JP6562999B2 - 光電池用途のための混合酸化および硫化ビスマスおよび銀 - Google Patents
光電池用途のための混合酸化および硫化ビスマスおよび銀 Download PDFInfo
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- JP6562999B2 JP6562999B2 JP2017503075A JP2017503075A JP6562999B2 JP 6562999 B2 JP6562999 B2 JP 6562999B2 JP 2017503075 A JP2017503075 A JP 2017503075A JP 2017503075 A JP2017503075 A JP 2017503075A JP 6562999 B2 JP6562999 B2 JP 6562999B2
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- 229910052709 silver Inorganic materials 0.000 title claims description 7
- 239000004332 silver Substances 0.000 title claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title description 4
- 230000003647 oxidation Effects 0.000 title description 4
- 238000007254 oxidation reaction Methods 0.000 title description 4
- NNLOHLDVJGPUFR-UHFFFAOYSA-L calcium;3,4,5,6-tetrahydroxy-2-oxohexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(=O)C([O-])=O.OCC(O)C(O)C(O)C(=O)C([O-])=O NNLOHLDVJGPUFR-UHFFFAOYSA-L 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims description 72
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- 239000000203 mixture Substances 0.000 claims description 17
- 229910010272 inorganic material Inorganic materials 0.000 claims description 10
- 238000003801 milling Methods 0.000 claims description 10
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 10
- 229910052738 indium Inorganic materials 0.000 claims description 9
- 150000002910 rare earth metals Chemical class 0.000 claims description 9
- 229910052793 cadmium Inorganic materials 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- 229910052745 lead Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
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- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 4
- -1 silver inorganic compounds Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 24
- 239000010949 copper Substances 0.000 description 13
- 239000011787 zinc oxide Substances 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 239000011324 bead Substances 0.000 description 7
- 238000006467 substitution reaction Methods 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000005670 electromagnetic radiation Effects 0.000 description 6
- 229910052714 tellurium Inorganic materials 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 150000002484 inorganic compounds Chemical class 0.000 description 5
- 229910052711 selenium Inorganic materials 0.000 description 5
- 239000011669 selenium Substances 0.000 description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 4
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
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- 230000001186 cumulative effect Effects 0.000 description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 2
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- 229910052710 silicon Inorganic materials 0.000 description 2
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- 231100000331 toxic Toxicity 0.000 description 2
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- 229910004613 CdTe Inorganic materials 0.000 description 1
- 229910000669 Chrome steel Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000001228 spectrum Methods 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
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur 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
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Description
Bi1−xMxAg1−y−εM’yOS1−zM’’z(I)
[式中:
