CN105140319B - A kind of thin-film solar cells and preparation method thereof - Google Patents
A kind of thin-film solar cells and preparation method thereof Download PDFInfo
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- CN105140319B CN105140319B CN201510351099.4A CN201510351099A CN105140319B CN 105140319 B CN105140319 B CN 105140319B CN 201510351099 A CN201510351099 A CN 201510351099A CN 105140319 B CN105140319 B CN 105140319B
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- layer
- tunnelling
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- rectification
- film solar
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- 239000010409 thin film Substances 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000004065 semiconductor Substances 0.000 claims abstract description 45
- 210000001142 back Anatomy 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 13
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 13
- 229910001512 metal fluoride Inorganic materials 0.000 claims abstract description 7
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 7
- 150000004767 nitrides Chemical class 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 31
- 239000010949 copper Substances 0.000 claims description 25
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 24
- 239000010408 film Substances 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 238000004528 spin coating Methods 0.000 claims description 13
- 239000011787 zinc oxide Substances 0.000 claims description 13
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 claims description 8
- 238000005240 physical vapour deposition Methods 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical group [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 6
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 6
- 238000010276 construction Methods 0.000 claims description 5
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 5
- 229960004643 cupric oxide Drugs 0.000 claims description 5
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- 239000011669 selenium Substances 0.000 claims description 4
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 4
- 229910003978 SiClx Inorganic materials 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- BTCDLVPEVFCYEU-UHFFFAOYSA-N cadmium;sulfanylidenecopper Chemical compound [Cd].[Cu]=S BTCDLVPEVFCYEU-UHFFFAOYSA-N 0.000 claims description 3
- 238000005229 chemical vapour deposition Methods 0.000 claims description 3
- 229940112669 cuprous oxide Drugs 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229910017083 AlN Inorganic materials 0.000 claims description 2
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical group [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- GQCYCMFGFVGYJT-UHFFFAOYSA-N [AlH3].[S] Chemical compound [AlH3].[S] GQCYCMFGFVGYJT-UHFFFAOYSA-N 0.000 claims description 2
- PIOQMRWHQXFDKN-UHFFFAOYSA-N [Cu]S[Cd][Zn] Chemical compound [Cu]S[Cd][Zn] PIOQMRWHQXFDKN-UHFFFAOYSA-N 0.000 claims description 2
- MTRXSNADWVEBGQ-UHFFFAOYSA-N [S].[Se].[Zn].[Cu] Chemical compound [S].[Se].[Zn].[Cu] MTRXSNADWVEBGQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 2
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 238000004549 pulsed laser deposition Methods 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 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 claims 1
- 229910052793 cadmium Inorganic materials 0.000 claims 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims 1
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 230000005611 electricity Effects 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 239000010410 layer Substances 0.000 description 313
- 238000012360 testing method Methods 0.000 description 45
- 238000000151 deposition Methods 0.000 description 30
- 229910004613 CdTe Inorganic materials 0.000 description 25
- 230000008021 deposition Effects 0.000 description 20
- 239000007789 gas Substances 0.000 description 19
- 239000000758 substrate Substances 0.000 description 18
- 239000012159 carrier gas Substances 0.000 description 16
- 239000011521 glass Substances 0.000 description 15
- 230000007704 transition Effects 0.000 description 15
- 238000004544 sputter deposition Methods 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 13
- 230000006798 recombination Effects 0.000 description 13
- 238000005215 recombination Methods 0.000 description 13
- 238000000137 annealing Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 230000031700 light absorption Effects 0.000 description 12
- GKPXMGUNTQSFGA-UHFFFAOYSA-N but-2-ynyl 1-methyl-3,6-dihydro-2h-pyridine-5-carboxylate;4-methylbenzenesulfonic acid Chemical group CC1=CC=C(S(O)(=O)=O)C=C1.CC#CCOC(=O)C1=CCCN(C)C1 GKPXMGUNTQSFGA-UHFFFAOYSA-N 0.000 description 11
- 238000005286 illumination Methods 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 11
- 230000003287 optical effect Effects 0.000 description 10
- 238000004088 simulation Methods 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000011010 flushing procedure Methods 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 238000007740 vapor deposition Methods 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- VXAPDXVBDZRZKP-UHFFFAOYSA-N nitric acid phosphoric acid Chemical compound O[N+]([O-])=O.OP(O)(O)=O VXAPDXVBDZRZKP-UHFFFAOYSA-N 0.000 description 5
- 238000002161 passivation Methods 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- 238000007738 vacuum evaporation Methods 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- 229910016553 CuOx Inorganic materials 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- YKYOUMDCQGMQQO-UHFFFAOYSA-L Cadmium chloride Inorganic materials Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 238000005566 electron beam evaporation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 230000005641 tunneling Effects 0.000 description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910005855 NiOx Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- -1 argon ion Chemical class 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 1
- BTTOHACVRWMHOB-UHFFFAOYSA-N [Zn].[Se].[S] Chemical compound [Zn].[Se].[S] BTTOHACVRWMHOB-UHFFFAOYSA-N 0.000 description 1
- 238000000637 aluminium metallisation Methods 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005092 sublimation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 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
- 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
- H01L31/0352—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 their shape or by the shapes, relative sizes or disposition of the semiconductor regions
- H01L31/035209—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 their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures
-
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
-
- 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
- Y02E10/543—Solar cells from Group II-VI materials
-
- 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
- Y02E10/549—Organic PV cells
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
This application discloses a kind of thin-film solar cells and preparation method thereof.The thin-film solar cells of the application, including preceding electrode layer, semiconductor layer, dorsum electrode layer and tunnelling rectification layer, tunnelling rectification layer is located between preceding electrode layer and semiconductor layer, or between semiconductor layer and dorsum electrode layer, or be located at simultaneously between preceding electrode layer and semiconductor layer, and between semiconductor layer and dorsum electrode layer；Tunnelling rectification layer is single or multiple lift structure, and the material of tunnelling rectification layer is at least one of metal oxide, metal nitride, metal sulfide, metal fluoride.The thin-film solar cells of the application, on the surface of preceding electrode layer and/or dorsum electrode layer, tunnelling rectification layer is set, rectification is carried out to electronics using tunnelling rectification layer, so as to effectively avoid the compound of carrier, the short circuit current and open-circuit voltage of solar cell are improved, and then improves electricity conversion.
Description
Technical field
The application is related to field of thin film solar cells, more particularly to a kind of improved thin-film solar cells of structure and
Its preparation method.
