KR101069576B1 - Method for fabricating the CI(G)S thin-film with dense microstructure using stoichiometric CI(G)S particles containing phases with low melting point - Google Patents

Abstract

The present invention comprises the steps of: a) mixing a copper compound, an indium compound and a selenium compound with a reaction solvent having a boiling point of 200 ° C. or higher;
b) a step of preparing CI (G) S particles in which CuSe and CuSe ₂ are formed by reacting the mixed solution with microwaves for 15 to 40 minutes at 200 to 300 ° C .; And
c) the above Coating and heat-treating CI (G) S particles containing CuSe and CuSe ₂ on the substrate to prepare a CI (G) S film;
It relates to a method for producing a CI (G) S film comprising a CI (G) S particles according to the invention is a low melting point secondary phase including CuSe and CuSe ₂ CI in the step c) through a heat treatment of about 550 ^° C Surprisingly, when the (G) S film is prepared, the density of the prepared CI (G) S film is excellent.

Description

Method for fabricating the CI (G) S thin-film with dense microstructure using stoichiometric containing denser microstructures using CIS particles with low melting point secondary phase CI (G) S particles containing phases with low melting point}

The present invention relates to a method of making a CI (G) S film.

A method of using metal oxide particles containing Cu, In, and Ga in the production of CI (G) S films through particle-based solution processes has been reported. This is a method of manufacturing a CI (G) S film by coating a mixture of metal oxide nanoparticles or a mixture of metal oxide and non-oxide on a substrate and reacting in a reducing atmosphere and a Se gas atmosphere (US Patent No. 6127202, U.S. Pat.No.6268014). However, the secondary reduction process must be made inevitably, and there is a problem in that a defect occurs in the film during the reduction process, which causes the unevenness of the reaction during the Se gas heat treatment process. In addition, in the case of producing a CI (G) S film using CI (G) S single-phase particles containing no oxide, the melting point of CI (G) S is 986 ^° C. At temperatures around 550 ^° C, the densification of the film is unlikely to occur, which significantly reduces the efficiency of solar cells.

On the other hand, the study on the formation of CI (G) S film through the synthesis of CuSe ₂ particles having low melting point and physical mixing with the CI (G) S particles to form dense CI (G) S film (Korea Patent 10- 2008-0021269) and core-shell structures of CuSe / CuSe ₂ and indium selenide having low melting points (Korean Patent 10-2008-0009345) have been reported. However, these methods have a disadvantage in that they add an additional process of physical mixing and forming a core-shell structure, and have a limitation in that stoichiometric ratio control for CI (G) S formation is difficult. In addition, there is a disadvantage in that the density of the final CI (G) S film is low and thus solar cell characteristics are deteriorated. Therefore, there is an urgent need for research and development of a new economical approach to producing dense and stoichiometric CI (G) S films through annealing at or near the process tolerance of 550 ^° C.

An object of the present invention is to provide a low-melting-point CuSe and CuSe ₂ secondary phase so as to produce a dense CI (G) S film for a film solar cell absorbing layer having excellent physical properties by an economic process while overcoming the problems of the prior art as described above. It aims at synthesize | combining CI (G) S particle | grains containing. In addition, the present invention is to form a CuSe and CuSe ₂ secondary phase in one process, and by adjusting the stoichiometric ratio of the overall Cu: In: Se from the synthesis step to the desired composition, surprisingly well stoichiometry without additional process We present a method for producing a CI (G) S film that is dramatically superior in fit density.

In order to achieve the above object, by producing a suitable stoichiometric ratio of CI (G) S particles containing CuSe and CuSe ₂ of the low melting point secondary phase of the present invention, the production of a new CI (G) S film with a significantly increased density Provide a method. Method for producing a CI (G) S film according to the present invention,

a) mixing a copper compound, an indium compound and a selenium compound with a reaction solvent having a boiling point of 200 ° C. or higher;

b) a step of preparing CI (G) S particles in which CuSe and CuSe ₂ are formed by reacting the mixed solution with microwaves for 15 to 40 minutes at 200 to 300 ° C .; And c) said Coating and heat-treating CI (G) S particles containing CuSe and CuSe ₂ on the substrate to prepare a CI (G) S film;

Characterized in that it comprises a.

In another aspect, the present invention provides a method for producing a CI (G) S film further comprising a gallium compound in step a).

