JPH0247252A - Production of composite material film - Google Patents

Abstract

PURPOSE:To form a TiC-SiC composite material film on a substrate at relatively low temp. by evaporating titanium by means of electron beam or hollow cathode discharge, introducing silicon compound gas and hydrocarbon gas, and ionizing and activating respective elements. CONSTITUTION:In a vacuum tank 1 in which evacuation is performed through an exhaust hole 12, Ti held in a crucible 3 is heated and evaporated by means of electron beam 8. Subsequently, a silicon compound gas, such as silane, disilane, and tetramethylsilane, as an Si source and a hydrocarbon gas, such as CH4 and C2H2, as a C source are introduced through a gas-introducing hole 7. Then, electric discharge is initiated by means of an ionization electrode 9 connected to an electric power source 13 to ionize and activate respective elements, and, at this time, a shutter 10 is opened and the above ionized and activated elements are introduced onto a substrate 2 of glass, etc. At the time ot the above treatment, a high-frequency electric power is impressed on the substrate 2, if necessary, and further the substrate 2 is heated via a heat source 11 up to the prescribed temp. By this method, the TiC-SiC composite material can be formed on the above substrate 2 without elevating ionization, activation, and substrate temps. up to >=about 200 deg.C.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention is directed to titanium carbide-silicon carbide (TiC-3iC) used as an electrical resistor in thermal heads, electronic circuits, etc.
) relates to a method for manufacturing a composite material membrane.

[Summary of the invention]

Using an electron beam evaporation source or a hollow cathode evaporation source as a titanium source, a silicon compound gas as a silicon source and a hydrocarbon gas as a carbon source are introduced into a vacuum chamber, and titanium carbide is deposited on the substrate.
A silicon carbide composite film is formed at low temperature.

[Conventional technology]

The conventional technology is a technology called thermal CVD (thermal chemical vapor deposition), which uses titanium tetrachloride (TiC14) gas, silicon tetrachloride (SiC1g) gas, and hydrocarbon gas such as methane as material gases in a reaction vessel. Introduced 1000″
By heating to about 50% Celsius, a chemical reaction was caused by the thermal energy, and a titanium carbide silicon carbide composite material film was formed on the substrate.

[Problem to be solved by the invention]

In the conventional technology described above, it is necessary to heat the material gas to about 1000 degrees Celsius in order to cause a chemical reaction using thermal energy.
A titanium carbide-silicon carbide composite film could not be formed.

Furthermore, titanium tetrachloride and silicon tetrachloride, which are material gases, generate corrosive chlorine (CI), which may cause damage to the reaction vessel and the exhaust system. In addition, chlorine may remain in the film and corrode the film.

[Means to solve the problem]

In order to solve the above problems, the present invention uses an electron beam heating type metal evaporation source or a hollow cathode discharge type metal evaporation source as a silicon source instead of using a gas such as titanium tetrachloride as a titanium source. Silicon compound gas such as silane, disilane, and tetramethylsilane and methane as a carbon source,
Hydrocarbon gas such as acetylene is introduced into a vacuum chamber, and each element is ionized and activated by discharge using an ionizing electrode or hollow cathode, forming a chikum carbide-silicon carbide composite material film without raising the substrate temperature above 200°C. made possible.

[Effect]

Titanium is evaporated using an electron bee heating method or hollow cathode discharge method metal evaporation source, ionized together with the introduced silicon compound gas and hydrocarbon gas, and the element is activated by the energy of the ions and electrons. However, a titanium carbide-silicon carbide composite film can be formed on a substrate.

〔Example〕

Embodiments of the present invention will be described with reference to the drawings.

FIG. 1 is a schematic diagram of an electron beam heating system used in carrying out the present invention. A substrate 2 is placed in a vacuum chamber 1, titanium is placed in a crucible 3, and the crucible is evacuated to a pressure of 10-' Torr or less. In the example, a glass plate was used as the substrate.

