KR100854247B1 - Manufacture method for absorber layer of thin film solar cell - Google Patents
Manufacture method for absorber layer of thin film solar cell Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000010409 thin film Substances 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 239000006096 absorbing agent Substances 0.000 title description 2
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010439 graphite Substances 0.000 claims abstract description 14
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003085 diluting agent Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 239000011593 sulfur Substances 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims abstract description 4
- 238000010521 absorption reaction Methods 0.000 claims abstract 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract 2
- UODXCYZDMHPIJE-UHFFFAOYSA-N menthanol Chemical compound CC1CCC(C(C)(C)O)CC1 UODXCYZDMHPIJE-UHFFFAOYSA-N 0.000 claims description 24
- 230000003647 oxidation Effects 0.000 claims description 23
- 238000007254 oxidation reaction Methods 0.000 claims description 23
- 239000002250 absorbent Substances 0.000 claims description 20
- 230000002745 absorbent Effects 0.000 claims description 20
- 238000005486 sulfidation Methods 0.000 claims description 18
- 239000001856 Ethyl cellulose Substances 0.000 claims description 9
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 9
- 229920001249 ethyl cellulose Polymers 0.000 claims description 9
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 9
- -1 phosphate ester Chemical class 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000007639 printing Methods 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 239000005361 soda-lime glass Substances 0.000 claims description 3
- 238000004544 sputter deposition Methods 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 10
- 239000010410 layer Substances 0.000 description 60
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 25
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 9
- 229910052951 chalcopyrite Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- RBORURQQJIQWBS-QVRNUERCSA-N (4ar,6r,7r,7as)-6-(6-amino-8-bromopurin-9-yl)-2-hydroxy-2-sulfanylidene-4a,6,7,7a-tetrahydro-4h-furo[3,2-d][1,3,2]dioxaphosphinin-7-ol Chemical compound C([C@H]1O2)OP(O)(=S)O[C@H]1[C@@H](O)[C@@H]2N1C(N=CN=C2N)=C2N=C1Br RBORURQQJIQWBS-QVRNUERCSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000000280 densification Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- LCUOIYYHNRBAFS-UHFFFAOYSA-N copper;sulfanylideneindium Chemical compound [Cu].[In]=S LCUOIYYHNRBAFS-UHFFFAOYSA-N 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229910001369 Brass Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 1
- 229910000058 selane Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical group O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- H—ELECTRICITY
- 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
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
-
- H—ELECTRICITY
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- 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
-
- 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
도 1은 본 발명의 일 실시예에 의한 박막 태양전지 흡수층의 제조 방법을 보인 흐름도이다.1 is a flowchart illustrating a method of manufacturing a thin film solar cell absorbing layer according to an embodiment of the present invention.
도 2는 본 발명의 실험에 사용된 분말 전구체를 합성하기 위한 반응 조건을 보인 표이다.2 is a table showing the reaction conditions for synthesizing the powder precursor used in the experiment of the present invention.
도 3은 본 발명의 실험에 사용된 CuInS2 페이스트의 배치 테이블이다.3 is a batch table of CuInS 2 paste used in the experiment of the present invention.
도 4는 용매열 반응에 의해 합성된 CuInS2와 CuS 입자의 XRD 패턴(x는 알려지지 않은 피크)을 보인 그래프이다.4 is a graph showing an XRD pattern (x is an unknown peak) of CuInS 2 and CuS particles synthesized by solvent thermal reaction.
도 5는 구형 CuInS2 나노입자와 CuS 다면체 화합물의 SEM 영상이다.5 is an SEM image of spherical CuInS 2 nanoparticles and a CuS polyhedron compound.
도 6은 황화처리 후 CuS가 도핑된 CuInS2 층의 XRD 패턴을 보인 그래프이다.6 is a graph showing an XRD pattern of CuInS 2 layer doped with CuS after sulfidation.
도 7은 황화처리 후 CuS가 도핑된 CuInS2 층의 SEM 영상이고, (a)는 단면 영상이고, (b)는 표면 영상이다.7 is an SEM image of a CuInS 2 layer doped with CuS after sulfidation, (a) is a cross-sectional image, and (b) is a surface image.
도 8은 가열판에서 300℃로 산화된 층과 산화처리 후 황화처리된 층의 XRD 패턴을 보인 그래프로서, (a)는 산화처리된 것이고, (b)는 산화처리 후의 황화처리된 것이다.8 is a graph showing an XRD pattern of a layer oxidized at 300 ° C. and a sulfided layer after oxidation, in which (a) is oxidized and (b) is sulfided after oxidation.
도 9는 CuS가 도핑된 CuInS2 층의 SEM 영상이고, (a)와 (b)는 각각 산화처리된 단면 영상이과 표면 영상이고, (c)와 (d)는 각각 산화처리 후에 황화처리된 단면 영상과 표면 영상이다.9 is an SEM image of CuS doped CuInS 2 layer, (a) and (b) are oxidized cross-sectional images and surface images, respectively, and (c) and (d) are sulfided cross sections after oxidation, respectively. Image and surface image.