The present invention is also characterized in that the heat treatment in step c) is a two-step heat treatment for 15 to 60 minutes after maintaining 15 to 60 minutes at 200 ~ 400 ℃, the temperature is increased to 500 ~ 600 ℃ CI (G) S It relates to a method for producing a membrane. Heat treatment in step c) is preferably carried out in an inert gas or Se gas atmosphere.

Hereinafter, the present invention will be described in more detail.

The CI (G) S particles according to the present invention are surprisingly when the CI (G) S film is prepared through heat treatment at about 550 ^° C. in step c) in a state of forming low melting point secondary phases CuSe and CuSe ₂ . The density of the prepared CI (G) S film is excellent and there is an effect that the stoichiometric ratio is satisfied.

In the present invention, the reaction solvent in step a) used a solvent having a boiling point of 200 ° C. or higher, unlike a low boiling point solvent used in the past, and b) CuSe and CuSe when heated to the above temperature by microwave irradiation. Formation of the secondary phase including _two is controlled. In addition, the prepared CI (G) S film has an excellent density and has an effect of satisfying a stoichiometric ratio.

In addition, even though the secondary phases of CuSe and CuSe ₂ are formed, the overall stoichiometric ratio of Cu: In: Se is determined by the composition ratio of copper, indium, gallium, and selenium compounds that are initially added. It can be controlled very easily. The reaction solvent is more preferably boiling point 200 ~ 450 ^o C. This is an advantage of the invention that is significantly superior to the existing methods of physically mixing or forming core-shell structures of low melting point CuSe / CuSe ₂ . In the present invention, the stoichiometric ratio of Cu: In: Se is preferably 0.7 to 1.3: 0.7 to 1.3: 1.7 to 2.3. If the gallium compound is further included, the stoichiometric ratio of Cu: In: Ga: Se is preferably 0.7-1.3: 0.7-1.3 0.7-1.3: 1.7-2.3.

In addition, the reaction solvent is more specifically characterized in that it comprises one or two or more selected from polyol solvents, amine solvents, and phosphine solvents.

The polyol solvents include diethylene glycol, diethylene glycol ethyl ether, diethylene glycol buthyl ether, triethylene glycol, and polyethylene glycol ethylene glycol, molecular weight; 200-100,000), polyethylene glycol diacrylate, polyethylene glycol dibenzonate, dipropylene glycol, tripropylene glycol (dipropylene glycol), glycerol (glycerol) may be included.

The amine solvents include diethyl amine, triethylamine, 1,3-propane diamine, 1,4-butane diamine, 1 1,5-pentane diamine, 1,6-hexane diamine, 1,7-heptane diamine, 1,8-octane diamine (octane diamine), diethylene diamine, diethylene triamine, toluene diamine, m-phenylenediamine, diphenyl methane diamine, Hexamethylene diamine, hexamethylene diamine, triethylene tetramine, tetraethylenepentamine, tetraethylenepentamine, hexamethylene tetramine, and the amine solvent may be used as a chelating agent.

The phosphine solvent includes trioctylphosphine and trioctylphosphineoxide.

The present invention is characterized in that in step b) by irradiating microwaves to the mixed solution for 15 to 40 minutes heat treatment at 200 ~ 300 ℃, the reaction temperature and reaction time of the surprisingly secondary phase of the CuSe and CuSe ₂ particles Formation can be controlled. As such, the formation of a secondary phase can be controlled through the use of a reaction solvent having a high boiling point, reaction time, and reaction temperature. In the present invention, in the step b), the production of a CI (G) S film having a power of 500 to 900 w Provide a method.

In the present invention, the CI (G) S particles prepared in step b) are characterized in that the molar ratio of CuSe and CuSe ₂ includes 1-20 vol% of each other independently of the volume of the entire CI (G) S particles. .

In the step a), the copper compound is CuO, CuO ₂ , CuOH, Cu (OH) ₂ , Cu (CH ₃ COO), Cu (CH ₃ COO) ₂ , CuF ₂ , CuCl, CuCl ₂ , CuBr, CuBr ₂ , CuI, Cu (ClO ₄ ) ₂ , Cu (NO ₃ ) ₂ , CuSO ₄ and one or more selected from the group consisting of hydrates thereof. The indium compound may be In ₂ O ₃ , In (OH) ₃ , In (CH ₃ COO) ₃ , InF ₃ , InCl, InCl ₃ , InBr, InBr ₃ , InI, InI ₃ , In (ClO ₄ ) ₃ , In ( NO ₃ ) ₃ , In ₂ (SO ₄ ) ₃ and one or more selected from the group consisting of hydrates thereof. The gallium compound may be Ga ₂ O ₃ , Ga (OH) ₃ , Ga (CH ₃ COO) ₃ , GaF ₃ , GaCl, GaCl ₃ , GaBr, GaBr ₃ , GaI, GaI ₃ , Ga (ClO ₄ ) ₃ , Ga ( NO ₃ ) ₃ , Ga ₂ (SO ₄ ) ₃ and one or more selected from the group consisting of hydrates thereof. The selenium compound may include one, two or more selected from the group consisting of Se, H ₂ Se, Na ₂ Se, K ₂ Se, Ca ₂ Se, (CH ₃ ) ₂ Se, and hydrates thereof.

