JPH04324628A - Manufacture of silicon thin film - Google Patents

Abstract

PURPOSE:To uniformly deposit an excellent polycrystalline or amorphous silicon thin film, and restrain the generation of particles in a vapor phase, by using hydrogenated silicon compound or gas containing hydrogenated silicon compound by adding hydrogen chloride gas to it. CONSTITUTION:In a method for forming a polycrystalline or amorphous silicon thin film by a low pressure CVD method using hydrogenated silicon compound or gas containing hydrogenated silicon compound, it is used by adding hydrogen chloride gas. For example, when a polycrystalline silicon thin film is formed by a LPCVD method using monosilane gas, the supply gas is set as two systems constituted of monosilane 1 and helium-diluted 0.1% hydrogen chloride gas 2, which are subjected to flow rate control and then supplied. A polycrystalline silicon thin film for a gate electrode is formed on a single crystal silicon substrate under the following conditions; 550-700 deg.C, 0.1-10.0Torr, monosilane gas 300cm<3>/min, and helium-diluted hydrogen chloride gas 200cm<3>/mim.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing polycrystalline or amorphous silicon thin films used in semiconductor chips, liquid crystal display panels, etc. by CVD.

0002

BACKGROUND OF THE INVENTION Conventional methods for manufacturing polycrystalline silicon thin films use monocrystalline silicon as a substrate for use as semiconductor chips (LSI), using monosilane (SiH 4 ) gas as a raw material with nitrogen dilution or without diluting gas. 0.3To
A low pressure CVD method (LPCVD) was used in which thermal decomposition deposition is carried out under a reduced pressure of around rr and at a substrate temperature of around 600 degrees Celsius. In addition, when forming an amorphous silicon thin film used in optical elements on a glass substrate, disilane (Si 2H 6) or trisilane (Si 3H 6), which has a lower decomposition temperature than monosilane, is used as a raw material to lower the reaction temperature. LPCV
D was used at a temperature of about 400 to 500 degrees Celsius.

0003

[Problems to be Solved by the Invention] Conventionally, when using a silicon hydride compound gas such as monosilane, disilane, or trisilane as a raw material, (1) the uniformity of the film thickness tends to deteriorate, and (2) particles form in the gas phase. (3) The quality of the film deteriorates due to pinholes in the film caused by the particles.
(4) Particularly when a higher-order silane such as disilane or trisilane is used, there is a problem in that the step coverage tends to deteriorate. Therefore, an object of the present invention is to provide a method for simultaneously solving the above problems by only changing the mixed gas components without changing other process conditions.

0004

[Means for Solving the Problems] The present invention solves the above-mentioned problems, and is directed to forming a polycrystalline or amorphous silicon thin film by a low pressure CVD method using a silicon hydride compound or a gas containing a silicon hydride compound. This method is characterized in that hydrogen chloride gas is added to a silicon hydride compound or a gas containing a silicon hydride compound.

[0005]

[Operation] It is well known that silicon hydride compound gases such as monosilane, disilane, and trisilane not only deposit directly on the substrate in the LPCVD reactor, but also decompose in the gas phase to produce active reaction intermediates. ing. The tendency of gas phase decomposition is stronger for higher order silanes. All of the problems to be solved by the present invention described above are solved by the reaction intermediate (silylene:
SiH2, etc.).

That is, (1) active intermediates whose surface reaction rate is higher than the gas phase diffusion rate cannot exist at a uniform concentration in the reactor, and the uniformity of the film thickness deteriorates; (2)
) Particles are self-generated by collision polymerization between active intermediates in the gas phase. (3) Particularly when disilane or trisilane is used, the amount of gas phase intermediates produced increases;
This can be explained by the fact that the active intermediate cannot diffuse even within the micron-order step and adheres to the side wall, resulting in poor coverage.

According to the present invention, active reaction intermediates generated in the gas phase, which are the cause of the above problems, can be selectively removed. That is, since the added hydrogen chloride gas reacts with an active gas phase intermediate to generate a stable chlorinated silicon compound gas (dichlorosilane, trichlorosilane, etc.), the reaction intermediate can be selectively removed.

