KR20140021805A - Method for preparing ci(g)s-based thin film introduced with aging step of slurry comprising binary nanoparticle and ci(g)s-based thin film prepared by the same - Google Patents
Method for preparing ci(g)s-based thin film introduced with aging step of slurry comprising binary nanoparticle and ci(g)s-based thin film prepared by the same Download PDFInfo
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- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
- H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
- H01L31/0749—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
본 발명은 태양전지용 CI(G)S계 박막의 제조방법에 관한 것으로, 보다 상세하게는, 이성분계 나노입자와 용액 전구체로부터 제조된 슬러리를 비진공 코팅법을 사용하여 CI(G)S계 박막을 제조하는 경우, 상기 슬러리를 일정 기간 숙성시킨 후 코팅함으로써 치밀화된 박막을 우수한 재현성으로 제조할 수 있는 이성분계 나노입자 하이브리드 방법을 이용한 고 밀도의 CI(G)S계 박막의 제조방법 및 그 방법에 의해 제조된 CI(G)S계 박막에 관한 것이다.The present invention relates to a method for manufacturing a CI (G) S-based thin film for solar cells, and more particularly, to a slurry prepared from two-component nanoparticles and a solution precursor using a non-vacuum coating method. In the case of preparing the method, a method of preparing a high density CI (G) S based thin film using a binary component nanoparticle hybrid method capable of producing a densified thin film with excellent reproducibility by coating the slurry after aging for a certain period of time and its method It relates to a CI (G) S-based thin film produced by.
최근 심각한 환경오염 문제와 화석 에너지 고갈로 차세대 청정에너지 개발에 대한 중요성이 증대되고 있다. 그 중에서도 태양전지는 태양 에너지를 직접 전기 에너지로 전환하는 장치로서, 공해가 적고, 자원이 무한적이며 반영구적인 수명이 있어 미래 에너지 문제를 해결할 수 있는 에너지원으로 기대되고 있다.Recently, serious environmental pollution problem and depletion of fossil energy are increasing importance for next generation clean energy development. Among them, the solar cell is a device that directly converts solar energy into electrical energy, and is expected to be an energy source capable of solving future energy problems due to its low pollution, infinite resources, and a semi-permanent lifetime.
태양전지는 광흡수층으로 사용되는 물질에 따라서 다양한 종류로 구분되며, 현재 가장 많이 사용되는 것은 실리콘을 이용한 실리콘 태양전지이다. 그러나 최근 실리콘의 공급부족으로 가격이 급등하면서 박막형 태양전지에 대한 관심이 증가하고 있다. 박막형 태양전지는 얇은 두께로 제작되므로 재료의 소모량이 적고, 무게가 가볍기 때문에 활용범위가 넓다. 이러한 박막형 태양전지의 재료로는 비정질 실리콘과 CdTe, CIS 또는 CIGS에 대한 연구가 활발하게 진행되고 있다.Solar cells are classified into various types according to materials used as light absorption layers, and at present, the most commonly used are silicon solar cells using silicon. However, as prices have soared recently due to a shortage of silicon, interest in thin-film solar cells is increasing. Thin-film solar cells are manufactured with a thin thickness, so they have a wide range of applications because of low consumption of materials and light weight. Research into amorphous silicon, CdTe, CIS, or CIGS is actively conducted as a material for such thin film solar cells.
CIS 박막 또는 CIGS 박막은 Ⅰ-Ⅲ-Ⅵ 화합물 반도체 중의 하나이며, 실험실적으로 만든 박막 태양전지 중에서 가장 높은 변환효율(20.3%)을 기록하고 있다. 특히 10 마이크론 이하의 두께로 제작이 가능하고, 장시간 사용 시에도 안정적인 특성이 있어, 실리콘을 대체할 수 있는 저가의 고효율 태양전지로 기대되고 있다. 특히 CIS 박막은 직접 천이형 반도체로서 박막화가 가능하고 밴드갭이 1.04 eV로 비교적 광변환에 적합하며, 광흡수 계수가 알려진 태양전지 재료 중 큰 값을 나타내는 재료이다. CIGS 박막은 CIS 박막의 낮은 개방전압을 개선하기 위하여 In의 일부를 Ga으로 대체하거나 S을 Se로 대체하여 개발된 재료이다.The CIS thin film or CIGS thin film is one of the I-III-VI compound semiconductors, and has the highest conversion efficiency (20.3%) among laboratory thin film solar cells. In particular, it can be manufactured to a thickness of less than 10 microns, and it is expected to be a low-cost, high-efficiency solar cell that can replace silicon because of its stable characteristics even when used for a long time. In particular, CIS thin film is a direct transition semiconductor that can be thinned and has a band gap of 1.04 eV, which is relatively suitable for light conversion, and exhibits a large value among solar cell materials with known light absorption coefficients. CIGS thin film is developed by replacing part of In with Ga or S with Se to improve the low open voltage of CIS thin film.
CIGS계 태양전지는 수 마이크론 두께의 박막으로 태양전지를 만드는데, 그 제조방법으로는 크게 진공에서의 증착을 이용하는 방법과, 비진공에서 전구체 물질을 도포한 후에 이를 열처리하는 방법이 있다. 그 중, 진공 증착에 의한 방법은 고효율의 흡수층을 제조할 수 있는 장점이 있는 반면에, 대면적의 흡수층 제조 시에 균일성이 떨어지고 고가의 장비를 이용하여야 하며 사용되는 재료의 20??50%의 손실로 인하여 제조단가가 높다는 단점이 있다. 반면에, 전구체 물질을 도포한 후 고온 열처리하는 방법은 공정 단가를 낮출 수 있으며 대면적을 균일하게 제조할 수 있으나, 흡수층 효율이 비교적 낮은 문제점이 있다.CIGS-based solar cells make a solar cell with a thin film of a few microns thick, the manufacturing method is largely a method using a vacuum deposition, and a method of applying a precursor material in a non-vacuum and heat treatment. Among them, the method by vacuum deposition has the advantage of manufacturing a highly efficient absorbing layer, while in the production of a large-area absorbing layer, it is inferior in uniformity and requires the use of expensive equipment and 20 ?? 50% of the material used. Due to the loss of manufacturing costs are high. On the other hand, the method of high temperature heat treatment after applying the precursor material can lower the cost of the process and uniformly produce a large area, but there is a problem that the absorption layer efficiency is relatively low.