Background technology
Thin-film solar cells is the main representative of second generation solar cell, using thin film semiconductor material as light-absorption layer,
Thickness greatly reduces the consumption of material, growth technique is simple, is easy to make light, bendable in micron and sub-micrometer scale
Bent device, cost performance is dominant, and industrialization prospect is fine.However, thin film semiconductor material defect is more, surface carrier is born
Lotus is serious, and cell photoelectric transformation efficiency only has 10%~20% at present, less than traditional crystal silicon solar batteries.
Based on above reason, how to reduce thin-film solar cells surface carrier it is compound, improve solar cell
Short circuit current and open-circuit voltage, be the important directions of thin-film solar cells research so as to improve electricity conversion,
It is the key factor for further expanding its application.For at present, it is to form one layer to reduce the compound main method of surface carrier
Very thick passivation layer, generally all it is more than 50nm passivation layer, passivation layer is then burnt during depositing electrode, makes electrode
Directly contacted with semiconductor layer, the requirement that this will be very high for battery manufacturing process and electrode material, so as to improve electricity
Pond cost.
The content of the invention
The purpose of the application is to provide a kind of improved thin-film solar cells of new structure and preparation method thereof.
The application employs following technical scheme：
The one side of the application discloses a kind of thin-film solar cells, including preceding electrode layer, semiconductor layer, back of the body electricity
Pole layer, and tunnelling rectification layer, tunnelling rectification layer be arranged at before between electrode layer and semiconductor layer, or tunnelling rectification layer set
Between semiconductor layer and dorsum electrode layer, or tunnelling rectification layer simultaneously be arranged at before between electrode layer and semiconductor layer, and
Between semiconductor layer and dorsum electrode layer；Tunnelling rectification layer is single or multiple lift structure, the single or multiple lift structure of tunnelling rectification layer
In every layer of material be metal oxide, metal nitride, metal sulfide, at least one of metal fluoride.
It should be noted that the application's on the surface of preceding electrode layer, and/or the surface of dorsum electrode layer it is critical that set
Tunnelling rectification layer is put, tunnelling rectification layer is electrode layer and/or dorsum electrode layer before whole covering, and electronics can be directed through the tunnel
Rectification layer is worn, reaches the purpose of rectification, so as to avoid the compound of carrier, improves the short circuit current and open circuit of solar cell
Voltage, and then improve electricity conversion；In a kind of implementation of the application, transformation efficiency can be than not adding tunnelling rectification
The solar cell of layer improves more than 5%, after optimal conditions, can typically improve more than 10%.In the application, semiconductor layer leads to
Often it is made up of N layers and P layers, specific N layers and P layers can use existing material, so as to form different thin film solar electricity
Pond, it is not specifically limited herein.
It should also be noted that, the tunnelling rectification layer of the application can be individual layer, merely by metal oxide, metal nitrogen
A kind of single layer structure of formation in compound, metal sulfide, metal fluoride；Can also be sandwich construction, for example, two layers, three
Layer or more layer, wherein every layer of material can be different, such as first deposit one layer of silica, redeposited one layer of aluminum oxide, thus
Form the tunnelling rectification layer of double-layer structure.The design principle of sandwich construction tunnelling rectification layer mainly considers tunnelling rectification layer with before
The interface compatibility of electrode layer or dorsum electrode layer, although some material tunnelling rectification effects are preferable, however, it is very difficult in preceding electrode layer
Or dorsum electrode layer surface forms good interface, the overall performance of solar cell is influenceed, therefore, it is necessary to using interface compatibility
Preferable material is previously deposited one layer, the redeposited preferable material of tunnelling rectification effect.For different preceding electrode layers or back of the body electricity
Pole layer, it is different from the compatibility of tunnelling rectification layer material, and therefore, the tunnelling rectification layer of sandwich construction, the material of each layer can be with
It is adjusted, is not specifically limited herein as the case may be.It is appreciated that the key of the application is to add a tunnelling
Rectification layer, and tunnelling rectification layer must possess two effects of tunnelling and rectification；As for electrode layer before other layers, semiconductor layer,
Dorsum electrode layer can refer to existing thin-film solar cells, be not specifically limited herein.In addition, preceding electrode layer, semiconductor
Layer, dorsum electrode layer are the basic structure of thin-film solar cells, it will be understood that the thin-film solar cells of the application can be with
Including others, each layer that existing thin-film solar cells possesses, as long as employing the tunnelling rectification layer of the application, to film too
Positive energy battery carries out rectification, belongs to the protection domain of the application, is not specifically limited herein.
It should also be noted that, in the application, tunnelling rectification layer is that electronics to be caused can be directed through, and reaches rectification
Purpose, experiment confirm that the generally conventional metal oxide used, metal nitride, metal sulfide, metal fluoride can
Reach the purpose, be not specifically limited herein；But in the preferred scheme of the application, in order to reach more preferable effect, it is entered
Go and be particularly limited to, this will be discussed in detail in follow-up scheme.
Preferably, metal oxide is aluminum oxide, silica, zinc oxide, titanium oxide, nickel oxide, stannous oxide, oxidation Asia
At least one of copper, cupric oxide, hafnium oxide, zirconium oxide.
Preferably, metal nitride is aluminium nitride and/or silicon nitride.
Preferably, metal sulfide is at least one of copper sulfide, cuprous sulfide, copper aluminium sulphur, zinc cadmium copper sulphur.
Preferably, metal fluoride is calcirm-fluoride and/or sodium fluoride.
Preferably, the thickness of tunnelling rectification layer is 0.1nm-50nm.
It should be noted that the tunnelling rectification layer of the application need not burn, that is to say, that back electrode or preceding electrode
It is not directly contacted with semiconductor layer, therefore, tunnelling rectification layer must possess two functions, i.e. tunnelling and rectification, through research
It was found that, it is necessary to possess preferable rectification effect, tunnelling rectification layer must possess certain thickness；But if tunnelling rectification layer
It is too thick, electron tunneling can be influenceed again, the problem of this is one conflicting.By substantial amounts of research and experiment, tunnel is finally determined
The thickness for wearing rectification layer is 0.1nm-50nm, can meet the effect of rectification, and and can enough has good tunnelling.
It is furthermore preferred that the thickness of tunnelling rectification layer is 0.5nm-20nm.
Preferably, thin-film solar cells is cadmium telluride diaphragm solar battery, copper-indium-galliun-selenium film solar cell, copper
At least one of zinc selenium sulfur thin-film solar cells, Ca-Ti ore type thin-film solar cells and organic thin film solar cell.
