JP5764016B2 - Cigs膜の製法およびそれを用いるcigs太陽電池の製法 - Google Patents
Cigs膜の製法およびそれを用いるcigs太陽電池の製法 Download PDFInfo
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
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Description
ため、層(B)を固相状態で、同じく固相状態の層(A)上に均一な厚みで積層できる。なお、この段階では各層の相互拡散は抑制されている。つぎに、この2層(A)、(B)が積層された積層体を加熱し、層(B)のCuとSeの化合物を溶融させ液相状態とすることにより、上記層(A)中に上記層(B)中のCuが急速に拡散する。このとき、層(B)は、先の過程で、均一な厚みで層(A)上に形成されているため、上記層(B)中のCuは、層(A)中に均一的に拡散され、大粒で均一な結晶粒が形成される。また、層(B)を一旦、固相として用いるため、Cu(2-x)Seが過剰にCIGS膜内に取り込まれることを抑制できる。さらに、本発明のCIGS膜の製法は、上記加熱工程終了時のCIGS膜が、0.95<Cu/(In+Ga)<1.30のモル比を満たすとともに、上記加熱工程時の温度を維持した状態で、上記加熱工程により得られたCIGS膜に、さらにInとGaとSeとを蒸着させて、上記CIGS膜が、0.70<Cu/(In+Ga)<0.95のモル比を満たすようにしている。このため、まず、上記加熱工程終了時のCIGS膜の組成が、0.95<Cu/(In+Ga)<1.30のモル比を満たすことにより、層(A)と層(B)との界面においても、Cu成分が充分に拡散され、結晶成長が起こるとともに、Cu(2-x)SeがCIGS膜内に過剰に取り込まれず、このCIGS膜を素子に用いた際の素子特性は低下しない。そして、上記加熱工程時の温度を維持した状態で、上記加熱工程により得られたCIGS膜に、さらにInとGaとSeとを蒸着し、上記CIGS膜の組成が、0.70<Cu/(In+Ga)<0.95のモル比を満たすようにしているため、CIGS膜全体において、わずかにCu不足の状態にすることができ、このCIGS膜を素子に用いた際に、より高効率の光吸収層とすることができる。したがって、この製法により得られたCIGS膜を用いたCIGS太陽電池は、変換効率が高くなるとともに、素子ごとの変換効率のばらつきが生じにくい。しかも、膜内に余剰なCu(2-x)Seが形成されないため、電池特性に悪影響を及ぼすこともない。
上記実施の形態と同様にして、CIGS太陽電池を製造した。すなわち、基板1として、SLG(大きさ30×30mm、厚み0.55mm)を用意し、この上に、Mo(厚み500nm)を積層し、裏面電極層2を形成した。そして、基板1保持温度を200℃にした状態で、In、Ga、Seを蒸着し、層(A)を形成した。つづいて、基板1保持温度を200℃に保ったままの状態で、上記層(A)上にCu、Seを蒸着し、層(B)を積層し、積層体6を形成した。この積層体6を、微量のSe蒸気を供給しつつ加熱し、基板1保持温度が550℃の状態を15分間保持し、結晶成長を行いCIGS膜3’を得た。さらに、このCIGS膜3’に、微量のSeガスを供給しつつ、基板1保持温度を550℃に保った状態で、In、Ga、Seを蒸着することで、目的のCIGS膜3(厚み2.0μm)を得た。このCIGS膜3を用いたCIGS太陽電池を実施例1品とした。なお、実施例1品を得るための概略図を〔図8(a)〕に示す。
実施例1と同様に、裏面電極層2が形成された基板1を準備した。そして、基板1の保持温度を200℃にした状態で、Cu、In、Ga、Seを蒸着し、わずかにCu過剰となるCu、In、Ga、Seからなる層を形成した。これを微量のSeガスを供給しつつ加熱し、基板1保持温度が550℃の状態で15分間保持し、結晶成長を行いCIGS膜’(図示せず)を得た。さらに、このCIGS膜’に、微量のSe蒸気を供給しつつ、基板1保持温度を550℃に保った状態で、In、Ga、Seを蒸着することで、目的のCIGS膜(厚み2.0μm)を得た。このCIGS膜を用いたCIGS太陽電池を比較例1品とした。なお、比較例1品を得るための概略図を〔図9〕に示す。
実施例1と同様に、裏面電極層2が形成された基板1を準備した。そして、基板1の保持温度を350℃にした状態で、In、Ga、Seを蒸着し、In、Ga、Seからなる層を形成した。つぎに、基板1の保持温度が550℃の状態となるよう加熱した状態で、この層の上に、Cu、Seを蒸着させ、結晶成長を行いCIGS膜''(図示せず)を得た。さらに、このCIGS膜''に、微量のSe蒸気を供給しつつ、基板1保持温度を550℃に保った状態で、In、Ga、Seを蒸着することで、目的のCIGS膜(厚み2.0μm)を得た。このCIGS膜を用いたCIGS太陽電池を比較例2品とした。なお、比較例2品を得るための概略図を〔図8(b)〕に示す。
擬似太陽光(AM1.5)を各実施例品および比較例品の表面面積以上の領域に照射し、その変換効率をソーラーシミュレーター(セルテスターYSS150、山下電装社)によって測定した。
各実施例品および比較例品に用いたCIGS膜のCu、In、Gaの含有量を、エネルギー分散型蛍光X線装置(EX−250、堀場製作所)を用いて測定し、これらの原子数濃度を元にCu/(In+Ga)の組成比を算出した。
Claims (6)
- CIGS太陽電池の光吸収層として用いられるCIGS膜の製法であって、インジウムとガリウムとセレンとを含む層(A)と、銅とセレンとを含む層(B)を、固相状態でこの順で基板に積層する積層工程と、上記層(A)および層(B)が積層された積層体を加熱し、上記層(B)を溶融させ液相状態とすることにより、上記層(A)中に上記層(B)中の銅を拡散させ、結晶成長させてCIGS膜を得る加熱工程とを有し、上記加熱工程終了時のCIGS膜が、0.95<銅/(インジウム+ガリウム)<1.30のモル比を満たすとともに、上記加熱工程時の温度を維持した状態で、上記加熱工程により得られたCIGS膜に、さらにインジウムとガリウムとセレンとを蒸着させることにより、上記CIGS膜が、0.70<銅/(インジウム+ガリウム)<0.95のモル比を満たすようにすることを特徴とするCIGS膜の製法。
- 上記積層工程を、100〜250℃の範囲の温度で行う請求項1記載のCIGS膜の製法。
- 上記加熱工程を、520℃以上の温度で行う請求項1または2記載のCIGS膜の製法。
- 上記積層工程の温度から上記加熱工程の温度への昇温を、昇温速度10℃/秒以上で行う請求項1〜3のいずれか一項に記載のCIGS膜の製法。
- 上記加熱工程において、セレン蒸気もしくはセレン化水素を供給し、CIGS膜表面のセレン分圧が、内部のセレン分圧よりも高い状態で維持されるようにする請求項1〜4のいずれか一項に記載のCIGS膜の製法。
