EP3126292A1 - Oxydes et sulfures mixtes de bismuth et cuivre pour application photovoltaïque - Google Patents
Oxydes et sulfures mixtes de bismuth et cuivre pour application photovoltaïqueInfo
- Publication number
- EP3126292A1 EP3126292A1 EP15713968.4A EP15713968A EP3126292A1 EP 3126292 A1 EP3126292 A1 EP 3126292A1 EP 15713968 A EP15713968 A EP 15713968A EP 3126292 A1 EP3126292 A1 EP 3126292A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- compound
- formula
- less
- elements
- particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000010949 copper Substances 0.000 title claims description 36
- 229910052802 copper Inorganic materials 0.000 title claims description 15
- 229910052797 bismuth Inorganic materials 0.000 title claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 13
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims description 13
- 150000003568 thioethers Chemical class 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 91
- 239000004065 semiconductor Substances 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 29
- 239000004020 conductor Substances 0.000 claims description 26
- 238000000227 grinding Methods 0.000 claims description 24
- 229910052749 magnesium Inorganic materials 0.000 claims description 16
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 150000004820 halides Chemical class 0.000 claims description 12
- 229910052738 indium Inorganic materials 0.000 claims description 12
- 229910010272 inorganic material Inorganic materials 0.000 claims description 12
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052793 cadmium Inorganic materials 0.000 claims description 10
- 150000002484 inorganic compounds Chemical class 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 229910052745 lead Inorganic materials 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 229910052733 gallium Inorganic materials 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052712 strontium Inorganic materials 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- 229910052716 thallium Inorganic materials 0.000 claims description 8
- 229910052718 tin Inorganic materials 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000005749 Copper compound Substances 0.000 claims description 3
- 239000012736 aqueous medium Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 150000001880 copper compounds Chemical class 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 150000001622 bismuth compounds Chemical class 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 27
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 24
- 239000011701 zinc Substances 0.000 description 15
- 239000011787 zinc oxide Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 238000006467 substitution reaction Methods 0.000 description 8
- 239000004570 mortar (masonry) Substances 0.000 description 7
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 230000005670 electromagnetic radiation Effects 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 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
- 239000000843 powder Substances 0.000 description 5
- 229910052711 selenium Inorganic materials 0.000 description 5
- 239000011669 selenium Substances 0.000 description 5
- 229910052714 tellurium Inorganic materials 0.000 description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011734 sodium Substances 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
- 229920001817 Agar Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000008272 agar Substances 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002244 precipitate 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
- 239000002904 solvent Substances 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- -1 Se or Te Chemical class 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
- 150000001412 amines Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000001955 cumulated 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
- 230000008021 deposition Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000008240 homogeneous mixture Substances 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000013082 photovoltaic technology Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 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 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 229940116411 terpineol Drugs 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000012780 transparent material Substances 0.000 description 2
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical class O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 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
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- GMSWRMUHJLKEIL-UHFFFAOYSA-N azane;ethene Chemical group N.C=C GMSWRMUHJLKEIL-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- AEOCXXJPGCBFJA-UHFFFAOYSA-N ethionamide Chemical compound CCC1=CC(C(N)=S)=CC=N1 AEOCXXJPGCBFJA-UHFFFAOYSA-N 0.000 description 1
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000001033 granulometry Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 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
- 238000009434 installation Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 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
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 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
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 150000003573 thiols Chemical class 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
- 238000002604 ultrasonography 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
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
- C01G29/006—Compounds containing, besides bismuth, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/547—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on sulfides or selenides or tellurides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—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
- H01L31/0248—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
- H01L31/0256—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 the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/06—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/50—Agglomerated particles
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3289—Noble metal oxides
- C04B2235/3291—Silver oxides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Definitions
- the present invention relates to the field of inorganic semiconductor compounds, in particular intended to provide a photocurrent, in particular by photovoltaic effect.
- photovoltaic technologies using inorganic compounds are mainly based on silicon technologies (over 80% of the market) and on thin film technologies (mainly CdTe and CIGS (Copper Indium Gallium Selenium), representing 20% of the market).
- CdTe and CIGS Copper Indium Gallium Selenium
- CZTS Cu 2 ZnSnSe 4
- the present invention proposes to use a new family of inorganic materials, whose inventors have now shown that, unexpectedly, they prove to have good efficiency, and that they have the advantage of not having to use, or at a very low level, rare or toxic metals of the type In, Te, Cd mentioned above, and furthermore offer the possibility of using anions, such as Se or Te, in a reduced content, even not to use this type of anions.