It should be noted that the tunnelling rectification layer of the application can apply to various thin-film solar cells, including but not
It is only limitted to cadmium telluride diaphragm solar battery, copper-indium-galliun-selenium film solar cell, copper zinc selenium sulfur thin-film solar cells, calcium titanium
Ore deposit type thin-film solar cells and organic thin film solar cell.
The another side of the application discloses the preparation method of the thin-film solar cells of the application, specifically, tunnelling rectification
Layer is using at least one of ald, physical vapour deposition (PVD), pulsed laser deposition, chemical vapor deposition and spin-coating method side
It is prepared by method.
The another side of the application also discloses what is prepared using the preparation method of the application, the film in more preferred scheme
Solar cell, its tunnelling rectification layer be ald prepare metal oxide layer, metal oxide layer be specially alumina layer,
Nickel oxide layer, copper oxide or titanium oxide layer, the thickness of metal oxide layer is 0.1nm-50nm, and preferable thickness is 0.5nm-
20nm。
The another side of the application also discloses what is prepared using the preparation method of the application, the film in more preferred scheme
Solar cell, the copper sulfide layer or sulphur copper cadmium layer that its tunnelling rectification layer is prepared for spin-coating method, copper sulfide layer or sulphur copper cadmium layer
Thickness is 0.1nm-50nm, and preferable thickness is 0.5nm-20nm.
The beneficial effect of the application is：
The thin-film solar cells of the application, tunnelling rectification layer, profit are set on the surface of preceding electrode layer and/or dorsum electrode layer
Rectification is carried out to electronics with tunnelling rectification layer, so as to effectively avoid the compound of carrier, improves the short circuit of solar cell
Electric current and open-circuit voltage, and then improve electricity conversion.
Brief description of the drawings
Fig. 1 is film solar battery structure schematic diagram in the embodiment of the present application, and (a) is only in preceding electrode layer and semiconductor
The structural representation of tunnelling rectification layer is set between layer；(b) for simultaneously between preceding electrode layer and semiconductor layer, semiconductor layer and
The structural representation of tunnelling rectification layer is set between dorsum electrode layer；
Fig. 2 is the CdTe solar cell SEM photographs that tunnelling rectification layer is provided with the embodiment of the present application, wherein, a is to cut open
Face figure, b are surface topography map；
Fig. 3 is that CdTe thin film solar cell is provided with tunnelling rectification layer in the embodiment of the present application and to be not provided with tunnelling whole
The effect diagram of fluid layer, a are the situation for being not provided with tunnelling rectification layer, and b is the situation for setting tunnelling rectification layer；
Fig. 4 is the rectification of CdTe thin film solar cell and the IV curves under tunnelling effect in the embodiment of the present application；
Fig. 5 be photovoltage curve in the embodiment of the present application under the rectification of CdTe thin film solar cell and tunnelling effect with
External quantum efficiency curve, a are photovoltage curve map, and b is external quantum efficiency curve map；
Fig. 6 is the preparation method flow chart of thin-film solar cells in the embodiment of the present application.
Embodiment
The thin-film solar cells of the application, as shown in figure 1, setting tunnel on the surface of preceding electrode layer and/or dorsum electrode layer
Rectification layer is worn, takes into account rectification and tunneling effect, i.e., while Carrier recombination is reduced, electric charge ensure that by tunnelling current
Transport, as shown in Figure 3.The tunnelling rectification layer added in the thin-film solar cells of the application, electronics can be directed through, no
Need to burn tunnelling rectification layer, compared with existing passivation layer, rectification effect is more preferable；Also, due to without burning step
Suddenly, preparation technology is simpler, and production cost also decreases.
The application is described in further detail below by specific embodiment.Following examples only are entered to advance to the application
One step illustrates, should not be construed as the limitation to the application.
Embodiment one
This example is tested using cadmium telluride diaphragm solar battery, and Al is formed using ald on CdTe surfaces2O3
Layer, i.e., the tunnelling rectification layer of this example, tunnelling rectification layer are arranged between semiconductor layer and dorsum electrode layer.
Basic preparation flow using sputtering method as shown in fig. 6, prepare transparent front electrode layer successively on the glass substrate
FTO, thickness can be 300nm~1 μm, and this example specifically prepares thickness 500nm transparent electrode layer；Then n-type transition zone is sputtered
CdS, thickness can be 100-200nm, and this example is specifically prepared for thickness 145nm n-type transition zone, uses vacuum evaporation deposition CSS
Prepare p-type light-absorption layer CdTe thin film, after carry out CdCl successively2The steps such as annealing, nitric acid phosphoric acid NP etchings and copper Cu doping
Suddenly, obtaining surface has the semiconductor layer of the film of dangling bonds, i.e. this example；Then atomic layer deposition is being utilized in semiconductor layer surface
Product forms Al2O3Layer, i.e. the tunnelling rectification layer of this example, ald temperature are 120 DEG C, background vacuum pressure 300mTorr.With
The lower continuous process of four steps forms a complete deposition cycle：(1) the trimethyl aluminium TMA of gas phase is carried along into by high-purity carrier gas
Reative cell, saturation adsorption reaction occurs on CdTe surfaces, and high-purity carrier gas of this example is more than 99.99% Ar or N using purity2,
Flow is 30sccm；(2) carrier gas purges, and takes unnecessary TMA and reaction residual gas out of reative cell, flushing times 25s；(3) gas
The water H of phase2O is carried along into reative cell by high-purity carrier gas, is chemically reacted with the TMA of step (1) absorption, generates Al2O3Layer；
(4) carrier gas purges, by unnecessary H2O and reaction residual gas take reative cell, flushing times 25s out of.So move in circles, Zhi Daochen
Product goes out the Al that thickness is 0.5nm2O3Layer, that is, obtain the tunnelling rectification layer of this example；It is thick in tunnelling rectification layer surface vapor deposition 40nm
Au electrodes, i.e. dorsum electrode layer, hereafter carry out 200 DEG C of annealing sintering；Obtain the thin-film solar cells of this example.
The thin-film solar cells prepared using electron-microscope scanning to this example is observed, as a result as shown in Fig. 2 its profile
As shown in a in Fig. 2, prepared CdTe crystal grain is bigger, and each interface is compact and complete；Surface topography is as shown in b in Fig. 2, as a result
It has been shown that, in one layer of Al of CdTe layer surface uniform deposition2O3Layer, does not influence surface topography.Fig. 4 current-voltage test result is said
The bright purpose that ballast and tunnelling can be realized through transpassivation rectification layer.