- 基板上に、裏面電極層を設ける工程と、光吸収層を設ける工程と、バッファ層を設ける工程と、透明導電層を設ける工程とを有するCIGS太陽電池の製法であって、上記光吸収層を設ける工程として、上記請求項1に記載のCIGS膜の製法を用いることを特徴とするCIGS太陽電池の製法。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011194933A JP5764016B2 (ja) | 2011-09-07 | 2011-09-07 | Cigs膜の製法およびそれを用いるcigs太陽電池の製法 |
EP12830489.6A EP2755242B1 (en) | 2011-09-07 | 2012-09-05 | Method for producing cigs film, and method for manufacturing cigs solar cell using same |
CN201280042573.XA CN103765604B (zh) | 2011-09-07 | 2012-09-05 | Cigs膜的制法和使用其的cigs太阳能电池的制法 |
KR1020147006884A KR101785771B1 (ko) | 2011-09-07 | 2012-09-05 | Cigs막의 제법 및 그것을 이용하는 cigs 태양 전지의 제법 |
PCT/JP2012/072590 WO2013035732A1 (ja) | 2011-09-07 | 2012-09-05 | Cigs膜の製法およびそれを用いるcigs太陽電池の製法 |
US14/241,007 US8962379B2 (en) | 2011-09-07 | 2012-09-05 | Method of producing CIGS film, and method of producing CIGS solar cell by using same |
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JP2011194933A JP5764016B2 (ja) | 2011-09-07 | 2011-09-07 | Cigs膜の製法およびそれを用いるcigs太陽電池の製法 |
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JP2013058540A JP2013058540A (ja) | 2013-03-28 |
JP5764016B2 true JP5764016B2 (ja) | 2015-08-12 |
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US (1) | US8962379B2 (ja) |
EP (1) | EP2755242B1 (ja) |
JP (1) | JP5764016B2 (ja) |
KR (1) | KR101785771B1 (ja) |
CN (1) | CN103765604B (ja) |
WO (1) | WO2013035732A1 (ja) |
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JP2014154762A (ja) * | 2013-02-12 | 2014-08-25 | Nitto Denko Corp | Cigs膜の製法およびそれを用いるcigs太陽電池の製法 |
JP2014152085A (ja) * | 2013-02-12 | 2014-08-25 | Nitto Denko Corp | Cigs膜の製法およびその製法を用いるcigs太陽電池の製法 |
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JP2015061062A (ja) * | 2013-09-20 | 2015-03-30 | 株式会社東芝 | 光電変換素子の製造方法 |
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JP2004342678A (ja) * | 2003-05-13 | 2004-12-02 | Rikogaku Shinkokai | Cu(In1−xGax)Se2膜の製造方法及び太陽電池 |
US20070169809A1 (en) * | 2004-02-19 | 2007-07-26 | Nanosolar, Inc. | High-throughput printing of semiconductor precursor layer by use of low-melting chalcogenides |
FR2886460B1 (fr) * | 2005-05-25 | 2007-08-24 | Electricite De France | Sulfurisation et selenisation de couches de cigs electrodepose par recuit thermique |
WO2007101135A2 (en) * | 2006-02-23 | 2007-09-07 | Van Duren Jeroen K J | High-throughput printing of semiconductor precursor layer from inter-metallic microflake particles |
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US20110174363A1 (en) * | 2010-01-21 | 2011-07-21 | Aqt Solar, Inc. | Control of Composition Profiles in Annealed CIGS Absorbers |
CN101768729B (zh) * | 2010-03-05 | 2012-10-31 | 中国科学院上海硅酸盐研究所 | 磁控溅射法制备铜铟镓硒薄膜太阳电池光吸收层的方法 |
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CN103765604B (zh) | 2016-08-17 |
CN103765604A (zh) | 2014-04-30 |
KR20140066189A (ko) | 2014-05-30 |
EP2755242B1 (en) | 2018-06-27 |
EP2755242A4 (en) | 2016-02-17 |
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