- One of the objects of the present invention is a new material comprising at least one compound of formula (I):
- M is a member or a mixture of elements selected from the group (A) consisting of Pb, Sn, Hg, Ca, Sr, Ba, Sb, In, Tl, Mg, rare earths,
- M ' is a member or a mixture of elements selected from the group (B) consisting of Ag, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Ga, Mg, Al, Cd,
- x, y and z are numbers less than 1, in particular less than 0.6, especially less than 0.5, for example less than 0.2,
- the elements M, M 'and M are generally substitution elements occupying respectively the place of the element Bi, of the element Cu and S element.
- material comprising at least one compound of formula (I) is meant a solid, generally in divided form (powder, dispersion) or in the form of a coating or a continuous or discontinuous layer on a support, and which comprises, or even consists of, a compound of formula (I).
- Ring earth means the elements of the group constituted by yttrium and scandium and the elements of the periodic classification of atomic number inclusive between 57 and 71.
- the element M may preferably be chosen from Sb, Pb, Ba and rare earth elements.
- the element M may for example be lutetium.
- the element M ' may preferably be chosen from the elements Ag, Zn, Mn.
- the element M ' may for example be the element Ag.
- the element M can in particular be the element I.
- the compound of formula (I) according to the invention corresponds to the following formula: Bi 1-x M x Cui - £ OS (l a), where x ⁇ 0, ⁇ is a number null or non-zero and M is an element or a mixture of elements selected from the group (A) consisting of Pb, Sn, Hg, Ca, Sr, Ba, Sb, In, Tl, Mg, rare earths.
- M is an element or a mixture of elements chosen from rare earths.
- the compound of formula (I) according to the invention corresponds to the following formula: -Y- BiCui £ M 'y OS (l b), where y ⁇ 0, ⁇ is a number zero or non-zero and M 'is a member or a mixture of elements selected from the group (B) consisting of Ag, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Ga, Mg, Al, Cd.
- M ' is an element or a mixture of elements chosen from the Ag and Zn elements.
- the compound of formula (I) according to the invention corresponds to the following formula: M z BiCuOS "1-z (l c), where z ⁇ 0, ⁇ is a number zero or non-zero and M" is a halogen.
- the invention also relates to different access routes to the material according to the invention.
- the subject of the invention is a first process for preparing the material according to the invention comprising a step of solid grinding of a mixture comprising at least inorganic compounds of bismuth and copper, and optionally at least one oxide, sulfide, oxysulfide, halide or oxyhalide of at least one element selected from Bi and the elements of group (A) consisting of Pb, Sn, Hg, Ca, Sr, Ba, Sb, In, Tl, Mg, the earths rare, and
- group (B) consisting of Ag, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Ga, Mg, Al, Cd.
- a solid form mixture comprising at least inorganic compounds of bismuth and copper is ground.
- the inorganic compounds of bismuth and copper present in the mixture are at least the compounds Bi 2 O 3 , Bi 2 S 3 and Cu 2 S.
- This grinding can be done according to any known means.
- This mixture can in particular be placed in an agate mortar.
- the grinding may for example be carried out with a planetary mill.
- grinding balls which consist for example of stainless steel balls, special chromium steel balls, agate balls, tungsten carbide balls , balls made of zirconium oxide.
- the grinding time can be adjusted according to the desired product. It may especially be between 20 minutes and 96 hours, in particular between 1 hour and 72 hours.
- the particle sizes referred to here can typically be measured by scanning electron microscopy (SEM).
- the subject of the invention is a second method for preparing the material according to the invention by carrying out a precipitation reaction comprising the following steps:
- step (e) filtration, and washing if necessary, of the compound of formula (I) obtained at the end of step (d).
- This method consists in carrying out a precipitation reaction by using soluble metal precursors in order to obtain a homogeneous mixture of the substitution elements in the material comprising the compound of formula (I).
- the different precursor solutions are prepared separately and then mixed together, whereby a homogeneous mixture and submicron particle sizes are obtained.
- the precipitation can be carried out by raising the temperature in particular to obtain a better crystallization.
- a precipitation can be carried out as follows: (a) - (b) providing a solution of the soluble metal precursors.
- a basic pH solution can be prepared in which:
- the elements Bi and of the group (A) are stabilized by complexation with a highly complexing polycarboxylate anion such as citrate, lactate, tartrate ...
- the copper is stabilized in the form of copper (I) by adding an excess of reducing agent (such as, for example, sodium thiosulfate, hydrazine, etc.),
- reducing agent such as, for example, sodium thiosulfate, hydrazine, etc.
- the copper and the elements of the group (B) can be kept soluble in basic medium either by the action of the basic pH (Al, Zn) or stabilized in basic medium by addition of ligands complexing the ion such as amine ligands (ammonia ethylene diamine, organic amine ).
- the subject of the invention is a third method for preparing the material according to the invention, comprising the following steps:
- a deagglomeration step can be carried out, for example, by means of an ultrasound probe.
- the inorganic bismuth and copper compounds provided in the mixture of step (a ') are at least Bi 2 O 3 and Cu 2 O.
- step (b') is advantageously carried out in the presence of a source of oxygen, such as water, nitrates or even carbonates.
- the source of sulfur employed in step (a ') may be chosen from sulfur, hydrogen sulphide H 2 S and its salts, an organic sulfur compound (thiol, thioether, thioamide, etc.), preferably a anhydrous or hydrated sodium sulphide.
- the oxides in the dispersed state are employed in step (a ') in the form of particles, typically in the form of powders, having a particle size of less than 10 ⁇ , in particular lower than at 5 ⁇ , preferably less than 1 ⁇ .
- This particle size can for example be obtained by prior grinding of the oxides (separately, or more advantageously in the case of oxide mixtures, this grinding can be carried out on the oxide mixture), for example, using a Micronizer type device or wet ball mill.
- step (b ') the dissolution is carried out in "hydrothermal conditions".
- hydrothermal conditions in the sense of the present description is meant that the step is conducted at a temperature above 180 ° C under the saturated vapor pressure of water.
- the temperature of step (b ') may be less than 240 ° C, or even less than 210 ° C, for example between 180 ° C and 200 ° C.
- step (b ') can be carried out without preliminary grinding, in which case it is however preferable to carry out the step at a temperature greater than 240 ° C., preferably greater than 250 ° C.
- step (b ') the mixture is placed in water at a temperature below the hydrothermal conditions (typically at a temperature at room temperature and under atmospheric pressure), then the temperature is slowly raised, advantageously at a rate of less than 10 ° C./min, for example between 0.5 and 5 ° C./min, typically 2.5 ° C./min, in typically operating in a closed environment (using a device such as a hydrothermal bomb, in particular a Parr bomb) until the operating temperature is reached.
- a temperature below the hydrothermal conditions typically at a temperature at room temperature and under atmospheric pressure
- the temperature is slowly raised, advantageously at a rate of less than 10 ° C./min, for example between 0.5 and 5 ° C./min, typically 2.5 ° C./min, in typically operating in a closed environment (using a device such as a hydrothermal bomb, in particular a Parr bomb) until the operating temperature is reached.
- step (b ') the dissolution is specifically carried out with stirring.
- This agitation can be carried out in particular by magnetic stirring, for example by placing the hydrothermal bomb, on a magnetic stirrer, the assembly being placed in a heating chamber (such as an oven).
- the temperature is maintained at at least 190 ° C for at least 12 hours, for example for 48 hours, or even 7 days.
- the solution obtained is, in step (c), typically reduced to an ambient temperature or more generally to a temperature of between 10 and 30 ° C. cooling, for example by decreasing the temperature by at least 1 ° C / min, preferably by a faster cooling, with a reduction typically of at least 3 ° C / min, for example from 3 to 5 ° C / min.
- This type of cooling typically leads to particles having a length of between 50 nm and 5 ⁇ , typically between 100 nm and 1 ⁇ , and a thickness of 50 nm.
- the material according to the invention is obtained by the first solid grinding process described above.
- the present invention further relates to the use of a material comprising at least one compound of formula (I):
- M is a member or a mixture of elements selected from the group (A) consisting of Pb, Sn, Hg, Ca, Sr, Ba, Sb, In, Tl, Mg, rare earths,
- M ' is an element or a mixture of elements selected from group (B) consisting of by Ag, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Ga, Mg, Al, Cd,
- x, y and z are numbers less than 1, in particular less than 0.6, especially less than 0.5, for example less than 0.2,
- the compound that is present in the semiconductor material is a substituted inorganic material, in particular of the p type.
- substitutions such as the substitution of the element Bi by rare earths or by the element Sb or alternatively the substitution of the element Cu by the element Ag
- these substitutions can, in particular by modifying the parameters and / or by changing the extension of the orbitals and their energy position, thus causing changes in the gap (valence band - conduction band).
- the aliovalent substitutions modify the degree of oxidation of the element Cu.
- the introduction of substituents in the structure of the semiconductor may, as the case may be, cause a reduction or an increase in the number of charge carriers.