By intensity modulated photovoltaic spectrum (IMVS) test, contrast increase rectification tunnel layer and not increased sample, really
Determine the contrast of battery minority carrier lifetime and improve more than 10%, the surface recombination of the raising explanation carrier of minority carrier lifetime
Reduce, so as to improve battery efficiency, illustrate that this technique effectively reduces the surface recombination of device carrier.Simulating
Under AM1.5 sunshine irradiation, illumination voltage-to-current test is carried out to the thin-film solar cells of this example, light source is ABET public
Take charge of production the model solar simulators of Sun 3000, voltage-current curve by Keithley company 2602A type figures source table
Test show that for test result as shown in figure 5, Fig. 5 (a) indicates battery efficiency result, Fig. 5 (b) illustrates the original that battery efficiency improves
Cause, illustrate there is good passivation effect, as a result show, the battery efficiency of this example improves 10% than not increased sample.Battery is imitated
Rate improves the raising for being mainly derived from open-circuit voltage (Voc) and fill factor, curve factor (FF), result explanation increase tunnel rectification layer
It is effectively improved transporting and receiving for carrier.
Embodiment two
This example is tested using cadmium telluride diaphragm solar battery, and unlike embodiment one, this example tunnels through whole
Fluid layer Al2O3Layer is arranged between semiconductor layer and preceding electrode layer.
Transparent electrode layer FTO is prepared using sputtering method successively on the glass substrate, this example thickness can be 300nm~1 μm,
This example specifically prepares thickness 500nm transparent electrode layer；Then Al is formed using ald in preceding electrode surface2O3Layer, i.e.,
The tunnelling rectification layer of this example, specific tunnel layer preparation technology can refer to the detailed process of embodiment one, and tunneling layer thickness is
1nm；Then in sputtering n-type transition zone CdS, thickness can be 100-200nm, and this example is specifically prepared for thickness 145nm n-type transition
Layer, using vacuum evaporation deposition CSS prepare p-type light-absorption layer CdTe thin film, after carry out CdCl successively2Annealing, nitric acid phosphoric acid
The steps such as NP is etched and copper Cu is adulterated, and the Au electrodes that vapor deposition 40nm is thick, i.e. dorsum electrode layer, hereafter carry out 200 DEG C and move back
Burn knot；Obtain the thin-film solar cells of this example.
The thin-film solar cells prepared using electron-microscope scanning to this example is observed, and is as a result shown, in transparent electrode layer
FTO surface uniform depositions have one layer of Al2O3Layer.
By intensity modulated photovoltaic spectrum (IMVS) test, determine that battery minority carrier lifetime improves more than 10%,
Illustrate that this technique effectively reduces the surface recombination of device carrier.Under simulation AM1.5 sunshine irradiation, to this example
Thin-film solar cells carries out illumination voltage-to-current test, and light source is the model sun optical modes of Sun 3000 of ABET companies production
Intend device, voltage-current curve show that test result is shown, this example by the 2602A type figures source table test of Keithley company
Battery efficiency improves 5%.Battery efficiency improves the raising for being mainly derived from open-circuit voltage (Voc) and fill factor, curve factor (FF), should
As a result explanation increase tunnel rectification layer is effectively improved transporting and receiving for carrier.
Embodiment three
This example is tested using copper-indium-galliun-selenium film solar cell, mainly in the back of the body electricity of CIGS thin-film solar
On the molybdenum Mo of pole cuprous oxide Cu is formed using physical gas-phase deposite method2The tunnelling rectification layer of O layers, i.e. this example；Tunnelling rectification layer
It is arranged between semiconductor layer and dorsum electrode layer.
Sputtered in substrate of glass and prepare metallic back electrode layer Mo, this example thickness using sputtering method successively on the glass substrate
Can be 500nm~1 μm, this example specifically prepares the metal electrode layer of 1 μm of thickness；Tunnel layer depositing temperature is 200 DEG C, background vacuum
Spend for 1.0 × 10-3Below Pa, it is passed through argon Ar and is partly led as reacting gas, (1) substrate as sputter gas, a small amount of oxygen
In the presence of the alternating electric field added by radio-frequency power supply, middle electronics vibrates back and forth for body thin film and target, and increase electronics with
The collision probability of gas molecule and ionize and produce argon ion Ar+And oxonium ion O2+；(2) Ar is ionized+Bombarded under electric field action
Target material surface simultaneously makes Cu atoms with certain energy to substrate motion, in motion process with O2+With reference to, and finally be deposited to lining
On bottom, and form Cu2O films, extend the time until depositing the Cu that thickness is 5nm2O layers, that is, obtain the tunnelling rectification of this example
Layer, i.e. the tunnelling rectification layer of this example；Then in sputtering p-type light-absorption layer CIGS CIGS, thickness can be 1-2um, and this example is specific
It is prepared for thickness 1.5um p-type light-absorption layer；Then in sputtering n-type transition zone CdS, this example thickness is 100-200nm, and this example has
Body prepares thickness 200nm n-type transition zone；Then respectively sputter before electrode intrinsic blocking layer intrinsic zinc oxide i-ZnO layers and
Electrode layer before Al-Doped ZnO AZO, thickness are respectively 100nm and 500nm, hereafter carry out 300 DEG C of annealing sintering；Obtain this example
Thin-film solar cells.
The thin-film solar cells prepared using electron-microscope scanning to this example is observed, and is as a result shown, in back electrode molybdenum Mo
Surface uniform deposition has one layer of cuprous oxide Cu2O layers.
By intensity modulated photovoltaic spectrum (IMVS) test, determine that battery minority carrier lifetime improves more than 10%,
Illustrate that this technique effectively reduces the surface recombination of device carrier.Under simulation AM1.5 sunshine irradiation, to this example
Thin-film solar cells carries out illumination voltage-to-current test, and light source is the model sun optical modes of Sun 3000 of ABET companies production
Intend device, voltage-current curve show that test result is shown, this example by the 2602A type figures source table test of Keithley company
Battery efficiency improves 10%.Battery efficiency improves the raising for being mainly derived from open-circuit voltage (Voc) and fill factor, curve factor (FF), should
As a result explanation increase tunnel rectification layer is effectively improved transporting and receiving for carrier.
