KR101116404B1 - Low Temperature Water-based Preparation Method of CI(G)S(CuInxGa1-xSe2) Nano Particles using Polyelectrolytes - Google Patents

Abstract

The present invention relates to a method for producing a nanoparticles of CI (G) S (CuIn _x Ga _1-x Se ₂ ; 0 <x≤1), which is a light absorbing layer material of a thin film compound solar cell, by aqueous reaction under low temperature. Specifically, a low temperature water-based CI (G) S nanoparticle comprising the step of producing a CI (G) S nanoparticle by reacting a copper compound and an indium compound, a complex obtained by an aqueous reaction of a polymer electrolyte, and a selenium compound to the complex. The present invention relates to a method for manufacturing an environment-friendly manufacturing method based on an aqueous solution.

Low temperature process, CIGS, polymer electrolyte, nanoparticles, aqueous reaction

Description

Low Temperature Water-based Preparation Method of CI (G) S (CuInxGa1-xSe2) Nano Particles using Polyelectrolytes}

The present invention is a low-temperature aqueous CI (G) S using a polymer electrolyte in the production of CI (G) S nanoparticles having excellent light absorption and optimal optical properties in a compound thin film solar cell without using a high temperature and harmful solvent It relates to a manufacturing method.

CI (G) S is known to be a very good material for use as a light absorption layer of a solar cell because it not only has the highest light absorption coefficient among semiconductors but also is very optically stable.

As a conventional method for producing CIS (or CIGS), Brian A. Korgel et al. Manufacture copper acetate, indium acetate, and selenium powder using an oleylamine solvent. How to do is known. However, this method can produce particles relatively quickly, but there is a problem that the reaction rate should be controlled by using chloroform, which is highly toxic at high reaction temperature (240 ° C), and should also be carried out in a box of nitrogen atmosphere. [J. Am. Chem. Soc., 130, 16770-16777, 2008].

In addition, a method of using microwave as a solvent heat in CIGS powder production has been reported [Inorg. Chem., 42, 7148-7155, (2003)], although microwaves used as solvent heat have the advantage of producing high purity materials in a short time, but due to low productivity, difficulty in continuous processing, and high energy usage. There is a disadvantage that the process cost can be increased.

Therefore, there is an increasing need for simpler and more economical manufacturing methods to improve poor manufacturing conditions and to secure productivity. In particular, in the manufacture of CI (G) S, the whole process can be carried out at low temperature without adding high-temperature heat, and the invention of eco-friendly and productive method through aqueous reaction is the future of CI (G) S solar cell. This is a task that must be developed for a wide supply.

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In order to solve the above problems, the present invention, unlike the other process that requires the use of harmful organic solvents and expensive waste facility costs in the production of nanoparticles of CuIn (Ga) Se ₂ as the light absorption layer material of the compound thin film solar cell. It is an object to produce in an economical and environmentally friendly manner by carrying out the reaction at a low temperature using an aqueous solvent. In addition, an object of the present invention is to provide a method for easily preparing not only CI (G) S nanoparticles but also precursor materials for dense film formation using complex formation reactions using relatively easy polymer electrolytes.

In order to achieve the above object, the present inventors have conducted a number of studies, suggesting a method for preparing a low-temperature aqueous CI (G) S (CuIn _x Ga _{1- x} Se ₂ ; 0 <x≤1) as follows. It became.

The present invention is a method for producing a low temperature water-based CI (G) S nanoparticles,

(a) reacting a polyelectrolyte, a copper compound, and an indium compound selected from polyethylenimine, sodium polyacrylate, and ammonium polyacrylate in an aqueous solvent to form a complex including copper and indium; And

(b) injecting a selenium compound into the complex aqueous solution (a) to produce CI (G) S nanoparticles at low temperature;

It provides a method for producing a low-temperature water-based CI (G) S nanoparticle comprising a.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The present invention provides a low-temperature aqueous CI (G) S nanoparticles, wherein a polyelectrolyte selected from polyethyleneimine, polyacrylic acid sodium salt and ammonium polyacrylate salt is used in an aqueous solution state using a source material containing copper or indium element. Form a complex containing chelates. Provided herein is a method for preparing low temperature aqueous CI (G) S (CuIn _x Ga _1-x Se ₂ ; 0 <x ≦ ₁ ) nanoparticles through final reaction with selenium or selenium compounds.

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The source material containing the element of copper or indium of the present invention may be any compound as long as it has a high solubility in an aqueous solvent, but preferably acetate, nitrate, carbonate, sulfate, chloride, iodide, bromide, Oxide, hydroxide, perchlorate, etc. can be selected and used, and a copper compound or an indium compound can use 1 or more types of compounds, respectively. In addition, the source material containing gallium element further added to the indium compound may be selected from nitrates, sulfates, chlorides and the like having solubility in an aqueous solvent.

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The selenium compound of the present invention may be a selenium compound including sodium, ammonium, and a linear or branched alkyl group, or a selenium compound further including sulfate (SO ₃ ^{2 −} ), preferably sodium selenide , Ammonium selenide, alkyl selenide (alkyl = methyl or ethyl), sodium selenite sulfite (Na ₂ SeSO ₃ ), and the like, and most preferably sodium selenite sulfite.

Na ₂ SeSO ₃ of the present invention may be prepared and used, Na ₂ SO ₃ and selenium powder (Selenium power) by mixing in an aqueous solution at 80 to 100 ℃, preferably 90 to 95 ℃, 1 hour to 12 hours , Preferably it is prepared by mixing for 2 to 4 hours.

Preferably, the aqueous solvent of step (a) of the present invention uses water, alcohol, or a mixture thereof, and water is preferably deionized water.

The amount of the polymer electrolyte used in the production of CI (G) S of the present invention is defined as [polymer electrolyte source (raw material) weight] / {[copper source (raw material) weight] + [indium source (raw material) weight]}. The amount of the polyelectrolyte added is preferably added in an amount of 1.0 wt% to 80 wt%, more preferably 10 wt% to 50 wt%, based on the total weight of copper and indium. If less than 1% by weight, as suggested by the present invention, the amount of the polymer electrolyte required to form a complex between copper metal and indium metal is insufficient, and after manufacture, it tends to be separated into a copper compound and an indium compound. . In addition, when an excessive amount of more than 80% by weight is not only involved in complex formation, but also directly participates in the reaction, it may be produced by separating copper and indium and selenium into unwanted compounds. In addition, by leaving a relatively large amount of residual polymer after the reaction, it may cause a disadvantage that must be removed after completion of the manufacturing process.

 The CI (G) S particles of the present invention had different sizes of the produced CI (G) S particles depending on the amount of the polymer electrolyte to be used. For example, the poly (Ethylenimine, PEI) polyelectrolyte may be used. In this case, the average particle size of CI (G) S was 10 nm at 5 wt%, 25 nm at 10 wt%, 40 nm at 30 wt%, and 70 nm at 50 wt%. In addition, when the polyelectrolyte of polyacrylic acid (PAA) is used, the average particle size of CI (G) S is 10 nm at 5% by weight, 20nm at 10% by weight, 40nm, 50% at 30% by weight. In the case of% it was 60 nm.

In the present invention, a selenium compound is added to a solution in which the complex is formed so that a molar ratio of [Cu]: [In]: [Se] is 1: 1: 2, or CuInSe ₂ material is prepared, or gallium nitrate or chloride is added to the indium acetate. CIGS (CuIn _x Ga _{1 - x} Se ₂ ; 0 <x <1) may be prepared by further adding gallium, and may be prepared even at a low temperature of room temperature. The addition of gallium causes the sum of the moles of indium and gallium to be equal to the moles of copper.

All of the above reaction of the present invention is particularly advantageous in the present invention in that it is prepared by reacting at 0 ~ 80 ℃, preferably room temperature.

Impurities in the solution in which the CI (G) S is formed are dissolved by adding distilled water, followed by removing the supernatant 2-3 times by centrifugation to remove the supernatant, thereby preparing desired nanoparticles.

Qualitative, quantitative analysis of the composition of the prepared product and the particle size distribution of the formed particles were confirmed through a particle size analyzer (ELS-800, Otsuka, Japan).

And X-ray Diffraction (XRD; D / max-A, Rigaku Japan, CuKα: λ = 1.54178 Å) was used to determine the crystal structure and orientation.

The manufacturing process according to the present invention can ensure the stability of the working environment because all processes are carried out in an aqueous state, unlike other processes that require harmful organic solvents and treatment of other waste solvents by using harmful organic solvents. It can be said that it has a very good advantage.

In addition, it is easy to handle during the manufacturing process and proceeds in the aqueous state using a polymer electrolyte that does not produce environmentally harmful substances, so it does not need a separate disposal facility, which is very economical and environmentally friendly. have.

The present invention is very economical compared to the conventional manufacturing method requiring a high temperature because it is manufactured at a low manufacturing reaction temperature (~ 25 ℃), and by increasing the capacity of the batch without the need for additional equipment to increase the batch It has the advantage of ensuring productivity.

In addition, by controlling the size of the intermediate complex by varying the ratio of the polymer electrolyte used in the complex formation and the concentration ratio of the precursors added, it is possible to control the particles of the finally produced CI (G) S in the nano-size dimension There is this.

Hereinafter, the present invention will be described in more detail based on the following examples. However, the examples are not intended to limit the invention only.

Example  One

First, di-water is prepared on a 50 ml basis, and then dissolved polyethylenimine (PEI, 40% aqueous solution) for complex formation (40% PEI aqueous solution = 1.60 g at 50% by weight). After stirring for about 10 minutes to fully dissolve, 0.554g (2.5mmol) of copper carbonate, which is a cationic raw material, and 0.731g (2.5mmol) of indium acetate were added thereto, followed by reaction for 1 hour to form a complex. It was. Na ₂ SO ₃ so that the molar ratio of [Cu]: [In]: [Se] in the solution is 1: 1: 2 50 ml of a 0.1 mol Na ₂ SeSO ₃ aqueous solution prepared by reacting + Se was added thereto, and the mixture was sufficiently stirred for 1 hour to finally prepare a CIS material. All these processes were performed at room temperature (25 ° C). The solution obtained after the reaction was black in color, and the structural analysis was analyzed by X-ray diffractometer (XRD). The sample used was a solution, and the solution was dried at 150 ° C., and the impurities in the prepared CIS solution were dissolved by adding distilled water, followed by centrifugation to separate the supernatant 2-3 times. After the removal process was performed, the obtained powder was analyzed using a powder.

As a result, as shown in FIG. 1, typical CuInSe ₂ (JCPDS-97-004-9933) peaks having 2-theta values of 26 °, 44 °, and 52 °, respectively, were confirmed.

Example  2

After preparing DI water on a 50 ml basis, sodium polyacrylate salt (35% aqueous solution) for complex formation was dissolved (for 50% by weight, PAA equivalent in 1.35 g of 35% aqueous solution). After stirring for about 10 minutes to fully dissolve, 0.554g (2.5mmol) of cation raw material and 0.731g (2.5mmol) of indium acetate are added thereto, followed by reaction for at least 1 hour to form a complex.

The next step was carried out in the same manner as in Example 1 described above.

As a result, typical CuInSe ₂ (JCPDS-97-004-9933) peaks with 2-theta values of 26 °, 44 ° and 52 °, respectively, were confirmed.

Example  3

After preparing DI water on a 50 ml basis, poly ammonium salt of polyacrylic acid salt (35% aqueous solution) for complex formation was dissolved (for 50% by weight, PAA equivalent of 1.835 g in 35% aqueous solution). After stirring for about 10 minutes to fully dissolve, 0.554g (2.5mmol) of cation raw material and 0.731g (2.5mmol) of indium acetate are added thereto, followed by reaction for at least 1 hour to form a complex.

The next step was carried out in the same manner as in Example 1 described above.

As a result, typical CuInSe ₂ (JCPDS-97-004-9933) peaks with 2-theta values of 26 °, 44 ° and 52 °, respectively, were confirmed.

Example  4

After preparing the di-water on a 50 ml basis, polyethyleneimine (PEI, 40% aqueous solution) for complex formation was dissolved in various ratios with respect to the sum of the weights of each copper metal and indium metal. The amount of PEI used was prepared by adding 5% by weight, 10% by weight, 30% by weight and 50% by weight relative to the sum of the weights of the copper metal and the indium metal used. For each experiment, the surfactant was stirred for about 10 minutes to completely dissolve, and then 0.554 g of a cationic raw material, copper carbonate, and 0.731 g of indium acetate were added thereto, followed by reaction for at least 1 hour for complex formation.

The following steps were performed identically to Example 1 described above

As a result, typical CuInSe ₂ (JCPDS-97-004-9933) peaks with 2-theta values of 26 °, 44 ° and 52 °, respectively, were confirmed.

Example  5

After preparing di-water on a 50 ml basis, sodium polyacrylate salt (35% aqueous solution) for complex formation was dissolved in various ratios with respect to the number of moles of copper and indium metal. The amount of sodium polyacrylate salt used was prepared by adding 1% by weight, 5% by weight, 10% by weight, 20% by weight, 30% by weight, 50% by weight, and 80% by weight, based on the total weight of copper metal and indium metal used. It was. For each experiment, the surfactant was stirred for about 10 minutes to fully dissolve, and then 0.554 g of copper carbonate, which is a cationic raw material, and 0.731 g of indium acetate were added thereto, followed by reaction for at least 1 hour for complex formation.

The following steps were performed identically to Example 1 described above

As a result, typical CuInSe ₂ (JCPDS-97-004-9933) peaks with 2-theta values of 26 °, 44 ° and 52 °, respectively, were confirmed.

Example  6

First, di-water is prepared on the basis of 50 ml, and then polyethylenimine (PEI, 40% aqueous solution) for complex formation is dissolved (50% by weight of PEI = 1.6 g in 40% aqueous solution). After stirring for about 10 minutes, the solution is sufficiently dissolved, and 0.554 g of copper carbonate, a cation raw material, indium acetate and gallium nitrate are added to (CI (G) S (CuIn _x Ga _{1). - x Se 2; 0 <x≤1} ) on the basis of the above formula, each of x = 0.95 (indium: 0.693g, gallium: 0.0319g), x = 0.7 (indium: 0.510g, gallium: 0.192g), x = 0.4 (indium: 0.291 g, gallium: 0.383 g) was added and allowed to react for at least 1 hour to form a complex.

The following steps were performed identically to Example 1 described above

As a result, a typical CuInGaSe ₂ (JCPDS-40-1488) peak having theta values of 26 °, 44 °, and 52 °, respectively, was confirmed.

Example  7

First, di-water is prepared on a 50 ml basis, and then dissolved polyethylenimine (PEI, 40% aqueous solution) for complex formation (50% by weight, equivalent to PEI in 40% aqueous solution = 1.6 g). After 10 minutes of stirring, the solution is sufficiently dissolved, 0.554 g of copper carbonate (Copper carbonate) and 0.731 g of indium acetate are added thereto, followed by reaction for at least 1 hour for complex formation. Na ₂ SO ₃ , so that the molar ratio of [Se] to [Cu] and [In] in the solution is 1: 1, 1: 2, and 1: _3. Reaction of Se to prepare Na ₂ SeSO ₃ aqueous solution in 0.5 mol (1: 1: 1 case), 0.1 mol (1: 1: 2 case) and 0.15 mol (1: 1: 3 case) To suit the molar ratio of and thoroughly stirred for 1 hour to finally prepare a CIS material. The following steps were performed identically to Example 1 described above

As a result, typical CuInSe ₂ (JCPDS-97-004-9933) peaks with 2-theta values of 26 °, 44 °, and 52 °, respectively, were confirmed.

Example  8

* First, prepare DI-water on a 50 ml basis, and then dissolve polyethyleneimine (PEI, 40% aqueous solution) for complex formation (for 50% by weight, equivalent to PEI in 40% aqueous solution = 1.6 g). . After 10 minutes of stirring, the solution is sufficiently dissolved, 0.554 g of copper carbonate (Copper carbonate) and 0.731 g of indium acetate are added thereto, followed by reaction for at least 1 hour for complex formation. Na ₂ SO _{3 in the solution} so that the molar ratio of [Se] to [Cu] and [In] is 1: 1: 2. 50 ml of 0.1 mol Na ₂ SeSO ₃ aqueous solution prepared by reacting + Se was added thereto, and the reaction temperature was changed to 25 ° C., 50 ° C., and 80 ° C., respectively, to finally prepare a CIS material. As a result, it was possible to confirm typical CuInSe ₂ (JCPDS-97-004-9933) peaks with 2-theta values of 26 °, 44 °, and 52 °, respectively. When the particle size is about 70 nm (the same as in Example 1), and the reaction temperature of 50 ° C and 80 ° C, the average particle size is 100 nm or more.

Comparative example  One

Based on 50 ml of di-water, 0.554 g of a cationic raw material copper and 0.731 g of indium acetate are dissolved. Na ₂ SO ₃ so that the molar ratio of [Cu]: [In]: [Se] in the solution is 1: 1: 2 50 ml of a 0.1 mol Na ₂ SeSO ₃ aqueous solution prepared by reacting + Se was added thereto, and the mixture was further stirred for 1 hour to finally terminate the reaction. All these processes were performed at room temperature (25 ° C). Structural analysis was performed using XRD. The sample used was a solution, and the solution was dried at 150 ° C., and the impurities in the prepared CIS solution were dissolved by adding distilled water, followed by centrifugation to separate the supernatant 2-3 times. After the removal process was carried out using the obtained powder (powder).

As a result, Cu ₂ Se (JCPDS-97-004-3224) and In ₂ Se ₃ (JCPDS-00-040-1408) were observed separately from the CI (G) S single phase as shown in FIG. 6, and Na ₂ A peak of SO ₄ (JCPDS-00-022-1399) was found.

