KR20160052140A - Copper Calcogenide Nano Particle for Manufacturing Light Absorbing Layer of Solar Cell and Method for Manufacturing the Same - Google Patents

Copper Calcogenide Nano Particle for Manufacturing Light Absorbing Layer of Solar Cell and Method for Manufacturing the Same Download PDF

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KR20160052140A
KR20160052140A KR1020140151991A KR20140151991A KR20160052140A KR 20160052140 A KR20160052140 A KR 20160052140A KR 1020140151991 A KR1020140151991 A KR 1020140151991A KR 20140151991 A KR20140151991 A KR 20140151991A KR 20160052140 A KR20160052140 A KR 20160052140A
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이연수
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주식회사 엘지화학
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    • B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
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Abstract

The present invention is a copper chalcogenide nanoparticle forming a light absorbing layer of a solar cell, wherein the size of the nanoparticle is in a range of 0.05 mu m or more to 2.0 mu m or less, and the nanoparticle is represented by the following formula Copper chalcogenide nanoparticles, copper chalcogenide nanoparticles, and water, as a solvent in the process of synthesizing the particles, and using an additive.
Cu 2 - x S 1 - y Se y (1)
Wherein 0? X? 0.25; y is 0 or 1;

Description

Technical Field [0001] The present invention relates to a copper chalcogenide nanoparticle for manufacturing a solar cell light absorbing layer and a method for manufacturing the same,

The present invention relates to copper chalcogenide nanoparticles for manufacturing a solar cell light absorbing layer and a method for producing the same.

Since the early days of development, solar cells have been fabricated using silicon (Si) as a light absorbing layer and semiconductor material, which are expensive manufacturing processes. A solar cell to manufacture more economical to make available to the industry, a thin film of a low cost to the structure of the solar cell CIGS (copper-indium-gallium-sulfo-di-selenide, Cu (In, Ga) ( S, Se) 2 ) Have been developed. The CIGS-based solar cell typically comprises a back electrode layer, an n-type junction, and a p-type light absorbing layer. The solar cell having the CIGS layer described above has a power conversion efficiency exceeding 19%.

The CI (G) S solar cell forms a photovoltaic layer with a thickness of a few microns to form a solar cell. Vacuum evaporation, which does not require a precursor, and thin film formation using a precursor, An ink coating method has been introduced in which sputtering, electrodeposition for forming a G) S thin film, and recent application of a precursor material under a non-vacuum and heat treatment thereof. Among them, the ink coating method can lower the process cost and can produce a large area uniformly, and recent studies have been actively conducted. As the precursors used in the ink coating method, metal chalcogenide compounds, bimetallic metals Various types of compounds or metals such as particles, metal salts, or metal oxides are used.

On the other hand, in order to improve the density and efficiency of the final formed thin film and the coating property in the manufacture of the thin film, it is necessary to uniformly form the size, shape and composition of the thin film solar cell based on nanoparticles for ink- In order to minimize the organic residue of the finally formed thin film, it is preferable to synthesize the nanoparticles using an additive or a solvent which can be easily removed in the washing process .

However, conventional synthetic methods mainly use an organic solvent having a high boiling point (for example, oleylamine) in order to control the uniform size, shape, and composition. Such a solvent ensures shape uniformity, Chain, it is difficult to easily remove by the washing process, so that carbon residue or the like may be generated during the formation of the thin film, and the size of the particles is also too small to be suitable for coating the ink produced by the particles there was. Furthermore, since the reaction temperature is 200 占 폚 or higher in the synthesis of nanoparticles, there is a problem that the ease of the process is deteriorated.

Therefore, the synthesized nanoparticles have a uniform size and shape, and the control of the particle size and the removal of remaining reactants are easy, so that the coating property is improved in forming the thin film, and the thin film solar cell There is a high need for batteries.

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems of the prior art and the technical problems required from the past.

The inventors of the present application have conducted intensive research and various experiments and have come up with the development of copper excess copper copper chalcogenide nanoparticles having a size of the nanoparticles of 0.05 mu m or more and 2.0 mu m or less, It is easy to control the size of the particles while having a uniform shape, composition and crystal phase, and it is easy to remove reactants remaining after synthesis of the particles. When a thin film is produced using the same, Can be suppressed, and the present invention has been accomplished.

Accordingly, the copper chalcogenide nanoparticles according to the present invention are copper chalcogenide nanoparticles forming a light absorbing layer of a solar cell, wherein the size of the nanoparticles is in the range of 0.05 mu m or more to 2.0 mu m or less, Is represented by the following general formula (1).

Cu 2 - x S 1 - y Se y (1)

Wherein 0? X? 0.25; y is 0 or 1;

Wherein the chalcogenide means a material comprising a Group VI element, for example sulfur (S) or selenium (Se).

In one specific example, the copper chalcogenide nanoparticles Cu 2 S 1 - y Se y ( where, y = 0 or 1), Cu 1 .97 ~ 1.94 S 1 - y Se y ( where, y = 0 Or 1), Cu 1 .8 S 1 - y Se y where y = 0 or 1 and Cu 1 .75 S 1 - y Se y where y = 0 or 1 (Y = 0 or 1) or Cu 1 .75 S 1 - y Se y (where y = 0 or 1), and more specifically Cu 2 S 1 - y Se y Of crystalline phase.

As described above, the copper-selenide nanoparticles according to the present invention, especially copper-selenide nanoparticles, contain copper in a molar ratio higher than that of selenium, and thus copper is relatively more abundant than conventional copper-selenide nanoparticles As a result, the particle size is small, and the shape can be made close to the spherical shape.

Generally, organic solvents such as oleylamine are mainly used as the solvent for the preparation of the copper chalcogenide nanoparticles through the conventional solution process. However, when the conventional organic solvent is used to synthesize nanoparticles rich in copper, such as Cu 2 S particles, the uniformity of the particles can be ensured, but the size of the particles is too small to be suitable for coating when forming a thin film There was a problem.

Accordingly, the inventors of the present application have conducted intensive research and, as a result, have found that when a solvent is used as an aqueous solvent and an appropriate amount of additives are used together, copper having a uniform particle size and shape, It is possible to synthesize chalcogenide nanoparticles.

The particle diameter of the copper chalcogenide nanoparticles according to the present invention may be in the range of 0.05 탆 or more to 2.0 탆 or less as described above, and preferably in the range of 0.05 탆 or more to 1.0 탆 or less.

Specifically, the particle diameter of the nano-particles having a crystalline phase of copper chalcogenide nanoparticles, Cu 2 S (Se) of the present invention can range from less than 0.5 ㎛ to 1.0 ㎛, of Cu 1.75 S (Se) The particle size of the nanoparticles having a crystal phase may be in the range of 0.05 mu m or more to 0.2 mu m or less.

If the particle diameter of the nanoparticles is too large, there is a problem that the voids between the particles in the final thin film become too large to reduce the film density. When the particle diameter of the nanoparticles is too small, , Cracks due to an increase in surface energy of nanoparticles, etc., are difficult to control, and thus there is a problem in coating properties when a thin film is formed, which is not preferable.

On the contrary, the nanoparticles of the present invention having a particle size within the above range have a uniform shape and size, and are suitable for forming a thin film.

The method of synthesizing the copper chalcogenide nanoparticles is described in detail,

(i) preparing a first solution by dispersing at least one kind of a Group VI source selected from the group consisting of sulfur (S) and selenium (Se) in water;

(ii) preparing a second solution by dispersing a copper (Cu) salt in water; And

(iii) mixing the first solution and the second solution and adding and adding an additive;

. ≪ / RTI >

That is, the method of synthesizing the copper chalcogenide nanoparticles according to the present invention can remove the solvent more easily by using an aqueous solvent such as water, which is not a conventional solvent having a long carbon chain as a solvent for preparing a solution But has an advantage that carbon residue or the like is not likely to be formed during the formation of the thin film.