A changeover switch 4 is installed on the board 2 installed in the vacuum chamber 1.
A high frequency power source 5 or a direct current power a6 is connected through the terminal, and a high frequency voltage or a direct current voltage can be applied.

First, introduce argon gas from the gas introduction lower, and
High frequency power of 13.56 MHz and 100 W of power is applied to the substrate 2 at a pressure of about 10-' to 2 x 10-'' Torr to cause a glow discharge of argon gas.This bombards the surface of the substrate with argon ions. Remove contaminants. After thoroughly cleaning the substrate surface, 1O-5
Evacuate to pressure below Torr.

Next, the titanium in the crucible 3 is heated and evaporated with an electron beam 8, and tetramethylsilane gas and acetylene gas are introduced from the gas introduction lower, and 5 x'to-' to 5 x 10
- Discharge is performed by the ionizing electrode 9 at a pressure of Torr to ionize and activate each element. At this time, if the shutter 10 is opened, a titanium carbide silicon carbide composite material film is formed on the substrate z. By changing the amount of titanium evaporated and the partial pressure of each material gas, the composition ratio of titanium carbide and silicon carbide in the formed film can be changed. In the example, a frequency of 13.56 Ml1z and a power of 1 were applied to the substrate 2 during film formation.
A high frequency power of 00 W was applied. In this way, by applying a negative DC voltage or high frequency voltage to the substrate during film formation, the incident energy of ions to the substrate increases.
A dense and hard film can be formed with good adhesion to the substrate.

By the above method, a titanium carbide-silicon carbide composite material film having a film thickness of about 1 μm was formed on the substrate in a film forming time of 10 minutes.

The quality of the film can be improved by introducing argon gas together with the material gas during film formation and bombarding the film with argon ions. Furthermore, if it is necessary to heat the substrate 2, heating #1) can also be used.

FIG. 2 is a schematic diagram of a hollow cathode discharge type device used to implement the present invention. This device is similar to the device shown in FIG. 1, except that argon gas is introduced into the hollow cathode 9, and titanium is heated and evaporated by hollow cathode discharge to ionize each element. A silicon carbide composite film can be obtained.

[Effects of the Invention] Unlike conventional techniques, high temperatures are not required, and a titanium carbide-silicon carbide composite film can be formed even on a substrate such as glass that has poor heat resistance. By changing film forming conditions such as the amount of evaporation of titanium and the partial pressure of each material gas, the composition ratio of titanium carbide and silicon carbide in the formed film can be changed.

In addition, since chloride is not used as a material gas, there is no possibility of damaging the exhaust pump or leaving chlorine in the membrane.

[Brief explanation of the drawing]

Figure 1 is a schematic diagram of an electron beam heating system used in the practice of the present invention, and Figure 2 shows a hollow cathode discharge system in which metal is heated by an electron beam and ionized by an ionizing electrode. This is a schematic diagram of a method device in which metal is heated, evaporated, and ionized by hollow cathode discharge. Vacuum chamber Substrate Crucible switch High frequency power supply DC power supply Gas inlet Electron beam ionization electrode shutter Heat source Exhaust port Ionization electrode power supply Hollow cathode power supply Argon gas inlet Applicant Seiko Electronic Industries Co., Ltd. Agent Patent attorney Keinosuke Hayashi

Claims (2)

[Claims] (1) Titanium is evaporated using an electron beam heating type metal evaporation source or a hollow cathode discharge type metal evaporation source as a titanium source, and a silicon compound gas such as silane, disilane, or tetramethylsilane is used as a silicon source, and methane is used as a carbon source. ,
A titanium carbide-silicon carbide composite material film is formed on the substrate by introducing hydrocarbon gas such as acetylene into a vacuum chamber and ionizing and activating each element by electric discharge from an ionizing electrode or hollow cathode. A method for manufacturing a composite membrane. (2) In claim 1, when forming a composite material film on a substrate, a titanium carbide-silicon carbide composite material film is formed on the substrate by applying a negative DC voltage or high frequency voltage to the substrate. A method for manufacturing a composite material membrane according to claim 1, characterized in that: