JP2013211524A - Cigs系化合物太陽電池 - Google Patents
Cigs系化合物太陽電池 Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 34
- 239000013078 crystal Substances 0.000 claims abstract description 27
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000004065 semiconductor Substances 0.000 claims description 12
- 230000031700 light absorption Effects 0.000 abstract description 29
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- 239000010410 layer Substances 0.000 description 130
- 238000004544 sputter deposition Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 21
- 239000010949 copper Substances 0.000 description 10
- 239000011701 zinc Substances 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 238000001755 magnetron sputter deposition Methods 0.000 description 6
- 239000011669 selenium Substances 0.000 description 6
- 229910052733 gallium Inorganic materials 0.000 description 5
- 229910052738 indium Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical group [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005234 chemical deposition Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000005477 sputtering target Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910003363 ZnMgO Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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- H01L31/0392—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
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Abstract
【解決手段】基板1上に、裏面電極層2と、CIGS光吸収層3と、バッファ層4と、透明電極層5とをこの順で備えたCIGS化合物太陽電池において、上記バッファ層4がIIa族金属およびZn酸化物の混晶からなり、上記混晶のX線回折によって示される特性が、下記の式(1)を満たすようにした。
0.5≦A/(A+B+C)<1・・・(1)
(ただし、A,B,Cはいずれも0ではない)
A:(002)面におけるピーク強度
B:(100)面におけるピーク強度
C:(101)面におけるピーク強度
【選択図】図1
Description
0.5≦A/(A+B+C)<1・・・(1)
(ただし、A,B,Cはいずれも0ではない)
A:(002)面におけるピーク強度
B:(100)面におけるピーク強度
C:(101)面におけるピーク強度
0<B/(A+B+C)<0.2 ・・・(2)
(ただし、A,B,Cはいずれも0ではない)
A:(002)面におけるピーク強度
B:(100)面におけるピーク強度
C:(101)面におけるピーク強度
0<C/(A+B+C)<0.3 ・・・(3)
(ただし、A,B,Cはいずれも0ではない)
A:(002)面におけるピーク強度
B:(100)面におけるピーク強度
C:(101)面におけるピーク強度
0.7<(A+C)/(A+B+C)<1 ・・・(4)
(ただし、A,B,Cはいずれも0ではない)
A:(002)面におけるピーク強度
B:(100)面におけるピーク強度
C:(101)面におけるピーク強度
0.5≦A/(A+B+C)<1・・・(1)
(ただし、A,B,Cはいずれも0ではない)
A:(002)面におけるピーク強度
B:(100)面におけるピーク強度
C:(101)面におけるピーク強度
(裏面電極層の形成)
まず、脱脂したソーダライムガラス(厚み0.55mm、大きさ20mm)からなる基板の表面に、マグネトロンスパッタ装置(アルバック社製、型番SH−450)を用いて、放電ガスにはアルゴンを使用し、スパッタ圧力が1Paとなるよう直流(DC)電源を用い、スパッタレート60m/minで、厚み0.8mmのMoからなる裏面電極層を形成した。