However, in the case of using an aqueous solvent as described above, since the reaction temperature can not be raised to 100 degrees or more due to a low boiling point of water, there is a problem that particles are not formed in a particle synthesis reaction requiring sufficient energy, There is a problem that by-products such as oxides can be formed.

To solve this problem, the nanoparticles according to the present invention are synthesized by adding an additive during the reaction. Specifically, the additive may be mercapto acid, and more specifically, may be 3-mercaptopropionic acid have.

As described above, when the nanoparticles are further synthesized by including the additive, spherical particles having a uniform shape can be formed even at a relatively low temperature. Since the additive has a property of dissolving well in an aqueous solution, Can be removed.

In order to synthesize the nanoparticles having the above-mentioned preferable range of the particle diameter, the amount of the additive is preferably 1 to 3 g per 100 mL of the solvent .

If the amount of the additive is excessively large, the particle size becomes very small to have a shape unsuitable for the coating, and it is not completely removed by washing and remains as a residue, and the amount of the additive is too small The pore size of the final thin film can be formed due to the increase of the particle size over a certain range, which is not preferable.

In one specific example, in step (iii), the temperature at which the mixing reaction is performed is 80 to 120 degrees, and the pH at which the mixing reaction is performed may be 9 to 13, 90 to 110 degrees, and the pH at which the mixing reaction is carried out may be 10 to 12. [

The water used as a solvent in the synthesis of the nanoparticles according to the present invention has a boiling point of only 100 ° C. and has a boiling point lower than that of the conventional organic solvent. Thus, the synthesis is carried out at about 100 ° C., Therefore, the copper-chalcogenide nanoparticles of copper and sulfur or selenium, which have a very high reactivity, can be easily mixed at a relatively low temperature as described above. .

The inventors of the present application have confirmed that the particle size of the nanoparticles can be controlled as desired by controlling the pH of the reaction, and the reaction is carried out at the pH in the above range to synthesize nanoparticles having a desired particle diameter It was possible.

If the pH is too high, the particle size becomes excessively large, thereby increasing the pore size between the particles in the final thin film, thereby decreasing the film density. When the pH is too low, the reactivity between ions is low, It is not easy to form and by-products are formed, which is not preferable.

In order to adjust the pH of the reaction, a pH adjuster may be used. The pH adjuster may be, for example, a monovalent or divalent metal hydroxide, a chloride, an inorganic substance such as carbonate, ammonia or an organic amine, Sodium (NaOH).

On the other hand, in one specific example, the copper (Cu) salt used to synthesize the particles is selected from the group consisting of chloride, bromide, iodide, nitrate, nitrite, and may be at least one form selected from the group consisting of sulfate, acetate, sulfite, acetylacetoate and hydroxide.

The Group VI source may be selected from the group consisting of Se, Na 2 Se, K 2 Se, CaSe, (CH 3 ) 2 Se, SeO 2 , SeCl 4 , H 2 SeO 3 , H 2 SeO 4 , Na 2 S, K 2 S, CaS, (CH 3 ) 2 S, H 2 SO 4 , S, Na 2 S 2 O 3 , NH 2 SO 3 H and their hydrates and thiourea, thioacetamide, selenoacetamide selenoacetamide) and selenourea (selenourea).

The present invention also provides an ink composition for forming a light absorbing layer comprising at least one of the above copper chalcogenide nanoparticles and chalcogenide nanoparticles containing gallium (Ga) and / or indium (In) A method for producing a thin film using the composition is provided.

In the above, the inclusion of at least one gallium and / or indium containing chalcogenide nanoparticles means that chalcogenide nanoparticles containing gallium, chalcogenide nanoparticles containing indium, and gallium and indium Or a chalcogenide nanoparticle having a chalcogenide nanoparticle.

