KR20110024157A - Water-based preparation method of ci(g)s(cuinxga1-xse2) nano particles using carboxylic derivatives - Google Patents
Water-based preparation method of ci(g)s(cuinxga1-xse2) nano particles using carboxylic derivatives Download PDFInfo
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- KR20110024157A KR20110024157A KR1020090082043A KR20090082043A KR20110024157A KR 20110024157 A KR20110024157 A KR 20110024157A KR 1020090082043 A KR1020090082043 A KR 1020090082043A KR 20090082043 A KR20090082043 A KR 20090082043A KR 20110024157 A KR20110024157 A KR 20110024157A
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- Prior art keywords
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- copper
- compound
- nanoparticles
- selenium
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Abstract
Description
본 발명은 태양광을 이용한 박막형 태양전지의 광흡수층 물질로 널리 사용 되고 있는 CI(G)S(CuInxGa1- xSe2; 0<x≤1)의 나노입자 제조 시 상대적으로 유해성이 없는 카르복시산 유도체를 이용하는 환경친화적인 수용액을 기초로 하는 제조방법이며, 고온열처리를 필요로 하지 않으므로 제조단가를 최저로 할 수 있으며, 대량생산에 적합한 CI(G)S 나노입자의 제조방법을 제공하는 것이다.The present invention is relatively harmless in the production of nanoparticles of CI (G) S (CuIn x Ga 1- x Se 2 ; 0 <x≤1), which is widely used as a light absorption layer material of thin-film solar cells using sunlight. It is a manufacturing method based on an environmentally friendly aqueous solution using a carboxylic acid derivative, and does not require high temperature heat treatment, thereby minimizing the manufacturing cost and providing a method for producing CI (G) S nanoparticles suitable for mass production. .
화합물 박막형 태양전지 중에서 높은 광 흡수와 전기적 광학적으로 우수한 Chalcopyrite 구조를 가지는 CI(G)S를 이용한 화합물 박막형 태양전지는 1-2마이크론 정도의 박막으로도 지금까지 ~20% 정도의 태양광변환 효율을 나타내고 있다. 따라서 많은 연구자들이 이를 이용한 태양전지개발에 박차를 가하고 있으며 향후 태양전지 시장의 30% 정도를 차지할 것으로 기대가 되고 있는 물질이다. Compound thin film solar cell using CI (G) S, which has high light absorption and electro-optical chromcopyrite structure among compound thin film solar cells, has a solar conversion efficiency of ~ 20% so far even with thin film of 1-2 micron. It is shown. Therefore, many researchers are speeding up the development of solar cells using this material and are expected to occupy 30% of the solar cell market in the future.
지금까지 CIS 또는 CI(G)S의 제조방법으로는 일반적으로 기상증착방법을 이 용하고 막의 치밀화를 위하여 기상법으로 셀레늄화하는 공정들이 많이 보고 되고 있다. 이는 상대적으로 높은 광변환 효율을 기대할 수는 있으나 고가의 장비 및 대량생산의 어려움 등의 문제점이 초래되고 있다 [R.Noufi, K. Zweibel(NREL), 2006 IEEE 4th World Conference on Photovoltaic Energy Conversion, vol.1, 317-320,(2006)].Until now, a number of processes for producing CIS or CI (G) S have generally been reported by using vapor deposition and selenium by gas phase for densification of membranes. This has the problems such as the difficulty of a relatively high photoelectric conversion efficiency can be expected to have expensive equipment and mass-production, but is caused [R.Noufi, K. Zweibel (NREL) , 2006 IEEE 4 th World Conference on Photovoltaic Energy Conversion, vol. 1, 317-320, (2006).
또한 David B. Mitzi(IBM) 등은 구리셀레늄 화합물과 인듐셀레늄 화합물을 미리 합성한 다음 강력한 환원성 물질인 하이드라진에 장시간 용해시킨 후 스핀코팅을 이용하여 CIGS박막을 제조한 방법을 보고 하였다. 비록 IBM에서 제조된 태양전지는13% 이상의 높은 광변환 효율을 나타내고 있지만, 전 공정이 장갑상자 내에서 행해지고 일주일 이상의 장시간 반응 그리고 상대적으로 취급이 용이하지 않은 하이드라진을 사용한다는 문제점이 있다[Advanced Materials, vol.20, 3657-3662,(2008)]. David B. Mitzi (IBM) et al. Reported a method of preparing a CIGS thin film using spin coating after synthesizing a copper selenium compound and an indium selenium compound in advance and dissolving it in a strong reducing substance, hydrazine, for a long time. Although solar cells manufactured by IBM have a high light conversion efficiency of more than 13%, there is a problem that the entire process is performed in a glove box and uses a long time reaction for more than a week and uses hydrazine, which is relatively easy to handle [Advanced Materials, vol. 20, 3657-3662, (2008)].
그리고 Brian A. Korgel 등이 구리아세테이트(Copper acetate)와 인듐아세테이트(Indium acetate) 그리고 셀레늄분말(selenium powder)을 올레일아민(Oleylamine) 용매를 이용하여 제조하는 방법을 보고하였다. 알려져 있다. 그러나 이 방법은 상대적으로 입자를 빠르게 제조할 수 있지만, 높은 반응온도(240℃)에서 독성이 강한 클로로포름을 이용하여 반응속도를 조절 하여야 하고 또한 진공장치 내에서 행해져야 한다는 문제점이 있다[J. Am. Chem. Soc., vol.130, 16770-16777,(2008)].Brian A. Korgel et al. Reported a method for preparing copper acetate, indium acetate, and selenium powder using an oleylamine solvent. Known. However, this method can produce particles relatively quickly, but there is a problem that the reaction rate must be controlled by using chloroform, which is toxic at high reaction temperature (240 ° C.), and also performed in a vacuum apparatus [J. Am. Chem. Soc., Vol. 130, 16770-16777, (2008).