つぎに、上記で形成された裏面電極層の上に、CIGS光吸収層を形成した。すなわち、真空蒸着装置のチャンバー内に、Ga、In、Cu、Seのそれぞれを蒸着源として配置し、このチャンバー内を真空度1×10-4Paとし、基板を、昇温速度550℃/hにて550℃まで加熱した。このとき、上記蒸着源をそれぞれGa(950℃)、In(780℃)、Cu(1100℃)、Se(140℃)となるように加熱し、これらの元素を同時に蒸発させることにより、上記裏面電極層の上にCIGS光吸収層を形成した。得られたCIGS光吸収層の組成(原子数%)は、Cu/III族=0.89、Ca/III族=0.31であり、膜厚は2.1μmであった。
つづいて、上記で形成されたCIGS光吸収層の上に、バッファ層を形成した。バッファ層は、図2に示す一対のターゲット6,6’が略V字に配置された対向ターゲットスパッタ装置(中心線に対するターゲット6,6’の角度θがそれぞれ10°)を用いて形成した。このとき、スパッタリングターゲットには、Zn0.85Mg0.15Oなる組成のターゲットを用い、ターゲット6’のエッジ6’aを基板1表面から160mm離れた位置に設置し、基板1の温度を25℃に設定した。本ターゲット6,6’を組成分析したところ、Mgに対して約3原子数%のCaが混在していた。スパッタ時の放電ガスにはアルゴンを用い、高周波(RF)電源にて、電力密度0.7W/cm2、スパッタ圧力0.3Paで、膜厚70nmとなるよう電力および形成時間を調整した。なお、ターゲット6’のエッジ6’aは、基板1から最短距離にある個所を示している。
さらに、上記で形成されたバッファ層の上に、透明電極層を形成した。透明電極層は、マグネトロンスパッタ装置(アルバック社製、型番SH−450)を用いて形成した。このとき、スパッタリングターゲットは、ITO(In2O3:90〔原子数%〕、SnO2:10〔原子数%〕)なる組成のターゲットを用いた。スパッタ時の放電ガスにはアルゴンガスおよびアルゴンガス流量の1/10のO2ガスを併用し、高周波(RF)電源にて、電力密度1.6W/cm2、スパッタ圧力0.3Pa、スパッタレート20nm/minで、厚み200nmのITO膜(透明電極層)を形成し、実施例1のCIGS太陽電池を得た。実施例1のバッファ層のX線回折によって示される特性は、A/(A+B+C)=0.6を示していた。
バッファ層形成の条件を、高周波(RF)電源にて、電力密度6.0W/cm2で行った他は、実施例1と同様にして、実施例2のCIGS太陽電池を得た。実施例2のバッファ層のX線回折によって示される特性は、A/(A+B+C)=0.8を示していた。
バッファ層形成の条件を、直流(DC)電源(電力密度6.0W/cm2)+高周波(RF)電源(電力密度6.0W/cm2)の重畳で行った他は、実施例1と同様にして、実施例3のCIGS太陽電池を得た。実施例3のバッファ層のX線回折によって示される特性は、A/(A+B+C)=0.7を示していた。
バッファ層形成の条件を、直流(DC)電源(電力密度2.5W/cm2)+高周波(RF)電源(電力密度0.5W/cm2)の重畳とし、スパッタ圧力0.1Paで、ター
ゲット6’のエッジ6’aを基板1表面から40mm離れた位置に設置し(Y=40mm)、基板1の温度を200℃に設定して、バッファ層の形成を行った他は、実施例1と同様にして、実施例4のCIGS太陽電池を得た。実施例4のバッファ層のX線回折によって示される特性は、A/(A+B+C)=0.6を示していた。
バッファ層形成の条件を、直流(DC)電源(電力密度2.5W/cm2)+高周波(RF)電源(電力密度1.5W/cm2)の重畳とし、スパッタ圧力0.1Paで、ター
ゲット6’のエッジ6’aを基板1表面から160mm離れた位置に設置し(Y=160mm)、基板1の温度を200℃に設定した他は、実施例1と同様にして、実施例5のCIGS太陽電池を得た。実施例5のバッファ層のX線回折によって示される特性は、A/(A+B+C)=0.7を示していた。
バッファ層の形成を、一般的なマグネトロンスパッタ装置(アルバック社製、型番SH−450)で行った他は、実施例1と同様にして、比較例1のCIGS太陽電池を得た。なお、マグネトロンスパッタは、直流(DC)電源(電力密度0.5W/cm2)を用いた。比較例1のバッファ層のX線回折によって示される特性は、A/(A+B+C)=0.2を示していた。
バッファ層形成条件を、直流(DC)電源(電力密度1.5W/cm2)で行った他は、比較例1と同様にして、比較例2のCIGS太陽電池を得た。比較例2のバッファ層のX線回折によって示される特性は、A/(A+B+C)=0.1を示していた。
バッファ層形成条件を、高周波(RF)電源(電力密度0.5W/cm2)で行った他は、比較例1と同様にして、比較例3のCIGS太陽電池を得た。比較例3のバッファ層のX線回折によって示される特性は、A/(A+B+C)=0.3を示していた。
バッファ層形成条件を、高周波(RF)電源(電力密度2.5W/cm2)で行った他は、比較例1と同様にして、比較例4のCIGS太陽電池を得た。比較例4のバッファ層のX線回折によって示される特性は、A/(A+B+C)=0.2を示していた。
バッファ層の形成に用いる対向ターゲットスパッタ装置に、直流(DC)電源(電力密度0.7W/cm2)を印加した他は、実施例1と同様にして、比較例5のCIGS太陽電池を得た。比較例5のバッファ層のX線回折によって示される特性は、A/(A+B+C)=0.2を示していた。
