JPS6082670A - Manufacture of silicon carbide film - Google Patents

Abstract

PURPOSE:To form inexpensively a silicon carbide film on a substrate by subjecting a carbonaceous compd. such as CH4 and a silicon compd. such as SiCl4 which is introduced along with a carrier gas to a gaseous phase reaction by the energy such as plasma. CONSTITUTION:A carrier gas such as H2 from a bomb 1 is passed through liquid SiCl4, SiBr4, SiI4, etc. in a water bath 7 to evaporate the liquid, and spouted from an opening of an electrode 10 into a vacuum vessel 20 along with CH4, C2H6, C2H4, C2H2, etc. from a bomb 2. In this case, a doping gas such as B2H6 from a bomb 3 is added at need. The inside of said vacuum vessel 20 is evacuated to appropriate pressure with a diffusion pump 16, a mechanical booster pump, rotary oil pumps 17a and 17b, etc., and a substrate 12 attached to an electrode 11 is heated to a suitable temp. by a heater 13 and rotated by a rotary motor 14. Under said conditions, plasma is discharged between both electrodes 10 and 11 with a high-frequency electric power source 15, and CH4, etc. and SiCl4, etc. are subjected to a gaseous phase reaction to form an SiC film on the substrate 12.

Description

[Detailed Description of the Invention] Akira Kito, silicon halide liquid, viz.
Silicon carbide is produced by introducing a carrier gas into at least one of EiC, BiBn, and BiX+, and causing a vapor phase reaction between the carrier gas and a carbon compound to form inexpensive silicon carbide on the substrate. Silicon carbide (hereinafter referred to as SiC) regarding the film manufacturing method
Because it has extremely hard properties and electrical properties of extremely high resistance, it is used in a wide range of fields such as passivation films for semiconductors and photoreceptor films for electrophotographic photoreceptors.

The OVD method is generally used as a conventional method for manufacturing EiC thin films.

This method uses high-frequency plasma, heat,
Another method is to decompose it with light 2 and then deposit a SiO film on the substrate.

However, the silicon hydride used in this method is a very expensive material. For example, monosilane gas n1f
The price is around 100 yen per liter, and disilane is several tens of times more expensive than monosilane gas.

Therefore, although it has very good resistance to EliC1d, it has the disadvantage that it is difficult to apply to devices that are expensive to manufacture.

The present invention eliminates these drawbacks, and its purpose is to produce SiC films in an inexpensive manner.

The details of the present invention will be explained with reference to Examples. There are methods for the envelope phase reaction using Kld' plasma, light, and ν, but since there is no major difference in film characteristics between them, plasma CVDVc will be described.

Example Pit 1 Figure 1 shows an apparatus used in the production of the present invention. In the same figure, 1 is a cylinder of gas, 2 is a cylinder of carbon compound, 3 is a cylinder of doping gas, and 40 to 4c are pressure regulating cylinders.
+5a, ~5c are mass flow controllers, 6a~6
e is gas piping, 7 is water bath, 8-point flow meter, 9-piece silicon halide, 10-piece high-frequency electrode with gas outlet, 11-piece high-frequency electrode, 12 is substrate, 13
1- is a substrate heating heater, 14 parallel girder rotation motor, 151
- is a high-frequency power supply, 16-piece oil scattering pump, 18-piece mechanical booster pump, 17a and 17b are oil rotary pumps,
It is a 19α to 19C pulp. 20 is a vacuum container.

The method for producing Si:O will be explained.

In advance, oil diffusion pump 16 and oil rotary pump 17cL
The inside of the vacuum chamber 20 is evacuated to below 5XiO-'Torr, and the temperature of the substrate is heated to 150 to 300°C by 1°C, for example, 200°C.
Control to ℃.

When the internal pressure of the vacuum container 20 reaches a certain pressure,
The exhaust system is switched from an oil diffusion pump to a series of mechanical booster 18 and oil rotary pump 17b.

At 1bj, carrier gas, i.e., hydrogen, argon,
A gas whose pressure is controlled to I Kg/cyn2 by a pressure regulator 4a is supplied from a cylinder 1 containing one of helium gases, for example, hydrogen gas, and the flow rate is adjusted to J O by a mass flow controller 5c.
The flow rate is controlled to about Oc c/min so that it does not flow into pipe 6C.

The gas passing through the pipe 6c is silicon halide 5ic.
t+, Sl+:Br+, Bi I4, for example, flows through the Bi Buddha liquid 9 to the pipe 6d.