- the substituted materials may in particular have a higher conductivity, which induces an improved conduction capacity, compared to its unsubstituted form, or conversely a lower conductivity.
- the inventors have now demonstrated that the materials corresponding to the above formula (I), in particular, when they are p-type, are capable of providing a photocurrent when they are irradiated under a wavelength greater than their gap (namely the generation of an electron-hole pair within the material under the effect of an incident photon of sufficient energy, the charged species formed (the electron and the "hole” (Ie the electron gap) being free to move to generate a current).
- the inventors have now demonstrated that the materials of the invention prove to be suitable for ensuring a photovoltaic effect.
- These compounds are placed close to each other in a manner known per se (ie in direct contact or at least at a sufficiently small distance to ensure the photovoltaic effect) to form a p-n type junction.
- the electron-hole pairs created by light absorption are dissociated at the pn junction and the excited electrons can be conveyed by the n-type semiconductor towards the anode, the holes being led towards the cathode via the p-type semiconductor.
- the photovoltaic effect is typically obtained by placing a material based on a semiconductor of formula (I) above, which is also specifically of the p type, in contact with a semiconductor n-type between two electrodes, in direct contact or optionally connected to at least one of the electrodes via an additional coating, for example a charge collection coating; and irradiating the photovoltaic device thus produced with adequate electromagnetic radiation, typically by the light of the solar spectrum.
- a material based on a semiconductor of formula (I) above which is also specifically of the p type, in contact with a semiconductor n-type between two electrodes, in direct contact or optionally connected to at least one of the electrodes via an additional coating, for example a charge collection coating; and irradiating the photovoltaic device thus produced with adequate electromagnetic radiation, typically by the light of the solar spectrum.
- an additional coating for example a charge collection coating
- the present invention relates to photovoltaic devices comprising, between a hole-conducting material and an electron-conducting material, a layer based on a compound of formula (I) of type p and a layer based on an n-type semiconductor, where:
- the layer based on the compound of formula (I) is in contact with the layer based on the n-type semiconductor; the layer based on the compound of formula (I) is close to the hole-conducting material;
- the n-type semiconductor layer is in proximity to the electron conducting material.
- the term "hole-conducting material” means a material which is capable of ensuring a flow of current between the p-type semiconductor and the electrical circuit.
- the n-type semiconductor employed in the photovoltaic devices according to the invention may be chosen from any semiconductor which exhibits an electron acceptor character which is more marked than the compound of formula (I) or a compound promoting the evacuation of electrons.
- the n-type semiconductor may be an oxide, for example ZnO, or TiO 2 , or a sulphide, for example ZnS.
- the hole-conducting material used in the photovoltaic devices according to the invention may be, for example, a suitable metal, such as gold, tungsten, or molybdenum; or a metal deposited on a support, or in contact with an electrolyte, such as Pt / FTO (platinum deposited on fluorine-doped tin dioxide); or a conductive oxide such as ⁇ (tin-doped indium oxide), for example, deposited on glass; or a p-type conductive polymer.
- a suitable metal such as gold, tungsten, or molybdenum
- Pt / FTO platinum deposited
- the hole-conducting material may comprise a hole-conducting material of the aforementioned type and a redox mediator, for example an electrolyte containing the ⁇ 2 / pair, in which case the hole-conducting material is typically Pt. / OTF.
- the electron-conducting material may be, for example, FTO, or AZO (aluminum-doped zinc oxide), or an n-type semiconductor.
- the holes generated at the p-n junction are extracted via the hole-conducting material and the electrons are extracted via the electron-conducting material of the aforementioned type.
- the hole-conducting material and / or the electron-conducting material is at least one material. partially transparent that allows to pass the electromagnetic radiation used.
- the at least partially transparent material is advantageously placed between the source of the incident electromagnetic radiation and the p-type semiconductor.
- the hole-conducting material may for example be a material chosen from a metal or a conductive glass.
- the electron-conducting material may be at least partially transparent, and is then chosen, for example, from FTO (fluorine-doped tin dioxide), or AZO (aluminum-doped zinc oxide), or a semiconductor.
- FTO fluorine-doped tin dioxide
- AZO aluminum-doped zinc oxide
- n-type conductor n-type conductor.
- the layer based on an n-type semiconductor which is in contact with the layer based on a compound of formula (I) of type p may also be at least partially transparent.
