JP6004460B2 - 太陽電池の製造方法、および太陽電池 - Google Patents
太陽電池の製造方法、および太陽電池 Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims description 26
- 230000031700 light absorption Effects 0.000 claims description 49
- 238000004544 sputter deposition Methods 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 32
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 28
- 229910001882 dioxygen Inorganic materials 0.000 claims description 28
- 229910052725 zinc Inorganic materials 0.000 claims description 23
- 229910052749 magnesium Inorganic materials 0.000 claims description 21
- 239000010408 film Substances 0.000 description 126
- 229910003363 ZnMgO Inorganic materials 0.000 description 94
- 239000011669 selenium Substances 0.000 description 31
- 230000015572 biosynthetic process Effects 0.000 description 29
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- 239000007789 gas Substances 0.000 description 19
- 239000011701 zinc Substances 0.000 description 18
- 229910052711 selenium Inorganic materials 0.000 description 17
- 239000000758 substrate Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000011777 magnesium Substances 0.000 description 15
- 229910052786 argon Inorganic materials 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 7
- 239000011787 zinc oxide Substances 0.000 description 7
- 229910052738 indium Inorganic materials 0.000 description 6
- 238000000151 deposition Methods 0.000 description 5
- 229910052733 gallium Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000008021 deposition Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002926 oxygen Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 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
- 230000008901 benefit Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- PNHVEGMHOXTHMW-UHFFFAOYSA-N magnesium;zinc;oxygen(2-) Chemical compound [O-2].[O-2].[Mg+2].[Zn+2] PNHVEGMHOXTHMW-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- -1 oxygen (activated oxygen Chemical class 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000010409 thin film Substances 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
- 238000001771 vacuum deposition Methods 0.000 description 1
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Description
基板1上に、裏面電極2、光吸収層3、バッファ層4(ZnMgO膜、ZnMgO層、以降、“ZnMgO膜4”とも呼ぶ)、透明電極5が、この順に形成されている。後述するように、本実施形態では、バッファ層4の光吸収層3と接する部分8の比抵抗値は、バッファ層4の透明電極5と接する部分9の比抵抗値よりも高い。さらに、透明電極5に接するように取り出し電極6が形成されている。基板1には、ソーダライムガラス(ソーダガラス)やステンレス等が用いられる。裏面電極2としては、モリブデン(Mo)、タングステン(W)等が用いられる。バッファ層4は、酸化マグネシウム亜鉛(ZnMgO)膜で形成されている。透明電極5には、アルミニウム(Al)含有ZnO(AZO)や、インジウム(In)と錫(Sn)の酸化物(ITO)等が用いられる。