따라서, 상대적으로 고가의 제조 조건을 개선하고 생산성을 확보하기 위하여 더욱 환경친화적이고 경제적인 제조방법에 대한 필요성이 더욱 증가하고 있다. 특히 CI(G)S의 제조에서 고온의 열을 부가하는 수단 없이 저온에서 CI(G)S 나노입자를 얻을 수 있고, 또한 경제적이고 생산적인 방법에 대한 발명이 향후 CI(G)S의 폭넓은 공급을 위해서는 반드시 개발되어야 하는 과제이다.Accordingly, there is an increasing need for a more environmentally friendly and economical manufacturing method to improve relatively expensive manufacturing conditions and to secure productivity. Especially in the manufacture of CI (G) S, CI (G) S nanoparticles can be obtained at low temperature without the means of adding high temperature heat. This is a task that must be developed for supply.
상기의 문제점을 해결하기 위하여 본 발명은 화합물 박막태양전지의 광흡수층 물질인 CI(G)S의 나노입자를 제조함에 있어서 유해한 유기용제 사용 및 고가의 폐기시설비를 필요로 하는 타공정과는 달리 수계용매를 이용하여 낮은 온도에서 반응을 수행함으로써 경제적이고, 환경친화적 방법으로 제조하는 것을 목적으로 한다. 또한 상대적으로 취급이 용이한 카르복시산 유도체를 이용한 착물 형성반응을 이용하여 CI(G)S 나노입자뿐 만 아니라 치밀한 막 형성의 전구체 물질을 용이하게 제조하는 방법을 제공하는 것을 목적으로 한다.In order to solve the above problems, the present invention is different from other processes requiring the use of harmful organic solvents and expensive waste facility costs in the production of nanoparticles of CI (G) S, which is a light absorption layer material of a 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 a solvent. Another 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 carboxylic acid derivatives.
상기와 같은 목적을 달성하기 위해 본 발명자들은 수많은 연구를 수행한 결과, 하기와 같이 카르복시산 유도체를 이용한 저온 수계 CI(G)S(CuInxGa1- xSe2; 0<x≤1) 나노입자의 제조방법을 제안하게 되었다.In order to achieve the above object, the present inventors have conducted a number of studies. As a result, low-temperature aqueous CI (G) S (CuIn x Ga 1- x Se 2 ; 0 <x≤1) nanoparticles using carboxylic acid derivatives as follows. Proposed a method for producing.
본 발명은 카르복시산 유도체를 이용한 저온 수계 CI(G)S 나노입자를 제조하는 방법에 있어서,The present invention provides a method for preparing low-temperature aqueous CI (G) S nanoparticles using a carboxylic acid derivative,
(a) 구리화합물과, 하기 화학식 1의 카르복시산 유도체를 수계용매 하에서 반응하여 구리착물을 형성하는 단계; 및(a) reacting a copper compound and a carboxylic acid derivative of Formula 1 under an aqueous solvent to form a copper complex; And
(b) 상기 (a) 단계의 구리착물 수용액에 셀레늄화합물을 투입하여 구리-셀레늄 착물을 형성하는 단계; 및(b) injecting a selenium compound into the aqueous copper complex solution of step (a) to form a copper-selenium complex; And
(c) 상기 (b) 단계의 구리-셀레늄 착물 수용액에 인듐화합물을 투입하여(c) adding an indium compound to the aqueous solution of copper-selenium complex of step (b);
저온 하에서 CI(G)S 나노입자를 생성하는 단계;Producing CI (G) S nanoparticles under low temperature;
를 포함하는 저온 수계 CI(G)S 나노입자의 제조방법을 제공한다.It provides a method for producing a low-temperature water-based CI (G) S nanoparticles comprising a.
[화학식 1][Formula 1]
상기 화학식 1에서, R1은 수소, 하이드록시기, 카르복시기, (C1-C6)알킬기, (C1-C6)알콕시기, (C1-C6)알킬티오기, (C1-C6)하이드록시알킬기, (C1-C6)하이드록시알콕시기, (C1-C6)하이드록시알킬티오기, (C1-C6)아미노알킬기, (C1-C6)아미노알콕시기, (C1-C6)아미노알킬티오기, (C1-C6)알콕시알킬기, (C2-C12)알콕시알콕시기, (C2-C12)알콕시알킬티오기, (C3-C7)사이클로알킬기, (C3-C7)사이클로알킬옥시기, (C3-C8)사이클로알킬(C1-C6)알킬옥시기, (C3-C7)사이클로알킬티오기, (C2-C6)알케닐기, (C2-C6)알케닐옥시기, (C2-C6)알케닐티오기, (C2-C6)알키닐기, (C2-C6)알키닐옥시기, (C2-C6)알키닐티오기, (C6-C12)아릴기, (C6-C12)아릴옥시기, (C6-C12)아릴티오기, (C1-C6)알킬(C6-C12)아릴기, (C1-C6)알킬(C6-C12)아릴옥시기, (C1-C6)알킬(C6-C12)아릴티오기, (C6-C12)아릴(C1-C6)알킬기, (C6-C12)아릴(C1-C6)알킬옥시기 및 (C6-C12)아릴(C1-C6)알킬티오기로부터 선택되며;In Formula 1, R 1 is hydrogen, a hydroxy group, a carboxy group, a (C1-C6) alkyl group, (C1-C6) alkoxy group, (C1-C6) alkylthio group, (C1-C6) hydroxyalkyl group, ( C1-C6) hydroxyalkoxy group, (C1-C6) hydroxyalkylthio group, (C1-C6) aminoalkyl group, (C1-C6) aminoalkoxy group, (C1-C6) aminoalkylthio group, (C1- C6) alkoxyalkyl group, (C2-C12) alkoxyalkoxy group, (C2-C12) alkoxyalkylthio group, (C3-C7) cycloalkyl group, (C3-C7) cycloalkyloxy group, (C3-C8) cycloalkyl ( C1-C6) alkyloxy group, (C3-C7) cycloalkylthio group, (C2-C6) alkenyl group, (C2-C6) alkenyloxy group, (C2-C6) alkenylthio group, (C2-C6) alky Nyl group, (C2-C6) alkynyloxy group, (C2-C6) alkynylthio group, (C6-C12) aryl group, (C6-C12) aryloxy group, (C6-C12) arylthio group, (C1-C6 ) Alkyl (C6-C12) aryl group, (C1-C6) alkyl (C6-C12) aryloxy group, (C1-C6) alkyl (C6-C12) arylthio group, (C6-C12) aryl (C1-C6) ) Alkyl group, (C6-C12) aryl (C1-C6) alkyloxy group and (C6-C12) aryl (C1) -C6) alkylthio group;
R2 및 R3은 서로 독립적으로 수소, 아민 및 카르복시기로부터 선택된다.R 2 and R 3 are independently of each other selected from hydrogen, amines and carboxyl groups.
이하, 본 발명을 상세하게 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
본 발명은 카르복시산 유도체를 이용한 저온 수계CI(G)S 나노입자를 제조하는 방법에 있어서, 상기 화학식 1로 표현되는 카르복시산 유도체를 포함한 수용액에 구리화합물을 투입하여 구리 착물을 형성한다. 여기에 셀레늄화합물 및 인듐화합물 혼합하고 저온 하에서 최종 반응함으로써 저온 수계 CI(G)S 나노입자의 제조방법을 제공할 수 있으며, 셀레늄화합물 및 임듐화합물은 갈륨화합물을 더 포함할 수 있다.The present invention provides a low temperature aqueous CI (G) S nanoparticles using a carboxylic acid derivative, in which a copper compound is added to an aqueous solution containing a carboxylic acid derivative represented by Formula 1 to form a copper complex. By mixing the selenium compound and the indium compound here and finally reacting at low temperature, it is possible to provide a method for producing low-temperature aqueous CI (G) S nanoparticles, and the selenium compound and the indium compound may further include a gallium compound.
본 발명의 상기 화학식 1의 카르복시산 유도체는 구체적으로 모노-카르복시산 유도체, 디-카르복시산 유도체, 트리-카르복시산 유도체, 테트라카르복시산유도체 및 아미노산 유도체로부터 선택되는 1종 이상을 포함할 수 있다.The carboxylic acid derivative of Chemical Formula 1 of the present invention may specifically include one or more selected from mono-carboxylic acid derivatives, di-carboxylic acid derivatives, tri-carboxylic acid derivatives, tetracarboxylic acid derivatives and amino acid derivatives.
본 발명의 상기 화학식 1의 카르복시산 유도체는 보다 구체적으로 트리나트륨시트르산, 트리암모늄시트르산, 시트르산, 알라닌, 아르기닌, 아스파라긴, 아스파트산, 벤질아스파르트산, 시스테인, 글루탐산, 글루타민, 글리신, 히스티딘, 이솔루신, 루신, 리신, 메티오닌, 오르니틴, 페닐알라닌, 프롤린, 세린, 트레오닌, 트립토판, 티로신 및 발린 등으로부터 선택되는 1종 이상의 카르복시산 유도체를 이용할 수 있으며, 이들로 한정하는 것은 아니다.The carboxylic acid derivative of Formula 1 of the present invention is more specifically trisodium citric acid, triammonium citric acid, citric acid, alanine, arginine, asparagine, aspartic acid, benzyl aspartic acid, cysteine, glutamic acid, glutamine, glycine, histidine, isoleucine One or more carboxylic acid derivatives selected from leucine, lysine, methionine, ornithine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine and the like can be used, but not limited thereto.
본 발명의 상기 구리화합물 또는 인듐화합물은 수계 용매에 높은 용해도를 갖는 화합물이면 어떠한 것이든 가능하지만, 바람직하게는 아세트산염, 질산염, 탄산염, 황산염, 염화물, 요오드화물, 브롬화물, 산화물, 수산화물, 과염소산염 등으로부터 선택하여 이용할 수 있으며, 구리화합물 또는 인듐화합물 각각에 대하여 1 종 이상의 화합물을 이용할 수 있다. 또한 인듐화합물에 더 첨가되는 갈륨 원소를 포함하는 소스 물질로는 수계용매에 용해도를 갖는 질산염, 황산염, 염화물 등으로부터 선택하여 이용할 수 있다.The copper compound or indium compound 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, perchloric acid It can select from a salt etc., and can use 1 or more types of compound with respect to a copper compound or an indium compound, 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.
본 발명의 상기 셀레늄화합물은 나트륨, 암모늄, 및 직쇄 또는 분지쇄의 알킬기를 포함하는 셀레늄화합물이거나, 여기에 설페이트(SO3 2 -)를 더 포함하는 셀레늄화합물일 수 있으며, 바람직하게는 나트륨셀레나이드, 암모늄셀레나이드, 알킬셀레나이드(알킬=메틸 또는 에틸), 셀레노아황산나트륨(Na2SeSO3) 등이 좋으며, 가장 바람직하게는 셀레노아황산나트륨이 가장 좋다.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.
본 발명의 상기 Na2SeSO3는 제조하여 사용할 수도 있는데, Na2SO3와 셀레늄분말(Selenium power)을 수용액 상에서 혼합하여 80 내지 100℃, 바람직하게는 90 내지 95℃로, 1시간 내지 12시간, 바람직하게는 2시간 내지 4시간 혼합하여 제조된다. 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.
본 발명의 상기 (a)단계의 수계 용매는 물, 알코올, 또는 이들의 혼합물을 이용하는 것이 바람직하며, 물은 탈이온수(Deionized water)을 사용하는 것이 좋다.Preferably, the aqueous solvent of step (a) of the present invention uses water, alcohol, or a mixture thereof, and water is preferably deionized water.