비진공 CIGS계 태양전지의 박막 제조에 있어서, 제조된 박막의 광 흡수 효율의 개선과 대량 생산을 위한 우수한 재현성 확보가 매우 중요하다. 제조된 박막의 광 흡수 효율 개선과 관련하여, CIS계 화합물 나노분말 사이의 공극에 충진원소를 개재시켜 열처리하는 등록특허 제10-1129194호가 개시되어 있다. 또한, 박막의 신뢰성 확보를 위해 공개특허 제10-2009-0043265호는 2성분계 나노입자 대신 3성분계 또는 4성분계 나노입자에 계면활성제로 코팅한 후 기판에 코팅하여 계면활성제를 제거하는 방법을 개시하고 있다. 그러나 사용된 계면활성제는 제거 공정을 통해 제거되어야 하고, 이러한 제거 공정의 실시는 우수한 재현성 확보를 어렵게 한다. In manufacturing a thin film of a non-vacuum CIGS solar cell, it is very important to improve the light absorption efficiency of the manufactured thin film and to secure excellent reproducibility for mass production. In connection with improving the light absorption efficiency of the prepared thin film, Patent No. 10-1129194 discloses a heat treatment by interposing a filling element in a space between nanoparticles of a CIS compound. In addition, Korean Patent Publication No. 10-2009-0043265 discloses a method for removing a surfactant by coating a three-component or four-component nanoparticle with a surfactant and then coating the substrate with a surfactant instead of the two-component nanoparticle. have. However, the surfactants used must be removed through a removal process, and the implementation of such removal process makes it difficult to ensure good reproducibility.
현재까지 보고된 여러 가지 방법에 의해 제조된 태양전지 박막 중, 특히 비진공에서 용액 전구체 물질을 도포하여 형성된 CIGS 박막은 기공이 많고 치밀화되지 못한 특성을 나타냄과 동시에 재현성 있게 박막을 제조하기가 어렵다. Among the solar cell thin films manufactured by various methods reported up to now, especially CIGS thin film formed by applying a solution precursor material in a non-vacuum, it is difficult to manufacture the thin film with reproducibility while showing many pores and undensified characteristics.
본 발명의 목적은 CIS 또는 CIGS 나노입자를 사용하는 방법과 용액 전구체를 사용하는 방법의 하이브리드 개념이 도입된 CIGS계 태양전지 박막의 제조방법에 있어서, 입자의 비결정 성장과 불순물의 최소화를 통한 박막의 치밀화를 통한 효율 개선 이외에 우수한 재현성을 확보할 수 있는 태양전지용 CI(G)S계 박막의 제조방법을 제공하는 데 있다.SUMMARY OF THE INVENTION An object of the present invention is a method of manufacturing a CIGS-based solar cell thin film in which a hybrid concept of a method using CIS or CIGS nanoparticles and a method using a solution precursor is introduced. In addition to improving efficiency through densification, there is provided a method of manufacturing a CI (G) S based thin film for solar cells that can secure excellent reproducibility.
상기 목적을 달성하기 위해, 본 발명은 CI(G)S계의 이성분계 나노입자, CI(G)S계 원소를 포함하는 용액 전구체, 용매 및 킬레이트제를 혼합하여 제조한 하이브리드형 슬러리를 사용하는 하이브리드 방법을 사용하여 박막을 치밀화시키고, 상기 하이브리드형 슬러리를 기판 상에 코팅하기 전에 5일 내지 10일 동안 숙성시킴으로써 우수한 재현성을 확보하는 특징으로 한다. In order to achieve the above object, the present invention is to use a hybrid slurry prepared by mixing a CI (G) S-based binary component nanoparticles, a solution precursor containing a CI (G) S-based element, a solvent and a chelating agent The thin film is densified using a hybrid method, and the hybrid slurry is aged for 5 to 10 days before coating the hybrid slurry on a substrate, thereby ensuring excellent reproducibility.
구체적으로는, 본 발명의 이성분계 나노입자 하이브리드 방법을 이용한 CI(G)S계 박막의 제조방법은, CI(G)S계의 이성분계 나노입자를 제조하는 단계(단계 a); 상기 이성분계 나노입자, CI(G)S계 원소를 포함하는 용액 전구체, 용매 및 킬레이트제를 혼합하여 하이브리드형 슬러리를 제조하는 단계(단계 b); 상기 하이브리드형 슬러리를 5일 내지 10일 동안 숙성하는 단계(단계 c); 숙성된 하이브리드형 슬러리를 비진공 코팅하여 CI(G)S계 박막을 형성하는 단계(단계 d); 및 상기 형성된 CI(G)S 박막에 셀렌화 열처리하는 단계(단계 e)를 포함한다.
Specifically, the method for producing a CI (G) S-based thin film using the binary-component nanoparticle hybrid method of the present invention comprises the steps of preparing a CI (G) S-based bicomponent nanoparticle (step a); Preparing a hybrid slurry by mixing the binary nanoparticles, a solution precursor containing a CI (G) S-based element, a solvent, and a chelating agent (step b); Aging the hybrid slurry for 5 to 10 days (step c); Non-vacuum coating the aged hybrid slurry to form a CI (G) S-based thin film (step d); And selenization heat treatment on the formed CI (G) S thin film (step e).
본 발명의 바람직한 실시예에 있어서, 상기 이성분계 나노입자는, Cu-Se, In-Se, Ga-Se, Cu-S, In-S 및 Ga-S 중 어느 하나일 수 있다.In a preferred embodiment of the present invention, the binary nanoparticles may be any one of Cu-Se, In-Se, Ga-Se, Cu-S, In-S and Ga-S.
상기 단계 a는, 저온 콜로이달 방법, 용매열 합성법, 마이크로웨이법 및 초음파 합성법 중 어느 하나일 수 있다.The step a may be any one of a low temperature colloidal method, solvent thermal synthesis method, microwave method and ultrasonic synthesis method.
상기 용액 전구체는, 상기 이성분계 나노입자에 포함되지 않은 CI(G)S계 단일원소를 적어도 하나 포함할 수 있다.The solution precursor may include at least one CI (G) S-based single element not included in the binary nanoparticle.
