KR101811354B1 - 광흡수층 표면에 포타슘 처리를 통한 czts계 박막 태양전지의 제조방법 - Google Patents
광흡수층 표면에 포타슘 처리를 통한 czts계 박막 태양전지의 제조방법 Download PDFInfo
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052700 potassium Inorganic materials 0.000 title claims abstract description 26
- 239000011591 potassium Substances 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title abstract description 20
- 239000006096 absorbing agent Substances 0.000 title 1
- 230000031700 light absorption Effects 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 15
- 239000011698 potassium fluoride Substances 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 11
- 238000000151 deposition Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 238000000224 chemical solution deposition Methods 0.000 claims description 8
- 238000004544 sputter deposition Methods 0.000 claims description 6
- ZQRRBZZVXPVWRB-UHFFFAOYSA-N [S].[Se] Chemical compound [S].[Se] ZQRRBZZVXPVWRB-UHFFFAOYSA-N 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000005118 spray pyrolysis Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000004070 electrodeposition Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000007650 screen-printing Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 238000000859 sublimation Methods 0.000 claims description 2
- 230000008022 sublimation Effects 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims 1
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- 230000000052 comparative effect Effects 0.000 description 6
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000010748 Photoabsorption Effects 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
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- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 239000004065 semiconductor Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- -1 CIS Chemical class 0.000 description 1
- 238000010794 Cyclic Steam Stimulation Methods 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
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Classifications
-
- H01L31/0445—
-
- H01L31/02168—
-
- H01L31/02366—
-
- H01L31/0288—
-
- H01L31/0392—
-
- H01L31/18—
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/10—Details of semiconductor or other solid state devices to be connected
- H01L2924/102—Material of the semiconductor or solid state bodies
- H01L2924/1025—Semiconducting materials
- H01L2924/1026—Compound semiconductors
- H01L2924/1082—Other
- H01L2924/10822—Copper zinc tin sulfide, CZTS [Cu2ZnSnS4]
-
- 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
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- Engineering & Computer Science (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
Abstract
Description
도 2는 종래의 CZTS계 박막 태양전지의 제조 공정 순서도이다.
도 3은 본 발명에 따른 광흡수층을 도핑하는 단계를 포함하는 CZTS계 박막 태양전지의 제조 공정 순서도이다.
도 4는 본 발명의 실시예 1 내지 실시예 3에 따라 제조된 CZTS계 박막 태양전지의 개방전압-단략전류를 나타낸 그래프이다.
도 5는 본 발명의 실시예 4 내지 6에 따라 제조된 CZTS계 박막 태양전지의 개방전압-단략전류를 나타낸 그래프이다.
샘플 | KF 무게비 (중량%) |
KF 공정조건 |
개방전압 (mV) |
단락전류 (mA/cm2) |
충진률 (%) |
효율 (%) |
비교예 | X | X | 36.7 | 29.6 | 44.9 | 4.9 |
실시예1 | 4.5 | 80℃ / 10분 | 27.8 | 15.7 | 25.0 | 1.1 |
실시예2 | 4.5 | 80℃ / 5분 | 33.2 | 29.3 | 35.4 | 3.4 |
실시예3 | 4.5 | 80℃ / 1분 | 37.4 | 33.9 | 60.3 | 7.6 |
실시예4 | 4.5 | 80℃ / 30초 | 35.4 | 33.3 | 58.8 | 6.9 |
실시예5 | 2.0 | 40℃ / 30초 | 37.3 | 31.6 | 63.2 | 7.4 |
실시예6 | 1.0 | 40℃ / 30초 | 39.0 | 30.4 | 49.6 | 5.9 |
200 : 제 1 전극
300 : 광흡수층
400 : 버퍼층
500 : 윈도우층
600 : 제 2 전극
Claims (9)
- 기판을 준비하는 단계;
상기 기판 상에 제 1 전극을 형성하는 단계;
상기 제 1 전극 상에 금속 전구체를 증착하는 단계;
상기 증착된 금속 전구체층을 황화 기체 분위기, 셀렌화 기체 분위기 또는 황-셀렌 혼합 기체 분위기 하에서 열처리하여 광흡수층을 형성하는 단계;
상기 광흡수층을 포타슘 플루로라이드(KF) 파우더(powder)를 2.0 중량 % 내지 4.5 중량 %를 포함하는 용액으로 도핑하는 단계; 및
상기 광흡수층 상에 CdS를 포함하는 버퍼층을 형성하는 단계를 포함하고,
상기 도핑하는 단계는 40℃ 내지 80℃의 온도를 지닌 KF 파우더를 포함하는 용액에 광흡수층을 30초 내지 1분 동안 디핑(dipping)시키는 것을 특징으로 하고,
상기 도핑하는 단계에서는 상기 광흡수층 표면의 구리 빈자리(Cu vacancy)가 형성되고,
상기 버퍼층을 형성하는 단계 후에, 상기 구리 빈자리에 Cd가 확산되는, CZTS계 박막 태양전지의 제조방법.
- 삭제
- 삭제
- 삭제
- 제 1항에 있어서,
상기 도핑하는 단계 후에, 상기 광흡수층 표면에 포타슘이 존재하는 것을 특징으로 하는, CZTS계 박막 태양전지의 제조방법. - 제 1항에 있어서,
상기 금속 전구체층이 스퍼터링법(sputtering), 증발법(evaporation), CVD법(Chemical vapor deposition), 유기금속화학기상증착(MOCVD), 근접승화법(Close-spaced sublimation, CSS), 스프레이 피롤리시스(Spray pyrolysis), 화학 스프레이법(Chemical spraying), 스크린프린팅법(Screeen printing), 비진공 액상성막법, CBD법(Chemical bath deposition), VTD법(Vapor transport deposition) 및 전착법(electrodeposition) 중에서 선택된 하나 이상의 방법에 의해 형성되는 것을 특징으로 하는, CZTS계 박막 태양전지의 제조방법. - 제 1항에 있어서,
상기 광흡수층이 CIS, CIGS 또는 CZTS인 것을 특징으로 하는, CZTS계 박막 태양전지의 제조방법. - 제 1항에 있어서,
상기 버퍼층 상에 윈도우층을 형성하는 단계; 및
상기 윈도우층 상에 제 2 전극을 형성하는 단계를 추가로 포함하는, CZTS계 박막 태양전지의 제조방법. - 제 1항, 제5항 내지 제 8항 중 어느 한 항의 방법에 따라 제조된, 박막 태양전지.
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Citations (2)
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JP2013004743A (ja) * | 2011-06-16 | 2013-01-07 | Showa Shell Sekiyu Kk | Czts系薄膜太陽電池の製造方法及びczts系薄膜太陽電池 |
JP2014130858A (ja) | 2012-12-28 | 2014-07-10 | Fujifilm Corp | 光電変換素子および光電変換素子のバッファ層の製造方法 |
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JP2013004743A (ja) * | 2011-06-16 | 2013-01-07 | Showa Shell Sekiyu Kk | Czts系薄膜太陽電池の製造方法及びczts系薄膜太陽電池 |
JP2014130858A (ja) | 2012-12-28 | 2014-07-10 | Fujifilm Corp | 光電変換素子および光電変換素子のバッファ層の製造方法 |
Non-Patent Citations (1)
Title |
---|
Marie Buffiere et al., "KCN Chemical Etch for Interface Engineering in Cu2ZnSnSe4 Solar Cells", ACS Appl. Mater. Interfaces 2015, Vol.7, pp.14690-14698* |
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