본 발명은 상기 화학식 1의 카르복시산 유도체를 이용한 저온 수계CI(G)S 나노입자를 제조하는 방법에 있어서, 상기 화학식 1의 카르복시산 유도체를 포함한 수용액에 구리 전구물질을 투입하고 10분 내지 2시간 정도 충분히 교반하여 구리2가의 이온과, 상기 화학식 1의 카르복시산 유도체와의 반응을 통해 푸른색의 이온 상태의 구리착물 수용액을 형성시킨다. 여기에 상기 셀레늄화합물을 투입하여 먼저 생성된 구리2가로 구성된 구리착물 수용액의 구리를 2가에서 1가로 환원시켜 초록색의 구리셀레늄을 포함한 구리와 셀레늄착물 수용액을 형성한다. 상기 용액을 충분히 1시간 이내의 범위에서 충분히 교반한 후, 상기 인듐화합물을 투입하여 1시간 이상 반응시켜 수계 CI(G)S(CuInxGa1- xSe2; 0<x≤1) 나노입자를 제조한다. 상기 반응은 모든 공정이 0 내지 80℃의 저온 분위기 하에서 수행된다.The present invention provides a low-temperature aqueous CI (G) S nanoparticles using the carboxylic acid derivative of the formula (1), the copper precursor is added to the aqueous solution containing the carboxylic acid derivative of the formula (1) for about 10 minutes to 2 hours Agitated to form an aqueous solution of a copper complex of blue ionic state through the reaction of a copper divalent ion with a carboxylic acid derivative of Chemical Formula 1. The selenium compound is added thereto to reduce the copper of the copper complex aqueous solution composed of the copper divalent formed first from divalent to monovalent to form an aqueous solution of copper and selenium complex containing green copper selenium. After sufficiently stirring the solution within the range of 1 hour, the indium compound was added and reacted for 1 hour or more, and the aqueous CI (G) S (CuIn x Ga 1- x Se 2 ; 0 <x≤1) nanoparticles To prepare. The reaction is carried out in a low temperature atmosphere of 0 to 80 ℃ all processes.
본 발명의 상기 화학식 1의 카르복시산 유도체를 이용한 저온 수계 CI(G)S 나노입자의 제조에 사용된 상기 카르복시산 유도체의 투입양은 [카르복시산소스(원료) 중량]/[구리소스(원료) 중량]×100(%)으로 정의 되고 구리소스(원료) 중량에 대하여 0.01 내지 80 중량%로 투입하는 것이 바람직하고, 1 내지 70 중량%로 투입하는 것이 더 바람직하다. 0.01 중량% 미만을 투입할 경우, 본 발명에서 제안하고 있듯이 구리금속과 인듐금속과의 착체 형성에 필요한 카르복시산 유도체의 양이 부족하여 제조 후 대체적으로 구리화합물 및 인듐화합물로 분리되어 제조되는 경향을 보인다. 또한 80 중량%를 초과하여 과다한 양을 투입하게 되면 착체 형성에 관계 하는것 뿐 만 아니라 반응에 직접적으로 참여할 수도 있어 구리 및 인듐과, 셀레늄과의 반응을 방해하여 원하지 않은 화합물로 분리되어 생성될 수 있으며, 또한 반응 후 상대적으로 많은 잔여 카르복시산 유도체를 남김으로써, 제조공정 완료 후, 제거해야 하는 단점을 초래할 수도 있다.The amount of the carboxylic acid derivative used in the preparation of the low temperature aqueous CI (G) S nanoparticles using the carboxylic acid derivative of Chemical Formula 1 of the present invention is [carboxylic acid source (raw material) weight] / [copper source (raw material) weight] × 100 It is defined as (%) and it is preferable to add in 0.01 to 80 weight% with respect to the weight of a copper source (raw material), and it is more preferable to add in 1 to 70 weight%. When less than 0.01% by weight, as suggested by the present invention, the amount of carboxylic acid derivatives required for complex formation between copper metal and indium metal is insufficient, so that after preparation, it is generally separated into copper compound and 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 number of residual carboxylic acid derivatives after the reaction, it may cause a disadvantage that must be removed after completion of the manufacturing process.
본 발명의 CI(G)S 입자는 투입된 상기 화학식 1의 카르복시산 유도체의 종류 에 따라 생성된 CI(G)S 입자의 크기가 달랐으며, 예를 들어, 트리CI (G) S particles of the present invention had a different size of the produced CI (G) S particles according to the type of the carboxylic acid derivative of Formula 1, for example,
나트륨시트르산(Trisodiumcitrate)의 경우, ~20 nm, 나트륨타르타르산(Sodium tartrate)인 경우 ~100 nm 의 CI(G)S 평균 입자크기를 나타내었다. 본 발명의 CI(G)S의 제조에서 상기 화학식 1의 카르복시산 유도체를 사용함으로써, CI(G)S의 평균 입자크기는 20 내지 400 nm임을 확인하였으며, 상기 카르복시산 유도체의 종류와 사용 양에 따라 입자크기를 다양하게 변화할 수 있다. In the case of sodium citrate (Trisodium citrate), the average particle size of CI (G) S of ~ 20 nm, ~ ~ 100 nm in the case of sodium tartrate. By using the carboxylic acid derivative of Formula 1 in the production of CI (G) S of the present invention, it was confirmed that the average particle size of CI (G) S is 20 to 400 nm, depending on the type and amount of the carboxylic acid derivative It can vary in size.
본 발명은 상기 착물이 형성된 용액에 [Cu]:[In]:[Se]의 몰비가 1:1:2가 되도록 셀레늄화합물과, 인듐화합물을 투입하여 CuInSe2 물질을 제조하거나, 상기 인듐화합물에 갈륨화합물을 더 첨가하여 CIGS(CuInxGa1 - xSe2; 0<x<1)를 제조할 수 있으며, 0 내지 80℃의 저온, 바람직하게는 상온 하에서 제조할 수 있다. 또한 상기 갈륨의 첨가는 인듐과 갈륨의 몰수의 합이 구리의 몰수와 동일하게 한다. 반응의 종결은 용액의 색상으로 구분할 수 있으며, 초록색을 띄는 용액은 반응함에 따라 점차적으로 검은색으로 변한다.The present invention provides a CuInSe 2 material by injecting a selenium compound and an indium compound so that the molar ratio of [Cu]: [In]: [Se] is 1: 1: 2 to the complex-formed solution, or to the indium compound. CIGS (CuIn x Ga 1 - x Se 2 ; 0 <x <1) may be prepared by further adding a gallium compound, and may be prepared at a low temperature of 0 to 80 ° C., preferably at room temperature. The addition of gallium also makes the sum of the moles of indium and gallium equal to the moles of copper. The termination of the reaction can be distinguished by the color of the solution, and the greenish solution gradually turns black as it reacts.