- partially transparent material is meant here a material that passes at least part of the incident electromagnetic radiation, useful for providing the photocurrent, and which can be:
- the compound of formula (I) employed according to the present invention is advantageously used in the form of isotropic or anisotropic objects having at least one dimension less than 50 ⁇ , preferably less than 20 ⁇ , typically less than 10 ⁇ , preferentially less than 5 ⁇ , generally less than 1 ⁇ , more preferably less than 500 nm, for example less than 200 nm, or even 100 nm.
- the dimension less than 50 ⁇ can be:
- the objects based on a compound of formula (I) are particles, typically having dimensions less than 10 ⁇ .
- These particles are preferably obtained according to one of the preparation methods of the invention.
- particles is meant here isotropic or anisotropic objects, which may be individual particles, or aggregates.
- the particle sizes referred to herein can typically be measured by scanning electron microscopy (SEM).
- the compound of formula (I) is in the form of platelet-type anisotropic particles, or agglomerates of a few tens to a few hundreds of particles of this type, these platelet-type particles typically having dimensions remaining less than 5 ⁇ . , (preferably less than 1 ⁇ , more preferably less than 500 nm), with a thickness which typically remains less than 500 nm, for example less than 100 nm.
- Particles of the type described according to the first variant can typically be employed in the state deposited on an n-type conductive or semiconductor support.
- a plate of ITO or metal covered with particles of formula (I) p type according to the invention can thus, for example play the role of a photoactive electrode for a photoelectrochemical device that can be used in particular as a photodetector.
- a photoelectrochemical type device implementing a photoactive electrode of the aforementioned type comprises an electrolyte which is generally a salt solution, for example a KCl solution, typically having a concentration of the order of 1 M, in which are immersed:
- the electrochemical device can comprise:
- a reference electrode for example, an Ag / AgCl electrode
- a counter-electrode for example, a platinum wire
- these three electrodes being interconnected, typically by a potentiostat.
- the electrolyte is an aqueous solution, which is most often the case, the water in the electrolyte is reduced to close to the photoactive electrode by the generated electrons, producing hydrogen and OH-ions ".
- OH "ions so produced will migrate to the against-electrode via the electrolyte; and the holes of the compound of formula (I) will be extracted via the ITO conductor and will enter the external electrical circuit.
- the oxidation of the OH " is carried out by means of the holes near the counter-electrode producing oxygen .
- the setting in movement of these charges (holes and electrons), induced by the absorption of the light of the compound of formula (I) generates a photocurrent.
- the device can in particular be used as a photodetector, the photocurrent being generated only when the device is illuminated.
- a photoactive electrode as described above can in particular be carried out by employing a suspension comprising the particles of a compound of formula (I) of the aforementioned type dispersed in a solvent, and by depositing this suspension on a support, for example a glass plate covered with ITO or a metal plate, by the wet method or any coating method, for example, by drop-casting, centrifugation ("spin-coating” in English) ), dipping ("dip-coating” in English), inkjet or serigraphy.
- a support for example a glass plate covered with ITO or a metal plate
- the wet method or any coating method for example, by drop-casting, centrifugation ("spin-coating" in English) ), dipping ("dip-coating” in English), inkjet or serigraphy.
- the particles based on a compound of formula (I) which are present in the suspension have an average diameter such as as measured by laser granulometry (for example, by means of a Malvern type laser particle size)
- the particles of compound of formula (I) may be previously dispersed in a solvent, for example, terpineol or ethanol.
- the suspension containing the particles of compound of formula (I) may be deposited on a support, for example a conductive oxide coated plate.
- the compound of formula (I) is in the form of a continuous layer based on the compound of formula (I), the thickness of which is less than 50 ⁇ , preferably less than 20 ⁇ , more preferably less than 10 ⁇ , for example less than 5 ⁇ and typically greater than 500 nm.
- continuous layer is meant here a homogeneous deposit made on a support and covering said support, not obtained by simply depositing a dispersion of particles on the support.
- the continuous layer based on a p-type compound of formula (I) according to this particular variant of the invention is typically placed in the vicinity of a n-type semiconductor layer between a hole conductive material. and an electron conducting material for forming a photovoltaic device for providing a photovoltaic effect.
- An n-type semiconductor in the use according to the invention may be a conductive oxide, for example ZnO, or TiO 2 , or a sulphide, for example ZnS.
- layer based on the compound of formula (I) means a layer comprising the compound of formula (I), preferably at least 50% by weight, or even at least 75% by weight. % by mass.
- the continuous layer according to the second variant consists essentially of the compound of formula (I), and typically comprises at least 95% by weight, or even at least 98% by weight, more preferably at least 99% by weight. by mass of the compound of formula (I).