[1] J. Klaer, I. Luck, A. Boden, R. Klenk, I.G. Perez, R. Scheer, "Thin Solid Films", 431-432 (2003) 534.[1] J. Klaer, I. Luck, A. Boden, R. Klenk, I.G. Perez, R. Scheer, "Thin Solid Films", 431-432 (2003) 534.
[2] J. Klaer, K. Siemer, I.Luck, D.Brㅴunig, "Thin Solid Films", 387 (2001) 169.[2] J. Klaer, K. Siemer, I. Luck, D. Brünig, "Thin Solid Films", 387 (2001) 169.
[3] C. Eberspacher, C. Fredric, K. Pauls, J. Serra, "Thin Solid Films", 387 (2001) 18.[3] C. Eberspacher, C. Fredric, K. Pauls, J. Serra, "Thin Solid Films", 387 (2001) 18.
[4] M. Kaelin, D. Rudmann, A.N. Tiwari, Sol. Energy 77 (2004) 749.[4] M. Kaelin, D. Rudmann, A.N. Tiwari, Sol. Energy 77 (2004) 749.
[5] V.K. Kapur, M. Fisher, R. Roe, in: R. Noufi, R.W. Birkmire, D. Lincot, H.W. Schock (Eds.), "Materials Research Society Symposium Proceeding", vol. 668, San Francisco, USA, 2001, p.H2.6.[5] V.K. Kapur, M. Fisher, R. Roe, in: R. Noufi, R.W. Birkmire, D. Lincot, H.W. Schock (Eds.), "Materials Research Society Symposium Proceeding", vol. 668, San Francisco, USA, 2001, p. H2.6.
[6] K.H. Kim, Y.G. Chun, K.H. Yoon, B.O.Park, Mater. Sci. Forum 449-452 (2004) 273.[6] K.H. Kim, Y.G. Chun, K.H. Yoon, B. O. Park, Mater. Sci. Forum 449-452 (2004) 273.
[7] Y.G. Chun, K.H. Kim, K.H. Yoon, "Thin Solid Films", 480-481 (2004) 46.[7] Y.G. Chun, K.H. Kim, K.H. Yoon, "Thin Solid Films", 480-481 (2004) 46.
[8] F.O. Adurodija, J. Song, I.O. Asia, K.H. Yoon, Sol. Energy Mater. Sol. Cells 58 (1999) 287.[8] F.O. Adurodija, J. Song, I.O. Asia, K.H. Yoon, Sol. Energy Mater. Sol. Cells 58 (1999) 287.
본 발명은 박막 태양전지에 관한 것으로, 특히 페이스트 코팅법을 이용하여 CuInS2 흡수층을 제조하고 황화처리를 하기 전에 산화처리를 공정을 도입하여 아주 치밀한 CuInS2 층을 형성하기에 적당하도록 한 박막 태양전지 흡수층의 제조 방법에 관한 것이다.The present invention relates to a thin film solar cell, and in particular, to prepare a CuInS 2 absorbent layer by using a paste coating method and to perform a oxidation process before sulfiding, a thin film solar cell suitable for forming a very dense CuInS 2 layer. It relates to a method for producing an absorbent layer.
일반적으로 태양전지는 태양 에너지를 전기에너지로 변환할 목적으로 제작된 광전지이다.In general, solar cells are photovoltaic cells manufactured for the purpose of converting solar energy into electrical energy.
CuInS2(황화구리인듐)은 1.5eV의 밴드갭과 비독성 성분 때문에 박막 태양 전지를 위한 훌륭한 흡수 물질 중의 하나이다. 태양 전지를 위한 최고의 효율은 주로 진공기반법(vacuum-based methods)(종래기술의 문헌 정보 [1] 및 [2] 참조, 이하에서는 문헌 정보의 번호만을 기재함)에 의해 얻어진다.CuInS 2 (copper indium sulfide) is one of the good absorbing materials for thin film solar cells because of its 1.5 eV bandgap and non-toxic components. The best efficiency for solar cells is obtained mainly by vacuum-based methods (see prior art document information [1] and [2], hereinafter only describing the number of document information).
그러나 간단하고 저렴한 증착(deposition) 방법은 공정의 복잡함과 태양 전지의 비용을 감소시킴으로서 얻어진다.However, a simple and inexpensive deposition method is obtained by reducing the complexity of the process and the cost of the solar cell.
최근의 나노 입자 합성과 처리 방법의 진보는 입자 형태의 전구체(precursor)를 비진공 상태에서 증착 및 소결 작업을 할 수 있도록 이끌었다([3], [4]).Recent advances in nanoparticle synthesis and processing methods have led to the deposition and sintering of precursors in the form of particles in a non-vacuum state [3] and [4].
이러한 접근 아이디어는 간단하고 빠른 기술에 의해 대규모 영역에서 적절한 양의 단일 층을 증착할 수 있도록 하였다.This approach idea enabled simple and fast techniques to deposit the right amount of single layer in large areas.
미세한 전구체는 스프레이(spraying), 딥 코팅(dip coating) 및 페이스트 코딩(paste coating)과 같은 간단한 기술을 이용하여 박막층 내로 증착될 수 있다. 특히, 페이스트 코팅법은 Cu(In,Ga)Se2(copper indium gallium selenide, CIGS, 구리인듐갈륨셀레늄) 물질에서 13%에 이르는 높은 셀 효율 때문에 최근에 주목할 만한 관심을 끌고 있다.Fine precursors may be deposited into the thin film layer using simple techniques such as spraying, dip coating and paste coating. In particular, the paste coating method has recently attracted notable attention due to the high cell efficiency of up to 13% in Cu (In, Ga) Se 2 (copper indium gallium selenide, CIGS, copper indium gallium selenium) materials.
그러나 공정에서 사용되는 H2Se(셀렌화수소)와 같은 강한 독성의 환원제는 많은 국가의 산업 제조 부문의 응용에서 제한되고 있다. 따라서 이러한 작업에서 CuInS2(황화구리인듐) 층이 스크린 인쇄법(screen printing)에 의해 증착되었고, 그의 치밀화(densification)를 할 필요성이 대두되었다.However, highly toxic reducing agents such as H 2 Se (hydrogen selenide) used in the process are limited in applications in industrial manufacturing sectors in many countries. Thus in this work a CuInS 2 (copper indium sulfide) layer was deposited by screen printing, and the need for its densification has arisen.
이에 본 발명은 상기와 같은 종래의 제반 문제점을 해결하기 위해 제안된 것으로, 본 발명의 목적은 페이스트 코팅법을 이용하여 CuInS2 흡수층을 제조하고 황화처리를 하기 전에 산화처리를 공정을 도입하여 아주 치밀한 CuInS2 층을 형성할 수 있는 박막 태양전지 흡수층의 제조 방법을 제공하는데 있다.Therefore, the present invention has been proposed to solve the above-mentioned conventional problems, and an object of the present invention is to prepare a CuInS 2 absorbent layer using a paste coating method and to introduce a very dense oxidation process before sulfiding. The present invention provides a method for manufacturing a thin film solar cell absorbing layer capable of forming a CuInS 2 layer.
상기와 같은 목적을 달성하기 위하여 본 발명의 일 실시예에 의한 박막 태양전지 흡수층의 제조 방법은,In order to achieve the above object, a method of manufacturing a thin film solar cell absorbing layer according to an embodiment of the present invention,
레진과 분산제를 준비하고, 희석제로 희석시키는 제 1 단계와; 상기 제 1 단계 후 CuInS2와 CuS로 분말 전구체를 구성하고, 상기 분말 전구체를 분쇄하는 제 2 단계와; 상기 제 2 단계 후 상기 전구체 페이스트를 기판에 분포하여 CuS-doped CuInS2 흡수층을 형성시키는 제 3 단계와; 상기 제 3 단계 후 상기 CuS-doped CuInS2 흡수층을 가열판에서 가열하여 공기 중의 산소와 결합되도록 하여 산화처리하는 제 4 단계와; 상기 제 4 단계 후 상기 CuS-doped CuInS2 흡수층을 황 분말이 들어있는 흑연상자에 넣은 후, 흑연상자를 가열하여, 연소된 황 분말이 황 가스(gas)로 되어 CuS-doped CuInS2 흡수층과 결합되도록 하여 황화처리하는 제 5 단계;를 포함하여 수행함을 그 기술적 구성상의 특징으로 한다.Preparing a resin and a dispersant and diluting with a diluent; A second step of constituting a powder precursor with CuInS 2 and CuS after the first step, and pulverizing the powder precursor; A third step of distributing the precursor paste on a substrate after the second step to form a CuS-doped CuInS 2 absorbent layer; A fourth step of oxidizing the CuS-doped CuInS 2 absorbing layer after the third step by heating the heated CuS-doped CuInS 2 layer in a heating plate to combine with oxygen in air; After the fourth step, the CuS-doped CuInS 2 absorbent layer was placed in a graphite box containing sulfur powder, and then the graphite box was heated to combine with the CuS-doped CuInS 2 absorbent layer as sulfur gas. The fifth step of the sulfidation process so as to; characterized in that the technical configuration.
이하, 상기와 같은 본 발명, 박막 태양전지 흡수층의 제조 방법의 기술적 사상에 따른 일 실시예를 도면을 참조하여 설명하면 다음과 같다.Hereinafter, an embodiment according to the present invention as described above, the technical idea of the manufacturing method of the thin film solar cell absorbing layer will be described with reference to the drawings.
도 1은 본 발명의 일 실시예에 의한 박막 태양전지 흡수층의 제조 방법을 보인 흐름도이다.1 is a flowchart illustrating a method of manufacturing a thin film solar cell absorbing layer according to an embodiment of the present invention.
이에 도시된 바와 같이, 레진과 분산제를 준비하고, 희석제로 희석시키는 제 1 단계(ST1)와; 상기 제 1 단계 후 CuInS2(황화구리인듐)와 CuS(황화구리)로 분말 전구체를 구성하고, 상기 분말 전구체를 분쇄하는 제 2 단계(ST2)와; 상기 제 2 단계 후 상기 전구체 페이스트를 기판에 분포하여 CuS-doped CuInS2(황화구리가 도핑된 황화구리인듐) 흡수층을 형성시키는 제 3 단계(ST3)와; 상기 제 3 단계 후 상기 CuS-doped CuInS2 흡수층을 가열판(hotplate)에서 가열하여 공기 중의 산소와 결합되도록 하여 산화처리하는 제 4 단계(ST4)와; 상기 제 4 단계 후 상기 CuS-doped CuInS2 흡수층을 황 분말이 들어있는 흑연상자에 넣은 후, 흑연상자를 가열하여, 연소된 황 분말이 황 가스(gas)로 되어 CuS-doped CuInS2 흡수층과 결합되도록 하여 황화처리하는 제 5 단계(ST5);를 포함하여 수행하는 것을 특징으로 한다.As shown therein, a first step (ST1) of preparing a resin and a dispersant and diluting with a diluent; A second step (ST2) of constituting a powder precursor with CuInS 2 (copper indium sulfide) and CuS (copper sulfide) after the first step, and pulverizing the powder precursor; A third step (ST3) of forming a CuS-doped CuInS 2 (copper sulfide doped copper sulfide) absorbing layer by distributing the precursor paste on a substrate after the second step; A fourth step (ST4) of heating the CuS-doped CuInS 2 absorbent layer after the third step by heating it in a hotplate to combine with oxygen in air; After the fourth step, the CuS-doped CuInS 2 absorbent layer was placed in a graphite box containing sulfur powder, and then the graphite box was heated to combine with the CuS-doped CuInS 2 absorbent layer as sulfur gas. And a fifth step (ST5) of sulfiding to be carried out.
상기 제 1 단계는, 레진으로 에틸셀룰로스(Ethylcellulose)를 사용하고, 분산제로 인산 에스테르(phosphate ester)를 사용하며, 희석제로 디하이드로 테르피네올(Dihydro terpineol)을 사용하는 것을 특징으로 한다.The first step is characterized in that using ethyl cellulose (Ethylcellulose) as a resin, phosphate ester (phosphate ester) as a dispersant, Dihydro terpineol (Dihydro terpineol) as a diluent.
상기 제 1 단계는, 레진인 에틸셀룰로스를 디하이드로 테르피네올에 의해 2 ~ 10%로 희석시키고, 분산제인 인산 에스테르를 디하이드로 테르피네올에 의해 30 ~ 70%로 희석시키는 것을 특징으로 한다.The first step is characterized in that ethyl cellulose, a resin, is diluted to 2 to 10% with dihydro terpineol, and a phosphate ester, a dispersant, is diluted to 30 to 70% with dihydro terpineol.
상기 제 2 단계는, 상기 분말 전구체를 트리플 롤 밀러(triple-roll miller)로 분쇄하는 것을 특징으로 한다.In the second step, the powder precursor is pulverized by a triple-roll miller.
상기 제 2 단계는, Cu(CuInS2) : Cu(CuS) 의 몰비(molar ratio)를 5:2로 설정한 것을 특징으로 한다.The second step is characterized in that the molar ratio of Cu (CuInS 2) to Cu (CuS) is set to 5: 2.
상기 제 3 단계는, 상기 기판(substrate)으로 DC(직류) 스퍼터링(sputtering)에 의해 0.1 ~ 10㎛ 두께로 몰리브덴 층이 코딩된 몰리브덴(Mo) 코팅 소다석회유리(soda lime glass)를 사용한 것을 특징으로 한다.The third step is characterized in that the molybdenum (Mo) coated soda lime glass coated with a molybdenum layer having a thickness of 0.1 ~ 10㎛ by DC (direct current) sputtering (substrate) as a substrate It is done.
상기 제 3 단계는, 상기 CuS-doped CuInS2 흡수층을 페이스트를 이용하여 형성할 때, 에멀젼(emulsion) 두께, 스퀴지(squeegee) 각도, 메시(mesh) 크기, 인쇄 속도, 스냅 오프(snap off) 거리를 포함한 인쇄 매개변수는 상수로 유지한 것을 특징으로 한다.In the third step, when the CuS-doped CuInS 2 absorbing layer is formed by using a paste, an emulsion thickness, a squeegee angle, a mesh size, a printing speed, a snap off distance Print parameters, including, characterized in that kept as a constant.
상기 제 4 단계는, 가열된 가열판(hotplate)이 20 ~ 50분 동안 200 ~ 350℃로 유지되도록 하여, CuS-doped CuInS2 흡수층의 산화처리를 수행하는 것을 특징으로 한다.In the fourth step, the heated hotplate is maintained at 200 to 350 ° C. for 20 to 50 minutes to perform oxidation treatment of the CuS-doped CuInS 2 absorbent layer.
상기 제 5 단계는, 가열된 흑연상자가 50 ~ 70분 동안 500 ~ 600℃로 유지되도록 하여, CuS-doped CuInS2 흡수층의 황화처리를 수행하는 것을 특징으로 한다.In the fifth step, the heated graphite box is maintained at 500 to 600 ° C. for 50 to 70 minutes to perform sulfidation of the CuS-doped CuInS 2 absorbent layer.
상기 제 5 단계는, 상기 황화처리가 불활성 상태의 폐쇄된 흑연 상자 내에서 실행되도록 하는 것을 특징으로 한다.The fifth step is characterized in that the sulfidation is carried out in a closed graphite box in an inert state.
상기 제 5 단계에서 불활성 상태는, 질소 가스를 이용한 것을 특징으로 한다.In the fifth step, the inert state is characterized in that the use of nitrogen gas.
이와 같이 구성된 본 발명에 의한 박막 태양전지 흡수층의 제조 방법의 바람직한 실시예를 첨부한 도면에 의거하여 상세히 설명하면 다음과 같다. 하기에서 본 발명을 설명함에 있어 관련된 공지 기능 또는 구성에 대한 구체적인 설명이 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명을 생략할 것이다. 그리고 후술되는 용어들은 본 발명에서의 기능을 고려하여 정의된 용어들로서, 이는 사용자, 운용자의 의도 또는 판례 등에 따라 달라질 수 있으며, 이에 따라 각 용어의 의미는 본 명세서 전반에 걸친 내용을 토대로 해석되어야 할 것이다.The preferred embodiment of the method for manufacturing a thin film solar cell absorbing layer according to the present invention configured as described above will be described in detail with reference to the accompanying drawings. In the following description of the present invention, detailed descriptions of well-known functions or configurations will be omitted if it is determined that the detailed description of the present invention may unnecessarily obscure the subject matter of the present invention. In addition, terms to be described below are terms defined in consideration of functions in the present invention, which may vary according to intention or precedent of a user or an operator, and thus, the meaning of each term should be interpreted based on the contents throughout the present specification. will be.
먼저 본 발명은 페이스트 코팅법을 이용하여 CuInS2 흡수층을 제조하고 황화처리를 하기 전에 산화처리를 공정을 도입하여 아주 치밀한 CuInS2 층을 형성하고자 한 것이다.First, the present invention intends to form a very dense CuInS 2 layer by preparing an CuInS 2 absorbing layer using a paste coating method and introducing an oxidation process before sulfiding.
본 발명을 상세히 설명하면 다음과 같다.The present invention is described in detail as follows.
1. 개요1. Overview
본 발명에서는 페이스트 코팅법을 이용하여 CuInS2(황화구리인듐) 흡수층이 제조되도록 하였다. 또한 치밀화를 위해서 흡수층에 CuS(황화구리)가 첨가되도록 하였다. 에틸셀룰로스(Ethylcellulose)와 인산 에스테르(phosphate ester)는 각각 레진(resin)과 분산제(dispersant)로 사용되었다. 디하이드로 테르피네올(Dihydro terpineol)은 용매로 사용되었다. CuInS2 흡수층은 흑연상자에서 황화처리가 되었지만 단지 CuS 의 첨가만으로는 치밀화를 이룰 수가 없었다. 그러나 CuS가 도핑된 CuInS2에 먼저 산화처리 과정이 적용되었고, 후에 황화처리를 수행하여 치밀한 CuInS2 흡수층을 얻을 수 있었다. 황동석(Chalcopyrite, 찰코파이라이트) 상이 산화처리에 의해 붕괴되었지만 황화처리에 의해서 다시 황동석(chalcopyrite) 상으로 재구성되었다.In the present invention, a CuInS 2 (copper indium sulfide) absorbing layer was prepared by using a paste coating method. In addition, CuS (copper sulfide) was added to the absorber layer for densification. Ethylcellulose and phosphate esters were used as resins and dispersants, respectively. Dihydro terpineol was used as a solvent. The CuInS 2 absorbent layer was sulfided in the graphite box, but could not be densified simply by adding CuS. However, the CuS doped CuInS 2 was first subjected to an oxidation treatment, and then sulfided to obtain a dense CuInS 2 absorbent layer. The chalcopyrite (chalcopyrite) phase collapsed by oxidation but was reconstructed back to chalcopyrite phase by sulfidation.