본 발명에서 상기 갈륨화합물은 질산염, 황산염, 및 염화물로부터 선택된다.In the present invention, the gallium compound is selected from nitrates, sulfates, and chlorides.
본 발명의 상기 모든 반응은 0~80℃, 좋게는 상온에서 반응하여 제조하는 것에서 특별히 본 발명의 장점이 더 있다.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.
상기 CI(G)S 가 형성된 용액 중 불순물은 증류수를 첨가하여 녹인 후 원심분리를 이용하여 상등액을 분리하는 과정을 2-3회씩 반복하여 수행한 후 원하는 나노입자를 제조한다.Impurities in the CI (G) S-formed solution are dissolved by adding distilled water, followed by repeating the process of separating the supernatant by centrifugation 2-3 times to prepare desired nanoparticles.
제조된 생성물의 조성에 대한 정성, 정량분석과 형성된 입자들의 입도 분포를 알아보기 위해 입도분석기(ELS-800, Otsuka, Japan)를 통해 확인하였다.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).
그리고 결정구조와 배향성을 알아보기 위해 X-ray Diffraction(XRD; D/max-A, Rigaku Japan, CuKα: λ=1.54178Å)을 사용하였다.And X-ray Diffraction (XRD; D / max-A, Rigaku Japan, CuKα: λ = 1.54178 Å) was used to determine the crystal structure and orientation.
본 발명에 따른 제조공정은 유해한 유기용제를 사용함으로써 작업환경의 유해성 유발 및 기타 폐기용제의 처리를 필요로 하는 타 공정과는 달리 모든 공정이 수계상태에서 진행되므로 작업환경의 안정성을 확보할 수 있다는 매우 우수한 장점을 가지고 있다고 할 수 있다The 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.
또한, 제조공정 시 취급이 용이하며 상대적으로 환경유해물질을 생산하지 않는 카르복시산 유도체를 이용하여 수계상태의 공정을 진행하므로 별도의 폐기시설이 필요하지 않아서 매우 경제적이며, 환경친화적인 공정이라는 장점을 가지고 있다. In addition, it is easy to handle during the manufacturing process and uses a carboxylic acid derivative that does not produce environmentally harmful substances. Therefore, it does not need a separate disposal facility, so it is very economical and environmentally friendly. have.
본 발명은 낮은 제조반응온도(~25°C)에서 제조되므로 고온을 필요로 하는 종래의 제조방법에 비해 매우 경제적이며, 또한, 부수적인 장치의 증설 없이 batch의 용량을 쉽게 증대시켜 제조를 수행함으로써 높은 생산성을 확보할 수 있다는 장점을 가지고 있다.The present invention is manufactured at a low production reaction temperature (~ 25 ° C), so it is very economical compared to the conventional production method requiring a high temperature, and also by performing the production by easily increasing the capacity of the batch without the addition of additional equipment It has the advantage of ensuring high productivity.
또한, 착물 형성으로 사용되는 카르복시산 유도체의 비와 첨가되는 전구물질의 농도 비를 달리 함으로서 중간착체의 크기를 제어하여 최종적으로 제조되는 CI(G)S의 입자를 나노 크기 차원에서 제어할 수 있다는 장점이 있다.In addition, by controlling the size of the intermediate complex by varying the ratio of the carboxylic acid derivative used for complex formation and the concentration ratio of the precursors added, it is possible to control the particles of the finally prepared CI (G) S in the nano size dimension There is this.
이하, 본 발명을 하기의 실시예에 의거하여 좀 더 상세히 설명하고자 한다. 단, 하기 실시예는 본 발명을 예시하기 위한 것일 뿐 한정하지는 않는다.Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are not intended to limit the invention only.
실시예Example 1 One
우선 초정제수(DI-water) 20 ml를 기준으로 하여 준비한 후, 착물 형성을 위해 트리나트륨시트르산(Trisodium Citrate; TSC) 1.25mmol(0.367g)에 용해시킨다. 10분 동안 교반하여 충분히 용해시킨 후 구리아세테이트(Copper acetate)를 3mmol(0.598g)을 첨가하여 착물 형성을 위해 20분 정도 교반한다. 이 준비된 용액에 12.6g Na2SO3과 7.89g 셀레늄분말(Selenium power)을 DI water 1000ml에 섞은 후 3시간, 95℃에서 반응시켜 제조한 0.1mol Na2SeSO3 수용액에서 60ml를 취해 먼저 제조된 구리수용액에 첨가한다. 이 용액은 30분 동안 충분히 반응한다. 3 mmol(0.876g) 인듐아세테이트를 DI water 20ml에 첨가한 용액을 서서히 위 용액에 투입한다. 이로써 총 용액의 부피는 100ml가 되게 하였다. 1시간이 지나면 용액은 점차 초록색에서 검은색으로 변하여 CuInSe2입자를 포함한 용액을 형성하게 된다. 구조분석은 XRD(X-선회절분석기)를 사용하여 분석하였다. 사용된 샘플은 용액상으로, 그리고 용액을 150℃로 건조 후 사용하였으며, 상기 제조한 CIS용액 중 불순물은 증류수를 첨가하여 녹인 후 원심분리를 이용하여 상등액을 분리하는 과정을 2-3회씩 반복하여 제거하는 과정을 수행한 후 취득된 분말을 사용하여 분석하였다. First, based on 20 ml of DI water, it is prepared, and then dissolved in 1.25 mmol (0.367 g) of trisodium citrate (TSC) to form a complex. After stirring for 10 minutes to fully dissolve, 3mmol (0.598g) of copper acetate is added and stirred for about 20 minutes to form a complex. 12.6 g Na 2 SO 3 and 7.89 g selenium powder (Selenium power) were mixed with 1000 ml of DI water for 3 hours, and 60 ml of 0.1 mol Na 2 SeSO 3 aqueous solution prepared by reacting at 95 ° C. was prepared first. Add to aqueous copper solution. This solution is fully reacted for 30 minutes. A solution of 3 mmol (0.876 g) indium acetate in 20 ml of DI water is slowly added to the stomach solution. This resulted in a total solution volume of 100 ml. After 1 hour, the solution gradually changes from green to black to form a solution containing CuInSe 2 particles. Structural analysis was performed using XRD (X-ray diffractometer). 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.