上記実施例1〜5、比較例1〜5のCIGS太陽電池をそれぞれ20個準備し、これらに擬似太陽光(AM1.5)を照射し、IV計測システム(山下電装社製、YSS−150)を用いて、それぞれの変換効率を測定した。得られた結果(平均)を下記の〔表1〕に示す。
2 裏面電極層
3 CIGS光吸収層
4 バッファ層
5 透明電極層
Claims (4)
- 基板上に、少なくともI-III-VI族化合物半導体層と、バッファ層と、透明電極層とをこの順で備え、上記バッファ層がIIa族金属およびZn酸化物の混晶とし、上記混晶のX線回折によって示される特性が、下記の式(1)を満たしていることを特徴とするCIGS系化合物太陽電池。
0.5≦A/(A+B+C)<1 ・・・(1)
(ただし、A,B,Cはいずれも0ではない)
A:(002)面におけるピーク強度
B:(100)面におけるピーク強度
C:(101)面におけるピーク強度 - 混晶のX線回折によって示される特性が、下記の式(2)を満たしている請求項1記載のCIGS系化合物太陽電池。
0<B/(A+B+C)<0.2 ・・・(2)
(ただし、A,B,Cはいずれも0ではない)
A:(002)面におけるピーク強度
B:(100)面におけるピーク強度
C:(101)面におけるピーク強度 - 混晶のX線回折によって示される特性が、下記の式(3)を満たしている請求項1または2記載のCIGS系化合物太陽電池。
0<C/(A+B+C)<0.3 ・・・(3)
(ただし、A,B,Cはいずれも0ではない)
A:(002)面におけるピーク強度
B:(100)面におけるピーク強度
C:(101)面におけるピーク強度 - 混晶のX線回折によって示される特性が、下記の式(4)を満たしている請求項1〜3のいずれか一項に記載のCIGS系化合物太陽電池。
0.7<(A+C)/(A+B+C)<1 ・・・(4)
(ただし、A,B,Cはいずれも0ではない)
A:(002)面におけるピーク強度
B:(100)面におけるピーク強度
C:(101)面におけるピーク強度
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TW102106515A TWI580060B (zh) | 2012-02-27 | 2013-02-25 | CIGS-based compound solar cells |
US14/376,761 US9947808B2 (en) | 2012-02-27 | 2013-02-25 | CIGS compound solar cell |
EP13755506.6A EP2804221B1 (en) | 2012-02-27 | 2013-02-25 | Cigs-compound solar cell |
KR1020147023188A KR101983422B1 (ko) | 2012-02-27 | 2013-02-25 | Cigs계 화합물 태양 전지 |
CN201380010209.XA CN104137272B (zh) | 2012-02-27 | 2013-02-25 | Cigs系化合物太阳能电池 |
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US9935214B2 (en) | 2015-10-12 | 2018-04-03 | International Business Machines Corporation | Liftoff process for exfoliation of thin film photovoltaic devices and back contact formation |
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US6259016B1 (en) | 1999-03-05 | 2001-07-10 | Matsushita Electric Industrial Co., Ltd. | Solar cell |
JP4662616B2 (ja) | 2000-10-18 | 2011-03-30 | パナソニック株式会社 | 太陽電池 |
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JP2000323733A (ja) * | 1999-03-05 | 2000-11-24 | Matsushita Electric Ind Co Ltd | 太陽電池 |
JP2010192689A (ja) * | 2009-02-18 | 2010-09-02 | Tdk Corp | 太陽電池、及び太陽電池の製造方法 |
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CN104137272A (zh) | 2014-11-05 |
EP2804221A4 (en) | 2015-10-28 |
KR101983422B1 (ko) | 2019-05-28 |
WO2013129296A1 (ja) | 2013-09-06 |
US20150027537A1 (en) | 2015-01-29 |
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