이를 위해 단일 상의 구성을 갖는 전구체(precursor)가 거의 치밀화하지 않 고 최종 합금막이 다공질을 갖기 때문에, 본 발명에서는 먼저 조밀층을 준비하기 위한 소결 첨가제로서 CuS 화합물을 사용하였다.For this purpose, since the precursor having a single phase structure is hardly densified and the final alloy film has a porous, in the present invention, a CuS compound was first used as a sintering additive for preparing a dense layer.
다음으로 CuS가 도핑된 CuInS2 (CuS-doped CuInS2) 층의 산화에 의한 치밀화에서 산화처리 효과를 연구했다.Next, the effect of oxidation treatment on densification by oxidation of CuS-doped CuInS 2 (CuS-doped CuInS 2 ) layer was studied.
2. 실험의 상세설명2. Detailed description of the experiment
레진(resin)인 에틸셀룰로스(STD10, 다우 케미컬 사)를 용매인 디하이드로 테르피네올(Dihydro terpineol)에 용해하여 6%의 레진 페이스트를 준비하였다. 다음으로 분산제인 인산 에스테르(RE610, 로디아)를 디하이드로 테르피네올로 50% 희석하였다. 분말 전구체는 CuInS2 와 CuS로 구성되었다.Resin ethylcellulose (STD10, Dow Chemical Co., Ltd.) was dissolved in a solvent of dihydro terpineol (Dihydro terpineol) to prepare a 6% resin paste. Next, the dispersant phosphate ester (RE610, Rhodia) was diluted 50% with dihydro terpineol. The powder precursor was composed of CuInS 2 and CuS.
Cu(CuInS2) : Cu(CuS) 의 몰비(molar ratio)는 5:2 였다.The molar ratio of Cu (CuInS 2) : Cu (CuS ) was 5: 2.
CuInS2 와 CuS는 공개 논문에 기록된 용매열(solvothermal) 방법에 의해 합성되었다([6], [7]).CuInS 2 and CuS were synthesized by the solvothermal method reported in the public literature [6], [7].
이 작업에 사용된 반응 조건은 도 2의 표에 보였다.The reaction conditions used for this work are shown in the table of FIG. 2.
도 2는 본 발명의 실험에 사용된 분말 전구체를 합성하기 위한 반응 조건을 보인 표이다.2 is a table showing the reaction conditions for synthesizing the powder precursor used in the experiment of the present invention.
또한 분말 예비물질은 레진 페이스트와 분산제로 혼합되었고, 연속적인 스크린 인쇄법 공정을 위해 적절한 점도와 유동성을 갖도록 CuInS2 페이스트를 준비하여 트리플 롤 밀러(triple-roll miller)를 사용하여 분쇄하였다.In addition, the powder preliminary material was mixed with the resin paste and the dispersant, and the CuInS 2 paste was prepared and ground using a triple-roll miller to have a viscosity and fluidity suitable for a continuous screen printing process.
배치 테이블은 도 3의 표에 보였다.The batch table is shown in the table in FIG.
도 3은 본 발명의 실험에 사용된 CuInS2 페이스트의 배치 테이블이다.3 is a batch table of CuInS 2 paste used in the experiment of the present invention.
기판(substrate)은 일반적인 DC(직류) 스퍼터링(sputtering)에 의해 약 1㎛ 두께로 몰리브덴 층이 코딩된 몰리브덴(Mo) 코팅 소다석회유리(soda lime glass)를 사용하였다.As a substrate, a molybdenum (Mo) coated soda lime glass in which a molybdenum layer was encoded to a thickness of about 1 μm by general DC (direct current) sputtering was used.
에멀젼(emulsion) 두께, 스퀴지(squeegee) 각도, 메시(mesh) 크기, 인쇄 속도, 스냅 오프(snap off) 거리 등의 인쇄 매개변수는 상수로 유지했다.Printing parameters such as emulsion thickness, squeegee angle, mesh size, print speed and snap off distance were kept constant.
한 번의 진행에서 전구체 페이스트(precursor paste)는 기판의 표면에 골고루 분포되었다.In one run, the precursor paste was evenly distributed on the surface of the substrate.
용매를 증발시키고 유기물을 태우기 위해 샘플은 오븐에서 50분 동안 80℃에서 250℃로 증가시키고, 40분 동안 250℃를 유지하여 건조시켰다.Samples were increased from 80 ° C. to 250 ° C. for 50 minutes in an oven and evaporated to maintain 250 ° C. for 40 minutes to evaporate the solvent and burn the organics.
황화처리는 황 분말이 들어있고, 불활성(질소) 상태인 폐쇄된 흑연 상자 내에서 실행되었다([8]).The sulfidation was carried out in a closed graphite box containing sulfur powder and in an inert (nitrogen) state ([8]).