그 결과 도 1와 같이 2-theta값이 각각 26?, 44?, 52? 의 전형적인 CuInSe2(JCPDS-97-004-9933) 피크를 확인하였다.As a result, 2-theta values are 26 ?, 44 ?, and 52 ?, respectively, as shown in FIG. A typical CuInSe 2 (JCPDS-97-004-9933) peak was identified.
실시예Example 2 2
우선 초정제수(DI-water) 20ml를 기준으로 하여 준비한 후, 착물 형성을 위해 트리암묘늄시트르산(Triammonium citrate) 1.25mmol(0.306g)에 용해시킨다. 10분 동안 교반하여 충분히 용해시킨 후 구리아세테이트 3mmol(0.598g)을 첨가하여 착물 형성을 위해 20분 동안 교반한다. 다음 단계인 셀레늄과 인듐의 첨가 실험은 상기 설명된 실시예 1과 동일하게 수행하였다First, 20 ml of di-water is prepared on the basis, and then dissolved in 1.25 mmol (0.306 g) of triammonium citrate to form a complex. After stirring for 10 minutes to fully dissolve, 3 mmol (0.598 g) of copper acetate is added and stirred for 20 minutes to form a complex. The next step, the addition of selenium and indium was performed in the same manner as in Example 1 described above.
그 결과, 도 2와 같이 2-theta값이 각각 26?, 44?, 52?의 전형적인 CuInSe2(JCPDS-97-004-9933) 피크를 확인하였다.As a result, as shown in Fig. 2, typical CuInSe 2 (JCPDS-97-004-9933) peaks having 2-theta values of 26 ?, 44 ?, and 52 ?, respectively, were confirmed.
실시예Example 3 3
우선 초정제수(DI-water) 20ml를 기준으로 하여 준비한 후, 착물 형성을 위해 타르트르산나트륨(Sodium Tartrate) 1.25mmol(0.287g)에 용해시킨다. 10분 동안 교반하여 충분히 용해시킨 후 구리아세테이트 3mmol(0.598g)을 첨가하여 착물 형성을 위해 20분 동안 교반한다. 다음 단계인 셀레늄과 인듐의 첨가 실험은 상기 설명된 실시예 1과 동일하게 수행하였다First, based on 20 ml of DI water, the solution is prepared and then dissolved in 1.25 mmol (0.287 g) of sodium tartrate to form a complex. After stirring for 10 minutes to fully dissolve, 3 mmol (0.598 g) of copper acetate is added and stirred for 20 minutes to form a complex. The next step, the addition of selenium and indium was performed in the same manner as in Example 1 described above.
그 결과, 도 2와 같이 2-theta값이 각각 26?, 44?, 52?의 전형적인 CuInSe2(JCPDS-97-004-9933) 피크를 확인하였다.As a result, as shown in Fig. 2, typical CuInSe 2 (JCPDS-97-004-9933) peaks having 2-theta values of 26 ?, 44 ?, and 52 ?, respectively, were confirmed.
실시예Example 4 4
우선 초정제수(DI-water)를 20ml를 기준으로 하여 준비한 후, 착물 형성을 위해 시트르산(Citric Acid) 1.25mmol(0.256g)에 용해시킨다. 10분 동안 교반하여 충분히 용해시킨 후 구리아세테이트 3mmol(0.598g)을 첨가하여 착물 형성을 위해 20분 동안 충분히 교반한다. 다음 단계인 셀레늄과 인듐의 첨가 실험은 상기 설명된 실시예 1과 동일하게 수행 하였다First, di-water is prepared based on 20 ml, and then dissolved in 1.25 mmol (0.256 g) of citric acid to form a complex. After stirring for 10 minutes to fully dissolve, 3 mmol (0.598 g) of copper acetate is added and stirred for 20 minutes to form a complex. The next step, the addition of selenium and indium was performed in the same manner as in Example 1 described above
그 결과, 2-theta값이 각각 26?, 44?, 52?의 전형적인 CuInSe2(JCPDS-97-004-9933) 피크를 확인하였다.As a result, typical CuInSe 2 (JCPDS-97-004-9933) peaks with 2-theta values of 26 ?, 44 ?, and 52 ?, respectively, were confirmed.
실시예Example 5 5
우선 초정제수(DI-water) 20 ml를 기준으로 하여 준비한 후, 착물 형성을 위해 투입되는 트리나트륨시트르산(Trisodium Citrate; TSC) 염의 투입양은 R(중량%)=[카르복시산염소스(원료)중량]/[구리소스(원료)중량]x100(%)로 정의되게 R=1중량%(0.0059g), R=5중량%(0.0295g), R=10중량%(0.059g), R=50중량%(0.295g), R=80중량%(0.472g)로 선택하여 각각 투입하여 실험을 진행 하였다. 다음 단계인 셀레늄과 인듐의 첨가 실험은 상기 설명된 실시예 1과 동일하게 수행 하였다First, based on 20 ml of DI water, the amount of trisodium citrate (TSC) salt added to form the complex is R (% by weight) = [carboxylate source (raw material) weight] R = 1 weight% (0.0059 g), R = 5 weight% (0.0295 g), R = 10 weight% (0.059 g), R = 50 weight % (0.295g), R = 80% by weight (0.472g) was selected to put into each experiment. The next step, the addition of selenium and indium was performed in the same manner as in Example 1 described above
그 결과 20nm, 30nm, 50nm, 80nm, 100nm, 110nm정도의 평균입자크기를 각각 나태내었으며, 2-theta값이 각각 26?, 44?, 52? 의 전형적인 CuInSe2(JCPDS-97-004-9933) 피크를 확인하였다.As a result, the average particle size of 20nm, 30nm, 50nm, 80nm, 100nm, 110nm was shown, and 2-theta values were 26 ?, 44 ?, and 52 ?, respectively. A typical CuInSe 2 (JCPDS-97-004-9933) peak was identified.