Example IV
This example is tested using copper-zinc-tin-sulfur CZTS thin-film solar cells, is sunk on CZTS surfaces using electron beam evaporation
Product method forms nickel oxide NiOxLayer, i.e., the tunnelling rectification layer of this example, tunnelling rectification layer are arranged on semiconductor layer and dorsum electrode layer
Between.
Sputtered in substrate of glass and prepare metallic back electrode layer Mo, this example thickness using sputtering method successively on the glass substrate
Can be 500nm~1 μm, this example specifically prepares the metal electrode layer of 1 μm of thickness；Then using electron beam evaporation method in metal electricity
Pole layer growth oxidation nickel OxLayer, as the tunnelling rectification layer of this example, specifically used electron beam evaporation NiO powder, in vacuum
For 1 × 10-3Below Pa, being passed through the oxygen that purity is 4mol/L makes air pressure increase to 2 × 10-2Pa, by electron beam current adjust to
Required evaporation power, evaporation rate 0.1nm/s, extend the time until depositing the NiO that thickness is 5nmxLayer；Then grow
P-type light-absorption layer copper-zinc-tin-sulfur CZTS layers：(1) Cu, Zn and Sn by Co-evaporated Deposition in the above-mentioned substrate for being coated with ZnO；(2)
Sulphur steam will be passed through by a valve in deposition process；(3) the CZTS films of system are moved back in air atmosphere at a temperature of 570 DEG C
Fiery 5min, thickness can be 1-2 μm, and this example is specifically prepared for the p-type light-absorption layer of 1.5 μm of thickness；Then electrode sheet before sputtering respectively
Electrode layer before barrier layer intrinsic zinc oxide i-ZnO layers and Al-Doped ZnO AZO is levied, thickness is respectively 100nm and 500nm,
Obtain the thin-film solar cells of this example.
The thin-film solar cells prepared using electron-microscope scanning to this example is observed, and is as a result shown, in dorsum electrode layer Mo
Surface uniform deposition has one layer of nickel oxide NiOxLayer.
By intensity modulated photovoltaic spectrum (IMVS) test, determine that battery minority carrier lifetime improves more than 10%,
Illustrate that this technique effectively reduces the surface recombination of device carrier.Under simulation AM1.5 sunshine irradiation, to this example
Thin-film solar cells carries out illumination voltage-to-current test, and light source is the model sun optical modes of Sun 3000 of ABET companies production
Intend device, voltage-current curve show that test result is shown, this example by the 2602A type figures source table test of Keithley company
Battery efficiency improves 10%.Battery efficiency improves the raising for being mainly derived from open-circuit voltage (Voc) and fill factor, curve factor (FF), should
As a result explanation increase tunnel rectification layer is effectively improved transporting and receiving for carrier.
Embodiment five
This example is tested using organic thin film solar cell, and metallorganic is utilized in organic film extinction layer surface
Chemical vapor deposition MOCVD methods form the tunnelling rectification layer of zinc oxide ZnO layer, i.e. this example, and tunnelling rectification layer, which is arranged on, partly leads
Between body layer and dorsum electrode layer.
Transparent electrode layer ITO is prepared using sputtering method successively on the glass substrate, this example thickness can be 300nm~1 μm,
This example specifically prepares thickness 500nm transparent electrode layer；Then transparent p-type transition zone is prepared using rotating coating respectively
PEDOT:Light-absorption layer is made with PCBM mixed solutions in PSS, and P3HT, and thickness is respectively 50nm and 200nm, and in 150 DEG C of bars
Anneal 20min under part, and obtaining surface has the semiconductor layer of the film of organic matter dangling bonds, i.e. this example；Then had using metal
Machine thing chemical gas-phase deposition system grows the tunnelling rectification layer of native oxide zinc layers, as this example in metal electrode layer, specifically makes
With electron level zinc source DEZn, oxidant H2O, argon gas (Ar) are the flow difference control device of carrier gas, zinc source and oxidant
10sccm and 50sccm, gas pressure in vacuum is stable in deposition process controls at 160 DEG C in 3.0torr, underlayer temperature, extends the time
Until depositing the ZnO layer that thickness is 5nm；Then metal fever evaporation coating method AM aluminum metallization Al electrodes are used, thickness 100nm, are obtained
Obtain the thin-film solar cells of this example.
The thin-film solar cells prepared using electron-microscope scanning to this example is observed, and is as a result shown, in semiconductor layer and
Uniform deposition has layer of ZnO layer between dorsum electrode layer.
By intensity modulated photovoltaic spectrum (IMVS) test, determine that battery minority carrier lifetime improves more than 10%,
Illustrate that this technique effectively reduces the surface recombination of device carrier.Under simulation AM1.5 sunshine irradiation, to this example
Thin-film solar cells carries out illumination voltage-to-current test, and light source is the model sun optical modes of Sun 3000 of ABET companies production
Intend device, voltage-current curve show that test result is shown, this example by the 2602A type figures source table test of Keithley company
Battery efficiency improves 10%.Battery efficiency improves the raising for being mainly derived from open-circuit voltage (Voc) and fill factor, curve factor (FF), should
As a result explanation increase tunnel rectification layer is effectively improved transporting and receiving for carrier.
Embodiment six
This example is tested using perovskite thin film solar cell, and aluminium oxide Al is formed using ald2O3And
Silicon oxide sio2The tunnelling rectification layer of composite bed, i.e. this example, tunnelling rectification layer are arranged between semiconductor layer and dorsum electrode layer.
Prepare transparent electrode layer FTO using sputtering method successively on the glass substrate, thickness can be 300nm~1 μm, this example
The specific transparent electrode layer for preparing thickness 500nm；Then n-type transition zone titanium oxide TiO is sputtered2, thickness can be 100-200nm,
This example is specifically prepared for thickness 150nm n-type transition zone, then distinguishes spin coating lead iodide PbI using two step method of spin coating2With
And methyl amine iodine CH3NH3I, obtaining surface has the light-absorption layer of the semiconductive thin film of dangling bonds, i.e. this example；Then in semiconductor
Layer surface forms aluminium oxide Al using ald2O3And silicon oxide sio2The tunnelling rectification layer of composite bed, i.e. this example, it is former
Sublayer depositing temperature is 120 DEG C, background vacuum pressure 300mTorr.The continuous process of four steps forms a complete deposition below
Cycle：(1) the trimethyl aluminium TMA of gas phase is carried along into reative cell by high-purity carrier gas, and saturation adsorption reaction occurs on CdTe surfaces,
High-purity carrier gas of this example is more than 99.99% Ar or N using purity2, flow 30sccm；(2) carrier gas purges, will be unnecessary
TMA and reaction residual gas take reative cell, flushing times 25s out of；(3) the water H of gas phase2O is carried along into reative cell by high-purity carrier gas,
Chemically reacted with the TMA of step (1) absorption, generate Al2O3Layer；(4) carrier gas purges, by unnecessary H2O and reaction residual gas band
Go out reative cell, flushing times 25s.So move in circles, until depositing the NiO that thickness is 0.5nmxLayer, that is, obtain this example
Tunnelling rectification layer；In the thick Au electrodes of tunnelling rectification layer surface vapor deposition 40nm, i.e. dorsum electrode layer, 200 DEG C are hereafter carried out
Annealing sintering；Obtain the thin-film solar cells of this example.