- the continuous layer based on a compound of formula (I) employed according to this embodiment can take several forms.
- the continuous layer may in particular comprise a polymer matrix and, dispersed within this matrix, particles based on a compound of formula (I), typically of dimensions less than 10 ⁇ , or even less than 5 ⁇ , especially of the type of those used in the first embodiment of the invention.
- a compound of formula (I) typically of dimensions less than 10 ⁇ , or even less than 5 ⁇ , especially of the type of those used in the first embodiment of the invention.
- the polymer matrix comprises a p-type conductive polymer, which may especially be chosen from polythiophene derivatives, more particularly from poly (3,4-ethylenedioxythiophene) derivatives: poly (styrenesulfonate) (PEDOT: PSS).
- polythiophene derivatives more particularly from poly (3,4-ethylenedioxythiophene) derivatives: poly (styrenesulfonate) (PEDOT: PSS).
- the particles based on the compound of formula (I) present in the polymer matrix preferably have dimensions of less than 5 ⁇ , which can in particular be determined by SEM.
- Figure 1 is a schematic sectional representation of a photoelectrochemical cell used in Example 4 described below;
- FIG. 2 is a diagrammatic representation in section of a photodetector device
- Figure 3 is a schematic sectional representation of a photovoltaic device
- FIG. 4 is a schematic sectional representation of a photovoltaic device according to the invention, not exemplified.
- a photoelectrochemical cell 10 which comprises:
- a photoactive electrode 11 consisting of a support 12 based on a glass covered with a 2 cm ⁇ 1 cm ITO conductive layer on which a layer 13 of thickness of the entire surface has been deposited over the entire surface; 1 ⁇ m particle-based order 14 of a compound of formula (I) according to the invention, the particles 14 were previously dispersed in terpineol and then deposited by coating ("Doctor Blade Coating" in English) on the conductive glass plate 1 1.
- the three electrodes 11, 15 and 16 are immersed in an electrolyte 17 of KCI at 1 M.
- the three electrodes are connected by a potentiostat 18.
- FIG. 2 a photodetector device 20 which comprises particles 21 of a compound of formula (I) according to the invention.
- This device comprises a layer 22 FTO of thickness of the order of 500 nm on which is electrodeposited a layer 23 of thickness of order 1 ⁇ ZnO based.
- the layer 24 with a thickness of the order of 1 ⁇ based on the particles 21 of a compound of formula (I) according to the invention is deposited on the surface of the layer 23 by depositing drops from a suspension of particles of a compound of formula (I) according to the invention at 25-30% by weight in ethanol.
- FIG. 3 is shown the photovoltaic device 30 which comprises particles 31 of a compound of formula (I) according to the invention.
- This device comprises a layer 32 FTO of thickness of the order of 500 nm on which is electrodeposited a layer 33 of thickness of order 1 ⁇ ZnO based.
- the layer 34 of thickness of about 1 m based on the particles 31 of a compound of formula (I) according to the invention is deposited on the surface of the layer 33 by depositing the drops from a suspension of particles of formula (I) according to the invention at 25-30% by weight in ethanol.
- FIG. 4 shows photovoltaic device 40 which comprises a layer 41 based on particles of a compound of formula (I) according to the invention deposited on a layer 42 based on ZnO by coating, layer 42 based on ZnO being prepared by the sol-gel deposition, the layer 41 being in contact with a layer 43 of gold and the layer 42 based on the ZnO being in contact with an FTO layer 44.
- a compound of formula (I) according to the invention Contacting a compound of formula (I) according to the invention with a n-type ZnO semiconductor forms a pn junction.
- the electrons generated go into the ZnO and the holes generated remain in the compound of formula (I) according to the invention.
- ZnO is in contact with FTO (electron conductor) to extract the electrons and the compound of formula (I) according to the invention is in contact with gold (conductor holes) to extract the holes.
- FTO electron conductor
- gold conductor holes
- a powder of BiCuo.sAgo.sOS was prepared by reactive grinding at room temperature, according to the following protocol:
- the mortar is then covered and placed in a Fritsch No. 6 planetary mill with a rotation speed of the order of 500 rpm. The grinding is continued for 120 min until a pure phase is obtained.
- a powder of BiCuOSo.slo.s was prepared by reactive grinding at room temperature, according to the following protocol:
- a powder of BiCu 0.7 Zn 0.3 OS was prepared by reactive grinding at room temperature, according to the following protocol:
- the mortar is then covered and placed in a Fritsch type planetary mill
- the mixture is heated moderately (50 ° C) for four hours. A colorless solution is obtained. It is preferable to use closed containers to avoid the oxidation of copper (I).