Heat treatment in step c) is characterized in that the two-step heat treatment for 15 to 60 minutes after maintaining 15 to 60 minutes at 200 ~ 400 ℃, the temperature is raised to 500 ~ 600 ℃, surprisingly when the heat treatment under the above conditions Dense membranes can be formed. The heat treatment may be performed in an inert gas or Se gas atmosphere, and a rapid thermal annealing system may be used.

In step c), the coating is spin coating, dip coating, drop casting, ink-jet printing, micro-contact printing, imprinting, gravure printing, gravure- One or more methods are selected from offset-printing, flexography printing, and screen printing.

The present invention has an advantage that a film having excellent density can be prepared by synthesizing CI (G) S particles containing low melting point CuSe and CuSe ₂ secondary phase by an economical process. In addition, the present invention has the advantage that can be adjusted from the synthesis step to the desired composition of the stoichiometric ratio of Cu: In: Se without additional process when producing a CI (G) S film.

Figure 1 shows the XRD analysis of the CIS particles prepared in Example 1.
Figure 2 shows the XRD analysis of the CIS film prepared in Example 1.
Figure 3 shows the observation of the CIS film prepared in Example 1 by using a SEM.
Figure 4 shows the XRD analysis of the CIS particles of Examples 1 to 3 and Comparative Examples 1 to 2 to observe the phase of the particles according to the reaction temperature.
Figure 5 shows the results of XRD analysis of the CIS particles prepared in Examples 1, 4 to 6 and Comparative Examples 3 to 4 in order to observe the phase of the particles according to the change in the reaction time.
Figure 6 shows the XRD analysis of the CIS particles prepared in Comparative Example 5.
Figure 7 shows the XRD analysis of the CIS film prepared in Comparative Example 5.
8 shows the CIS film prepared in Comparative Example 5 by observing using a SEM.

Example 1

CIS Preparation of Particles

Copper acetate monohydrate (Cu acetate monohydrate), Indium acetate (Indium acetate), selenium powder (Se powder) in a molar ratio of 1: 1: 2 and mixed mixture 3.2g 20g Into polyethylene glycol 400 was stirred for 1 hour. The mixed solution was heated at a power of 800 W for 2 minutes using microwave, reacted at 280 ° C. for 25 minutes, and cooled for 20 minutes to prepare particles. In order to recover the synthesized particles by centrifugation for 30 minutes at 25000rpm using ethanol to wash and recover the particles but repeated three times to recover the particles. The recovered particles were dried in a vacuum oven at 40 ℃ to prepare CuInSe ₂ (CIS) particles having a secondary phase containing CuSe.

The prepared CuInSe ₂ (CIS) particles were subjected to XRD analysis, and the results are shown in FIG. 1.

CIS film Produce

Ink was prepared using the prepared CIS particles. The ink was added to the prepared CIS particles to 15wt% in a solvent in which 1.785g of ethylene glycol and 0.765g of ethanol were mixed, and an ink was prepared by performing a ball milling process to improve dispersibility. A film was formed on the soda-lime glass on which molybdenum was deposited by a bar coating method. The formed film was put in a vacuum oven and dried at 80 ° C., and the dried film was heat-treated in an atmosphere of Se gas. The heat treatment was continued for 20 minutes after the temperature was raised to 250 ℃ at a temperature increase rate of 5 ℃ per minute. The temperature was further raised to 530 ° C. at a temperature increase rate of 5 ° C. per minute, and maintained for 20 minutes. And cooling was performed by furnace cooling, and the CIS film | membrane was manufactured. XRD analysis for the phase analysis of the prepared membrane is shown in Figure 2 below.

The prepared CIS film was observed using SEM, and is shown in FIG. 3.

