JP2008510310A - 半導体基板、特に黄銅鉱薄膜太陽電池の吸収層上に硫化亜鉛バッファ層を化学浴析出により施与する方法 - Google Patents
半導体基板、特に黄銅鉱薄膜太陽電池の吸収層上に硫化亜鉛バッファ層を化学浴析出により施与する方法 Download PDFInfo
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- 239000010409 thin film Substances 0.000 title claims abstract description 13
- 238000000224 chemical solution deposition Methods 0.000 title claims abstract description 12
- 239000004065 semiconductor Substances 0.000 title claims abstract description 10
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 229910052951 chalcopyrite Inorganic materials 0.000 title claims abstract description 8
- 239000005083 Zinc sulfide Substances 0.000 title claims description 18
- 229910052984 zinc sulfide Inorganic materials 0.000 title claims description 18
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 title claims description 11
- 238000010521 absorption reaction Methods 0.000 title description 3
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 22
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 7
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000006096 absorbing agent Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052980 cadmium sulfide Inorganic materials 0.000 abstract description 9
- 238000000151 deposition Methods 0.000 abstract description 6
- 230000008021 deposition Effects 0.000 abstract description 6
- 231100000331 toxic Toxicity 0.000 abstract description 5
- 230000002588 toxic effect Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 229910052793 cadmium Inorganic materials 0.000 abstract description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 2
- 229940065285 cadmium compound Drugs 0.000 abstract description 2
- 150000001662 cadmium compounds Chemical class 0.000 abstract description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 231100000925 very toxic Toxicity 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 38
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 8
- 239000011701 zinc Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000010949 copper Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
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- 239000011733 molybdenum Substances 0.000 description 3
- 238000006862 quantum yield reaction Methods 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
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- 238000007740 vapor deposition Methods 0.000 description 2
- 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
- 229910000943 NiAl Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
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- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001678 elastic recoil detection analysis Methods 0.000 description 1
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- 238000009432 framing Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- -1 sulfide ions Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229940100888 zinc compound Drugs 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- 235000009529 zinc sulphate Nutrition 0.000 description 1
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Abstract
Description
本発明は、半導体基板、特に黄銅鉱薄膜太陽電池の吸収層上に硫化亜鉛バッファ層を化学浴析出により施与する方法に関する。本方法は、例えば、II−VI族の「スーパーストレート」薄膜太陽電池及び黄銅鉱「スーパーストレート」薄膜太陽電池の製造にも適用することができる。
− ZnS層を用いることにより、目下のところ有毒なカドミウム化合物を用いてのみ可能な効率と比べて比肩しうるか、もしくはそれより大きい効率を達成することが初めて可能になった。従って本方法は同じ結果をもたらす際に顕著に無公害である。
− この析出は、工程を簡単に自動化できるように、1作業段階で実施する(一回のみの10分間のサイクル)。
− この析出は、慣用の方法での析出ほど長く継続させない。1〜2nm/分の析出速度が達成される。このより厚い層は、極めて均質かつコンパクトであり、その上方にi−ZnO層が存在しない電池も可能である。
− 大きな変更なしで、慣用の装置構成と同じ装置構成を使用することができる。「アップスケーリング」も簡単に行うことができる。
− 硫化亜鉛バッファ層は、硫化カドミウム層と比べて、より大きいバンドギャップを有し、従ってより大きいスペクトル領域において有効であり、かつより大きい電流効率を供給するという利点を有する。
図1は、試料被覆用の試験装置を示し、
図2は、達成された試料の量子収率を示し、かつ
図3は、電流電圧曲線を示す。
基板:ガラス
背面のコンタクト層:モリブデン
吸収剤:CuInS2
バッファ層:ZnS
窓層:i−ZnO/ZnO:Ga
光の当たるコンタクト:NiAl。
1)0.05〜0.5モル/lの硫酸亜鉛と、0.2〜1.5モル/lのチオ尿素(SC(NH2)2)とを有する高温溶液(70〜90℃)を、二重に蒸留された水から製造する(供給部4により示す)。
2)この溶液を、更に長時間にわたって撹拌する。
3)次いで、NH3溶液(25%)を添加する(供給部6により示す)。間もなく白色沈殿物が観察され、これを更に連続的な撹拌により溶解させる。pH値10〜11の完全に澄明な溶液が生ずる。
4)試料1を、試料保持部7に固定し、そして浸漬させる。この析出の間、この溶液を更に撹拌し、かつその温度を更に維持する。
5)約10分後に、この試料1を取出し、最初に澄明な溶液は濁り始める。
6)この試料1を、水/アンモニア溶液で洗浄し、そして窒素流で乾燥させる。
7)試料1の吸収剤上に生じる層厚は、約10〜15nmである。
8)この方法を繰り返して、より厚い皮膜層を達成してよい。3回のサイクルにより、約60nmの層厚がもたらされる。このサイクル間では、洗浄及び乾燥は省いてよい。
9)次いで、被覆された試料1を100〜180℃で空気中で所定の時間にわたって加熱板上で熱処理する。
Zn2++nTU=[Zn(TU)n]2+ (1)
NH3を添加すると、過剰のZn2+から第2の錯体が形成される。
反応(1)及び(2)からZn錯体が解離すると、Zn陽イオンが遊離する。
Claims (4)
- 半導体基板、特に黄銅鉱薄膜太陽電池の吸収層上に硫化亜鉛バッファ層を化学浴析出により施与する方法において、以下の段階:
0.05〜0.5モル/lの硫酸亜鉛と0.2〜1.5モル/lのチオ尿素とを蒸留水中に70〜90℃の温度で溶解させる段階、
約25%アンモニアを、この水の量の3分の1の大きさで添加する段階、
この溶液が澄明になった後に、約10分にわたってこの半導体基板をこの溶液中に浸漬させ、その達成される温度をこの時間内で実質的に一定に維持する段階を特徴とする方法。 - 硫化亜鉛バッファ層をより厚く施与するために、少なくとも1回繰り返すことを特徴とする、請求項1に記載の方法。
- 溶液を連続的に撹拌することを特徴とする、請求項1又は2に記載の方法。
- 事前にアンモニア/水−溶液中で処理された半導体基板を、浸漬の後にアンモニア/水−溶液により洗浄し、窒素により乾燥させ、次いで約100〜180℃で熱処理することを特徴とする、請求項1又は2に記載の方法。
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PCT/DE2005/001431 WO2006018013A1 (de) | 2004-08-18 | 2005-08-11 | Verfahren zum aufbringen einer zinksulfid-pufferschicht auf ein halbleitersubstrat mittels chemischer badabscheidung, insbesondere auf die absorberschicht einer chalkopyrit-dünnschicht-solarzelle |
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US7704863B2 (en) | 2010-04-27 |
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