- the cation solution (Bi, Cu, Zn) is added to the Na 2 S solution. A black precipitate forms immediately. The solution is stirred at 90 ° C for four hours. It is then filtered, washed with distilled water and dried at 80 ° C. in an oven.
- the device described in FIG. 1 was used, polarizing the working electrode at a potential of -0.8 V vs. Ag / AgCl.
- the system is irradiated under an incandescent lamp (whose color temperature is 2700 K) alternating periods of darkness and periods of light.
- the intensity of the current increased when the system was placed in the light. It is a photocurrent confirming the ability of each of the compounds Ci to C 3 to generate a photocurrent.
- This photocurrent is cathodic (i.e., negative) which is consistent with the fact that each of these compounds C 1 to C 3 is a p-type semiconductor.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Ceramic Engineering (AREA)
- Electromagnetism (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Manufacturing & Machinery (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Photovoltaic Devices (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Light Receiving Elements (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1400832A FR3019539B1 (fr) | 2014-04-04 | 2014-04-04 | Oxydes et sulfures mixtes de bismuth et cuivre pour application photovoltaique |
PCT/EP2015/097023 WO2015150591A1 (fr) | 2014-04-04 | 2015-04-03 | Oxydes et sulfures mixtes de bismuth et cuivre pour application photovoltaïque |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3126292A1 true EP3126292A1 (fr) | 2017-02-08 |
Family
ID=51483460
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP15713968.4A Withdrawn EP3126292A1 (fr) | 2014-04-04 | 2015-04-03 | Oxydes et sulfures mixtes de bismuth et cuivre pour application photovoltaïque |
Country Status (7)
Country | Link |
---|---|
US (1) | US20170022072A1 (ko) |
EP (1) | EP3126292A1 (ko) |
JP (1) | JP6563478B2 (ko) |
KR (1) | KR20160142320A (ko) |
CN (1) | CN106660821B (ko) |
FR (1) | FR3019539B1 (ko) |
WO (1) | WO2015150591A1 (ko) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11424320B2 (en) * | 2016-06-30 | 2022-08-23 | Flosfia Inc. | P-type oxide semiconductor and method for manufacturing same |
CN108465473B (zh) * | 2018-03-13 | 2021-01-26 | 清华大学 | 铋铜硫氧和/或其复合材料及其制备方法和用途、温度影响的光催化降解甲醛的设备和方法 |
CN112108156B (zh) * | 2019-06-20 | 2023-05-02 | 天津城建大学 | 一种Ag纳米颗粒修饰的MgFe2O4纳米棒复合薄膜的制备方法 |
KR102697833B1 (ko) * | 2022-04-20 | 2024-08-21 | 아주대학교산학협력단 | 태양광 증기 발생 장치 및 이를 포함하는 해수 담수화 장치 |
CN115161685B (zh) * | 2022-06-29 | 2024-06-21 | 安徽师范大学 | 一种Bi掺杂硫化亚铜介孔纳米带阵列结构材料、制备方法及其应用 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100657949B1 (ko) * | 2005-02-05 | 2006-12-14 | 삼성전자주식회사 | 원통형 연질 태양전지 및 그의 제조방법 |
EP2319082B1 (en) * | 2008-08-29 | 2017-11-15 | LG Chem, Ltd. | New compound semiconductor and producing method thereof, and solar cell and thermoelectric conversion element using the same |
JP5959516B2 (ja) * | 2010-08-18 | 2016-08-02 | ライフ テクノロジーズ コーポレーション | 電気化学的検出装置のためのマイクロウェルの化学コーティング法 |
FR2996355B1 (fr) * | 2012-09-28 | 2016-04-29 | Rhodia Operations | Oxydes et sulfures mixtes de bismuth et cuivre pour application photovoltaique |
FR3019540A1 (fr) * | 2014-04-04 | 2015-10-09 | Rhodia Operations | Oxydes et sulfures mixtes de bismuth et argent pour application photovoltaique |
-
2014
- 2014-04-04 FR FR1400832A patent/FR3019539B1/fr not_active Expired - Fee Related
-
2015
- 2015-04-03 EP EP15713968.4A patent/EP3126292A1/fr not_active Withdrawn
- 2015-04-03 WO PCT/EP2015/097023 patent/WO2015150591A1/fr active Application Filing
- 2015-04-03 JP JP2017503074A patent/JP6563478B2/ja not_active Expired - Fee Related
- 2015-04-03 CN CN201580018047.3A patent/CN106660821B/zh not_active Expired - Fee Related
- 2015-04-03 KR KR1020167029118A patent/KR20160142320A/ko not_active Application Discontinuation
- 2015-04-03 US US15/301,487 patent/US20170022072A1/en not_active Abandoned
Non-Patent Citations (2)