상기 용매는, 알코올계 용매일 수 있다.The solvent may be an alcohol solvent.
상기 알코올계 용매는, 에탄올, 메탄올, 펜탄올, 프로판올 및 부탄올로 이루어진 군으로부터 선택된 어느 하나일 수 있다.The alcohol solvent may be any one selected from the group consisting of ethanol, methanol, pentanol, propanol and butanol.
상기 킬레이트제는, 모노에탄올아민(MEA), 디에탄올아민(DEA), 트리에탄올아민(TEA), 에틸렌디아민, 에틸렌디아민아세트산(EDTA), 니트릴로트리아세트산(NTA), 하이드록시에틸렌디아민트리아세트산(HEDTA), 글리콜-비스(2-아미노에틸에테르)-N,N,N',N'-테트라아세트산(GEDTA), 트리에틸렌테트라아민헥사아세트산(TTHA), 하이드록시에틸이미노디아세트산(HIDA) 및 디하이드록시에틸글리신(DHEG)으로 이루어진 군으로부터 선택된 어느 하나일 수 있다.The chelating agent is monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), ethylenediamine, ethylenediamineacetic acid (EDTA), nitrilotriacetic acid (NTA), hydroxyethylenediaminetriacetic acid (HEDTA ), Glycol-bis (2-aminoethylether) -N, N, N ', N'-tetraacetic acid (GEDTA), triethylenetetraamine hexaacetic acid (TTHA), hydroxyethyliminodiacetic acid (HIDA) and di It may be any one selected from the group consisting of hydroxyethyl glycine (DHEG).
상기 단계 b는, 상기 슬러리 성분이 혼합 및 분산되도록 초음파 처리하는 단계를 더 포함할 수 있다.The step b may further comprise the step of sonicating the slurry components to be mixed and dispersed.
상기 단계 c는, 숙성 동안 초음파 처리 단계를 더 포함할 수 있다.Step c may further comprise an ultrasonic treatment step during aging.
상기 단계 d의 비진공 코팅은, 스프레이법, 초음파 스프레이법, 스핀코팅법, 닥터블레이드법, 스크린 인쇄법 및 잉크젯 프린팅법 중 어느 하나로 수행할 수 있다.The non-vacuum coating of step d may be performed by any one of a spray method, an ultrasonic spray method, a spin coating method, a doctor blade method, a screen printing method, and an inkjet printing method.
상기 단계 d는, 코팅 후 건조하는 단계를 더 포함할 수 있다.Step d may further include a step of drying after coating.
상기 단계 d는, 상기 코팅 및 건조 단계를 순차적으로 반복하여 복수 회 수행할 수 있다.The step d may be performed a plurality of times by sequentially repeating the coating and drying step.
상기 단계 e는, 500∼530℃의 기판 온도에서 30∼60분간 수행할 수 있다.
Step e may be performed at a substrate temperature of 500 to 530 ° C. for 30 to 60 minutes.
상기 목적을 달성하기 위한 본 발명의 이성분계 나노입자를 이용한 CI(G)S계 박막은, 태양전지의 광흡수층으로 이용되는 CI(G)S계 박막으로서, 상기 CI(G)S계 박막은, CI(G)S계의 이성분계 나노입자 및 CI(G)S계 단일원소를 적어도 하나 포함하는 용액 전구체를 포함하는 하이브리드형 슬러리를 5일 내지 10일 동안 숙성시킨 후 비진공 코팅된 박막일 수 있다.
The CI (G) S based thin film using the binary nanoparticles of the present invention for achieving the above object is a CI (G) S based thin film used as a light absorption layer of a solar cell, the CI (G) S based thin film , A hybrid slurry comprising a solution precursor including at least one CI (G) S-based two-component nanoparticles and a CI (G) S-based single element and then aged for 5 to 10 days, followed by a non-vacuum coated thin film Can be.
상기 목적을 달성하기 위한 본 발명의 태양전지는, CI(G)S계 박막을 광흡수층으로 이용하는 태양전지로서, 상기 CI(G)S계 박막은 CI(G)S계의 이성분계 나노입자 및 CI(G)S계 단일원소를 적어도 하나 포함하는 용액 전구체를 포함하는 하이브리드형 슬러리를 5일 내지 10일 동안 숙성시킨 후 비진공 코팅된 박막일 수 있다.The solar cell of the present invention for achieving the above object is a solar cell using a CI (G) S-based thin film as the light absorption layer, the CI (G) S-based thin film is a binary component nanoparticles of CI (G) S-based and The hybrid slurry including a solution precursor including at least one CI (G) S-based single element may be non-vacuum coated thin film after aging for 5 to 10 days.
본 발명은 이성분계 나노입자와 용액 전구체를 포함한 슬러리를 코팅하기 전에 5일 내지 10일 동안 숙성시킴으로써 CI(G)S계 태양전지 박막 제조 시 우수한 재현성 확보가 가능하고, 따라서 생산된 박막의 신뢰도를 향상시킬 수 있다. According to the present invention, it is possible to secure excellent reproducibility in manufacturing a CI (G) S based solar cell thin film by aging for 5 to 10 days before coating the slurry including the binary nanoparticles and the solution precursor, thus improving the reliability of the thin film produced. Can be improved.
또한, 이성분계 나노입자와 용액 전구체를 포함한 슬러리를 사용하여 비진공 코팅을 함으로써 불순물을 최소화하여 기공을 줄이고, 입자성장을 향상시켜 박막의 구조를 치밀화할 수 있어, 박막 태양전지의 광흡수층으로 사용시 박막 태양전지의 효율을 향상시킬 수 있다. In addition, non-vacuum coating using slurry containing binary nanoparticles and solution precursor minimizes impurities, reduces pores, improves particle growth, and makes the structure of thin films thin, so that it can be used as a light absorption layer of thin film solar cells. The efficiency of the thin film solar cell can be improved.
도 1은 본 발명의 실시예 1에 따라 제조된 CIS계 박막 표면의 SEM 이미지이다.
도 2는 본 발명의 실시예 1에 따라 제조된 CIS계 박막을 이용한 태양전지의 효율곡선이다. 1 is an SEM image of the surface of a CIS-based thin film prepared according to Example 1 of the present invention.
2 is an efficiency curve of a solar cell using a CIS-based thin film prepared according to Example 1 of the present invention.
