JPS6034013A - Manufacture of solid thin film - Google Patents

Abstract

PURPOSE:To obtain a solid thin film with uniform quality by a method wherein a gas to be an energy source is excited by a plasma generated by a glow discharge and the ions and the light in the gas are removed and high energy molecules in semi-stable condition are taken out and decomposition reaction of material gas molecules in a high vacuum chamber is generated with those high energy molecules. CONSTITUTION:Argon gas A and xenon gas B, which are to be the 1st and the 2nd energy sources are supplied from containers 1 and 2 into an optical trap 4 in which a hollow cathode 3 for plasma generation is contained through valves 16 and 17 respectively. A semi-stable condition generating apparatus 6, in which ion collecting electrodes 5 are provided, is protruded from an opening at the center part of the trap 4 and the tip of the apparatus 6 is inserted into a reaction chamber 11. A holder on which a substrate 7 is held is provided in the chamber 11 and a heater 8 is provided outside the chamber 11 and to the backside of the holder. A high vacuum evacuator 9 with a valve 12 and a large capacity exhausting equipment 10 with a valve 13 are connected to the chamber 11. After the above preparation, silane gas C in a container 14 is introduced into the chamber 11 through a valve 15.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a solid thin film using the energy generated when metastable gaseous molecules collide with gaseous raw material molecules.

(Prior art and its problems) Conventional methods for producing solid thin films from gaseous raw material molecules include the following methods (1), (2), and (2).

■ Thermal CVD method, in which gaseous raw materials are thermally decomposed and the decomposition products are deposited on a substrate.

■ Plasma CVD method in which raw material gas is introduced into plasma created by glow discharge, decomposed, and deposited on a substrate.

■ Photo-CVD method in which raw material gas is irradiated with light, decomposed by photochemical reaction, and deposited on a substrate.

In the above cases (1) and (2), since the range of energy applied to the raw material gas is wide, many types of decomposition products such as ionic species and radical species are generated, which inhibits homogenization of film quality and suppresses the film growth rate.

In addition, in the case of (2) above, specific decomposition products can be selectively produced by selecting the wavelength of the irradiated light, but there are only a few types of light sources that utilize the extreme ultraviolet region.
Since the output is low, the range of use is extremely limited, and there are drawbacks such as preventing the introduction of light into the reaction tank.

(Purpose of the invention) This invention was made to eliminate the above-mentioned drawbacks, and aims to obtain a homogeneous solid thin film by utilizing metastable molecules with inherent high energy in reactions. .

(Summary of the Invention) In order to achieve the above object, the present invention provides specific excitation energy to raw material molecules through a reaction between gaseous molecules in a metastable state having unique excitation energy and raw material gas molecules to decompose them. This is a method for producing a solid thin film in which decomposition products are deposited on a substrate.

(Embodiments of the Invention) Hereinafter, an embodiment of the method for producing a solid thin film of the present invention will be described with reference to the drawings.

In the figure, 1 and 2 are the first. A container filled with gas A and gas B serving as a second energy source, 3 a hollow cathode electrode for plasma generation, 4 an optical trap for condensing the light generated by the hollow cathode electrode 3;
5 is an ion converter electrode that focuses charged electrons generated in the hollow cathode electrode 3; 6 is a metastable state generation device that extracts molecules in a metastable state; T is a substrate; 8 is a heater that generates heat for the substrate T; 9 is a A high vacuum evacuation device, 10 a large displacement evacuation device, 11 a reaction vessel for molecular energy exchange, 12.13 pulp for controlling the exhaust inside the reaction vessel 11, and 14 for injecting into the reaction vessel 11. Raw material gas C
container, 15 is a pulp for controlling the raw material gas C, 16
．． 17 is a pulp that controls the energy source gases A and B;

Next, the operation will be explained.

When using a rare gas as the energy source gas, for example, a container 1 for gas A and a container 2 for gas B are connected via a pulp 16° 1T.

Gas A is excited by goo discharge at the hollow cathode electrode 3 and is separated into gas ions A and gas A in a metastable state. The light emitted within the hollow cathode electrode 3 is absorbed by the optical trap 4, and the ionized gas ions A are removed by the ion collector electrode 5.
, are introduced into the reaction vessel 11. Here, when changing the excitation energy of the metastable gas, use the container 2 of gas B.
Therefore, gas B is mixed into the metastable state generating device 6 through the gas BY pulse 11, and gas B is changed from the metastable state caused by gas A.
By transferring energy to the metastable state, only the gas B in the metastable state can be contained in the metastable state generating device 6.

