JP2014513413A - 五元化合物半導体CZTSSeおよび薄膜太陽電池の製造方法 - Google Patents
五元化合物半導体CZTSSeおよび薄膜太陽電池の製造方法 Download PDFInfo
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 81
- 150000001875 compounds Chemical class 0.000 title claims abstract description 72
- 239000010409 thin film Substances 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 239000011669 selenium Substances 0.000 claims abstract description 162
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 139
- 239000002243 precursor Substances 0.000 claims abstract description 112
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 98
- 239000011593 sulfur Substances 0.000 claims abstract description 98
- 238000000034 method Methods 0.000 claims abstract description 95
- 239000010949 copper Substances 0.000 claims abstract description 91
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 85
- 239000011701 zinc Substances 0.000 claims abstract description 72
- 239000011135 tin Substances 0.000 claims abstract description 68
- 239000000758 substrate Substances 0.000 claims abstract description 58
- 230000008569 process Effects 0.000 claims abstract description 56
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 54
- 229910052798 chalcogen Inorganic materials 0.000 claims abstract description 52
- 150000001787 chalcogens Chemical class 0.000 claims abstract description 51
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052802 copper Inorganic materials 0.000 claims abstract description 45
- 229910052718 tin Inorganic materials 0.000 claims abstract description 45
- 238000010438 heat treatment Methods 0.000 claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 39
- 239000006096 absorbing agent Substances 0.000 claims abstract description 36
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052951 chalcopyrite Inorganic materials 0.000 claims abstract description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 23
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 23
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000002739 metals Chemical class 0.000 claims abstract description 20
- -1 sulfur and selenium Chemical class 0.000 claims abstract description 4
- 230000007423 decrease Effects 0.000 claims description 16
- 238000001704 evaporation Methods 0.000 claims description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims 1
- 238000000151 deposition Methods 0.000 abstract description 21
- 239000007789 gas Substances 0.000 description 84
- 229910007610 Zn—Sn Inorganic materials 0.000 description 23
- 230000008021 deposition Effects 0.000 description 14
- 238000012545 processing Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000013078 crystal Substances 0.000 description 10
- 239000011261 inert gas Substances 0.000 description 8
- 239000002019 doping agent Substances 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 229910052733 gallium Inorganic materials 0.000 description 6