이하 본 발명에 따른 CI(G)S계 박막 제조방법을 구체적으로 설명한다.Hereinafter, a method of manufacturing a CI (G) S-based thin film according to the present invention will be described in detail.
여기서, CI(G)S계 박막이란, CIS계 또는 CIGS계 박막을 의미하는 것으로 정의한다.Here, CI (G) S-based thin film is defined as meaning CIS-based or CIGS-based thin film.
본 발명의 CI(G)S계 박막의 제조방법은, CI(G)S계의 이성분계 나노입자 및 용액 전구체를 포함한 슬러리를 제조한 후 이를 비진공 코팅하고 열처리하여 치밀한 CI(G)S계 박막을 제조할 수 있다. 구체적인 방법은 아래에서 설명한다.In the method for producing a CI (G) S-based thin film of the present invention, after preparing a slurry including a CI (G) S-based bicomponent nanoparticles and a solution precursor, a non-vacuum-coated and heat-treated it is a dense CI (G) S-based Thin films can be prepared. The specific method is described below.
우선, CI(G)S계 이성분계 나노입자를 제조한다(단계 a).First, CI (G) S-based bicomponent nanoparticles are prepared (step a).
상기 이성분계 나노입자는 IB-ⅢA-ⅥA족 화합물 반도체를 구성하는 원소 중 두 가지 성분으로 이루어지는 나노입자를 의미한다. 예를 들면, Cu-Se, In-Se, Ga-Se, Cu-S, In-S, Ga-S 조합의 이성분계 나노입자 등을 들 수 있다. 더 바람직하게는, Cu-Se는 CuSe, Cu2Se, 또는 Cu2-xSe(0<x<1)일 수 있고, In-Se는 In2Se3일 수 있고, Ga-Se는 Ga2Se3일 수 있고, Cu-S는 CuS 또는 Cu2-xS(0<x<1)일 수 있고, In-S는 InS 또는 In2S3일 수 있고, Ga-S는 GaS 또는 Ga2S3일 수 있다. The two-component nanoparticles refer to nanoparticles composed of two components among the elements constituting the IB-IIIA-VIA compound semiconductor. For example, bicomponent nanoparticles of Cu-Se, In-Se, Ga-Se, Cu-S, In-S, and Ga-S combinations may be mentioned. More preferably, Cu-Se may be CuSe, Cu 2 Se, or Cu 2-x Se (0 <x <1), In-Se may be In 2 Se 3 , and Ga-Se is Ga 2 Se 3 , Cu-S may be CuS or Cu 2-x S (0 <x <1), In-S may be InS or In 2 S 3 , and Ga-S may be GaS or Ga 2 S 3 can be.
상기 이성분계 나노입자는 저온 콜로이달 방법, 용매열 합성법, 마이크로웨이법, 초음파 합성법 등 본 발명이 속하는 기술 분야에서 알려진 방법에 따라 제조될 수 있다.The bicomponent nanoparticles can be prepared according to methods known in the art, such as low temperature colloidal method, solvent thermal synthesis method, microwave method, ultrasonic synthesis method.
다음으로, 상기 이성분계 나노입자와 용액 전구체를 포함하는 하이브리드형 슬러리를 제조한다(단계 b).Next, to prepare a hybrid slurry containing the two-component nanoparticles and a solution precursor (step b).
상기 슬러리는 단계 a에서 제조한 CIS계의 이성분계 나노입자, 전구체 용액, 용매 및 킬레이트제를 혼합하여 제조한다.The slurry is prepared by mixing the CIS-based bicomponent nanoparticles prepared in step a, a precursor solution, a solvent and a chelating agent.
여기서, 상기 용액 전구체는 CIS 또는 CIGS 박막을 형성하기 위한 원소를 포함하는 용액을 뜻하고, 상기 이성분계 나노입자에 포함되지 않은 원소를 포함하되, CIS 또는 CIGS 박막 구성의 비율에 부합하도록 제조한다. 즉, 나노입자가 Cu-Se이면 용액 전구체는 염화물이나 아세테이트염인 In 전구체를 킬레이트제로 용해시켜 제조한 후 나노입자와 혼합하여 슬러리를 제조한다.Here, the solution precursor means a solution containing an element for forming a CIS or CIGS thin film, and includes an element not included in the binary nanoparticles, and is prepared to meet the ratio of CIS or CIGS thin film composition. That is, when the nanoparticles are Cu-Se, the solution precursor is prepared by dissolving an In precursor, which is a chloride or an acetate salt, with a chelating agent, followed by mixing with the nanoparticles to prepare a slurry.
상기 용매는 메탄올, 에탄올, 펜탄올, 프로판올, 부탄올 등의 알코올계 용매를 적용할 수 있다.The solvent may be an alcohol solvent such as methanol, ethanol, pentanol, propanol, butanol and the like.
상기 킬레이트제(chelating agent)는 그 자체로서 점도를 가지므로 바인더로 사용할 수 있다. 이성분계 나노입자를 용액 전구체와 사용하기 위해서는 반드시 킬레이트제를 통해 나노입자와 금속 이온을 결합시켜줘야 하고, 따라서 박막이 치밀화되어 매끄럽게 된다. 또한, 킬레이트제의 슬러리 내 비율은 상기 용액 전구체의 킬레이팅이 가능한 몰비율로 첨가한다.The chelating agent has a viscosity as such and can be used as a binder. In order to use the binary nanoparticles with a solution precursor, the nanoparticles and the metal ions must be combined through a chelating agent, and thus the thin film becomes denser and smooth. In addition, the ratio of the chelating agent in the slurry is added at a molar ratio capable of chelating the solution precursor.
킬레이트제는, MEA(monoethanolamine), DEA(diethanolamine), TEA(triethanolamine), 에틸렌디아민(ethylenediamine), EDTA(ethylenediaminetetraacetic acid), NTA(nitrilotriacetic acid), HEDTA(hydroxyethyl ethylenediamine triacetic acid), GEDTA(glycol ether diamine tetraacetic acid), TTHA(triethylene tetraamine hexaacetic acid), HIDA(hydroxyethyl iminodiacetic acid), DHEG(dihydroxy ethyl glycine) 등을 적용할 수 있다.Chelating agents include monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), ethylenediamine (ethylenediamine), ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), hydroxyethyl ethylenediamine triacetic acid (HEDTA), and glycol ether diamine (GEDTA). tetraacetic acid), TTHA (triethylene tetraamine hexaacetic acid), HIDA (hydroxyethyl iminodiacetic acid), DHEG (dihydroxy ethyl glycine) and the like can be applied.