Example 2

CIS Preparation of Particles

Example 1 was carried out in the same manner as in Example 1, but the temperature was raised to 800W output using a microwave to react at 250 ℃, the rest was carried out in the same manner as in Example 1.

CIS film Produce

It carried out similarly to Example 1 above.

Example 3

CIS Preparation of Particles

Example 1 was carried out in the same manner as in Example 1 except that the temperature was raised to 800W using microwave to react at 200 ° C., and the rest was performed in the same manner as in Example 1.

CIS film Produce

It carried out similarly to Example 1 above.

Example 4

CIS Preparation of Particles

The same process as in Example 1 was performed except that the reaction was performed for 30 minutes by raising the temperature to 800W using microwave, and the rest was performed in the same manner as in Example 1.

CIS film Produce

It carried out similarly to Example 1 above.

[Example 5]

CIS Preparation of Particles

The same procedure as in Example 1 was performed except that the reaction was performed for 20 minutes by raising the temperature to 800W using microwave, and the rest was performed in the same manner as in Example 1.

CIS film Produce

It carried out similarly to Example 1 above.

[Example 6]

CIS Preparation of Particles

Example 1 was carried out in the same manner as in Example 1 except that the reaction was carried out for 15 minutes by heating to 800W output using microwave, and the rest was performed in the same manner as in Example 1.

CIS film Produce

It carried out similarly to Example 1 above.

[Comparative Example 1]

CIS Preparation of Particles

Example 1 was carried out in the same manner as in Example 1, but the temperature was raised to 800W output using a microwave there is a difference in the reaction at 150 ℃, the rest was carried out in the same manner as in Example 1.

CIS film Produce

It carried out similarly to Example 1 above.

Comparative Example 2

CIS Preparation of Particles

Example 1 was carried out in the same manner as in Example 1, but the temperature was raised to 800W output using a microwave to react at 100 ℃, the rest was carried out in the same manner as in Example 1.

CIS film Produce

It carried out similarly to Example 1 above.

[Comparative Example 3]

CIS Preparation of Particles

The same procedure as in Example 1 was performed except that the reaction was performed for 10 minutes by raising the temperature to 800W using microwave, and the rest was performed in the same manner as in Example 1.

CIS film Produce

It carried out similarly to Example 1 above.

[Comparative Example 4]

CIS Preparation of Particles

The same procedure as in Example 1 was performed except that the reaction was performed for 5 minutes by heating to 800W output using microwave, and the rest was performed in the same manner as in Example 1.

CIS film Produce

It carried out similarly to Example 1 above.

In order to observe the phase of the particles according to the change in the reaction temperature, the XRD analysis of the CIS particles of Examples 1 to 3 and Comparative Examples 1 and 2 is shown in Figure 4 below.

4 a) shows XRD analysis results of CIS particles of Comparative Example 2 (reaction temperature 100 ° C.), b) Comparative Example 1 (reaction temperature 150 ° C.), and Example 3 (reaction temperature 200 ° C.). and d) Example 2 (reaction temperature 250 ° C.) e) XRD analysis of Example 1 (reaction temperature 280 ° C.).

In order to observe the phase of the particles according to the change in the reaction time, XRD analysis of the CIS particles prepared in Examples 1, 4-6 and Comparative Examples 3-4 was carried out and the results are shown in FIG. 5. .

5 a) shows XRD analysis results of CIS particles of Comparative Example 4 (reaction time 5 minutes), b) Comparative Example 3 (reaction time 10 minutes) and c) Example 6 (reaction time 15 minutes) , d) Example 5 (reaction time 20 minutes), e) Example 1 (reaction time 25 minutes), f) is the result of XRD analysis of the CIS particles of Example 4 (reaction time 30 minutes).

[Comparative Example 5]

CIS Preparation of Particles

Copper acetate monohydrate (Cu acetate monohydrate), Indium acetate (Indium acetate), selenium powder (Se powder) in a molar ratio of 1: 1: 2 and mixed mixture 3.2g was added to 20g of ethylene glycol and then stirred for 1 hour. The mixed solution was heated at a power of 800 W for 2 minutes using microwave, reacted at 280 ° C. for 25 minutes, and cooled for 20 minutes to prepare particles. In order to recover the synthesized particles by centrifugation for 30 minutes at 25000rpm using ethanol to wash and recover the particles but repeated three times to recover the particles. The recovered particles were dried in a vacuum oven at 40 ℃ to prepare CuInSe ₂ (CIS) particles. XRD analysis was performed for phase analysis of the prepared CIS particles, and the results are shown in FIG. 6. The prepared CIS particles were a single phase and had a stoichiometric ratio of Cu: In: Se of 26:26:48.

