CN104779307A - Copper zinc tin selenium solar cell device and manufacturing method thereof - Google Patents
Copper zinc tin selenium solar cell device and manufacturing method thereof Download PDFInfo
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- CN104779307A CN104779307A CN201510222224.1A CN201510222224A CN104779307A CN 104779307 A CN104779307 A CN 104779307A CN 201510222224 A CN201510222224 A CN 201510222224A CN 104779307 A CN104779307 A CN 104779307A
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- PCRGAMCZHDYVOL-UHFFFAOYSA-N copper selanylidenetin zinc Chemical compound [Cu].[Zn].[Sn]=[Se] PCRGAMCZHDYVOL-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000004519 manufacturing process Methods 0.000 title abstract 3
- 239000011521 glass Substances 0.000 claims abstract description 88
- 239000000758 substrate Substances 0.000 claims abstract description 77
- 229920001721 polyimide Polymers 0.000 claims abstract description 67
- 239000004642 Polyimide Substances 0.000 claims abstract description 58
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 43
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 32
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 32
- 239000011733 molybdenum Substances 0.000 claims abstract description 32
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims abstract description 24
- 239000011787 zinc oxide Substances 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000010276 construction Methods 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims description 68
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 63
- 239000011701 zinc Substances 0.000 claims description 44
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 31
- 229910052725 zinc Inorganic materials 0.000 claims description 28
- 239000010949 copper Substances 0.000 claims description 25
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 24
- 238000000151 deposition Methods 0.000 claims description 24
- 239000011135 tin Substances 0.000 claims description 24
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 claims description 20
- 238000004140 cleaning Methods 0.000 claims description 20
- 238000010792 warming Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000004062 sedimentation Methods 0.000 claims description 19
- 239000003292 glue Substances 0.000 claims description 17
- 239000011669 selenium Substances 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 239000004411 aluminium Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 230000008021 deposition Effects 0.000 claims description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- 229910052711 selenium Inorganic materials 0.000 claims description 14
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 13
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 12
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 12
- 239000011975 tartaric acid Substances 0.000 claims description 12
- 235000002906 tartaric acid Nutrition 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 8
- 239000005695 Ammonium acetate Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 229940043376 ammonium acetate Drugs 0.000 claims description 8
- 235000019257 ammonium acetate Nutrition 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- 229910052718 tin Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- 239000001119 stannous chloride Substances 0.000 claims description 5
- 235000011150 stannous chloride Nutrition 0.000 claims description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- -1 cooling Substances 0.000 claims description 4
- 230000005518 electrochemistry Effects 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- XMXNVYPJWBTAHN-UHFFFAOYSA-N potassium chromate Chemical class [K+].[K+].[O-][Cr]([O-])(=O)=O XMXNVYPJWBTAHN-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000010583 slow cooling Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229960001296 zinc oxide Drugs 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- 238000013459 approach Methods 0.000 claims description 2
- 239000010408 film Substances 0.000 abstract description 101
- 239000010409 thin film Substances 0.000 abstract description 8
- 239000013078 crystal Substances 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 4
- 230000007547 defect Effects 0.000 description 5
- 238000004070 electrodeposition Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- 229910007610 Zn—Sn Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910002058 ternary alloy 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
- H01L31/02—Details
-
- 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
- H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
-
- 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
-
- 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
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention provides a copper zinc tin selenium solar cell device which is based on a polyimide film-soda glass composite substrate. The copper zinc tin selenium solar cell device is composed of glass, polyimide, a molybdenum back contact layer, a copper zinc tin selenium absorption layer, a cadmium sulfide buffer layer, a transparent window layer high-resistance intrinsic zinc oxide thin film, a transparent window layer low-resistance zinc oxide thin film and an upper aluminum electrode, and a laminated construction is formed. The manufacturing method includes the steps that firstly, the polyimide is coated on the surface of the glass, and the polyimide film-soda glass composite substrate is formed in a curing mode; then, all layers of films are manufactured on the surface of the substrate sequentially; after a complete copper zinc tin selenium solar cell is manufactured, the cell is separated from the soda glass composite substrate, and the flexible copper zinc tin selenium solar cell with the polyimide film as the substrate is obtained. The copper zinc tin selenium solar cell device and the manufacturing method have the advantages that a copper zinc tin selenium film based on the polyimide film-soda glass composite substrate is large in crystal grain size, the flexible cell is manufactured through the rigid substrate, implementation is easy to conduct, and large-scale application and popularization are facilitated.