The thin-film solar cells prepared using electron-microscope scanning to this example is observed, and is as a result shown, in semiconductor layer and
Uniform deposition has the tunnelling rectification layer of a double-layer structure, i.e. aluminium oxide Al between dorsum electrode layer2O3Layer and silicon oxide sio2Layer is multiple
The tunnelling rectification layer of conjunction.
By intensity modulated photovoltaic spectrum (IMVS) test, determine that battery minority carrier lifetime improves more than 10%,
Illustrate that this technique effectively reduces the surface recombination of device carrier.Under simulation AM1.5 sunshine irradiation, to this example
Thin-film solar cells carries out illumination voltage-to-current test, and light source is the model sun optical modes of Sun 3000 of ABET companies production
Intend device, voltage-current curve show that test result is shown, this example by the 2602A type figures source table test of Keithley company
Battery efficiency improves 10%.Battery efficiency improves the raising for being mainly derived from open-circuit voltage (Voc) and fill factor, curve factor (FF), should
As a result explanation increase tunnel rectification layer is effectively improved transporting and receiving for carrier.
Embodiment seven
This example is tested using cadmium telluride diaphragm solar battery, and oxygen is formed using physical vapour deposition (PVD) on CdTe surfaces
SiClx SiO2Layer, i.e., the tunnelling rectification layer of this example, tunnelling rectification layer are arranged between semiconductor layer and dorsum electrode layer.
Prepare transparent electrode layer FTO using sputtering method successively on the glass substrate, thickness can be 300nm~1 μm, this example
The specific transparent electrode layer for preparing thickness 500nm；Then n-type transition zone CdS is sputtered, thickness can be 100-200nm, and this example is specific
Be prepared for thickness 145nm n-type transition zone, using vacuum evaporation deposition CSS prepare p-type light-absorption layer CdTe thin film, after enter successively
Row CdCl2The steps such as annealing, nitric acid phosphoric acid NP etchings and copper Cu doping, obtaining surface has the film of dangling bonds, i.e.,
The semiconductor layer of this example；Then silicon oxide sio is formed using physical vapour deposition (PVD) in semiconductor2Layer, the tunnelling rectification of level this example
Layer, tunnel layer depositing temperature are 200 DEG C, and background vacuum pressure is 1.0 × 10-3Below Pa, argon Ar is passed through as sputter gas,
(1) substrate is semiconductive thin film with target in the presence of the alternating electric field added by radio-frequency power supply, and middle electronics vibrates back and forth,
And increase the collision probability of electronics and gas molecule and ionize and produce argon ion Ar+；(2) Ar is ionized+Target is bombarded under electric field action
Material surface simultaneously makes SiO2Deposited to certain energy on substrate, and form SiO2Film, extend the time be until depositing thickness
2nm SiO2Layer, that is, obtain the tunnelling rectification layer of this example；In the thick Au electrodes of tunnelling rectification layer surface vapor deposition 40nm, i.e.,
Dorsum electrode layer, hereafter carry out 200 DEG C of annealing sintering；Obtain the thin-film solar cells of this example.
The thin-film solar cells prepared using electron-microscope scanning to this example is observed, and is as a result shown, on CdTe surface
Uniform deposition has one layer of SiO2Layer.
By intensity modulated photovoltaic spectrum (IMVS) test, determine that battery minority carrier lifetime improves more than 10%,
Illustrate that this technique effectively reduces the surface recombination of device carrier.Under simulation AM1.5 sunshine irradiation, to this example
Thin-film solar cells carries out illumination voltage-to-current test, and light source is the model sun optical modes of Sun 3000 of ABET companies production
Intend device, voltage-current curve show that test result is shown, this example by the 2602A type figures source table test of Keithley company
Battery efficiency improves 10%.Battery efficiency improves the raising for being mainly derived from open-circuit voltage (Voc) and fill factor, curve factor (FF), should
As a result explanation increase tunnel rectification layer is effectively improved transporting and receiving for carrier.
Embodiment eight
This example is tested using cadmium telluride diaphragm solar battery, and oxidation is formed using ald on CdTe surfaces
Copper CuOxLayer, i.e., the tunnelling rectification layer of this example, tunnelling rectification layer are arranged between semiconductor layer and dorsum electrode layer.
Prepare transparent electrode layer FTO using sputtering method successively on the glass substrate, thickness can be 300nm~1 μm, this example
The specific transparent electrode layer for preparing thickness 500nm；Then n-type transition zone CdS is sputtered, thickness can be 100-200nm, and this example is specific
Be prepared for thickness 145nm n-type transition zone, using vacuum evaporation deposition CSS prepare p-type light-absorption layer CdTe thin film, after enter successively
Row CdCl2The steps such as annealing, nitric acid phosphoric acid NP etchings and copper Cu doping, obtaining surface has the film of dangling bonds, i.e.,
The semiconductor layer of this example；Then CuO is being formed using ald in semiconductor layer surfacexLayer, i.e. the tunnelling rectification of this example
Layer, ald temperature are 120 DEG C, background vacuum pressure 300mTorr.The continuous process of four steps forms one completely below
Deposition cycle：(1) gas phase [Cu (iPr-Me-AMD)]2Reative cell is carried along into by high-purity carrier gas, occurred on CdTe surfaces full
And adsorption reaction, high-purity carrier gas of this example are more than 99.99% Ar or N using purity2, flow 30sccm；(2) carrier gas is blown
Wash, by it is unnecessary [Cu (iPr-Me-AMD)]2Reative cell, flushing times 25s are taken out of with reaction residual gas；(3) the water H of gas phase2O
Reative cell is carried along into by high-purity carrier gas, with step (1) absorption [Cu (iPr-Me-AMD)]2Chemically react, generate CuOx
Layer；(4) carrier gas purges, by unnecessary H2O and reaction residual gas take reative cell, flushing times 25s out of.So move in circles, directly
To deposit thickness be 0.5nm CuOxLayer, that is, obtain the tunnelling rectification layer of this example；In tunnelling rectification layer surface vapor deposition
Au electrodes thick 40nm, i.e. dorsum electrode layer, hereafter carry out 200 DEG C of annealing sintering；Obtain the thin-film solar cells of this example.