In order to form the CIGS thin film of the present invention, since the ink composition essentially contains copper (Cu), indium (In), and gallium (Ga), the ink composition contains the copper chalcogenide nanoparticles (In) -containing chalcogenide nanoparticles, gallium (Ga) -containing chalcogenide nanoparticles, or gallium (Ga) -indium (In) (Cu), indium (In), and gallium (Ga), for example, a combination of copper (Cu), indium (In), and gallium (Ga).

The method for producing a thin film using the ink composition is, specifically,

(i) a process for producing an ink by dispersing copper chalcogenide nanoparticles and chalcogenide nanoparticles containing gallium and / or indium in a solvent;

(ii) coating the ink on a substrate on which electrodes are formed; And

(iii) drying the ink coated on the substrate on which the electrode is formed, followed by heat treatment;

. ≪ / RTI >

In one specific example, the solvent of the above-mentioned process (i) can be used without particular limitation as long as it is a general organic solvent, and specifically, alkanes, alkenes, alkynes, aromatics, ketons, nitriles, ethers, esters, organic halides, alcohols, amines, thiols, and the like. an organic solvent selected from thiols, carboxylic acids, phosphines, phosphites, phosphates, sulfoxides, and amides is used alone Or one or more organic solvents selected from these may be used in a mixed form.

Specifically, the alcohol-based solvent is selected from the group consisting of ethanol, 1-propanol, 2-propanol, 1-pentanol, 2- Hexanol, 2-hexanol, 3-hexanol, heptanol, octanol, EG (ethylene glycol), DEGMEE (diethylene glycol) monoethyl ether, ethylene glycol monomethyl ether (EGMME), ethylene glycol monomethyl ether (EGMEE), ethylene glycol diethyl ether (EGDEE), ethylene glycol monopropyl ether (EGMPE), ethylene glycol monobutyl ether 2-methyl-1-propanol, cyclopentanol, cyclohexanol, propylene glycol propyl ether (PGPE), DEGDME (diethylene glycol dimethyl ether), 1 (1,3-propanediol), 1,4-BD (1,4-butanediol), 1,3-BD (1,3-butanediol) , Alpha-terpineol, DEG (diethylene glycol), glycerol, 2- ethylamino (2-amino-2-methyl-1-propanol), 2- (methylamino) ethanol, 2- Can be mixed daily.

The amine-based solvent is selected from the group consisting of triethylamine, dibutylamine, dipropylamine, butylamine, ethanolamine, DETA (diethylenetriamine), TETA (triethylenetetraine) Triethanolamine, 2-aminoethyl piperazine, 2-hydroxyethyl piperazine, dibutylamine, and tris (2-aminoethyl) amine (tris (2-aminoethyl) amine).

The thiol-based solvent may be one or more kinds of mixed solvents selected from among 1,2-ethanedithiol, pentanethiol, hexanethiol, and mercaptoethanol.

The alkane solvent may be one or more kinds of mixed solvents selected from the group consisting of hexane, heptane and octane.

The aromatic solvent may be one or more kinds of mixed solvents selected from the group consisting of toluene, xylene, nitrobenzene, and pyridine.

The organic halide solvent may be at least one compound selected from the group consisting of chloroform, methylene chloride, tetrachloromethane, dichloroethane, and chlorobenzene. have.

The nitrile solvent may be acetonitrile.

The ketone solvent may be one or more kinds of mixed solvents selected from the group consisting of acetone, cyclohexanone, cyclopentanone, and acetyl acetone.

The ethers solvent may be one or more daily for mixing selected from ethyl ether, tetrahydrofurane, and 1,4-dioxane.

The sulfoxides solvent may be one or more daily for mixing selected from dimethyl sulfoxide (DMSO) and sulfolane.

The amide solvent may be one or more kinds of mixed solvents selected from DMF (dimethyl formamide), and NMP (n-methyl-2-pyrrolidone).

The ester solvent may be one or more daily for mixing selected from ethyl lactate, r-butyrolactone, and ethyl acetoacetate.

The carboxylic acid solvent may be selected from the group consisting of propionic acid, hexanoic acid, meso-2,3-dimercaptosuccinic acid, thiolactic acid ), And thioglycolic acid.

However, the solvents may be but one example.

In some cases, it may be prepared by further adding an auxiliary agent to the ink of the above-mentioned process (i).

The adjuvant may be, for example, a mixture of a dispersant, a surfactant, a polymer, a binder, a crosslinking agent, an emulsifier, a defoamer, a desiccant, a filler, an extender, a thickener, a film conditioning agent, an antioxidant, a flow agent, Polyvinylpyrrolidone (PVP), polyvinyl alcohol, Anti-terra 204, Anti-terra 205, and the like can be used. Ethyl cellulose, and DISPERS BYK 110 (DispersBYK 110).

The method of forming the coating layer of the process (ii) may be performed by, for example, a wet coating, a spray coating, a spin coating, a doctor blade coating, a contact printing, an upper feed reverse printing, feed reverse printing, nozzle feed reverse printing, gravure printing, micro gravure printing, reverse micro gravure printing, roller coating, slot die coating, Capillary coating, inkjet printing, jet deposition, spray deposition, and the like.

The heat treatment in step (iii) may be performed at a temperature ranging from 300 to 800 degrees Celsius.

The present invention also provides a thin film produced by the above method.

The thin film may have a thickness within the range of 0.5 탆 to 3.0 탆, and more specifically, the thickness of the thin film may be 0.5 탆 to 2.5 탆.

When the thickness of the thin film is less than 0.5 탆, the density and quantity of the light absorbing layer are not sufficient and the desired photoelectric efficiency can not be obtained. When the thickness of the thin film exceeds 3.0 탆, The probability of recombination is increased, resulting in a reduction in efficiency.

Furthermore, the present invention provides a thin film solar cell manufactured using the thin film.

A method of manufacturing a thin film solar cell is already known in the art and a description thereof will be omitted herein.

As described above, the copper chalcogenide nanoparticles according to the present invention have a particle diameter in the range of 0.05 μm or more and 2.0 μm or less and have a uniform shape, composition and crystal phase, It has an effect of having an appropriate size.

Since the copper chalcogenide nanoparticles according to the present invention can be synthesized by using water as a solvent in the solution process, the reaction temperature can be lowered, and the easiness of the process using a conventional organic solvent can be improved, It is possible to control the particle size as desired when the pH range is appropriately adjusted. In addition, the additive and the pH adjusting agent are preferably used in a water-soluble It is possible to easily remove the solvent and the like even in a simple water washing process, thereby improving the uniformity of the particles.

Figure 1 is a SEM photograph of a Cu 1 .75 S nanoparticles formed by the first embodiment;
Figure 2 is a SEM photograph of a Cu 1 .75 S nanoparticles formed by the second embodiment;
3 is an XRD graph of Examples 1 and 1 .75 S Cu nanoparticles formed by the two;
4 is a SEM photograph of Cu 2 S nanoparticles formed by Example 3;
5 is an XRD graph of Cu 2 S nanoparticles formed by Example 3;
6 is a graph showing TEM images and distribution of particle diameters of Cu 2 S nanoparticles formed by Comparative Example 1. FIG.

Hereinafter, the present invention will be described with reference to Examples. However, the following Examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

≪ Example 1 >

Cu 1 .75 Synthesis of S particles (synthesized by the method according to the present invention the nanoparticles in sheep of the additive to near the lower limit of the range)

3 mmol of 3-mercaptopropionic acid was added to an aqueous solution containing 7.5 mmol of Cu (NO 3 ) 2 , 30 ml of a 2M solution of NaOH was added thereto to make a clear solution, and 15 mmol of thioacetamide into an aqueous solution containing thioacetamide) Raise the temperature to 100 degrees, and then, pH 10 and maintaining the 100 ° and 3 hours and stirred to react for, after the particles are formed, to give the particles formed by centrifugal separation Cu 1 .75 S Particles were prepared. An electron micrograph (SEM) and an XRD graph obtained by analyzing the formed particles are shown in Figs. 1 and 3. The average particle diameter is around 150 nm.