[0008] Therefore, a high quality silicon thin film can be uniformly deposited by simply adding a hydrogen chloride gas line to an existing device without making any major changes to the device shape or the like. Note that since only a small amount of hydrogen chloride is added, it is preferable to use hydrogen chloride gas pre-diluted with helium or the like. In the present invention, there is no problem in including such a diluent gas. That is, the present invention is applicable to any case where a silicon hydride compound or a gas containing a silicon hydride compound is used.

[0009]

【Example】

Example 1 FIG. 1 shows an apparatus for producing a polycrystalline silicon thin film by the LPCVD method using monosilane gas. The gases to be supplied are two systems, monosilane 1 and helium diluted 0.1% hydrogen chloride gas 2, which are supplied with their flow rates adjusted by thermal mass flow controllers 3A and 3B, respectively. The reaction apparatus is a vertical electric furnace 4 having a rotation mechanism 8 in which a wafer support boat 6, a boat support stand 7, a quartz inner tube 9, etc. are housed in a quartz bell jar 5. Rotary pump 11 for pressure reduction and gas replacement
, an exhaust system using a mechanical booster pump 10 is provided.

Using this apparatus, a polycrystalline silicon thin film for a gate electrode was formed on a 6-inch single crystal silicon substrate at 550 to 700 degrees Celsius, 0.1 to 10.0 Torr, and monosilane gas at 30° C.
When produced under the conditions of 0 cubic centimeters/minute and helium-diluted hydrogen chloride gas at 200 cubic centimeters/minute, a high-quality thin film with an in-plane film thickness uniformity of 0.2% or less was obtained.

Embodiment 2 FIG. 2 shows an apparatus for producing an amorphous silicon thin film on a glass substrate by the LPCVD method using disilane gas. Since there are a large number of dangling bonds in an amorphous silicon thin film, it is necessary to terminate these with hydrogen in order to obtain semiconductor properties. For this reason, it is necessary to perform hydrogenation after film formation, and this embodiment also includes a radical annealing device for this purpose.

That is, this apparatus consists of three chambers: a load lock chamber 15, a thin film deposition chamber 13, and a hydrogen radical annealing chamber 17. After installing the glass substrate 14 in the load lock chamber 15,
The chamber was deaerated and transferred to the thin film deposition chamber 13. The feed gas was 12% disilane and 0% helium diluted.
There are two systems: 1% hydrogen chloride gas and 2. The conditions for thin film deposition were 450 to 550 degrees Celsius, 0.1 to 10.0 Torr,
The reaction was carried out using disilane at 15 cubic centimeters/minute and helium diluted hydrogen chloride gas at 35 cubic centimeters/minute.

[0013] After this step, the load lock chamber 1 is
5 to the hydrogen radical annealing chamber 17. In this step, the dangling bonds of amorphous silicon present in the thin film were combined with hydrogen atoms. Hydrogen is supplied to the hydrogen radical annealing chamber 17 from a hydrogen gas cylinder 19 via a thermal mass flow controller 3C, to which mercury gas evaporated from a mercury constant temperature bath 18 is added. The mercury atoms were excited by irradiating ultraviolet rays with a low-pressure mercury lamp 16, and the energy of the mercury atoms was used to generate hydrogen radicals. Hydrogen radicals reacted with silicon on the amorphous silicon thin film, allowing hydrogen to diffuse from the surface and improving the film quality.

[0014]

[Effects of the Invention] As explained above, according to the present invention, it is possible to deposit a high-quality polycrystalline or amorphous silicon thin film with good uniformity, and the generation of particles in the gas phase can also be suppressed. Can be done.

[Brief explanation of drawings]

FIG. 1 is a diagram showing an example of an apparatus for producing a polycrystalline silicon thin film by the method of the present invention.

FIG. 2 is a diagram showing an example of an apparatus for producing an amorphous silicon thin film by the method of the present invention.

Claims (1)

[Claims] Claim 1. A method for forming a polycrystalline or amorphous silicon thin film by low pressure CVD using a silicon hydride compound or a gas containing the silicon hydride compound, the method comprising: containing the silicon hydride compound or the silicon hydride compound; A method for producing a silicon thin film, characterized in that hydrogen chloride gas is added to the gas.