JPH0554733A - Manufacture of surface conductive transparent vapor deposition film coated body - Google Patents

Abstract

PURPOSE:To provide a vapor deposition film coated body suitably used for the antistatic of aparatuses, electronic matetrials, eledtromagnetic wave shielding materials, and macromolecule electrodes, etc. CONSTITUTION:A copper sulfide vapor deposition film is formed on a base material surface by plasma sputtering with cupric sulfide as a target, and then is treated by a hydrogen sulfide gas at request to manufacture a surface conductive transparent vapor deposition film coated body. This easily provides a vapor deposition film coated body having a main body of cuprous sulfide excellent in both transparency and conductivity, or that having a main body of the cupric sulfide keeping transparency and also moreover excellent in conductivity.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a surface conductive transparent vapor deposition film coated body. More specifically, the present invention forms a copper sulfide vapor deposition film having excellent transparency and conductivity on the surface of any base material without impairing its physical properties, for example, antistatic equipment, electronic materials, and electromagnetic waves. The present invention relates to a method for efficiently producing a surface conductive transparent vapor-deposited film coating useful for a shield material, a polymer electrode and the like.

[0002]

2. Description of the Related Art In recent years, conductive film coatings have been attracting attention as new functional materials because they can be used as, for example, antistatic devices, electronic materials, electromagnetic wave shielding materials, polymer electrodes and the like. As a method for producing this conductive film coated body, a method of forming an electroconductive thin film layer by depositing indium-tin-oxide (hereinafter abbreviated as ITO) or copper sulfide on the surface of a base material is conventionally known. ..

As a method for depositing the ITO, a vacuum vapor deposition method, a sputtering method or the like is usually used.
The ITO thin film formed by these has good transparency, but has the disadvantage that the conductivity is about 100 Ω / □ and that expensive indium must be used. On the other hand, in the method of depositing copper sulfide, the copper sulfide is stable and is a good conductor having an electric conductivity that is lower by one to two orders of magnitude than that of metallic copper, and also has good transparency. It is advantageous.

As a method for depositing copper sulfide on the surface of a substrate, for example, a wet method using a copper compound and a sulfur compound and a sputtering method of cuprous sulfide are known. However, in these methods, the composition of the copper sulfide deposited on the surface of the base material is completely or mostly cuprous sulfide, and the cuprous sulfide has a surface resistance value and transparency almost inversely proportional to each other. Therefore, there is a drawback that it is difficult to obtain a copper sulfide film coated body having both a low surface resistance value and a high light transmittance.

Further, a method has been proposed in which the cuprous sulfide film once formed is subjected to a secondary treatment to convert it into a copper iodide film or a cupric sulfide film (Japanese Patent Laid-Open No. 60-211704, Japanese Patent Laid-Open No. 11-21704). (Kaisho 63-313420). However, these methods have a drawback that although either conductivity or transparency can be improved, the other is lowered.

[0006]

Under these circumstances, the present invention provides cuprous sulfide having excellent conductivity and transparency, which can be used in the fields of solar cells, electroluminescent elements, semiconductors and the like. Efficiently manufacture a copper sulfide coating mainly composed of copper sulfide and a copper sulfide film mainly composed of cupric sulfide, which has excellent transparency and is suitable for fields requiring low resistance. The purpose is to provide a method of doing.

[0007]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that by using cupric sulfide as a target and performing plasma sputtering, conductivity and transparency are improved. Both of which provide excellent copper sulfide vapor-deposited film mainly composed of cuprous sulfide, and by subjecting this copper sulfide vapor-deposited film to hydrogen sulfide gas treatment, it is possible to further improve the conductivity while maintaining transparency. It has been found that the copper sulfide film is mainly composed of dicopper, and based on this finding, the present invention has been completed.

That is, the present invention is characterized in that a copper sulfide vapor-deposited film is formed on the surface of a base material by plasma sputtering targeting cupric sulfide, and then treated with hydrogen sulfide gas if desired. The present invention provides a method for producing a conductive transparent vapor-deposited film coated body.

The material of the base material used in the method of the present invention is not particularly limited, and those conventionally used as the base material of the surface conductive film coating can be used, but a plastic having transparency is particularly preferable. Glass and the like are suitable. The shape is not particularly limited, but a thin film is preferable.

In the method of the present invention, cupric sulfide is used as the target, and a copper sulfide vapor-deposited film is formed on the surface of the substrate by sputtering. At this time, pure cupric sulfide may be used as the target. However, copper sulfide mainly containing cupric sulfide may be used. As the sputtering conditions, the pressure is usually selected in the range of 0.01 to 5 Torr, preferably 0.1 to 0.2 Torr, and the temperature is usually room temperature. On the other hand, the output and time are related to other conditions and are greatly influenced by the form of the base material and the scale of the device.

A high-frequency plasma device is preferably used for sputtering, and the frequency is about 10 to 100 MHz, generally 1 in an inert gas atmosphere such as argon.
Plasma is generated using a high frequency of 3.56 MHz,
A copper sulfide vapor deposition film having a thickness of 1 μm or less is formed on the surface of the base material.

The copper sulfide vapor-deposited film thus formed is mainly composed of cuprous sulfide obtained by decomposing cupric sulfide, and was obtained by directly sputtering cuprous sulfide. It is superior in conductivity and transparency as compared with vapor-deposited films and other copper sulfide films obtained by conventional techniques.

