JPH079065B2 - Method for forming zinc sulfide thin film - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a zinc sulfide thin film used in electronic devices and a method for forming the same.

2. Description of the Related Art Conventionally, zinc sulfide thin films have been widely used in the field of electronics, especially by doping with manganese, for electroluminescence panels and the like.

The zinc sulfide thin film has been formed on the substrate by a sputtering method, a vapor deposition method or the like.

Problems to be Solved by the Invention The above-mentioned method for forming a zinc sulfide thin film has poor productivity because it is carried out in a vacuum vessel, continuous operation is difficult, or very expensive production equipment is required. Further, the size of the product is regulated by the size of the vacuum container, and there is a problem that it is difficult to manufacture a large area.

The present invention aims to form a zinc sulfide thin film without using a vacuum container.

Means for Solving the Problems The means for solving the above problems according to the present invention is to provide an organozinc compound having at least one zinc-sulfur bond therein with at least one bond with manganese-sulfur as a dopant. Forming a mixture with an organic manganese compound contained therein on a substrate and forming it by thermal decomposition in an oxidizing atmosphere, or forming by firing in an inert atmosphere after thermal decomposition.

Examples of the organozinc compound having at least one zinc-sulfur bond inside it that can be used in the present invention include various zinc mercaptides, various thiocarboxylic acids, and zinc salts of dithiocarboxylic acids.

Examples of the organic manganese compound having at least one manganese-sulfur bond inside as a doping agent include manganese mercaptide, thiocarboxylic acid salt, and dithiocarboxylic acid salt.

The substrate can be arbitrarily selected as long as it can withstand the thermal decomposition temperature. Since the thermal decomposition temperature is usually about 320 to 450 ° C, inexpensive soda lime glass or the like can be sufficiently used.

By carrying out the thermal decomposition in the air or in an oxidizing atmosphere such as an oxygen atmosphere, it is possible to completely decompose carbon and hydrogen which are organic components. In order to further increase the degree of sintering, when the temperature is raised to a high temperature, the zinc sulfide thin film is oxidized in an oxidizing atmosphere and becomes a thin film containing oxides. Is effective.

By using the above-mentioned means of the present invention, a zinc thin film can be formed without using a vacuum container, which has been a problem of the conventional method. There is an effect that the area can be easily manufactured.

Practical Example Hereinafter, an example will be described.

(Example 1) Zinc lauryl mercaptide and manganese octyl mercaptide were mixed and dissolved in tetralin, coated on a alumina substrate with a spinner, dried at 150 ° C, and the solvent was volatilized, and then 450 ° C in the atmosphere, Pyrolysis for 1 hour. As a result, a substantially colorless crack-free uniform thin film of hardened zinc having a film thickness of 500 to 5000Å was obtained. As a result of subjecting this thin film to atomic analysis,
It was confirmed that zinc sulfide was generated. In addition, no carbon or hydrogen remained in the film.

(Example 2) Zinc lauryl mercaptide and manganese octyl mercaptide were mixed and dissolved in tetralin, applied on a alumina substrate with a spinner, dried at 150 ° C, and the solvent was volatilized, and then 450 ° C in the atmosphere, Thermal decomposition for 30 minutes. After that, it is baked in a nitrogen stream at 700 ° C. for 1 hour. As a result, the film thickness is 500 ~ 5000Å
An almost colorless crack-free uniform thin film of zinc sulfide was obtained. As a result of subjecting this thin film to elemental analysis, it was confirmed that zinc sulfide was generated. In addition, no carbon or hydrogen remained in the film. Further, as a result of observation with a scanning electron microscope, crystal growth was remarkable as compared with a film which was only thermally decomposed in an oxidizing atmosphere.

(Example 3) Zinc thiobenzoate and manganese thiobenzoate were mixed and dissolved in tetralin, coated on a alumina substrate with a spinner, dried at 150 ° C to volatilize the solvent, and then 450 in air.
Thermal decomposition at ℃ for 1 hour. As a result, an almost colorless thin film of zinc sulfide having a film thickness of 500 to 5000Å and having almost no crack was obtained. As a result of subjecting this thin film to elemental analysis, it was confirmed that zinc sulfide was generated. In addition, no carbon or hydrogen remained in the film.

(Example 4) Zinc thiobenzoate and manganese thiobenzoate were mixed and dissolved in tetralin, coated on a alumina substrate with a spinner, dried at 150 ° C, and the solvent was volatilized, and then 450 in the air.
Thermal decomposition at ℃ for 30 minutes. After that, it is baked in a nitrogen stream at 700 ° C. for 1 hour. As a result, an almost colorless thin film of zinc sulfide having a film thickness of 500 to 5000Å and having almost no crack was obtained. As a result of subjecting this thin film to elemental analysis, it was confirmed that zinc sulfide was generated. In addition, no carbon or hydrogen remained in the film. Further, as a result of observation with a scanning electron microscope, crystal growth was remarkable as compared with a film which was only thermally decomposed in an oxidizing atmosphere.

As described above, the zinc sulfide thin film and the method for forming the same according to the present invention include an organometallic compound having at least one zinc-sulfur bond in its interior and at least one bond with sulfur as an dopant in the organozinc compound. By using a mixture with a compound, forming the mixture on a substrate and forming it by thermal decomposition in an oxidizing atmosphere, and by forming it by firing in an inert atmosphere after thermal decomposition, the sputtering method and the vapor deposition method can be used. In comparison, productivity is improved, very expensive equipment is not required, large-area manufacturing can be easily performed, and its practical effect is great.

Continuation of the front page (56) Reference JP 55-140705 (JP, A) JP 59-116378 (JP, A) JP 60-243280 (JP, A) JP 62-146276 (JP , A)

Claims (2)

[Claims] 1. A mixture of an organozinc compound having at least one zinc-sulfur bond in the interior thereof and an organomanganese compound having at least one manganese-sulfur bond therein as a dopant is formed on a substrate, A method for forming a zinc sulfide thin film, which is characterized by being formed by thermal decomposition in an oxidizing atmosphere. 2. A mixture of an organozinc compound having at least one zinc-sulfur bond in its interior with an organomanganese compound having at least one manganese-sulfur bond in its interior as a dopant is formed on a substrate, A method for forming a zinc sulfide thin film, which comprises performing pyrolysis in an oxidizing atmosphere, and then firing in an inert atmosphere.