그러나 본 발명의 범위가 여기에 한정되지 않으며 CI(G)S계 박막을 형성하는 나노입자와 금속이온을 킬레이트하여 화합물을 형성할 수 있는 리간드인 킬레이트제는 본 발명의 범주 내에서 모두 적용할 수 있다.However, the scope of the present invention is not limited thereto, and the chelating agent, which is a ligand capable of chelating the nanoparticles and the metal ions that form the CI (G) S-based thin film, to form a compound, may be applied within the scope of the present invention. have.
이때, 상기 슬러리의 농도를 조절하기 위해 CI(G)S계 화합물 나노입자의 비율을 조절할 수 있고, 상기 슬러리의 점도 및 킬레이팅 정도를 조절하기 위하여 킬레이트제의 비율을 조절할 수 있다.In this case, the ratio of the CI (G) S-based compound nanoparticles may be adjusted to adjust the concentration of the slurry, and the ratio of the chelating agent may be adjusted to adjust the viscosity and chelating degree of the slurry.
상기 슬러리는 분산과 혼합을 위해 초음파처리를 할 수 있다.The slurry may be sonicated for dispersion and mixing.
다음으로, 상기 하이브리드형 슬러리를 5일 내지 10일 동안 숙성한다(단계 c).Next, the hybrid slurry is aged for 5 to 10 days (step c).
본 발명에 따른 가장 중요한 기술적 특징은 하이브리드형 슬러리를 기판 상에 코팅하기 전에 숙성시키는 것이다. 하이브리드형 슬러리를 숙성시킨 후 코팅함으로써, 박막의 태양광 흡수 효율과 매우 밀접한 관련이 있는 Cu/In의 비와 박막 두께를 최적화시킬 수 있고, 여러 번 반복 실험에도 재현성이 우수하다. The most important technical feature according to the invention is the aging of the hybrid slurry prior to coating on the substrate. By aging and coating the hybrid slurry, it is possible to optimize the Cu / In ratio and the thickness of the thin film, which are closely related to the solar absorption efficiency of the thin film, and have excellent reproducibility even in the repeated experiments.
본 발명에 따른 단계 c의 숙성 기간은 5일 내지 10일이어야 하고, 바람직하게는 7일이다. 숙성기간이 5일 미만이면, Cu/In의 비가 최고 효율을 나타내는 0.9와 비교하여 현저히 낮고, 10일을 초과하면 숙성 기간이 길어져 전체 공정 시간의 장기화를 초래할 수 있다. The maturation period of step c according to the invention should be 5 days to 10 days, preferably 7 days. If the aging period is less than 5 days, the ratio of Cu / In is significantly lower than 0.9, which shows the highest efficiency. If the aging period is longer than 10 days, the aging period may be longer, resulting in a prolonged process time.
바람직하게는, 숙성 기간 동안 초음파 처리하는 단계를 더 포함할 수 있다. 초음파를 처리함으로써 슬러리 내 입자의 효과적인 분산을 달성할 수 있다.
Preferably, the method may further include sonicating during the aging period. By sonication, effective dispersion of the particles in the slurry can be achieved.
이후, 상기 하이브리드형 슬러리를 기판에 비진공 코팅하여 CI(G)S계 박막을 형성한다(단계 d).Thereafter, the hybrid slurry is non-vacuum-coated on the substrate to form a CI (G) S-based thin film (step d).
본 발명에서 CI(G)S계 박막 형성은 비진공 코팅에 의해 수행되는 것을 특징으로 한다. 비진공 코팅을 수행하는 방법으로는 스프레이법, 초음파 스프레이법, 스핀코팅법, 닥터블레이드법, 스크린 인쇄법, 잉크젯 프린팅법 등 본 발명이 속하는 기술 분야에서 잘 알려진 비진공 코팅법을 모두 적용할 수 있다. 이와 같은 비진공 코팅법을 적용함으로써 제조 비용을 절감할 수 있다.CI (G) S-based thin film formation in the present invention is characterized in that it is performed by a non-vacuum coating. The non-vacuum coating method may be applied to all of the non-vacuum coating methods well known in the art, such as spray method, ultrasonic spray method, spin coating method, doctor blade method, screen printing method and inkjet printing method. have. By applying such a non-vacuum coating method, manufacturing cost can be reduced.
상기 코팅 후에는 건조 과정을 수행하며, 이를 통해, 상기 용매를 제거할 수 있다.After the coating is carried out a drying process, through which the solvent can be removed.
상기 비진공 코팅 및 건조 과정을 반복 수행하여 목적하는 두께의 CI(G)S계 박막을 형성할 수 있다. 이때, 반복 횟수는 경우에 따라 다르나 2회 내지 3회 수행하는 것이 바람직하다.
The non-vacuum coating and drying process may be repeated to form a CI (G) S-based thin film having a desired thickness. At this time, although the number of repetitions varies depending on the case, it is preferable to perform 2 to 3 times.
최종적으로, 상기 단계 d에서 형성된 CI(G)S계 박막에 대해 셀렌화 열처리 공정을 수행한다(단계 e).Finally, the selenization heat treatment process is performed on the CI (G) S-based thin film formed in step d (step e).
셀렌화 열처리 공정은 비진공 코팅법에서 필수적인 공정으로, 셀레늄 고체에 열을 가해 증발시켜 형성된 셀레늄 증기를 공급하면서, 상기 박막이 형성된 기판의 온도를 높여 수행할 수 있다. 이에 의해, 상기 단계 d를 거친 전구체 박막에 셀렌화가 이루어지고, 동시에, 박막 내 구조가 최종적으로 치밀화되면서 CI(G)S계 박막이 완성된다.The selenization heat treatment process is an essential process in the non-vacuum coating method. The selenium heat treatment process may be performed by supplying selenium vapor formed by applying heat to the selenium solid and evaporating it to increase the temperature of the substrate on which the thin film is formed. As a result, selenization is performed on the precursor thin film that has passed through step d, and at the same time, the structure of the thin film is finally compacted, thereby completing a CI (G) S-based thin film.