The thin-film solar cells prepared using electron-microscope scanning to this example is observed, and is as a result shown, on CdTe surface
Uniform deposition has one layer of cupric oxide CuOxLayer.
By intensity modulated photovoltaic spectrum (IMVS) test, determine that battery minority carrier lifetime improves more than 10%,
Illustrate that this technique effectively reduces the surface recombination of device carrier.Under simulation AM1.5 sunshine irradiation, to this example
Thin-film solar cells carries out illumination voltage-to-current test, and light source is the model sun optical modes of Sun 3000 of ABET companies production
Intend device, voltage-current curve show that test result is shown, this example by the 2602A type figures source table test of Keithley company
Battery efficiency improves 10%.Battery efficiency improves the raising for being mainly derived from open-circuit voltage (Voc) and fill factor, curve factor (FF), should
As a result explanation increase tunnel rectification layer is effectively improved transporting and receiving for carrier.
Embodiment nine
This example is tested using cadmium telluride diaphragm solar battery, and Cu is formed using spin-coating method on CdTe surfacesxS layers,
I.e. the tunnelling rectification layer of this example, tunnelling rectification layer are arranged between semiconductor layer and dorsum electrode layer.
Prepare thickness 500nm transparent electrode layer using sputtering method successively on the glass substrate；Then n-type transition is sputtered
Layer CdS, thickness can be 100-200nm, and this example is specifically prepared for thickness 145nm n-type transition zone, uses vacuum evaporation deposition
CSS prepares p-type light-absorption layer CdTe thin film, carries out CdCl2Annealing obtains the semiconductor layer of this example；By the CuCl of special ratios2
Be dissolved in configuration precursor liquid in the solvent (DMF or DMSO) of specified quantitative with sulphur source (thiocarbamide or thioacetamide), using spin-coating method and
Hot plate processing obtains CuxThe tunnelling rectification layer of S layers, i.e. this example, spin coating rotating speed are 3000rpm, spin-coating time 30s, at hot plate
It is 200 DEG C to manage temperature, processing time 5min.In the thick Au electrodes of tunnelling rectification layer surface vapor deposition 40nm, i.e. back electrode
Layer, hereafter carry out 200 DEG C of annealing sintering；Obtain the thin-film solar cells of this example.
The thin-film solar cells prepared using electron-microscope scanning to this example is observed, and is as a result shown, on CdTe surface
Uniform deposition has one layer of CuxS layers.
By intensity modulated photovoltaic spectrum (IMVS) test, determine that battery minority carrier lifetime improves more than 10%,
Illustrate that this technique effectively reduces the surface recombination of device carrier.Under simulation AM1.5 sunshine irradiation, to this example
Thin-film solar cells carries out illumination voltage-to-current test, and light source is the model sun optical modes of Sun 3000 of ABET companies production
Intend device, voltage-current curve show that test result is shown, this example by the 2602A type figures source table test of Keithley company
Battery efficiency improves 10%.Battery efficiency improves the raising for being mainly derived from open-circuit voltage (Voc) and fill factor, curve factor (FF), should
As a result explanation increase tunnel rectification layer is effectively improved transporting and receiving for carrier.
Embodiment ten
This example is tested using CdTe thin film solar cell, and Zn is deposited with immersion method on FTO transparent conducting glass1-x- yCdxCuyS electrically conducting transparent Window layers, form hetero-junctions by subsequent treatment and CdTe and be prepared into photoelectric transformation efficiency
Solar cell device.
First on the FTO Jing Guo cleaning treatment the Zn that a layer thickness is 100~200nm is prepared with immersion method1-x- yCdxCuyS transparency conducting layers, then utilize the CdTe extinctions for entering Space Sublimation method on previous transparency conducting layer and being deposited about 5 μ m-thicks
Layer.Carry out CdCl successively afterwards2Processing, nitric acid-phosphoric acid NP etching and Cu/Au back electrodes evaporation, so as to obtain the glass of this example/
SnO2:F/Zn1-x-yCdxCuyThe thin film solar cell of S/CdTe/Cu-Au back electrodes.
The thin-film solar cells prepared using electron-microscope scanning to this example is observed, and is as a result shown, in FTO electrically conducting transparents
The surface uniform deposition of glass has one layer of Zn1-x-yCdxCuyS layers.
By intensity modulated photovoltaic spectrum (IMVS) test, determine that battery minority carrier lifetime improves more than 10%,
Illustrate that this technique effectively reduces the surface recombination of device carrier.Under simulation AM1.5 sunshine irradiation, to this example
Thin-film solar cells carries out illumination voltage-to-current test, and light source is the model sun optical modes of Sun 3000 of ABET companies production
Intend device, voltage-current curve show that test result is shown, this example by the 2602A type figures source table test of Keithley company
Battery efficiency improves 10%.Battery efficiency improves the raising for being mainly derived from open-circuit voltage (Voc) and fill factor, curve factor (FF), should
As a result explanation increase tunnel rectification layer is effectively improved transporting and receiving for carrier.
Embodiment 11
This example is tested using organic thin film solar cell, and titanium dioxide TiO is formed using solution spin coating2Layer, i.e.,
The tunnelling rectification layer of this example, tunnelling rectification layer are arranged between semiconductor layer and FTO electrode layers.
Specifically prepare thickness 500nm transparent electrode layer using sputtering method this example successively on the glass substrate；Then exist
Spin coating prepares TiO in FTO substrates2Layer, thickness can be 0.1-50nm, and this example is specifically prepared for 5nm thickness tunnelling rectification layers, use
Solution spin-coating method is prepared for P3HT：PCBM is the film of active layer material, is then evaporated in vacuo 10nm MoO successively3And 120nm
Ag, carry out 150 DEG C of annealings；Obtain the thin-film solar cells of this example.
The thin-film solar cells prepared using electron-microscope scanning to this example is observed, and is as a result shown, in FTO electrode layers
Surface uniform deposition has layer of titanium dioxide TiO2Layer.