Comparative example  2

Dissolve 0.336g of copper chloride and 0.55g of indium chloride based on 50ml of di-water. 50 ml of an aqueous 0.1 mol Na ₂ SeSO ₃ solution prepared by reacting Na ₂ SO ₃ + Se was added to the solution so that the molar ratio of [Cu]: [In]: [Se] was 1: 1: 2. The mixture was stirred sufficiently to finally terminate the reaction.

The next step was carried out in the same manner as in Comparative Example 1 described above

As a result, Cu ₂ Se (JCPDS-97-004-3224) and In ₂ Se ₃ (JCPDS-00-040-1408) were observed separately from CI (G) S single phase, and Na ₂ SO ₄ (JCPDS- 00-022-1399) peak was confirmed.

Comparative example  3

Dissolve 0.554 g of copper acetate and 0.731 g of indium acetate, which are cationic raw materials, based on 50 ml of di-water. 50 ml of an aqueous 0.1 mol Na ₂ SeSO ₃ solution prepared by reacting Na ₂ SO ₃ + Se was added to the solution so that the molar ratio of [Cu]: [In]: [Se] was 1: 1: 2. The mixture was stirred sufficiently to finally terminate the reaction.

The next step was carried out in the same manner as in Comparative Example 1 described above.

As a result, Cu ₂ Se (JCPDS-97-004-3224) and In ₂ Se ₃ (JCPDS-00-040-1408) were observed separately from CI (G) S single phase, and Na ₂ SO ₄ (JCPDS- 00-022-1399) peak was confirmed.

Comparative example  4( Molar ratio change )

It proceeded in the same manner as in Example 6. Na ₂ SO ₃ , so that the molar ratio of [Se] to [Cu] and [In] in the solution is 1: 4. To react with + Se to prepare a 0.2mol Na ₂ SeSO ₃ aqueous solution, 50ml was added to the molar ratio and sufficiently stirred for 1 hour to finally prepare a CIS material. The next step was performed in the same manner as in Example 6 described above.

As a result, Cu ₂ Se (JCPDS-97-004-3224) and In ₂ Se ₃ (JCPDS-00-040-1408) were observed separately from CI (G) S single phase, and Na ₂ SO ₄ (JCPDS- 00-022-1399) peak was confirmed.

1 is XRD crystallinity data of CIS particles prepared in Example 1. FIG.

Figure 2 is XRD crystallinity data of the CIS particles prepared in Example 2.

3 is XRD crystallinity data of particles prepared in Comparative Example 1. FIG.

Claims (10)

(a) reacting a polyelectrolyte, a copper compound, and an indium compound selected from polyethylenimine, sodium polyacrylate, and ammonium polyacrylate in an aqueous solvent to form a complex including copper and indium; And (b) adding a selenium compound to the complex aqueous solution (a) to produce CI (G) S nanoparticles at 0 to 80 ° C .; Method for producing a water-based CI (G) S nanoparticles comprising a. delete The method of claim 1, The polymer electrolyte is a method of producing a water-based CI (G) S nanoparticles, characterized in that added to 1.0 to 80% by weight relative to the sum of the copper compound and the indium compound. The method of claim 1, The aqueous solvent of step (a) is water, alcohol, or a method for producing the aqueous CI (G) S nanoparticles using a mixture thereof. The method of claim 1, The selenium compound of step (b) is the preparation of aqueous CI (G) S nanoparticles selected from sodium selenite sulfite (Na ₂ SeSO ₃ ), alkyl selenide (alkyl = methyl or ethyl), sodium selenide and ammonium selenide Way. The method of claim 5, The selenium compound is a method for producing aqueous CI (G) S nanoparticles, characterized in that sodium selenium sulfite. The method of claim 1, The copper compound and the indium compound of step (a) are at least one aqueous CI selected from acetate, nitrate, carbonate, sulfate, chloride, iodide, bromide, oxide, hydroxide and perchlorate containing copper or indium ( G) Method of producing S nanoparticles. The method of claim 1, The copper compound, the indium compound and the selenium compound is a method of producing a water-based CI (G) S nanoparticles, characterized in that the metal is supplied so that the molar ratio of copper, indium, and selenium 1: 1: 2. The method of claim 8, Method for producing a water-based CI (G) S nanoparticles comprising the step of adding a further gallium so that indium and gallium is x: 1-x (0 <x <1) with respect to 1 mole of copper in the step (a). delete

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