바람직하게는 500∼530℃의 기판 온도에서 30∼60분간 수행할 수 있다.
Preferably it can be performed for 30 to 60 minutes at a substrate temperature of 500 to 530 ℃.
또한, 본 발명은 상기 제조방법에 따라 제조된 CI(G)S계 박막을 제공한다.In addition, the present invention provides a CI (G) S-based thin film prepared according to the manufacturing method.
또한, 본 발명은 상기 CI(G)S계 박막을 광흡수층으로 포함하는 태양전지를 제공한다.
In addition, the present invention provides a solar cell comprising the CI (G) S-based thin film as a light absorption layer.
이하, 본 발명의 바람직한 실시예를 들어 상세히 설명한다.
Hereinafter, a preferred embodiment of the present invention will be described in detail.
실시예 1Example 1
글로브 박스 내에서 CuI 0.286 g을 증류된 피리딘 용매 30 ㎖와 혼합하고, 이를 증류된 메탄올 20 ㎖ 안에 녹아있는 Na2Se 0.094 g와 혼합시켰다. 이는 원자비로 Cu : Se = 2 : 1에 해당하며, 그 후 메탄올/피리딘 혼합물을 0℃ 아이스 배스 안에서 기계적으로 교반하면서 7분 동안 반응시켜 Cu-Se 나노입자를 포함하는 콜로이드를 합성하였다. 상기 콜로이드를 10000 rpm으로 약 10분간 원심분리 후 1분간 초음파 처리를 하고 증류된 메탄올로 세척하였다. 이러한 과정을 반복하여 생산물안의 부산물 및 피리딘을 완전히 제거하여 고순도의 Cu-Se 이성분계 나노입자를 합성하였다.In a glove box, 0.286 g of CuI were mixed with 30 ml of distilled pyridine solvent and it was mixed with 0.094 g of Na 2 Se dissolved in 20 ml of distilled methanol. This corresponds to Cu: Se = 2: 1 in atomic ratio, after which the methanol / pyridine mixture was reacted for 7 minutes with mechanical stirring in an
다음으로, 상기 Cu-Se 나노입자 0.2543g, 인듐 아세테이트 0.5508g, 킬레이트제로서, 모노에탄올아민 0.3406g 및 용매인 메탄올 1.4008g을 혼합한 후, 초음파 처리를 60분간 수행하여 CIS계 하이브리드형 슬러리를 제조하였다. 이때, 원자비로 Cu-Se 이성분계 나노입자 : 인듐 아세테이트 = 1 : 3를 유지하였고, 인듐 아세테이트 : 킬레이트제 = 1 : 3을 유지하였다. 메탄올은 점도에 맞게 조절하여 첨가하였다. Next, 0.2543 g of the Cu-Se nanoparticles, 0.5508 g of indium acetate, and 0.3406 g of monoethanolamine and 1.4008 g of methanol as a solvent were mixed, followed by ultrasonication for 60 minutes to prepare a CIS hybrid slurry. Prepared. At this time, Cu-Se bicomponent nanoparticles: indium acetate = 1: 1 was maintained at an atomic ratio, and indium acetate: chelating agent = 1: 1. Methanol was added to adjust the viscosity.
이후, 제조된 하이브리드형 슬러리를 7일 동안 숙성하였다. 숙성된 하이브리드형 슬러리를 Mo 박막이 증착된 소다라임 유리기판상에 스핀 코팅법을 사용하여 코팅하였다. 이때, 상기 유리 기판의 회전속도는 800rpm, 회전시간은 20초로 설정하였다. 코팅 후, 핫플레이트 상에서 3 단계에 걸친 건조를 수행하였다. 이때, 1 단계 건조는 80℃에서 5분, 2 단계는 120℃에서 5분, 3 단계는 200℃에서 5분 동안 건조하였다. 이와 같은 코팅 및 건조 공정을 3회 반복수행하여 소정의 두께를 갖는 전구체 박막을 형성하였다. Thereafter, the prepared hybrid slurry was aged for 7 days. The mature hybrid slurry was coated on a soda-lime glass substrate on which Mo thin films were deposited using spin coating. At this time, the rotation speed of the glass substrate was set to 800 rpm, the rotation time was 20 seconds. After coating, three stages of drying were performed on a hotplate. At this time, the first stage of drying 5 minutes at 80 ℃, the second stage 5 minutes at 120 ℃, the third stage was dried for 5 minutes at 200 ℃. This coating and drying process was repeated three times to form a precursor thin film having a predetermined thickness.
마지막으로, 기판 온도 530℃에서 Se 증기를 공급하면서 60분간 셀렌화(selenization) 열처리하여 CIS계 박막을 제조하였다.
Finally, a CIS-based thin film was manufactured by selenization heat treatment for 60 minutes while supplying Se vapor at a substrate temperature of 530 ° C.
실시예 1에 따라 제조된 CIS계 박막 표면의 SEM 이미지를 도 1에 나타내었고, 실시예 1에 따라 제조된 CIS계 박막을 이용한 태양전지의 효율곡선을 도 5에 나타내었다. 도 1로부터 확인할 수 있는 바와 같이, 실시예에 따른 CIS계 박막은 입자 성장이 잘 이루어지고, 박막의 치밀화도 향상되었을 뿐 아니라 기공이 거의 관찰되지 않았다.
The SEM image of the surface of the CIS-based thin film prepared according to Example 1 is shown in FIG. 1, and the efficiency curve of the solar cell using the CIS-based thin film prepared according to Example 1 is illustrated in FIG. 5. As can be seen from Figure 1, the CIS-based thin film according to the embodiment is well grown particles, the densification of the thin film is improved as well as almost no pores were observed.
실시예 2~3Examples 2 to 3
재현성 결과를 비교하기 위해, 실시예 1과 동일하게 실시하여 CIS계 박막을 제조하였다.
In order to compare the reproducibility results, a CIS-based thin film was prepared in the same manner as in Example 1.
실시예 4Example 4
5일의 숙성 기간을 거친 것을 제외하고는, 실시예 1과 동일하게 실시하여 CIS계 박막을 제조하였다.
A CIS-based thin film was prepared in the same manner as in Example 1 except that the aging period of 5 days was passed.