CIS film Produce

Ink was prepared using the prepared single-phase CIS particles. The ink was added to the prepared CIS particles to 15wt% in a solvent in which 1.785g of ethylene glycol and 0.765g of ethanol were mixed, and an ink was prepared by performing a ball milling process to improve dispersibility. A film was formed on the soda-lime glass on which molybdenum was deposited by a bar coating method. The formed film was put in a vacuum oven and dried at 80 ° C., and the dried film was heat-treated in an atmosphere of Se gas. The heat treatment was continued for 20 minutes after the temperature was raised to 250 ℃ at a temperature increase rate of 5 ℃ per minute. The temperature was further raised to 530 ° C. at a temperature increase rate of 5 ° C. per minute, and maintained for 20 minutes. And cooling was performed by furnace cooling, and the CIS film | membrane was manufactured. XDR analysis for the phase analysis of the prepared CIS film is shown in Figure 7 below. And the structure of the prepared CIS film was observed by using a SEM shown in Figure 8 below.

Figure 1 shows the XRD analysis of the CIS particles prepared in Example 1. Figure 2 shows the XRD analysis of the CIS film prepared in Example 1. Figure 3 shows the observation of the CIS film prepared in Example 1 by using a SEM.

Figure 4 shows the XRD analysis of the CIS particles of Examples 1 to 3 and Comparative Examples 1 to 2 to observe the phase of the particles according to the reaction temperature.

Figure 5 shows the results of XRD analysis of the CIS particles prepared in Examples 1, 4 to 6 and Comparative Examples 3 to 4 in order to observe the phase of the particles according to the change in the reaction time.

Figure 6 shows the XRD analysis of the CIS particles prepared in Comparative Example 5.

Figure 7 shows the XRD analysis of the CIS film prepared in Comparative Example 5. 8 shows the CIS film prepared in Comparative Example 5 by observing using a SEM.

As shown in FIG. 1, when the high boiling point polyethylene glycol 400 was synthesized as a reaction solvent, the prepared CIS particles contained a secondary phase including CuSe. This is the result of the transition reaction to the CISe phase being controlled by the nature of the solvent resulting in the presence of secondary phases. Even if such a secondary phase was present, the ratio of Cu: In: Se did not differ significantly from the composition ratio of the raw material precursor added as a result of the EDX measurement. (Cu: In: Se = 29:28:43) The slightly smaller proportion of Se is due to the presence of secondary phases present as oxides, and the Cu: In: Se The stoichiometric ratio of 1: 1: 1 could be easily optimized.

4 shows that the presence of a secondary phase including CuSe is controlled according to the change of reaction temperature. At the reaction temperature below 200 ^o C, the CIS phase could not be formed and was mostly composed of secondary phases. As the reaction temperature increases above 250 ^o C, the secondary phases are actively transitioned to CIS, and as a result Particles in which a secondary phase containing CuSe and a CIS are mixed are formed.

This secondary phase and CIS phase mixture can be controlled according to the reaction time, which can be seen in Figure 5 below. As shown in FIG. 5, it can be seen that as the reaction time increases, the secondary phase including CuSe decreases and the CIS phase increases. Therefore, in order to form a dense film, CIS exists as a columnar, It is preferable to include CuSe, which can be obtained through the control of the reaction solvent, reaction temperature, reaction time when preparing the CIS particles.

As can be seen in Figures 2 and 3, Example 1 according to the present invention was found to form a film having a dense microstructure while having a CISe single phase. The composition of the CIS film obtained in Example 1 was 25:23:52 in terms of stoichiometric ratio Cu: In: Se.

As can be seen in Figure 6, it can be seen that the CIS particles prepared by Comparative Example 5 is a CIS single-phase CIS particles that do not have a secondary phase. And the CIS particles prepared by Comparative Example 5 is Cu in a stoichiometric ratio : In: Se was 26:26:48.

As can be seen in Figures 7 and 8 below it can be seen that the CIS particles prepared by Comparative Example 5 is a single phase, and has a microstructure with a significantly lower density. The stoichiometric ratio of Cu: In: Se was 25:26:49.