두 단계의 온도 프로파일(profile)이 필름 공정에서 사용된다. 첫 번째 단계는 30분 동안 250℃를 유지하는 것이고, 두 번째 단계는 60분 동안 550℃를 유지하는 것이다.Two temperature profiles are used in the film process. The first step is to hold 250 ° C. for 30 minutes and the second step is to hold 550 ° C. for 60 minutes.
층들의 구조적 특성은 CuKα 방사선의 엑스선 회절 분석기(X-ray diffractometer, XRD)를 이용하여 분석하였다. 층들의 미세구조(microstructure)는 주사전자현미경(scanning electron microscopy, SEM)에 의해 관찰하였다.The structural properties of the layers were analyzed using an X-ray diffractometer (XRD) of CuKα radiation. The microstructure of the layers was observed by scanning electron microscopy (SEM).
3. 결과 및 토의3. Results and discussion
도 4는 용매열 반응에 의해 합성된 CuInS2와 CuS 입자의 XRD 패턴(x는 알려지지 않은 피크)을 보인 그래프이다.4 is a graph showing an XRD pattern (x is an unknown peak) of CuInS 2 and CuS particles synthesized by solvent thermal reaction.
도 4에서 보인 패턴은 생성물들이 각각 정방정계 황동과 상과 단순 육방정계 상 임을 나타낸다.The pattern shown in Figure 4 indicates that the products are tetragonal brass and phase and simple hexagonal phase, respectively.
두 가지의 상이 관찰되었다. : CuInS2 상의 알려지지 않은 피크(도 4에서 x 심볼)와 CuS 상의 Cu9S5 피크.Two phases were observed. : Unknown peak on CuInS 2 (x symbol in FIG. 4) and Cu 9 S 5 peak on CuS.
구형의 CuInS2 나노입자(약 60nm)와 다면체의 CuS 화합물 입자의 SEM 영상이 도 5에 보여진다.SEM images of spherical CuInS 2 nanoparticles (about 60 nm) and polyhedral CuS compound particles are shown in FIG. 5.
도 5는 구형 CuInS2 나노입자와 CuS 다면체 화합물의 SEM 영상이다.5 is an SEM image of spherical CuInS 2 nanoparticles and a CuS polyhedron compound.
도 6은 황화처리 후 CuS가 도핑된 CuInS2 층의 XRD 패턴을 보인 그래프이다.6 is a graph showing an XRD pattern of CuInS 2 layer doped with CuS after sulfidation.
도 6의 패턴은 명백한 황동광 상을 보여준다.The pattern of FIG. 6 shows a clear chalcopyrite image.
도 4에서 x 심볼로 표시된 알려지지 않은 피크는 황화처리 후 제거된다.Unknown peaks, indicated by x symbols in FIG. 4, are removed after sulfidation.
황화처리에 사용된 황의 양이 두 가지 상의 제거에서 중요한 역할을 하는 것으로 보여진다.The amount of sulfur used in the sulfidation process appears to play an important role in the removal of the two phases.
비록 황화처리 후 층의 결정화가 확실히 일어나지만, 층의 치밀화는 여전히 획득되지 않는다.Although the crystallization of the layer certainly takes place after sulfidation, densification of the layer is still not obtained.
도 7은 황화처리 후 CuS가 도핑된 CuInS2 층의 SEM 영상이고, (a)는 단면 영상이고, (b)는 표면 영상이다.7 is an SEM image of a CuInS 2 layer doped with CuS after sulfidation, (a) is a cross-sectional image, and (b) is a surface image.
도 7에서와 같이 다공질 층이 관찰된다. 이는 층의 치밀화가 단지 소결 첨가제에 의해서는 획득되지 않는다는 것을 나타낸다.A porous layer is observed as in FIG. 7. This indicates that densification of the layer is not obtained only by the sintering additive.
따라서 산화 과정은 황화처리 전에 도입되어야 한다.The oxidation process must therefore be introduced before the sulfidation.
도 8은 가열판(hotplate)에서 300℃로 산화된 층과 산화처리 후 황화처리된 층의 XRD 패턴을 보인 그래프로서, (a)는 산화처리된 것이고, (b)는 산화처리 후의 황화처리된 것이다.8 is a graph showing XRD patterns of a layer oxidized at 300 ° C. and a sulfided layer after oxidation in a hotplate, in which (a) is oxidized and (b) is sulfided after oxidation. .
도 8에 보인 바와 같이, CuInS2 상의 황동광 구조는 산화처리 과정에서 산소와의 반응으로 거의 붕괴되었지만, 황화처리에 의해 황동광 상으로 완전히 재구성되었다. 또한 MoO2 필름은 Mo 필름과 산소와의 반응에 의해 생성되었다. MoO2 필름과 Mo 필름 사이에 옴접촉(ohmic contact)이 만들어지기 때문에 MoO2 필름은 Mo 전극으로의 전자 흐름을 막지 않는다. As shown in FIG. 8, the chalcopyrite structure of CuInS 2 phase was almost collapsed by reaction with oxygen during the oxidation treatment, but was completely reconstituted into chalcopyrite phase by sulfidation. MoO 2 films were also produced by the reaction of Mo films with oxygen. Since the ohmic contacts (ohmic contact) is created between the film and the Mo film MoO 2 MoO 2 film does not block the flow of electrons to the Mo electrode.