실시예 5Example 5
재현성 결과를 비교하기 위해, 실시예 4와 동일하게 실시하여 CIS계 박막을 제조하였다.
In order to compare the reproducibility results, a CIS-based thin film was prepared in the same manner as in Example 4.
비교예 1Comparative Example 1
3일의 숙성 기간을 거친 것을 제외하고는, 실시예 1과 동일하게 실시하여 CIS계 박막을 제조하였다.
A CIS-based thin film was prepared in the same manner as in Example 1 except that the aging period of 3 days was passed.
비교예 2Comparative Example 2
재현성 결과를 비교하기 위해, 비교예 1과 동일하게 실시하여 CIS계 박막을 제조하였다.
In order to compare the reproducibility results, a CIS-based thin film was prepared in the same manner as in Comparative Example 1.
비교예 3Comparative Example 3
숙성 기간을 거치지 않고, 하이브리드형 슬러리를 기판 상에 바로 코팅한 것을 제외하고는, 실시예 1과 동일하게 실시하여 CIS계 박막을 제조하였다.
A CIS-based thin film was prepared in the same manner as in Example 1, except that the hybrid slurry was directly coated on a substrate without passing through a aging period.
비교예 4Comparative Example 4
재현성 결과를 비교하기 위해, 비교예 3과 동일하게 실시하여 CIS계 박막을 제조하였다.
In order to compare the reproducibility results, a CIS-based thin film was prepared in the same manner as in Comparative Example 3.
실시예 1 내지 5 및 비교예 1 내지 4에서의 조건 및 결과를 하기 표 1에 나타냈다. The conditions and results in Examples 1 to 5 and Comparative Examples 1 to 4 are shown in Table 1 below.
()Thin film thickness
()
일반적으로 Cu/In 비가 0.9에 가까워질수록, 박막 두께가 약 1.5∼2.0 ㎛ 범위 이내일 경우, 태양광 흡수층의 효율의 최적화되는 것으로 알려져 있다. 상기 표 1로부터, 숙성 단계가 추가된 실시예 1 내지 3 및 실시예 4와 5의 결과로부터 재현성이 우수함이 입증되었고, 숙성 기간이 7일(실시예 1 내지 3) 및 5일(실시예 4 및 5)인 경우, 숙성 기간이 3일(비교예 1 및 2), 그리고 0일(비교예 3 및 4)인 경우에 비해 제조된 박막의 효율이 더 높았음을 확인할 수 있다.
In general, as the Cu / In ratio approaches 0.9, it is known that the efficiency of the solar absorption layer is optimized when the thin film thickness is within the range of about 1.5 to 2.0 mu m. From Table 1, it was proved that the reproducibility is excellent from the results of Examples 1 to 3 and Examples 4 and 5 to which the aging step was added, and the aging period was 7 days (Examples 1 to 3) and 5 days (Example 4 And 5), it can be seen that the efficiency of the prepared thin film was higher than the aging period of 3 days (Comparative Examples 1 and 2) and 0 days (Comparative Examples 3 and 4).
이상 본 발명을 바람직한 실시예에 대해서 설명하였으나, 본 발명은 상술한 특정 실시예에 한정되는 것은 아니며, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자라면 그 기술적 사상을 벗어나지 않고 다양하게 변형 실시할 수 있을 것이다. 따라서 본 발명의 권리범위는 특정 실시예가 아니라, 첨부된 특허청구범위에 의해 정해지는 것으로 해석되어야 한다.While the present invention has been described with respect to preferred embodiments, the present invention is not limited to the above-described specific embodiments, and those skilled in the art to which the present invention pertains have various modifications without departing from the technical spirit. You can do it. Accordingly, the scope of the present invention should be construed as being determined not by the specific embodiments but by the appended claims.
Claims (15)
상기 이성분계 나노입자, CI(G)S계 원소를 포함하는 용액 전구체, 용매 및 킬레이트제를 혼합하여 하이브리드형 슬러리를 제조하는 단계(단계 b);
상기 하이브리드형 슬러리를 5일 내지 10일 동안 숙성하는 단계(단계 c);
숙성된 하이브리드형 슬러리를 비진공 코팅하여 CI(G)S계 박막을 형성하는 단계(단계 d); 및
상기 형성된 CI(G)S 박막에 셀렌화 열처리하는 단계(단계 e)를 포함하는 CI(G)S계 박막의 제조방법.
Preparing a bicomponent nanoparticle having a CI (G) S system (step a);
Preparing a hybrid slurry by mixing the binary nanoparticles, a solution precursor containing a CI (G) S-based element, a solvent, and a chelating agent (step b);
Aging the hybrid slurry for 5 to 10 days (step c);
Non-vacuum coating the aged hybrid slurry to form a CI (G) S-based thin film (step d); And
Method of producing a CI (G) S-based thin film comprising the step (step e) selenization heat treatment to the formed CI (G) S thin film.
상기 이성분계 나노입자는,
Cu-Se, In-Se, Ga-Se, Cu-S, In-S 및 Ga-S로 이루어지는 군으로부터 선택되는 어느 하나인 것을 특징으로 하는 CI(G)S계 박막의 제조방법.
The method according to claim 1,
The two-component nanoparticles,
Cu-Se, In-Se, Ga-Se, Cu-S, In-S and Ga-S, any one selected from the group consisting of CI (G) S-based thin film manufacturing method.
상기 단계 a는,
저온 콜로이달 방법, 용매열 합성법, 마이크로웨이법 및 초음파 합성법로 이루어지는 군으로부터 선택되는 어느 하나의 방법에 의하는 것을 특징으로 하는 CI(G)S계 박막의 제조방법.
The method according to claim 1,
The step (a)
A low temperature colloidal method, a solvent thermal synthesis method, a microwave method, and a method for producing a CI (G) S-based thin film, characterized in that any one selected from the group consisting of ultrasonic synthesis method.
상기 용액 전구체는,
상기 이성분계 나노입자에 포함되지 않은 CI(G)S계 단일원소를 적어도 하나 포함하는 것을 특징으로 하는 CI(G)S계 박막의 제조방법.
The method according to claim 1,
The solution precursor,
Method for producing a CI (G) S-based thin film, characterized in that it comprises at least one CI (G) S-based single element not included in the binary nanoparticles.
