JPS61166978A - Formation of thin sulfide film - Google Patents

Abstract

PURPOSE:To form a thin metallic sulfide film having good crystallinity easily and inexpensively by forming an org. metallic compd. layer having internally a metal-sulfur bond on a substrate then decomposing thermally the same in an inert gas contg. hydrogen sulfide. CONSTITUTION:The org. metallic compd. having internally at least one metal- sulfur bond is coated by printing, etc., on the substrate by using a suitable solvent and is then predried by heating to evaporate the solvent, by which the org. metallic compd. layer is formed. Various metallic mercaptides various metallic salt, etc., thiocarboxylic acid or dithiocarboxylic acid are usable for the above-mentioned org. metallic compd. The above-mentioned org. metallic compd. layer is thereafter thermally decomposed in the inert gas mixed with the hydrogen sulfide. The thin metallic sulfide film having good crystallinity is thus easily formed on the inexpensive substrate of glass, etc., in high productivity.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for forming metal sulfide thin films used in various electronic devices.

Conventional technology Traditionally, zinc sulfide, cadmium sulfide, lead sulfide.

Metal sulfides such as copper sulfide are widely used in the electronics field in the form of thin films or crystals. Thin films of these compounds have heretofore been mainly formed using techniques such as vacuum evaporation or sputtering.

Problems to be Solved by the Invention The above-mentioned conventional method is performed in a vacuum container, resulting in poor productivity, difficulty in continuous operation, or requiring very expensive production equipment. In addition, the size of the product is determined by the size of the vacuum container, making it difficult to manufacture a large area.

Means for Solving the Problems The present invention solves the above problems by forming an organometallic compound layer containing at least one metal-sulfur bond on a substrate by printing or other methods. , the metal sulfide is formed by thermally decomposing the organometallic compound layer in an inert gas mixed with hydrogen sulfide.

Examples of the organometallic compound having at least one internal metal-sulfur bond that can be used in the present invention include various metal mercaptides, various thiocarboxylic acids, and various metal salts of dithiocarbo/acids. Methods for synthesizing these compounds are known.

The substrate on which the organometallic compound is laminated can be arbitrarily selected as long as it can withstand thermal decomposition temperatures. Usually, the thermal decomposition temperature is about 350 to 450, so an inexpensive glass plate can be used.

Effect: By using the means of the present invention described above, a metal sulfide thin film can be formed without using a vacuum container, which is a bottleneck in conventional methods, so productivity can be improved in the production of thin films. , and can be easily manufactured over a large area.

Examples Example 1 Zinc lauryl mercaptide (J,
109o (1933)) is dissolved in a hydrocarbon solvent and applied onto a glass plate using a spinner.

The coated glass plate was pre-dried at about 150''C to volatilize the solvent and then sso'cd in a firing oven.

Bake for 1 hour. The inside of the firing furnace has a hydrogen sulfide concentration of 2 to 1.
0% nitrogen gas flow.

On the fired glass plate, the film is transparent and has a thickness of 100 mm.
A thin film of about 5,000 people was formed, and X-ray diffraction measurements confirmed that it was cyanogonal zinc sulfide.

<Example 2> Lead lauryl mercaptide obtained by reacting lauryl mercaptan with lead acetate in a water-alcohol solvent is dissolved in a hydrocarbon solvent and coated onto a glass plate using a spinner.

The coated glass plate is pre-dried at about 150℃ to volatilize the solvent, and then fired in a firing furnace at 550"C for 11 hours. Inside the furnace is a nitrogen gas stream with a hydrogen sulfide concentration of 2 to 10%. do. .

On the fired glass plate, the film is transparent and has a thickness of 1000~
A thin film of 500 mm was formed, and X-ray diffraction measurements confirmed that it was lead sulfide.

<Example 3> Cadmium mercaptide obtained by reacting lauryl mercaptan with cadmium acetate in a water-ethanol solvent is dissolved in a hydrocarbon solvent and coated onto a glass plate using a spinner.

The coated glass plate was pre-dried at about 150"C to volatilize the solvent, and then heated in a firing oven at 550"C.

Bake for 1 hour. The inside of the firing furnace has a hydrogen sulfide concentration of 2 to 10
% nitrogen gas flow.

On the fired glass plate, the film is transparent and has a thickness of 100~
A thin film was formed at a temperature of 500° and was confirmed to be cadmium sulfide by X-ray diffraction measurement.

<Example 4> Potassium thiobenzoate A (Org, 5ynth, , rv 924 (19
63)) is reacted with zinc acetate to synthesize zinc thiobenzoate. This is dissolved in a hydrocarbon solvent and applied onto a glass plate using a spinner.

The coated glass plate is pre-dried at approximately 150°C to volatilize the solvent, and then fired in a firing furnace at 560"C for 51 hours. Inside the firing furnace, a nitrogen gas stream with a hydrogen sulfide concentration of 2 to 10% is used. do.

On the fired glass plate, the film is transparent and has a thickness of 100 mm.
A thin film of 5,000 people was formed, and it was confirmed by X-ray diffraction measurements that it was cyclized zinc sulfide.

<Example 5> Zinc simylcarbitioate (J , Mm.

Chem, Soc 513106 (192B)) is dissolved in a hydrocarbon solvent and coated on a glass plate by various coating methods (screen printing, etc.).

The coated glass plate is pre-dried at about 150 °C to volatilize the solvent and then fired in a firing oven at 55Q for 1 hour. Inside the firing furnace, there is a nitrogen gas flow with a hydrogen sulfide concentration of 2 to 10%.

On the fired glass plate, the film is transparent and has a thickness of 1000~
A thin film of 6,000 people was formed, and X-ray diffraction measurements confirmed that it was cyclized zinc sulfide.

In addition to the effects of the invention, as can be seen from the examples, by adopting the method according to the present invention, productivity is superior compared to manufacturing methods such as vacuum evaporation or sputtering, and extremely expensive production equipment is not required. It also has the characteristic of being extremely useful industrially in that it is easy to manufacture over a large area.

Furthermore, the method according to the present invention has good crystallinity and film formation properties at low temperatures; in the case of zinc sulfide, the conventional method
α-type large-scale zinc sulfide produced at C or higher is s o o
It can also be said that it is an effective method in that it can be obtained with a firing temperature of about 'c.

Claims (4)

[Claims] (1) After forming an organometallic compound layer containing at least one metal-sulfur bond on the substrate, the organometallic compound layer is thermally decomposed in an inert gas containing hydrogen sulfide. A method for forming a sulfide thin film, characterized by: (2) Claim 1, characterized in that the organometallic compound having a metal-sulfur bond is a metal mercaptide.
A method for forming a sulfide thin film as described in Section. (3) The method for forming a sulfide thin film according to claim 1, wherein the organometallic compound having a metal-sulfur bond is a metal thiocarboxylate. (4) The method for forming a sulfide thin film according to claim 1, wherein the organometallic compound having a metal-sulfur bond is a metal dithiocarboxylate.