By intensity modulated photovoltaic spectrum (IMVS) test, determine that battery minority carrier lifetime improves more than 10%,
Illustrate that this technique effectively reduces the surface recombination of device carrier.Under simulation AM1.5 sunshine irradiation, to this example
Thin-film solar cells carries out illumination voltage-to-current test, and light source is the model sun optical modes of Sun 3000 of ABET companies production
Intend device, voltage-current curve show that test result is shown, this example by the 2602A type figures source table test of Keithley company
Battery efficiency improves 10%.Battery efficiency improves the raising for being mainly derived from open-circuit voltage (Voc) and fill factor, curve factor (FF), should
As a result explanation increase tunnel rectification layer is effectively improved transporting and receiving for carrier.
Above content is to combine the further description that specific embodiment is made to the application, it is impossible to assert this Shen
Specific implementation please is confined to these explanations.For the application person of an ordinary skill in the technical field, do not taking off
On the premise of conceiving from the application, some simple deduction or replace can also be made, should all be considered as belonging to the protection of the application
Scope.
Claims (10)
1. a kind of thin-film solar cells, including preceding electrode layer, semiconductor layer and dorsum electrode layer, it is characterised in that：Also include tunnel
Rectification layer is worn, the tunnelling rectification layer is arranged between the preceding electrode layer and semiconductor layer, or tunnelling rectification layer is arranged at
Between the semiconductor layer and dorsum electrode layer, or tunnelling rectification layer simultaneously be arranged at before between electrode layer and semiconductor layer, with
And between semiconductor layer and dorsum electrode layer；
The tunnelling rectification layer is sandwich construction, every layer of material in the sandwich construction of tunnelling rectification layer is metal oxide,
At least one of metal nitride, metal sulfide, metal fluoride；
The thin-film solar cells is cadmium telluride diaphragm solar battery, copper-indium-galliun-selenium film solar cell, copper zinc selenium sulfur
At least one of thin-film solar cells, Ca-Ti ore type thin-film solar cells and organic thin film solar cell.
2. thin-film solar cells according to claim 1, it is characterised in that：The metal oxide is aluminum oxide, oxygen
At least one of SiClx, zinc oxide, titanium oxide, nickel oxide, stannous oxide, cuprous oxide, cupric oxide, hafnium oxide, zirconium oxide.
3. thin-film solar cells according to claim 1, it is characterised in that：The metal nitride is aluminium nitride, nitrogen
At least one of SiClx.
4. thin-film solar cells according to claim 1, it is characterised in that：The metal sulfide is copper sulfide, sulphur
Change at least one of cuprous, copper aluminium sulphur, zinc cadmium copper sulphur.
5. thin-film solar cells according to claim 1, it is characterised in that：The metal fluoride is calcirm-fluoride, fluorine
Change at least one of sodium.
6. thin-film solar cells according to claim 1, it is characterised in that：The thickness of the tunnelling rectification layer is
0.1nm-50nm。
7. thin-film solar cells according to claim 1, it is characterised in that：The thickness of the tunnelling rectification layer is
0.5nm-20nm。
8. the preparation method of the thin-film solar cells according to claim any one of 1-7, it is characterised in that：The tunnelling
Rectification layer uses at least one in ald, physical vapour deposition (PVD), pulsed laser deposition, chemical vapor deposition and spin-coating method
It is prepared by kind method.
9. thin-film solar cells prepared by preparation method according to claim 8, it is characterised in that：The tunnelling rectification
The metal oxide layer that layer is prepared for ald, the metal oxide layer is specially alumina layer, nickel oxide layer, copper oxide
Or titanium oxide layer, the thickness of the metal oxide layer is 0.1nm-50nm.
10. thin-film solar cells prepared by preparation method according to claim 8, it is characterised in that：The tunnelling is whole
Fluid layer is copper sulfide layer or sulphur copper cadmium layer prepared by spin-coating method, and the thickness of copper sulfide layer or sulphur copper the cadmium layer is 0.1nm-
50nm。
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| CN105609637B (en) * | 2016-03-04 | 2017-12-19 | 北京大学深圳研究生院 | The method of deposition oxide film, organic field effect tube and preparation method thereof |
| CN105895809B (en) * | 2016-05-09 | 2018-12-28 | 浙江海洋大学 | A kind of preparation method of the ZnO film for reversed structure polymer solar battery |
| CN106129172B (en) * | 2016-07-01 | 2017-07-04 | 江苏微导纳米装备科技有限公司 | A kind of crystal silicon solar batteries surface passivation method of adjustable charge density |
| CN108074989A (en) * | 2016-11-14 | 2018-05-25 | Lg电子株式会社 | Solar cell and its manufacturing method |
| CN106711242A (en) * | 2017-01-17 | 2017-05-24 | 中国科学技术大学 | Cadmium telluride film solar cell and preparation method thereof |
| CN108538949A (en) * | 2017-03-03 | 2018-09-14 | 无锡马丁格林光伏科技有限公司 | A kind of back structures of thermophotovoltaic |
| CN107180880B (en) * | 2017-05-23 | 2019-08-27 | 北京大学深圳研究生院 | A kind of ultra-thin translucent thin film solar cell and preparation method thereof |
| CN107946471B (en) * | 2017-11-28 | 2021-01-26 | 金寨嘉悦新能源科技有限公司 | Heterojunction photovoltaic cell based on silicon nanowire array and preparation method thereof |
| CN107946470B (en) * | 2017-11-28 | 2021-01-12 | 上海迈电科技有限公司 | Heterojunction solar cell and preparation method thereof |
| JP7099867B2 (en) * | 2018-05-16 | 2022-07-12 | 日本化学工業株式会社 | Photosintered composition and method for forming a conductive film using the same |
| CN109841703B (en) * | 2019-01-30 | 2021-06-11 | 暨南大学 | All-inorganic perovskite photoelectric detector and preparation method thereof |
| CN109888098A (en) * | 2019-04-04 | 2019-06-14 | 杨富强 | A kind of perovskite solar battery and preparation method thereof mixing cuprous sulfide in calcium titanium ore bed |
| CN110227492A (en) * | 2019-04-29 | 2019-09-13 | 中国科学院山西煤炭化学研究所 | A kind of Nano semiconductor photochemical catalyst and preparation method thereof |
| CN112838143A (en) * | 2020-12-31 | 2021-05-25 | 横店集团东磁股份有限公司 | Deposition method of aluminum oxide film in PERC battery |
| CN114664952A (en) * | 2022-03-15 | 2022-06-24 | 北京大学深圳研究生院 | Thin-film solar cell back contact structure and preparation method and application thereof |
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