≪ Example 2 >

Synthesis of Cu 1 .75 S particles (synthesized by the method according to the invention nanoparticles written near the upper limit of the amount of additive ranges)

5 mmol of 3-mercaptopropionic acid was added to an aqueous solution containing 7.5 mmol of Cu (NO 3 ) 2 , 30 ml of a 2M solution of NaOH was added thereto to make a clear solution, and 15 mmol of thioacetamide into an aqueous solution containing thioacetamide) Raise the temperature to 100 degrees, and then, pH 10 and maintaining the 100 ° and 3 hours and stirred to react for, after the particles are formed, to give the particles formed by centrifugal separation Cu 1 .75 S Particles were prepared. An electron micrograph (SEM) and an XRD graph obtained by analyzing the formed particles are shown in Fig. 2 and Fig. 3. The average particle diameter is around 70 nm.

≪ Example 3 >

Synthesis of Cu 2 S particles (nanoparticles synthesized by the method according to the present invention)

5 mmol of 3-mercaptopropionic acid was added to an aqueous solution containing 7.5 mmol of Cu (NO 3 ) 2 , 50 ml of a 2M solution of NaOH was added thereto to make a clear solution, and 15 mmol of thioacetamide thioacetamide was added and the temperature was raised to 100 ° C. The mixture was stirred for 3 hours while maintaining the pH at 10 and 100 ° C. After the particles were formed, the particles were purified by centrifugation to obtain Cu 2 S particles . An electron micrograph (SEM) and an XRD graph obtained by analyzing the formed particles are shown in FIGS. 4 and 5. FIG. The average particle diameter is around 0.8 占 퐉.

≪ Comparative Example 1 &

Synthesis of Cu 2 S nanoparticles ( nanoparticles synthesized in conventional oleylamine solvents)

Add 1 mmol of Cu (acac) 2 and 0.5 mmol of S, add 20 ml of oleylamine, fill the reaction system with argon gas for 20 minutes, and heat to 200 ° C for 1 hour. The formed particles were purified by centrifugation to produce Cu 2 S particles. An electron microscope (TEM) image of the formed particles and a graph showing the distribution of the particle diameter are shown in Fig. The average particle diameter is about 12 nm.

Those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.

Claims (23)