상기 용매는,
알코올계 용매인 것을 특징으로 하는 CI(G)S계 박막의 제조방법.
The method according to claim 1,
The solvent may be,
Method for producing a CI (G) S-based thin film, characterized in that the alcohol solvent.
상기 알코올계 용매는,
에탄올, 메탄올, 펜탄올, 프로판올 및 부탄올로 이루어진 군으로부터 선택된 어느 하나인 것을 특징으로 하는 CI(G)S계 박막 제조방법.
The method according to claim 5,
The alcohol solvent,
CI (G) S-based thin film manufacturing method, characterized in that any one selected from the group consisting of ethanol, methanol, pentanol, propanol and butanol.
상기 킬레이트제는,
모노에탄올아민(MEA), 디에탄올아민(DEA), 트리에탄올아민(TEA), 에틸렌디아민, 에틸렌디아민아세트산(EDTA), 니트릴로트리아세트산(NTA), 하이드록시에틸렌디아민트리아세트산(HEDTA), 글리콜-비스(2-아미노에틸에테르)-N,N,N',N'-테트라아세트산(GEDTA), 트리에틸렌테트라아민헥사아세트산(TTHA), 하이드록시에틸이미노디아세트산(HIDA) 및 디하이드록시에틸글리신(DHEG)으로 이루어진 군으로부터 선택된 어느 하나인 것을 특징으로 하는 CI(G)S계 박막 제조방법.
The method according to claim 1,
The chelating agent,
Monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), ethylenediamine, ethylenediamineacetic acid (EDTA), nitrilotriacetic acid (NTA), hydroxyethylenediaminetriacetic acid (HEDTA), glycol-bis (2-aminoethyl ether) -N, N, N ', N'-tetraacetic acid (GEDTA), triethylenetetraamine hexaacetic acid (TTHA), hydroxyethyliminodiacetic acid (HIDA) and dihydroxyethylglycine ( DHEG) CI (G) S-based thin film manufacturing method, characterized in that any one selected from the group consisting of.
상기 단계 b는,
상기 슬러리 성분이 혼합 및 분산되도록 초음파 처리하는 단계를 더 포함하는 것을 특징으로 하는 CI(G)S계 박막 제조방법.
The method according to claim 1,
Step b,
CI (G) S-based thin film manufacturing method characterized in that it further comprises the step of ultrasonic treatment so that the slurry components are mixed and dispersed.
상기 단계 c는,
숙성 동안 초음파 처리하는 단계를 더 포함하는 것을 특징으로 하는 CI(G)S계 박막 제조방법.
The method according to claim 1,
The step c)
CI (G) S-based thin film manufacturing method characterized in that it further comprises the step of ultrasonication during aging.
상기 단계 d의 비진공 코팅은,
스프레이법, 초음파 스프레이법, 스핀코팅법, 닥터블레이드법, 스크린 인쇄법 및 잉크젯 프린팅법 중 어느 하나로 수행하는 것을 특징으로 하는 CI(G)S계 박막 제조방법.
The method according to claim 1,
The non-vacuum coating of step d,
CI (G) S-based thin film manufacturing method characterized in that performed by any one of a spray method, ultrasonic spray method, spin coating method, doctor blade method, screen printing method and inkjet printing method.
상기 단계 d는,
코팅 후 건조하는 단계를 더 포함하는 것을 특징으로 하는 CI(G)S계 박막 제조방법.
The method according to claim 1,
Step d is
CI (G) S-based thin film manufacturing method characterized in that it further comprises a step of drying after coating.
상기 단계 d는,
상기 코팅 및 건조 단계를 순차적으로 반복하여 복수 회 수행하는 것을 특징으로 하는 CI(G)S계 박막 제조방법.
The method of claim 11,
Step d is
CI (G) S-based thin film manufacturing method characterized in that the coating and drying steps are performed repeatedly a plurality of times.
상기 단계 e는,
500∼530℃의 기판 온도에서 60∼90분간 수행하는 것을 특징으로 하는 CI(G)S계 박막 제조방법.
The method according to claim 1,
The step (e)
CI (G) S-based thin film manufacturing method characterized in that performed for 60 to 90 minutes at a substrate temperature of 500 ~ 530 ℃.
상기 CI(G)S계 박막은, CI(G)S계의 이성분계 나노입자 및 CI(G)S계 단일원소를 적어도 하나 포함하는 용액 전구체를 포함하는 하이브리드형 슬러리를 5일 내지 10일 동안 숙성시킨 후 코팅된 박막인 CI(G)S계 박막.
As a CI (G) S based thin film used as a light absorption layer of a solar cell,
The CI (G) S-based thin film is a hybrid slurry including a solution precursor including at least one CI (G) S-based bicomponent nanoparticle and a CI (G) S-based single element for 5 days to 10 days. CI (G) S based thin film which is a thin film coated after aging.
상기 CI(G)S계 박막은 CI(G)S계의 이성분계 나노입자 및 CI(G)S계 단일원소를 적어도 하나 포함하는 용액 전구체를 포함하는 하이브리드형 슬러리를 5일 내지 10일 동안 숙성시킨 후 코팅된 박막인 태양전지.
As a solar cell using a CI (G) S-based thin film as a light absorption layer,
The CI (G) S based thin film is a hybrid slurry including a solution precursor including at least one CI (G) S based binary component nanoparticle and a CI (G) S based single element for 5 to 10 days. Solar cell is a thin film after coating.
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| CN114904744A (en) * | 2022-04-14 | 2022-08-16 | 南京邮电大学 | Blade coating method for preparing copper indium selenium film and application thereof |
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| KR20090110090A (en) * | 2008-04-17 | 2009-10-21 | 엘지전자 주식회사 | Synthesis method for indium selenide nanoparticles by ultrasonic waves and a compound semiconductor solar cell comprising the said |
| KR101064521B1 (en) * | 2009-03-06 | 2011-09-14 | 한국과학기술연구원 | CIGS fine particles and Method for preparing the same |
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| CN114904744A (en) * | 2022-04-14 | 2022-08-16 | 南京邮电大学 | Blade coating method for preparing copper indium selenium film and application thereof |
| CN114904744B (en) * | 2022-04-14 | 2023-07-04 | 南京邮电大学 | Knife coating method for preparing copper indium selenium film and application thereof |
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