실시예Example 6 6
우선 초정제수(DI-water) 20 ml를 기준으로 하여 준비한 후, 착물 형성을 위해 트리나트륨시트르산(Trisodium Citrate; TSC) 1.25mmol(0.367g)에 용해시킨다. 10분 동안 교반하여 충분히 용해시킨 후 구리아세테이트(Copper acetate)를 3mmol(0.598g)을 첨가하여 착물 형성을 위해 20분 정도 교반한다. 상기 용액에 [Cu]와[In]에 대한 [Se]의 몰비가 1:1, 1:2, 그리고 1:3이 되도록, Na2SO3 + Se 를 반응시켜 Na2SeSO3수용액을 각각 0.05mol(1:1:1경우), 0.1mol(1:1:2경우), 0.15mol(1:1:3경우)로 제조하여 60ml를 각각의 몰비에 맞게 투입하여 1시간 동안 충분히 교반하여 최종적으로 CIS 물질을 제조하였다. 다음 단계는 상기 설명된 실시예 1과 동일하게 수행 하였다First, based on 20 ml of DI water, it is prepared, and then dissolved in 1.25 mmol (0.367 g) of trisodium citrate (TSC) to form a complex. After stirring for 10 minutes to fully dissolve, 3mmol (0.598g) of copper acetate is added and stirred for about 20 minutes to form a complex. 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 0.05mol (1: 1: 1 case), 0.1mol (1: 1: 2 case) and 0.15mol (1: 1: 3 case), respectively, 60ml 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
그 결과 2-theta값이 각각 26?, 44?, 52? 의 전형적인 CuInSe2(JCPDS-97-004-9933) 피크를 확인하였다.As a result, the 2-theta values were 26 ?, 44 ?, and 52 ?, respectively. A typical CuInSe 2 (JCPDS-97-004-9933) peak was identified.
실시예Example 7 7
실시예 1과 동일하게 수행하였으며, 구리 및 셀레늄의 착물이 형성된 수용액에 투입되는 인듐아세테이트(Indium acetate) 그리고 질산갈륨(Gallium nitrate)의 양은 (CI(G)S(CuInxGa1- xSe2; 0<x≤1)을 상기식에 의거하여,각각 x=0.95(인듐: 0.83g, 갈륨:0.038g), x=0.7(인듐: 0.613g, 갈륨:0.23g), x=0.4(인듐: 0.35g, 갈륨:0.46g)을 투입한 후 착체 형성을 위해 최소 1시간 동안 반응을 시킨다. 다음 단계는 상기 설명된 실시예 1과 동일하게 수행 하였다In the same manner as in Example 1, the amount of indium acetate (G) and gallium nitrate (Gallium nitrate) added to the aqueous solution formed with a complex of copper and selenium was (CI (G) S (CuIn x Ga 1- x Se 2). Based on the above formula, x = 0.95 (indium: 0.83 g, gallium: 0.038 g), x = 0.7 (indium: 0.613 g, gallium: 0.23 g), x = 0.4 (indium); : 0.35 g, gallium: 0.46 g) was added and allowed to react for at least 1 hour to form a complex The following steps were carried out in the same manner as in Example 1 described above.
그 결과, theta값이 각각 27?, 45?, 53? 의 전형적인 CuInGaSe2(JCPDS-40-1488) 피크를 확인할 수 있었다.As a result, theta values were 27 ?, 45 ?, and 53 ?, respectively. Typical CuInGaSe 2 (JCPDS-40-1488) peaks were found.
실시예Example 8 8
실시예 1과 동일하게 수행하였으며, 반응 온도를 25℃, 50℃, 그리고 80℃로 각각 달리하여 실험을 수행하여 최종적으로 CIS 물질을 제조하였다. 그 결과, 25℃ 상온 반응의 경우 입자 크기가 약 20nm, 50℃와 80℃의 반응 온도의 경우는 평균 100nm및 200nm 입자 크기를 각각 나타내었다. 또한, 2-theta값이 각각 26?, 44?, 52?의 전형적인 CuInSe2(JCPDS-97-004-9933) 피크를 확인하였다.The experiment was performed in the same manner as in Example 1, and the reaction temperature was changed to 25 ° C., 50 ° C., and 80 ° C., respectively, to finally prepare a CIS material. As a result, the particle size of the reaction temperature of 25 ℃ room temperature, the average of 100 nm and 200 nm particle size for the reaction temperature of 50 ℃ and 80 ℃, respectively. In addition, typical CuInSe 2 (JCPDS-97-004-9933) peaks with 2-theta values of 26 ?, 44 ?, and 52 ?, respectively, were confirmed.