As copper chalcogenide nanoparticles forming a light absorbing layer of a solar cell,
The particle diameter of the nanoparticles is in the range of 0.05 mu m or more and 2.0 mu m or less,
Wherein the nanoparticles are represented by the following formula (1): < EMI ID =
Cu 2 - x S 1 - y Se y (1)
Wherein 0? X? 0.25; y is 0 or 1; The copper-chalcogenide nanoparticle according to claim 1, wherein the nanoparticles have a particle size in a range of 0.05 mu m or more to 1.0 mu m or less. The method of claim 1, wherein the nanoparticles are selected from the group consisting of Cu 2 S 1 - y Se y where y = 0 or 1, Cu 1.97 to 1.94 S 1 -y Se y where y = 0 or 1, Cu 1 .8 S 1 - y Se y (where, y = 0 or 1), and Cu 1.75 S 1-y Se y ( where, y = 0 or 1), characterized in that it has at least one crystal phase selected from the group consisting of Copper chalcogenide nanoparticles. The method of claim 3, wherein the nanoparticles are selected from the group consisting of Cu 2 S 1 - y Se y (where y = 0 or 1) or Cu 1.75 S 1 -y Se y (where y = 0 or 1) Wherein the copper nanoparticles have an average particle size of from 1 to 10 nm. 5. The nanocomposite material according to claim 4, wherein the particle diameter of the nanoparticles having a crystal phase of Cu 2 S 1 - y Se y (where y = 0 or 1) is in the range of 0.5 μm or more to 1.0 μm or less. Nanoparticles. 4 wherein, Cu 1 .75 to 1 S - y Se y grain size of nano-particles having a crystalline phase of (where, y = 0 or 1) is copper knife, characterized in that a range between 0.05 to 0.2 ㎛ ㎛ Congenide nanoparticles. A method for synthesizing copper chalcogenide nanoparticles according to claim 1,
(i) preparing a first solution by dispersing at least one kind of a Group VI source selected from the group consisting of sulfur (S) and selenium (Se) in water;
(ii) preparing a second solution by dispersing a copper (Cu) salt in water; And
(iii) mixing the first solution and the second solution and adding and adding an additive;
Wherein the copper nanoparticles are nanoparticles. 8. The method for synthesizing copper chalcogenide nanoparticles according to claim 7, wherein the additive is mercapto acid. The method according to claim 8, wherein the mercapto acid is 3-mercaptopropionic acid. 8. The method of claim 7, wherein the amount of the additive is 1 to 3 g per 100 mL of the solvent. The method according to claim 7, wherein in the step (iii), the temperature at which the mixing reaction is performed is 80 to 120 degrees, and the pH at which the mixing reaction is performed is 9 to 13. The method for producing the copper chalcogenide nanoparticles . 12. The method according to claim 11, wherein in step (iii), the temperature at which the mixing reaction is carried out is from 90 to 110 degrees, and the pH at which the mixing reaction is performed is from 10 to 12. The method for producing copper chalcogenide nanoparticles . The method of claim 7, wherein the copper salt is selected from the group consisting of chloride, bromide, iodide, nitrate, nitrite, sulfate, acetate, , Sulfite (s), acetylacetoate salt (s), and hydroxide (s). The method for synthesizing copper chalcogenide nanoparticles according to claim 1, The method of claim 7, wherein the Group VI sources Se, Na 2 Se, K 2 Se, CaSe, (CH 3) 2 Se, SeO 2, SeCl 4, H 2 SeO 3, H 2 SeO 4, Na 2 S, K 2 S, CaS, (CH 3 ) 2 S, H 2 SO 4 , S, Na 2 S 2 O 3 , NH 2 SO 3 H and their hydrates, thiourea, thioacetamide, , And selenourea. 2. A method for synthesizing copper chalcogenide nanoparticles, comprising: An ink composition for producing a light absorbing layer, comprising at least one of copper chalcogenide nanoparticles according to claim 1 and chalcogenide nanoparticles containing gallium and / or indium. A method of producing a thin film using the ink composition for producing a light absorbing layer according to claim 15,
(i) a process for producing an ink by dispersing copper chalcogenide nanoparticles and chalcogenide nanoparticles containing gallium and / or indium in a solvent;
(ii) coating the ink on a substrate on which electrodes are formed; And
(iii) drying the ink coated on the substrate on which the electrode is formed, followed by heat treatment;
Wherein the thin film is formed on the substrate. The method of claim 16, wherein the solvent of step (i) is selected from the group consisting of alkanes, alkenes, alkynes, aromatics, ketons, nitriles, Ethers, esters, organic halides, alcohols, amines, thiols, carboxylic acids, hydrogenated amines, and the like. wherein the organic solvent is at least one organic solvent selected from the group consisting of phosphines, phosphates, sulfoxides, and amides. The method of manufacturing a thin film according to claim 16, wherein the ink of the step (i) is prepared by further comprising an auxiliary agent. 19. The method of claim 18, wherein the adjuvant is selected from the group consisting of polyvinylpyrrolidone (PVP), polyvinylalcohol, Anti-terra 204, Anti-terra 205, ethyl cellulose, Disperse BYK 110 (DispersBYK 110), and the like. 17. The method of claim 16, wherein the coating of step (ii) is performed by wet coating, spray coating, doctor blade coating, or ink jet printing. 17. The method of claim 16, wherein the heat treatment in step (iii) is performed at a temperature in the range of 400 to 900 degrees Celsius. 22. A thin film produced by the process according to any one of claims 16 to 21. 22. A thin film solar cell produced using the thin film according to claim 22.
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