At this time, the temperature of 5iOt4 is 21° CVC (M) by the water bath 7. The partial pressure of SiC at 21°C is 200 mW TO7'r, and the carrier gas carries 5iO14 gas i◇1 through the pipe 6dK. .

On the other hand, the flow rate of a carbon compound such as methane gas (CiH4) is controlled to about 100 cc/mi by using a mass flow controller 5b, and then the gas is transferred from a cylinder 2 containing a carbon compound such as methane gas (CiH4) to a pressure of IKVCIn2 using a pressure regulator 4b. 6b.

Hoy HeJ + Peripheral pressure 54 c+ Mass flow controller 5α, piping 6ah In the doping gas system, as soon as boron is doped into SiC, diborane (B
If you want to dope 2H,) with phosphorus, dilute the phosphine (PH3) gas appropriately and fill it into a cylinder.
It flows through piping 6α. These gases are mixed in the piping 6e and introduced into the vacuum container from the outlet of the electrode 1i10. Using pulp for controlling the flow rate of 8 pulps, the flow rate is adjusted so that the pressure inside the vacuum container is 0.7 to 1.37 Orr.

In this state, the rotary motor 14 rotates the electrode 11 attached to the substrate 12f at approximately 5 r, p, rn, and applies high frequency power between the thunderbolt 10 and the electric body 11 to generate electric power 11 L plasma emission. .

The frequency of high frequency is usually 15.56MHz, but 4M
Hz may also be used. In addition, the high frequency −■ force is determined when the diameter of the electrode is 30
In the case of cmφ, it is 300 to 800 W.

Generally, when the high frequency power is in the above range, the growth rate of long SiC on the substrate increases as the power increases. For example, the growth rate of long SiC on the substrate at 500 W is about 5 μrr V/H, Approximately 7 tons for 800W
trn/H.

In the above example, 5iC is used as a silicon halide.
Although the case where 7!4 is used is explained, the same result can be obtained also in case of 5iBn or Si process number by appropriately controlling the temperature of the water bath. Further, even with a cylindrical shape such as an electrophotographic photoreceptor, a similar sia film can be obtained with different electrodes. Similar results were obtained for carbon compounds such as ethane, ethylene, and acetylene in addition to methane.

Analyzing the manufacturing cost of the fJic model, we found that the conventional method, namely plasma CV using monosilane gas and methane gas,
I) In the K method, the proportion of gasification is 30% of the total.
~40Ll). This is because monosilane gas is very expensive.゛Look, monosilane gas costs around 100 yen per gram.
The price is 5 to 10 times higher than that of hydrogen, methane, argon, helium, etc.

In the present invention, a silicon halide of less than 10 yen per 12 parts is used instead of monosilane gas, and the Sia layer is formed at almost the same growth rate as when monosilane gas is used. Therefore, the manufacturing cost of SiC (d is approximately 70% of the conventional cost).

Now that SiC films are being applied to a variety of devices, the reduction in manufacturing costs is of great value, and the application fields are wide, including electrophotographic photoreceptors, solar cells, and other thin film devices.

[Brief explanation of drawings]

FIG. 1 shows an apparatus used for manufacturing the present invention. 1...Carrier Ganu cylinder 2...Carbon compound cylinder 3...Doping gas cylinder 4α~4c...
...Pressure regulators 5a to 5C, "°・mass 70-control-ra 6a
~6e...Gas piping 7...J-turbus 8...Flow meter 9...Silicon halocare '4h1a...Curved gas outlet High frequency electrode 11... High frequency type (Y 12... Substrate 13... Middle substrate heater 14... Substrate rotation motor 15 Mountains... High frequency power source 16... ...Oil diffusion pump 17ct~17b...Oil rotary pump 18...
・・Mechanical No Nuta Bomb 19a~19c・・・・
・Balun 20・・・・・・Vacuum containers and above Applicant: Suwa Zunkosha Co., Ltd. Fubujin, Promoter: Tsutomu Mogami

Claims (1)

[Claims] 1) A method for producing a silicon carbide film by gas phase reaction of a carbon compound and a silicon compound, in which the carbon compound is mekun (C!) (4), ethane (02H6), ethylene (C
Using 2J (4) or acetylene (0 zHz), a silicon halide such as Siam, 5iBr4, or 5Z14 as the silicon compound, reacting the two packages in a gas phase, and depositing silicon carbide on a substrate at an appropriate temperature. 1. A method of manufacturing a silicon carbide film, comprising: forming a silicon carbide film. 2) Plasma,
The method for producing a silicon carbide film according to claim 1, characterized in that heat or light energy is used.