Mが、Pb、Sn、Hg、Ca、Sr、Ba、Sb、In、Tl、Mg、希土類金属からなる群(A)から選択される元素または元素の混合物であり、
M’が、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Al、Cd、Pt、Pdからなる群(B)から選択される元素または元素の混合物であり、
M’’がハロゲンであり、
x、yおよびzが、1より小さい、特に0.6より小さい、特に0.5より小さい、例えば0.2より小さい数であり、
0≦ε<0.2である]の少なくとも1つの化合物を含む新規な材料である。
任意選択によりBiとPb、Sn、Hg、Ca、Sr、Ba、Sb、In、Tl、Mg、希土類金属からなる群(A)からの元素とから選択される少なくとも1つの元素の少なくとも1つの酸化物、硫化物、オキシ硫化物、ハロゲン化物またはオキシハロゲン化物と、
任意選択によりAgとTi、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Al、Cd、Pt、Pdからなる群(B)からの元素とから選択される少なくとも1つの元素の少なくとも1つの酸化物、硫化物、オキシ硫化物、ハロゲン化物またはオキシハロゲン化物とを含む混合物のソリッドミリングの工程を含む、本発明による材料を調製するための方法である。
Bi1−xMxAg1−y−εM’yOS1−zM’’z(I)
[式中:
Mが、Pb、Sn、Hg、Ca、Sr、Ba、Sb、In、Tl、Mg、希土類金属からなる群(A)から選択される元素または元素の混合物であり、
M’が、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Al、Cd、Pt、Pdからなる群(B)から選択される元素または元素の混合物であり、
M’’がハロゲンであり、
x、yおよびzが、1より小さい、特に0.6より小さい、特に0.5より小さい、例えば0.2より小さい数であり、
0≦ε<0.2である]の少なくとも1つの化合物を含む材料の、
特に光電気化学または光化学用途のための、特に光電流をもたらすための半導体としての使用である。
− pタイプの半導体の性質を有する第1の化合物と、
− nタイプの半導体の性質を有する第2の化合物とを組み合わせて使用することによって得られる。
− 式(I)の化合物をベースとした層が、n型半導体をベースとした層と接触しており、
− 式(I)の化合物をベースとした層が正孔伝導性材料に近接しており、
− n型半導体をベースとした層が電子伝導性材料に近接している。
− 入射電磁界を完全には吸収しない材料、および/または
− 電磁線の一部が、材料に当たらずにこの電磁線を通過させることができる(典型的に孔、スリットまたは隙間を含む)有孔の形態である材料であってもよい。
− 等方性物体の場合は平均直径、
− 異方性物体の場合は厚さまたは横径であってもよい。
− 上述のタイプの光活性電極(本発明に従う式(I)の化合物の粒子で覆われたITOまたは金属板)、
− 参照電極、および
− 対電極
が浸漬され、
これらの3つの電極は典型的にポテンショスタットによって一緒に連結される。
− 光活性電極として:式(I)の化合物の粒子で覆われた担体(ITO板など)、
− 参照電極として:例えば、Ag/AgCl電極、および
− 対電極として:例えば、白金線
を含んでもよく、
これらの3つの電極は典型的にポテンショスタットによって一緒に連結される。
− 2cm×1cmのITOの導電層で覆われたガラスをベースとした担体12からなり、その上に表面全体にわたり本発明に従う式(I)の化合物の粒子14をベースとした厚さ約1μmの層13が堆積される光活性電極11であって、粒子14がテルピネオール中に予め分散され、次に、導電性ガラス板11上へのコーティング(ドクターブレードコーティング)によって堆積される、光活性電極11と、
− (Ag/AgCl)参照電極15と、
− 対電極(白金線)16と、を含む光電気化学電池10を示す。
BiAgOS粒子を調製するための方法
BiAgOS粉末は、以下の手順に従って、室温での反応性ミリングによって調製された。
0.685gのBi2S3、1.243gのBi2O3および0.991gのAg2Sを瑪瑙ミリングビーズの存在下で瑪瑙乳鉢内に置く。
光電気化学デバイス内での化合物C1の使用
図1に記載されたデバイスは、作用電極をAg/AgClに対して−0.8Vの電位に分極して使用された。システムは、白熱電球(2700Kの色温度)下で暗時と点灯時と交互で照明される。システムが照明下に置かれる時に電流の強さが増加した。これは、100μA.cm−2に測定された光電流であり、これは、化合物C1が光電流を発生する能力を裏づける。この光電流はカソード電流(すなわち負側)であり、それは、化合物C1がp型半導体であるという事実と一致している。
Claims (13)
- 式(I):
Bi1−xMxAg1−y−εM’yOS1−zM’’z(I)
[式中:
Mが、Pb、Sn、Hg、Ca、Sr、Ba、Sb、In、Tl、Mg、希土類金属からなる群(A)から選択される元素または元素の混合物であり、
M’が、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Al、Cd、Pt、Pdからなる群(B)から選択される元素または元素の混合物であり、
M’’がハロゲンであり、
x、yが、0.5より小さい数であり、zがゼロであり、ε=0である]の少なくとも1つの化合物を含む材料。 - x、yおよびzがゼロであり、式(I)の化合物が、以下の式:
BiAgOS
に相当する、請求項1に記載の材料。 - xまたはyの少なくとも1つがゼロではない、請求項1に記載の材料。
- ビスマスおよび銀の無機化合物の少なくとも1つと、
任意選択によりBiと群(A)からの元素とから選択される少なくとも1つの元素の少なくとも1つの酸化物、硫化物、オキシ硫化物、ハロゲン化物またはオキシハロゲン化物と、
任意選択によりAgと群(B)からの元素とから選択される少なくとも1つの元素の少なくとも1つの酸化物、硫化物、オキシ硫化物、ハロゲン化物またはオキシハロゲン化物
とを含む混合物のソリッドミリングの工程を含む、請求項1〜3のいずれか一項に記載の材料を調製するための方法。 - 半導体としての請求項1〜3のいずれか一項に記載の材料の使用。
- 光電気化学または光化学用途のための、請求項5に記載の使用。
- 光電流をもたらすための、請求項6に記載の使用。
- 式(I)の化合物が、50μm未満の少なくとも1つの寸法を有する等方性または異方性物体の形態で使用される、請求項5〜7のいずれか一項に記載の使用。
- 式(I)の化合物が、10μm未満の寸法を有する粒子の形態で使用される、請求項8に記載の使用。
- 式(I)の化合物が、プレートレットタイプの異方性粒子、またはこのタイプの数十〜数百の粒子の凝集体の形態である、請求項9に記載の使用。
- 式(I)の化合物が、その厚さが50μm未満である式(I)の化合物をベースとした連続した層の形態であり、式(I)の化合物をベースとした層が、少なくとも95質量%の比率で式(I)の化合物を含む層である、請求項8に記載の使用。
- 式(I)の化合物が、その厚さが50μm未満である式(I)の化合物をベースとした連続した層の形態であり、式(I)の化合物をベースとした層が、ポリマーマトリックスと、このマトリックス中に分散された、5μm未満の寸法を有する式(I)の化合物をベースとした粒子とを含む、請求項8に記載の使用。
- 正孔伝導性材料と電子伝導性材料との間に、請求項1〜3のいずれか一項に記載の式(I)のp型化合物をベースとした層と、n型半導体をベースとした層とを含む光電池デバイスであって、
− 式(I)のp型化合物をベースとした層が、n型半導体をベースとした層と接触しており、
− 式(I)のp型化合物をベースとした層が正孔伝導性材料に近接しており、
− n型半導体をベースとした層が電子伝導性材料に近接している、光電池デバイス。
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