- 238000005240 physical vapour deposition Methods 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052738 indium Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910002056 binary alloy Inorganic materials 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910002058 ternary alloy Inorganic materials 0.000 description 4
- 238000002207 thermal evaporation Methods 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910017518 Cu Zn Inorganic materials 0.000 description 2
- 229910017755 Cu-Sn Inorganic materials 0.000 description 2
- 229910017752 Cu-Zn Inorganic materials 0.000 description 2
- 229910017927 Cu—Sn Inorganic materials 0.000 description 2
- 229910017943 Cu—Zn Inorganic materials 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000002679 ablation Methods 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 208000024234 coloboma, osteopetrosis, microphthalmia, macrocephaly, albinism, and deafness Diseases 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005566 electron beam evaporation Methods 0.000 description 2
- BFMKFCLXZSUVPI-UHFFFAOYSA-N ethyl but-3-enoate Chemical compound CCOC(=O)CC=C BFMKFCLXZSUVPI-UHFFFAOYSA-N 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- PHPKKGYKGPCPMV-UHFFFAOYSA-N [SeH-]=[Se].[In+3].[SeH-]=[Se].[SeH-]=[Se] Chemical compound [SeH-]=[Se].[In+3].[SeH-]=[Se].[SeH-]=[Se] PHPKKGYKGPCPMV-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000010549 co-Evaporation Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- IRPLSAGFWHCJIQ-UHFFFAOYSA-N selanylidenecopper Chemical compound [Se]=[Cu] IRPLSAGFWHCJIQ-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- H01L21/02518—Deposited layers
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Abstract
Description
− 硫黄分は、半導体表面において最大値を有し、素地界面へ向かって減少し、かつ素地界面において最小値を有する、あるいは、
− 硫黄分は、半導体表面において最小値を有し、素地界面へ向かって増大し、かつ素地界面において最大値を有する、あるいは、
− 硫黄分は、半導体表面において第1の最大値を有し、素地界面へ向かって最小値まで減少し、次いで、再び増加して、素地界面において第2の最大値を有する、あるいは、
− 硫黄分は、半導体表面において第1の最小値を有し、素地界面へ向かって最大値まで増加し、次いで、再び減少して、素地界面において第2の最小値を有する、ように実装されることが可能である。
− 銅分が、亜鉛および錫の合計分より少ないか、
− 銅分が、亜鉛および錫の合計分に等しいか、
− 銅分が、亜鉛および錫の合計分より多くなる、ように実装されることが可能である。
− 亜鉛分が、錫分より少ないか、
− 亜鉛分が、錫分に等しいか、
− 亜鉛分が、錫分より多くなる、ように実装されることが可能である。
− 硫黄分は、半導体表面において最大値を有し、素地界面へ向かって減少し、かつ素地界面において最小値を有する、あるいは、
− 硫黄分は、半導体表面において最小値を有し、素地界面へ向かって増大し、かつ素地界面において最大値を有する、あるいは、
− 硫黄分は、半導体表面において第1の最大値を有し、界面へ向かって最小値まで減少し、次いで、再び増加して、素地界面において第2の最大値を有する、あるいは、
− 硫黄分は、半導体表面において第1の最小値を有し、素地界面へ向かって最大値まで増加し、次いで、再び減少して、素地界面において第2の最小値を有する、ように実装される。
− 銅分が少ない、すなわち、銅分がZnおよびSnの合計分より少ない(Cu/(Zn+Sn)<1)か、あるいは、
− 化学量論的である、すなわち、銅分がZnおよびSnの合計分に等しい(Cu/(Zn+Sn)=1)か、あるいは、
− 銅分が多い、すなわち、銅分が、ZnおよびSnの合計分より多い(Cu/(Zn+Sn)>1)、ように実装されることが可能である。
− 亜鉛分が少ない、すなわち、亜鉛分が、錫分より少ない(Zn/Sn<1)か、あるいは、
− 化学量論的である、すなわち、亜鉛分が、錫分に等しい(Zn/Sn=1)か、あるいは、
− 亜鉛分が多い、すなわち、亜鉛分が、錫分より多い(Zn/Sn>1)、ように実装されることが可能である。