Title |
---|
None * |
See also references of WO2015150591A1 * |
Also Published As
Publication number | Publication date |
---|---|
JP6563478B2 (ja) | 2019-08-21 |
KR20160142320A (ko) | 2016-12-12 |
FR3019539B1 (fr) | 2016-04-29 |
WO2015150591A1 (fr) | 2015-10-08 |
JP2017517473A (ja) | 2017-06-29 |
US20170022072A1 (en) | 2017-01-26 |
CN106660821A (zh) | 2017-05-10 |
CN106660821B (zh) | 2018-09-18 |
FR3019539A1 (fr) | 2015-10-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Wang et al. | Synthesis of shape-controlled monodisperse wurtzite CuIn x Ga1–x S2 semiconductor nanocrystals with tunable band gap | |
EP2877277B1 (fr) | Procédé de preparation de solution colloïdale de particules amorphes | |
Ramasamy et al. | Routes to copper zinc tin sulfide Cu 2 ZnSnS 4 a potential material for solar cells | |
WO2015150591A1 (fr) | Oxydes et sulfures mixtes de bismuth et cuivre pour application photovoltaïque | |
Chen et al. | Synthesis of CuInS2 quantum dots/In2S3/ZnO nanowire arrays with high photoelectrochemical activity | |
WO2014049172A2 (fr) | Oxydes et sulfures mixtes de bismuth et cuivre pour application photovoltaïque | |
EP3114704B1 (fr) | Procédé de préparation de couche mince d'absorbeur a base de sulfure(s) et séléniures(s) de cuivre, zinc et étain, couche mince recuite et dispositif photovoltaïque obtenus | |
Alsulami et al. | Optical characteristics of chemically deposited MnSb2S4 thin films | |
Bianca et al. | Indium Selenide/Indium Tin Oxide Hybrid Films for Solution‐Processed Photoelectrochemical‐Type Photodetectors in Aqueous Media | |
Sharma et al. | Visible-light induced photosplitting of water using solution-processed Cu2BaSnS4 photoelectrodes and a tandem approach for development of Pt-free photoelectrochemical cell | |
Jawad et al. | An alternative method to grow Ge thin films on Si by electrochemical deposition for photonic applications | |
EP3126293B1 (fr) | Oxydes et sulfures mixtes de bismuth et argent pour application photovoltaique | |
Eskandari et al. | Enhanced photovoltaic performance of a cadmium sulfide/cadmium selenide-sensitized solar cell using an aluminum-doped zinc oxide electrode | |
Chavhan et al. | Study on photoelectrochemical solar cells of nanocrystalline Cd0. 7Zn0. 3Se-water soluble conjugated polymer | |
Joshi et al. | Morphological engineering of novel nanocrystalline Cu2Sn (S, Se) 3 thin film through annealing temperature variation: assessment of photoelectrochemical cell performance | |
Resende et al. | An investigation of photovoltaic devices based on p‐type Cu2O and n‐type γ‐WO3 junction through an electrolyte solution containing a redox pair | |
Supérieure-Kouba | Fabrication and characterization of CuInSe2 thin film solar cells with fluorine doped ZnO as new buffer layer | |
BABU | FINAL PROGRESS REPORT OF THE WORK DONE ON THE MAJOR RESEARCH PROJECT (1-04-2013 to 31-03-2017) | |
Kafashan et al. | Investigation the effect of In-doping on the structural and optical properties of electrodeposited SnS thin film | |
Çetinkaya | The effects of additive on photovoltaic performance of Cu2ZnSnS4 promising solar absorbers | |
EP3080332B1 (fr) | Bain à persulfate et procédé pour le dépôt chimique d'une couche | |
Kassim et al. | Influence of triethanolamine on the properties of chemical bath deposited nickel sulphide thin films | |
Wang | Solution processed kesterite light absorber on titania electron conductor for photovoltaic application | |
Oekermann | Electrodeposition of Nanostructured ZnO Films and Their Photoelectrochemical Properties | |
Kirsanova | Engineering of Semiconductor Nanocomposites for Harvesting and Routing of Optical Energy |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20161104 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20171220 |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: RHODIA OPERATIONS Owner name: LE CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN |
|
18W | Application withdrawn |
Effective date: 20200708 |