도 9는 CuS가 도핑된 CuInS2 층의 SEM 영상이고, (a)와 (b)는 각각 산화처리된 단면 영상이과 표면 영상이고, (c)와 (d)는 각각 산화처리 후에 황화처리된 단면 영상과 표면 영상이다.9 is an SEM image of CuS doped CuInS 2 layer, (a) and (b) are oxidized cross-sectional images and surface images, respectively, and (c) and (d) are sulfided cross sections after oxidation, respectively. Image and surface image.
도 9에서와 같이, 비록 산화처리에 의해 황동광 구조가 붕괴되었지만 아주 치밀한 CuInS2 층이 얻어진다. 또한 황화처리에 의해 황동광 구조가 완전히 재생되기 때문에, 황동과 구조의 붕괴는 문제가 되지 않는다.As in FIG. 9, a very dense CuInS 2 layer is obtained, although the chalcopyrite structure is collapsed by the oxidation treatment. In addition, since the brine structure is completely regenerated by sulfidation, the collapse of the brass and the structure does not become a problem.
이것이 산화처리 공정이 필요한 이유이다.This is why an oxidation treatment process is necessary.
4. 결론4. Conclusion
페이스트 코팅법을 이용하여 CuInS2 흡수층이 제조되었다. CuInS2 와 CuS는 용매열 법에 의해 합성되고, 전구체는 분말(powder)로 사용된다. 에틸셀룰로스와 인산 에스테르는 각각 레진과 분산제로 사용된다. 디하이드로 테르피네올은 에틸셀룰로스와 인산 에스테르를 희석시키기 위하여 용매로 사용되었다. CuS-doped CuInS2 흡수층은 황화처리 만으로는 치밀화를 이룰 수 없었다. 그러나 황화처리를 하기 전에 산화처리 공정을 도입하면 아주 치밀한 CuInS2 층으로 이끌어 갈 수 있다. 황동광 상이 산화처리에 의해 거의 붕괴되었지만, 황화처리에 의해 황동광 상으로 재구성되었다.CuInS 2 absorbent layer was prepared using paste coating method. CuInS 2 and CuS are synthesized by the solvent heating method, and the precursor is used as a powder. Ethylcellulose and phosphate esters are used as resins and dispersants, respectively. Dihydro terpineol was used as a solvent to dilute ethylcellulose and phosphate esters. The CuS-doped CuInS 2 absorbent layer could not be densified by sulfidation alone. However, if the oxidation process is introduced before sulfiding, very dense CuInS 2 Can lead to layers. The chalcopyrite phase was almost collapsed by oxidation, but reconstituted by sulphides into chalcopyrite.
이처럼 본 발명은 페이스트 코팅법을 이용하여 CuInS2 흡수층을 제조하고 황화처리를 하기 전에 산화처리를 공정을 도입하여 아주 치밀한 CuInS2 층을 형성하게 된다.As such, the present invention forms a very dense CuInS 2 layer by introducing an oxidation treatment process before preparing the CuInS 2 absorbent layer using a paste coating method and sulfiding.
이상에서 살펴본 바와 같이, 본 발명에 의한 박막 태양전지 흡수층의 제조 방법은 페이스트 코팅법을 이용하여 CuInS2 흡수층을 제조하고 황화처리를 하기 전에 산화처리를 공정을 도입하여 아주 치밀한 CuInS2 층을 형성할 수 있는 효과가 있다.As described above, in the method of manufacturing the thin film solar cell absorbing layer according to the present invention, a CuInS 2 absorbing layer is prepared by using a paste coating method and an oxidation treatment is introduced before the sulfidation to form a very dense CuInS 2 layer. It can be effective.
이상에서 본 발명의 바람직한 실시예에 한정하여 설명하였으나, 본 발명은 이에 한정되지 않고 다양한 변화와 변경 및 균등물을 사용할 수 있다. 따라서 본 발명은 상기 실시예를 적절히 변형하여 응용할 수 있고, 이러한 응용도 하기 특허청구범위에 기재된 기술적 사상을 바탕으로 하는 한 본 발명의 권리범위에 속하게 됨은 당연하다 할 것이다.Although the above has been described as being limited to the preferred embodiment of the present invention, the present invention is not limited thereto and various changes, modifications, and equivalents may be used. Therefore, the present invention can be applied by appropriately modifying the above embodiments, it will be obvious that such application also belongs to the scope of the present invention based on the technical idea described in the claims below.
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