− 1つまたは2つの蒸着ソースからのSおよび/またはSeの(連続的または同時的)熱蒸着(PVD[物理的気相成長法])であって、場合により、ドーパントまたはドーパント含有化合物の蒸着によるドーパント(例えば、Na)の添加を伴う。
− 個々のカルコゲン(SまたはSe)が元素形態で含まれるターゲット(元素ターゲット)からのスパッタリング。
− 数K/秒範囲の高速加熱速度、
− 400℃を超える、好ましくは500℃を超える最高温度、
− 基板面積(横方向)およびその層厚にわたる高い温度均一性、
− 熱処理中の少なくとも1つのカルコゲン(Seおよび/またはS)の十分に高い制御可能および再現可能な分圧の保証(Se損失および/またはS損失の防止)、
− ガスの温度−時間プロファイルが適切である、例えばH2、N2、Ar、Sガス、Seガス、H2S、H2Seおよびこれらの組合せであるプロセスガスの制御された供給、を必要とする。
図2は、五元化合物半導体CZTSSeより成る吸収体2を製造するための第1の手順を示す。
図3は、五元化合物半導体CZTSSeより成る吸収体2を製造するための別の方法を示す。不必要な反復を避けるために、実施例1との相違点のみを説明する。よって、その他については、実施例1に関して行った説明を参照されたい。
図4は、五元化合物半導体CZTSSeより成る吸収体2を製造するための別の方法を示す。不必要な反復を避けるために、実施例1との相違点のみを説明する。よって、その他については、実施例1に関して行った説明を参照されたい。
2 吸収体
3 基板
4 裏面電極
5 第1の前駆体層
6 第2の前駆体層
7 層構造物
8 矢印
9 表面
10 界面
11 前駆体層スタック
12 素地
13 プロセスチャンバ
Claims (10)
- Cu2ZnSn(S,Se)4型の五元黄錫亜鉛鉱/黄錫鉱より成る化合物半導体を製造するための方法であって、
第1の前駆体層(5)と第2の前駆体層(6)より成る少なくとも1つの前駆体層スタック(11)を製造するステップであって、第1の段階において、素地(12)上へ金属である銅、亜鉛および錫を蒸着することによって第1の前駆体層(5)が生成され、かつ第2の段階において、第1の前駆体層(5)上へカルコゲンである硫黄および/またはセレンを蒸着することによって第2の前駆体層(6)が生成されるステップと、
第1の前駆体層(5)の金属および第2の前駆体層(6)の少なくとも1つのカルコゲンが化合物半導体(2)に反応的に変換されるように、プロセスチャンバ(13)において少なくとも1つの前駆体層スタック(11)を熱処理するステップと、
少なくとも1つの前駆体層スタック(11)を熱処理する間に、少なくとも1つのプロセスガスをプロセスチャンバ(13)へ送り込むステップであって、第2の前駆体層(6)に硫黄およびセレンから選択されるカルコゲンが含まれていれば、プロセスガス内に個々のもう一方のカルコゲンおよび/または個々のもう一方のカルコゲンを含有する化合物が含まれ、あるいは、第2の前駆体層(6)に2つのカルコゲン、即ち硫黄およびセレンが含まれていれば、プロセスガス内に硫黄および/またはセレン、および/または硫黄含有化合物、および/またはセレン含有化合物が含まれているステップとを含む、方法。 - 化合物半導体(2)の表面(9)から素地(12)との界面(10)へ向かう硫黄深さプロファイルが、
硫黄分が、表面(9)において最大値を有し、界面(10)へ向かって減少し、かつ界面(10)において最小値を有するように、あるいは、
硫黄分が、表面(9)において最小値を有し、界面(10)へ向かって増大し、かつ界面(10)において最大値を有するように、あるいは、
硫黄分が、表面(9)において第1の最大値を有し、界面(10)へ向かって最小値まで減少し、次いで、再び増加して、界面(10)において第2の最大値を有するように、あるいは、
硫黄分が、表面(9)において第1の最小値を有し、界面(10)へ向かって最大値まで増加し、次いで、再び減少して、界面(10)において第2の最小値を有するように実装される、請求項1に記載の方法。 - 硫黄深さプロファイルが、硫黄分の相対変動が深さプロファイルの少なくとも一部を少なくとも10%超えることになるように実装される、請求項2に記載の方法。
- 金属である銅、亜鉛および錫の個々の層より成る層スタックが、数回連続的に蒸着され、かつ/または、
カルコゲンである硫黄およびセレンの個々の層より成る層スタックは、数回連続的に蒸着される、請求項1から請求項3のいずれか一項に記載の方法。 - 前駆体層スタック(11)が、数回連続的に蒸着される、請求項1から請求項4のいずれか一項に記載の方法。
- 少なくとも1つのプロセスガスが、1つまたは複数の第2の時間間隔の間に送り込まれ、第2の時間間隔は、その都度、熱処理が実行される第1の時間間隔より短い、請求項1から請求項5のいずれか一項に記載の方法。
- 第1の前駆体層(5)が、
銅分が、亜鉛および錫の合計分より少ないように、かつ、
亜鉛分が、錫分より多いように実装される、請求項1から請求項6のいずれか一項に記載の方法。 - 2つの前駆体層(5、6)が、カルコゲンの合計分の金属の合計分に対する比が1より大きいか等しいように実装される、請求項1から請求項7のいずれか一項に記載の方法。
- 素地(12)上に配置されるCu2ZnSn(S,Se)4型の五元黄錫亜鉛鉱/黄錫鉱より成る化合物半導体で構成される吸収体(2)を有する薄膜太陽電池であって、化合物半導体(2)は、化合物半導体(2)の表面(9)から素地(12)との界面(10)へ向かう予め規定可能な硫黄深さプロファイルを有し、硫黄深さプロファイルは、
硫黄分が、表面(9)において最大値を有し、界面(10)へ向かって減少し、かつ界面(10)において最小値を有するように、あるいは、
硫黄分が、表面(9)において最小値を有し、界面(10)へ向かって増大し、かつ界面(10)において最大値を有するように、あるいは、
硫黄分が、表面(9)において第1の最大値を有し、界面(10)へ向かって最小値まで減少し、次いで、再び増加して、界面(10)において第2の最大値を有するように、あるいは、
硫黄分が、表面(9)において第1の最小値を有し、界面(10)へ向かって最大値まで増加し、次いで、再び減少して、界面(10)において第2の最小値を有するように実装される、薄膜太陽電池。 - 薄膜太陽電池の、または薄膜太陽モジュールの吸収体(2)を製造するための、Cu2ZnSn(S,Se)4型の五元黄錫亜鉛鉱/黄錫鉱より成る化合物半導体を製造するための請求項1から請求項8のいずれか一項に記載の方法の使用。
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