On the other hand, the substrate T in one reaction vessel 11 is heated to the optimum temperature for film growth by the heater 8, and the inside of the reaction vessel 11 is preliminarily pumped to 10''7 torr by the high vacuum evacuation device 9.

Close the pulp 16 while being evacuated to the following pressure, introduce molecules of gas A in a metastable state, open the pulp 1T, and use the large displacement exhaust device 10 to raise the pressure to 10~] torr. After adjusting with pulp 1T, raw material gas Cy! - When the pulp 15Y is introduced into the reaction vessel 11 from the container 14 and the molecules of the raw material gas C and the metastable gas A collide with each other, the molecules of the raw material gas C are decomposed and deposited on the substrate T. .

Next, specific examples of the present invention, (11, f2), and (at) will be explained. Here, in each specific example, the inside of the metastable state generating device 6 and the reaction vessel 11 are set as the following conditions.

(Conditions) Reaction vessel 110 diameter f 3 cm, pressure inside reaction vessel 11 ft 1 torr 0, displacement of large displacement exhaust device 10 1
00 m''/hr, the voltage applied to the hollow cathode electrode 3 is 200 to 250 V, and the applied current is Y1 to 10 mA.

[Specific Example 1] Argon gas is used as gas A, xenon gas is used as gas B, and silane gas is used as source gas C.

A metastable state molecule of argon is created under the above conditions, and xenon gas is introduced thereto to produce a metastable state molecule of xenon having an energy of 8.2 eV.
was generated and introduced into the reaction vessel 11, and 20 mi
! When the silane gas of the raw material gas C was mixed at a ratio of /min, a hydrogen-based amorphous silicon film was deposited on the substrate T heated to 250 to 300°C.

Further, in the above specific example 1m, when argon gas is used as the energy source gas and the reaction is performed under the same conditions, metastable molecules of argon gas having an energy source of 11.5 eV are generated.

When the metastable molecules of the generated argon gas and the silane gas are mixed into the reaction vessel 11, the silane gas is ionized and a hydrogen-based amorphous silicon film containing microcrystals is deposited on the substrate T.

[Specific Example 2] Argon gas is used as gas A, nitrogen or oxygen is used as gas B, and silane gas is used as source gas C.

When reacted under the above-mentioned conditions, nitrogen or oxygen metastable molecules are generated. When the generated nitrogen or oxygen metastable molecules and silane gas are mixed into the reaction vessel 11,
A Siz N l-X or 5i) (0+-x thin film was deposited on the substrate T.

[Specific Example 3] The hydrogen-based amorphous silicon film of Specific Example 1 above is used as the substrate T.
After being deposited on top, argon gas is added as gas A,
When oxygen is used as gas B and the reaction is performed outside the above prefecture, an additional 5iz is formed on the hydrogen-based amorphous silicon film.
A thin film of O+-x was deposited. That is, a multilayer film of a semiconducting hydrogen-based amorphous silicon film and an insulating silicon oxide film was created.

(Effects of the Invention) According to the method for producing a solid thin film of the present invention, various decomposition products of gas decomposed by plasma and serving as an energy source are removed by optical and electrical means, and a novel and high-performance method is achieved. It generates a metastable gas with high energy, and uses this high energy to decompose and deposit source gas molecules, making it possible to form thin films with uniform quality. Further, it has the advantage that the solid thin M can be easily formed into multiple layers by repeating the manufacturing process.

[Brief explanation of drawings]

The drawing is a schematic configuration diagram showing an example of an apparatus for carrying out the present invention. In the figure, 1.2 is the first. a container filled with a second energy source gas; 3 a po-cathode electrode; 4 an optical trap;
5 is an ion converter electrode, 6 is a metastable state generator, 7 is
is the substrate, 8 is the heater, 9 is the crystalline exhaust system, 1o is the large exhaust system, 11 is the reaction vessel, 12.13 is the valve,
14 raw material gas containers, 15, 16, 17 are pulp.

Claims (1)

[Claims] 0) Excite a gas that serves as an energy source with plasma generated by glue discharge, remove ions and light from the generated gas, extract molecules in a metastable state with high energy, and introduce them into a high-vacuum reaction vessel. The high energy of the raw material gas molecules is induced, and this excitation energy is transferred to the second
A method for producing a solid thin film according to claim 1, wherein the solid thin film is obtained by creating metastable state molecules of a second energy source gas by applying force to an energy source gas.