図2に例示する太陽電池は、図1で例示する太陽電池の、バッファ層4と透明電極5との間に高抵抗バッファ層7が設けられている構造である。
図3は、本発明の一実施形態に係る太陽電池の製造工程の一例を示す工程図である。
本実施形態では、バッファ層4を、真空容器内でスパッタリング法により形成する。真空容器内には、少なくとも希ガスと酸素ガスとを供給できればよい。
例えばCIGS膜のように、Seを含有する光吸収層は、空孔(セレン空孔)が形成されやすい。Seを含有する光吸収層上にバッファ層となるZnMgO膜をスパッタリング法で形成すると、光吸収層は、スパッタ粒子やイオンの入射によりスパッタダメージを受け、より多くの空孔が形成される。特に、上記スパッタダメージにより、Seを含有する光吸収層からセレンが抜け出してセレン空孔が形成されてしまい、光吸収層中のキャリア濃度が減少してしまう。
なお、明細書内に記載する「成膜圧力」とは、真空容器内の圧力を意味する。
なお、本実施形態におけるカソードとは、ターゲットホルダに限定するものではなく、スパッタ放電のために電力が供給される部分を意味する。
基板1としてのソーダライムガラス上に、裏面電極2としてMo膜をスパッタリング法にて800nm成膜した。次に、Mo膜上に、光吸収層3としてCIGS膜を多元蒸着三段階法により1.8μm成膜した。成膜したCIGS膜のGaとInの組成比は、Ga/(Ga+In)=0.3であった。次に、基板をKCN溶液に浸漬させ、表面の余剰なCu2Seを除去し、真空雰囲気下にて250℃で30分間加熱した。
本実施例では、実施例1の太陽電池の製造条件に対して、CIGS膜の組成と、第1の工程で形成するZnMgO膜の膜厚を変更して、太陽電池を作製した。具体的には、実施例2では、Ga/(Ga+In)=0.25のCIGS膜を形成し、第1の工程において成膜するZnMgO膜の膜厚を4nmとした。
本実施例では、実施例1の太陽電池の製造工程における、高抵抗バッファ層を形成せずに、太陽電池を作製した。高抵抗バッファ層以外の層については、実施例1と同じ条件で形成した。
バッファ層としてのZnMgO膜の形成を行う際に、酸素導入しながらのスパッタリング工程である第1の工程を行なわない以外は、実施例1と同じ製造方法にて太陽電池を作製した。すなわち、スパッタリングガスはアルゴンガスのみを用いて、ZnMgO膜を100nm形成した。アルゴン流量は12sccm、成膜圧力は0.2Pa、供給電力は350Wの条件でスパッタリングを行った。ターゲットとして、MgO濃度13mol%のZnMgOターゲットを用いた。
Claims (4)
- 真空容器内で行われる太陽電池の製造方法であって、
Seを含有する光吸収層を成膜する工程と、
酸素ガスを導入しながら、スパッタリング法により、ZnおよびMgを含む酸化物を前記光吸収層に接するように成膜する第1の工程と、
前記酸素ガスの導入を止めて、スパッタリング法により、前記第1の工程において成膜した前記ZnおよびMgを含む酸化物上に、さらにZnおよびMgを含む酸化物を成膜する第2の工程と
を有することを特徴とする太陽電池の製造方法。 - 前記第1の工程における前記真空容器内の圧力は、前記第2の工程における前記真空容器内の圧力よりも高いことを特徴とする請求項1に記載の太陽電池の製造方法。
- 前記第1の工程の後、前記真空容器内に設けられたカソードへの電力供給を止めることなく、前記真空容器内で前記第2の工程を行なうことを特徴とする請求項1に記載の太陽電池の製造方法。
- Seを含有する光吸収層と、
透明電極層と、
前記光吸収層と前記透明電極層との間に、前記光吸収層に接して設けられたZnおよびMgを含む酸化物層とを備え、
前記ZnおよびMgを含む酸化物層の前記光吸収層側の部分の比抵抗値は、前記ZnおよびMgを含む酸化物層の前記透明電極層側の部分の比抵抗値よりも高いことを特徴とする太陽電池。
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Patent Citations (6)
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JP2000323733A (ja) * | 1999-03-05 | 2000-11-24 | Matsushita Electric Ind Co Ltd | 太陽電池 |
JP2002124688A (ja) * | 2000-10-18 | 2002-04-26 | Matsushita Electric Ind Co Ltd | 太陽電池 |
JP2004158619A (ja) * | 2002-11-06 | 2004-06-03 | Matsushita Electric Ind Co Ltd | 電子デバイスおよびその製造方法 |
WO2005069386A1 (ja) * | 2004-01-13 | 2005-07-28 | Matsushita Electric Industrial Co., Ltd. | 太陽電池とその製造方法 |
US20110039366A1 (en) * | 2009-07-24 | 2011-02-17 | Solopower, Inc. | Method and apparatus for deposition of graded or multi-layer transparent films |
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TWI514611B (zh) | 2015-12-21 |
WO2014155444A1 (ja) | 2014-10-02 |
TW201507189A (zh) | 2015-02-16 |
JPWO2014155444A1 (ja) | 2017-02-16 |
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