실시예Example 9 (대용량증가) 9 (large capacity increase)
우선 초정제수(DI-water) 200 ml를 기준으로 하여 준비한 후, 착물 형성을 위해 트리나트륨시트르산(Trisodium Citrate; TSC) 12.5mmol(3.67g)에 용해시킨다. 10분 동안 교반하여 충분히 용해시킨 후 구리아세테이트(Copper acetate)를 30mmol(5.98g)을 첨가하여 착물 형성을 위해 20분 정도 교반한다. 이 준비된 용액 에 12.6g Na2SO3과 7.89g 셀레늄분말(Selenium power)을 DI water 1000ml에 섞은 후 3시간, 95℃에서 반응시켜 제조한 0.1mol Na2SeSO3 수용액에서 600ml를 취해 먼저 제조된 구리수용액에 첨가한다. 이 용액은 30분 동안 충분히 반응한다. 30mmol(8.76g) 인듐아세테이트를 DI water 200ml에 첨가한 용액을 서서히 위 용액에 투입한다. 이로써 총 용액의 부피는 1000ml가 되게 하였다. 다음 단계는 상기 설명된 실시예 1과 동일하게 수행 하였다First, based on 200 ml of DI-water, it is prepared, and then dissolved in 12.5 mmol (3.67 g) of trisodium citrate (TSC) to form a complex. After stirring for 10 minutes to fully dissolve, the addition of 30mmol (5.98g) of copper acetate (Copper acetate) is stirred for about 20 minutes to form a complex. 12.6 g Na 2 SO 3 and 7.89 g selenium powder (Selenium power) were mixed in 1000 ml of DI water and reacted at 95 ° C. for 3 hours to prepare 600 ml of 0.1 mol Na 2 SeSO 3 aqueous solution. Add to aqueous copper solution. This solution is fully reacted for 30 minutes. A solution of 30 mmol (8.76 g) indium acetate added to 200 ml of DI water is slowly added to the stomach solution. This resulted in a total solution volume of 1000 ml. The following steps were performed identically to Example 1 described above
그 결과 도 1와 같이 2-theta값이 각각 26?, 44?, 52? 의 전형적인 CuInSe2(JCPDS-97-004-9933) 피크를 확인하였다.As a result, 2-theta values are 26 ?, 44 ?, and 52 ?, respectively, as shown in FIG. A typical CuInSe 2 (JCPDS-97-004-9933) peak was identified.
비교예Comparative example 1 One
우선 초정제수(DI-water)를 20ml를 기준으로 하여 준비한 후 카르복시산 유도체의 첨가 없이 구리아세테이트 3mmol(0.598g)을 첨가하여 5분 동안 교반한다. 다음 단계는 상기 설명된 실시예 1과 동일하게 수행하였다.First, di-water is prepared on the basis of 20 ml, and then 3 mmol (0.598 g) of copper acetate is added without addition of a carboxylic acid derivative and stirred for 5 minutes. The next step was carried out in the same manner as in Example 1 described above.
그 결과 CIS 단일상이 생성되지 않고 각각Cu2Se(JCPDS-97-004-3224) 와 In2Se3(JCPDS-00-040-1408) 그리고 Na2SO4(JCPDS-00-022-1399)피크를 확인하였다.As a result, no CIS single phase was produced, but Cu 2 Se (JCPDS-97-004-3224) and In 2 Se 3 (JCPDS-00-040-1408) and Na 2 SO 4 (JCPDS-00-022-1399), respectively. The peak was confirmed.
비교예Comparative example 2 2
우선 초정제수(DI-water)를 20ml를 기준으로 하여 준비한 후, 글루콘 산(Gluconic Acid) 1.25mmol(0.271g)를 용해시킨다. 10분 동안 교반하여 충분히 용해시킨 후 양이온 원료물질인 구리아세테이트 3mmol(0.598g)을 첨가하여 착물 형성을 위해 20분 동안 충분히 교반한다. 이 준비된 용액에 0.1mol(12.6g) Na2SO3과 셀레늄 분말(7.89g)을 DI water 1000ml에 섞은 후 3시간, 95℃에서 반응시켜 제조한 Na2SeSO3 수용액에서 60ml를 취해 먼저 제조된 구리수용액에 첨가한다. 다음 단계는 상기 설명된 실시예 1과 동일하게 수행 하였다First, di-water is prepared based on 20 ml, and then 1.25 mmol (0.271 g) of gluconic acid is dissolved. After stirring for 10 minutes to fully dissolve, 3 mmol (0.598 g) of acetonitrile raw material was added thereto, followed by stirring for 20 minutes to form a complex. 0.1 mol (12.6 g) Na 2 SO 3 and selenium powder (7.89 g) were mixed in 1000 ml of DI water and reacted at 95 ° C. for 3 hours to prepare 60 ml of Na 2 SeSO 3 aqueous solution. Add to aqueous copper solution. The following steps were performed identically to Example 1 described above
그 결과 CIS 단일상이 생성되지 않고 각각Cu2Se(JCPDS-97-004-3224) 와 In2Se3(JCPDS-00-040-1408) 그리고 Na2SO4(JCPDS-00-022-1399) 피크를 확인하였다.As a result, no CIS single phase was produced, but Cu 2 Se (JCPDS-97-004-3224) and In 2 Se 3 (JCPDS-00-040-1408) and Na 2 SO 4 (JCPDS-00-022-1399), respectively. The peak was confirmed.
비교예Comparative example 3 3
우선 초정제수(DI-water)를 20ml를 기준으로 하여 준비한 후, 에틸렌글리콜(Ethylene Glycol) 1.25mmol(0.075g)l에 용해시킨다. 10분 동안 교반하여 충분히 용해시킨 후 구리아세테이트 3mmol(0.598g)을 첨가하여 착물 형성을 위해 20분 동안 충분히 교반한다. 다음 단계는 상기 설명된 실시예 1과 동일하게 수행하였다First, di-water is prepared based on 20 ml, and then dissolved in 1.25 mmol (0.075 g) of ethylene glycol (Ethylene Glycol). After stirring for 10 minutes to fully dissolve, 3 mmol (0.598 g) of copper acetate is added and stirred for 20 minutes to form a complex. The next step was performed in the same manner as in Example 1 described above.
그 결과 CIS 단일상이 생성되지 않고 각각Cu2Se(JCPDS-97-004-3224) 와 In2Se3(JCPDS-00-040-1408) 그리고 Na2SO4(JCPDS-00-022-1399) 피크를 확인하였다.As a result, no CIS single phase was produced, but Cu 2 Se (JCPDS-97-004-3224) and In 2 Se 3 (JCPDS-00-040-1408) and Na 2 SO 4 (JCPDS-00-022-1399), respectively. The peak was confirmed.
도 1는 실시예 1에서 제조된 CIS입자의 XRD 결정성 data 이다.1 is XRD crystallinity data of CIS particles prepared in Example 1. FIG.
도 2은 실시예 2에서 제조된 CIS입자의 XRD 결정성 data 이다.Figure 2 is XRD crystallinity data of the CIS particles prepared in Example 2.
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