of two or more.Since this methylhydrodiene polysilane contains silicon atoms and carbon atoms at the same time in one molecule, silicon carbide generated by this decomposition is The deposited film is homogeneous, giving the advantage that the growth rate of the film is several times faster than when monosilane is used.The method for producing this methylhydrodiene polysilane is known, This is achieved by thermally decomposing polydimethylsilane at 350°C or higher, or by reacting methyl glolide with metal silicon.
It can be obtained by reducing methyl chlorodisilane, which is a by-product during the direct synthesis of rosilane.

To carry out the method of the present invention, this methylhydrodiene polysilane may be treated by the Glazma OVD method. First, the substrate to be treated is placed in a reaction chamber, and then the reaction chamber is heated to a temperature of 0.01 to After reducing the pressure to the system, methylhydrodiene polysilane is introduced together with hydrogen, helium, and argon gases as carrier gases, and then high-frequency power is applied to the system to generate a glazma. This reaction temperature needs to be adjusted depending on the heat resistance temperature of the substrate, but it should be at least 100°C, preferably 150°C.
It is better to set it to the above. However, if the temperature is lower than 150°C, absorption of 2090tyn due to SiH bonds will occur in the obtained silicon carbide coating, which may cause problems in terms of durability and heat resistance. It is best to stop the supply of the carrier gas and the methylhydrodienepolysilane as a raw material, and supply only the gases serving as the carbon source, nitrogen source and oxygen source, and age at this temperature for 20 minutes or more. You can remove stupid disadvantages. Note that the upper limit of this reaction temperature is preferably 700°C or less, but from an economic standpoint, if this is too high, there is a risk that a uniform and dense film may not be obtained due to the difference in thermal expansion coefficient between the substrate and the coating film. Therefore, the temperature is preferably 500°C or less, although it depends on the type of base material.

In the method of the present invention, as described above, this methyl 81'drodiene polysilane simultaneously contains carbon atoms and silicon atoms, and the ratio thereof can be changed.
There is no need to add other carbon sources or gases as silicon sources to this reaction system, but methane and ethane can be used as carbon sources for the above-mentioned aging purposes, and carbon dioxide can be used as a nitrogen source.

Ammonia gas - N2H4 etc., oxygen gas, water vapor etc. as an oxygen source, and ζ2 as a mixed gas of 00. CO2, N2O-0H30H, etc. may be used.

Although the film thickness of the silicon carbide plate coating film obtained by the method of the present invention varies depending on the purpose, when strength is required for the coating film (second is that it is made from several microns to several tens of microns and has durability without requiring strength). If the purpose is to improve surface hardness, gas impermeability, adhesion, etc., it may be several microns or less.Also, the atomic ratio of carbon to silicon in this silicon carbide coating is determined by the starting material. Although it varies depending on the structure of the methylhydrodiene polysilane, that is, its overall ratio of silicon atoms to carbon atoms, this is arbitrary for the purpose of the present invention, and any ratio may be used.

The silicon carbide overcoat film formed by the method of the present invention is said to be useful for modifying various materials, such as improving the lubricity of ceramics such as silicon nitride, sialon, and mullite. For use.

For surface treatment to strengthen the rust prevention surface of iron ore, non-ferrous metal alloy products, etc. Also for surface protection of electrical and electronic components such as solar power regulators, solar power generation surface pipes, plates, and various types of workpieces. In addition to being used for various purposes, it can also be widely used for surface treatments aimed at strengthening various types of glass, improving adhesion, improving gas permeability, etc.

Next, examples of the method of the present invention will be given.

Example 1゜Reaction ii, 12th 100 wa x 50 w + 1 x 1 m, i3
5 x 10" in the system after placing the substrate listed on
The pressure was then reduced to 12°C, and the substrate was then heated using a heater to the temperature shown in Table 1.

Next, various methylhydrodiene polysilanes listed in Table 1, which had been preheated to a predetermined temperature, were introduced into the reaction chamber together with a 3:1 mixed gas of argon and hydrogen as a carrier gas. After applying a high frequency power (50W) of \CC103, 56MHz to generate plasma and depositing silicon carbide produced by decomposition of this polysilane on the substrate, the corrosion resistance and corrosion resistance of the obtained substrate were evaluated. When the abrasion resistance and heat resistance were measured using the following methods, the results shown in Table 1, C, and II were obtained.

For the purpose of &X comparison, Table 1 also lists test results for base materials treated in the same manner using a mixed gas of monosilane and methane as the starting material, and for each untreated base material.

(Corrosion Resistance) After being immersed in a 1:1 mixture of concentrated hydrofluoric acid and concentrated nitric acid for 2 hours at room temperature, the condition of -7 was examined.

(Abrasion resistance) It was determined whether the surface condition had a Vickers hardness of 1500 h/mj or more.

(Heat resistance) After heating at 400° C. for 8 hours, the state of the film was observed using an electron microscope.

Example 2 The substrates listed in Table 2 were treated in the same manner as in Example 1 to form a silicon carbide plate coating of two μm thickness on one substrate.
When the corrosion resistance, abrasion resistance, adhesion and gas impermeability of these two materials were examined using the following method, the results shown in 1, 2, and 2 were obtained.

Note that Table 2 also lists the physical properties of the substrates that were not subjected to such treatment.

(Corrosion resistance) Same as Example 1 (Abrasion resistance) The surface condition was examined to see if the Vickers hardness was 1000 Ky/an'' or higher.

(Adhesion) An epoxy resin was used to determine if the adhesive strength was 60~/d or more.

(Measure the gas impermeability and oxygen permeability, and the gas permeability is 100.0./-
・Checked whether the pressure was below the atmospheric pressure for 24 hours.

Claims (1)

[Claims] 1. General formula (0H3)aSibH8\to1 b<4-
2b+1≧a≧1.2b+1≧C≧l−a+ a=
A method for producing a surface coating film, comprising depositing silicon carbide generated by decomposing at least one type of methylhydrodiene polysilane represented by 2 b + 2 ) on a substrate. 2. The method for producing a surface coating film according to claim 1, wherein the carbide film is deposited by plasma vapor deposition. 3. Glass, metal - ceramic, glasstic. Claim 1, wherein a silicon carbide cumulative coating is deposited on a substrate such as wood by ζ plasma vapor deposition method.