In the present invention, in order to further increase the conductivity of the copper sulfide vapor-deposited film mainly composed of cuprous sulfide thus obtained while maintaining transparency, the vapor deposition film may be sulfided if desired. It can be converted into a copper sulfide vapor-deposited film mainly containing cupric sulfide by performing hydrogen gas treatment.

The concentration of hydrogen sulfide gas used in this treatment is not particularly limited, but it is advantageous to dilute it with an inert gas such as nitrogen or argon because it is easy to handle, and it is usually diluted with nitrogen. Hydrogen sulfide concentration is 10% by volume
Something is used.

The upper limit of the treatment temperature depends on the heat resistant temperature of the substrate, but is usually room temperature to 200 ° C.
, The processing time depends on the processing temperature,
Although it cannot be determined unconditionally, usually several tens of minutes to several hours are sufficient. Further, the pressure is not particularly limited, but the treatment is usually performed under atmospheric pressure.

In this way, the copper sulfide vapor-deposited film mainly containing cuprous sulfide is converted into the copper sulfide vapor-deposited film mainly containing cupric sulfide, and the transparency is not impaired and the surface conductivity is further improved. It is possible to obtain a copper sulfide vapor deposition film coating excellent in

[0017]

According to the present invention, by using cupric sulfide as a target and performing sputtering, a copper sulfide vapor-deposited film mainly composed of cuprous sulfide having excellent transparency and conductivity is formed on the surface of a substrate. It is easily formed, and this vapor-deposited film coating is used for, for example, a solar cell or an electroluminescence device,
Alternatively, it is useful as a conductive material in the field of semiconductors.

Further, by treating the above-mentioned copper sulfide vapor-deposited film with hydrogen sulfide gas, a vapor-deposited film coated body having excellent conductivity while maintaining transparency can be obtained, which has a low resistance such as an electromagnetic wave shielding material. It is preferably used for applications where the property is required.

[0019]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 Commercially available polyethylene terephthalate film (50 mm
X50 mm), using a cupric sulfide target having a purity of 99.5% and a diameter of 75 mm, sputtering was performed for 5 minutes under the conditions of argon plasma, temperature room temperature, pressure 0.1 Torr, and output 150 W to form a copper sulfide vapor deposition film. Formed.

The vapor-deposited film-coated film obtained was light brown transparent and had a visible light transmittance of the maximum transmission region (700 n).
m) and the surface resistance was 120Ω / □. The composition of the vapor-deposited film was determined by X-ray photoelectron spectroscopy (XPS
As a result of analysis, it was confirmed to be completely cuprous sulfide.

Comparative Example 1 In Example 1, instead of the cupric sulfide target,
Example 1 was repeated except that a cuprous sulfide target having a purity of 99.5% and a diameter of 75 mm was used.

The vapor-deposited film-coated film thus obtained was dark brown and transparent, and had a visible light transmittance of 30% or less in the maximum transmission region (around 700 nm) and a surface resistance of 60.
It was about 0Ω / □. As a result of XPS analysis of the composition of the deposited film, it was confirmed that cupric sulfide and cuprous sulfide were present in approximately equal amounts.

Comparative Example 2 Argon plasma treatment (0.02 Torr, output 600)
(W, 20 minutes) commercial polyethylene terephthalate film is dipped in an aqueous solution containing 0.1 mol / l of copper sulfate and 0.1 mol / l of sodium thiosulfate, heated while stirring, and at 60 ° C. The reaction was carried out for 30 minutes.

After completion of the reaction, the excess copper sulfate was removed by ultrasonic cleaning. The obtained film is dark brown and transparent,
Visible light transmittance is 2 in the maximum transmission region (around 700 nm)
It was 0% or less and the surface resistance was 40 Ω / □. As a result of XPS analysis of the composition of the copper sulfide thin film, it was confirmed that cupric sulfide and cuprous sulfide were present in substantially equal amounts.

Example 2 The light brown film obtained in Example 1 was treated at 150 ° C. for 2 hours in a 10% by volume hydrogen sulfide gas diluted with nitrogen. The obtained film is light green and has a visible light transmittance of 50 in the maximum transmission region (around 550 nm).
%, And the surface resistance was 15Ω / □ or less. As a result of XPS analysis, the composition of the deposited film was confirmed to be completely cupric sulfide.

Comparative Example 3 The procedure of Example 2 was repeated except that the dark brown film obtained in Comparative Example 1 was used. The obtained film is transparent in dark green and has a visible light transmittance of the maximum transmission region (550 nm).
20% or less and the surface resistance was 2Ω / □ or less. As a result of XPS analysis, the composition of the deposited film was confirmed to be completely cupric sulfide.

Comparative Example 4 The procedure of Example 2 was repeated except that the dark brown film obtained in Comparative Example 2 was used. The obtained film is transparent in dark green and has a visible light transmittance of the maximum transmission region (550 nm).
20% or less and the surface resistance was 2Ω / □ or less. Moreover, the composition of the copper sulfide thin film was confirmed by XPS analysis to be completely cupric sulfide.

Claims (2)

[Claims] 1. A method for producing a surface-conductive transparent vapor-deposited film coated body, which comprises forming a copper sulfide vapor-deposited film on the surface of a substrate by plasma sputtering using cupric sulfide as a target. 2. A surface conductive transparent vapor deposition film coating, comprising forming a copper sulfide vapor deposition film on the surface of a base material by plasma sputtering using cupric sulfide as a target, and then treating with a hydrogen sulfide gas. Body manufacturing method.