Claims (12)

a) mixing a copper compound, an indium compound and a selenium compound with a reaction solvent having a boiling point of 200 ° C. or higher;
b) a step of preparing CI (G) S particles in which CuSe and CuSe ₂ are formed by reacting the mixed solution with microwaves for 15 to 40 minutes at 200 to 300 ° C .; And
c) the above Coating and heat-treating CI (G) S particles containing CuSe and CuSe ₂ on the substrate to prepare a CI (G) S film;
Method for producing a CI (G) S film comprising a. The method of claim 1,
The method of producing a CI (G) S film further comprising a gallium compound in step a). The method of claim 1,
The heat treatment in step c) is a method of producing a CI (G) S film, characterized in that the two-step heat treatment for 15 to 60 minutes after maintaining 15 to 60 minutes at 200 ~ 400 ℃, the temperature is increased to 500 ~ 600 ℃. The method of claim 1,
The reaction solvent in step a) is a method for producing a CI (G) S membrane, characterized in that it comprises one or two or more from a polyol solvent, an amine solvent and a phosphine solvent. The method of claim 1,
The reaction solvent in step a) is diethylene glycol, diethylene glycol ethyl ether, diethylene glycol butyl ether, triethylene glycol, polyethylene Glycol (poly (ethylene glycol), molecular weight; 200 ~ 100,000), polyethylene glycol diacrylate, polyethylene glycol dibenzonate, dipropylene glycol , Tripropylene glycol, glycerol, diethyl amine, triethylamine, 1,3-propane diamine, 1,4-butanediamine (1,4-butane diamine), 1,5-pentane diamine, 1,6-hexanediamine, 1,7-heptane diamine (1,7- heptane diamine, 1,8-octane diamine, diethylene diamine, diethyl Diethylene triamine, toluene diamine, m-phenylenediamine, diphenyl methane diamine, hexamethylene diamine, triethylene tetraamine ), Tetraethylenepentaamine (tetraethylenepentamine), hexamethylene tetramine (hexamethylene tetramine), trioctylphosphine (trioctylphosphine) and trioctylphosphine oxide (CI) containing one or two or more from the group consisting of trioctylphosphineoxide ) S film production method. The method of claim 1,
In step a), the copper compound is CuO, CuO ₂ , CuOH, Cu (OH) ₂ , Cu (CH ₃ COO), Cu (CH ₃ COO) ₂ , CuF ₂ , CuCl, CuCl ₂ , CuBr, CuBr ₂ , CuI , Cu (ClO ₄ ) ₂ , Cu (NO ₃ ) ₂ , CuSO ₄ And a method for producing a CI (G) S film comprising one or two or more selected from the group consisting of hydrates thereof. The method of claim 1,
The indium compound in step a) is In ₂ O ₃ , In (OH) ₃ , In (CH ₃ COO) ₃ , InF ₃ , InCl, InCl ₃ , InBr, InBr ₃ , InI, InI ₃ , In (ClO ₄ ) ₃ , In (NO ₃ ) ₃ , In ₂ (SO ₄ ) ₃ And a method for producing a CI (G) S film comprising one or two or more selected from the group consisting of hydrates thereof. The method of claim 2,
In the step a), the gallium compound is Ga ₂ O ₃ , Ga (OH) ₃ , Ga (CH ₃ COO) ₃ , GaF ₃ , GaCl, GaCl ₃ , GaBr, GaBr ₃ , GaI, GaI ₃ , Ga (ClO ₄ ) ₃ , Ga (NO ₃ ) ₃ , Ga ₂ (SO ₄ ) ₃ And a method for producing a CI (G) S film comprising one or two or more selected from the group consisting of hydrates thereof. The method of claim 1,
The selenium compound in step a) comprises one or two or more selected from the group consisting of Se, H ₂ Se, Na ₂ Se, K ₂ Se, Ca ₂ Se, (CH ₃ ) ₂ Se and hydrates thereof Process for preparing CI (G) S membrane. The method of claim 1,
CI (G) S particles prepared in step b) is characterized in that the molar ratio of CuSe and CuSe ₂ includes 1 to 20 vol% independently of each other relative to the volume of the total CI (G) S particles (G) ) S film production method. The method of claim 1,
The c) heat treatment in step c) is carried out in an inert gas or Se gas atmosphere, characterized in that the CI (G) S film manufacturing method. The method of claim 1,
In step c), the coating is spin coating, dip coating, drop casting, ink-jet printing, micro-contact printing, imprinting, gravure printing, gravure- A method for producing a CI (G) S film, which is a method selected from at least one of offset-printing, flexography printing, and screen printing.

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