Description
Technical field
The present invention relates to thin film solar cell technical field, particularly a kind of copper-zinc-tin-selenium solar cell device based on polyimide film-soda glass compound substrate and preparation method thereof.
Background technology
Copper-zinc-tin-selenium material (CZTS) belongs to I-III-VI race quaternary compound semiconductor, has the crystal structure of chalcopyrite.Copper-zinc-tin-selefilm film too can battery from the nineties in 20th century occur since, be first made, after this, obtain very fast development, and progressively will realize industrialization.This battery has following characteristics: 1) energy gap of copper-zinc-tin-selenium is about 1.5eV; 2) copper-zinc-tin-selenium is a kind of direct gap semiconductor, to the absorption coefficient of visible ray up to 10
5cm
-1, copper-zinc-tin-selenium absorber thickness only needs 1.5-2.5 μm, and the thickness of whole battery is 3-4 μm; 3) Radiation hardness is strong, compares and is suitable as space power system; 4) conversion efficiency is high, and the small size copper-zinc-tin-selenium solar cell conversion efficiency that American I BM companies in 2014 and Solar Frontier, Tokyo answer chemical industry and prosperous energy photoelectricity (DelSolar) joint development to develop is up to 12.6%; 5) low light level characteristic is good; 6) rich in mineral resources, non-toxic.Therefore copper-zinc-tin-selenium polycrystalline thin-film solar cell is expected to one of main product becoming solar cell of future generation.
Aerospace field needs solar cell to have higher quality than power, namely wishes that the solar cell of unit mass can send more electricity.The surface modeling of ground photovoltaic building and the photovoltaic plant etc. of movable type are required that solar cell has flexibility, foldability and is not afraid of to fall touch, this promotes the development of flexible solar cell.Due to relatively strong heat-resisting ability and the comparatively applicable coefficient of expansion, polyimides (PI) is shown one's talent wherein.
But the thermal coefficient of expansion of polyimides still well cannot mate with copper-zinc-tin-selenium material itself.When temperature is higher, polyimides can produce larger deformation, causes copper-zinc-tin-selefilm film comparatively loose, easily comes off.So underlayer temperature is lower when preparing based on the copper-zinc-tin-selenium of polyimide substrate at present.Thus cause that the thin film crystallization that grows is second-rate, crystal grain is tiny, defect is more, adds the compound of charge carrier, shorten the life-span of few son, and then have impact on battery performance.
Summary of the invention
The object of the invention is for above-mentioned existing problems, provide a kind of copper-zinc-tin-selenium solar cell device and preparation method thereof, this solar cell device is the copper-zinc-tin-selenium solar cell based on polyimide film-soda glass compound substrate, it prepares flexible battery with rigidity substrate, copper-zinc-tin-selefilm film crystalline quality based on polyimide film-soda glass compound substrate is good, crystal grain is large, and defect is few.
Technical scheme of the present invention:
A kind of copper-zinc-tin-selenium solar cell device, for the copper-zinc-tin-selenium solar cell based on polyimide film-soda glass compound substrate, formed by glass, polyimides, molybdenum back contact, copper-zinc-tin-selenium absorbed layer, cadmium sulfide resilient coating, transparent window layer high resistant native oxide zinc film, transparent window layer low-resistance zinc oxide aluminum film and aluminium top electrode and formed laminated construction, wherein substrate is made up of soda glass and the polyimide film that is grown on its surface, the thickness of soda glass is 1.5-2mm, and polyimides film thickness is 25-30 μm; Molybdenum back contact comprises resistive formation film and low resistivity layer film, and wherein the thickness of resistive formation film is 80-120nm, and the thickness of low resistivity layer film is 600-700nm; The chemical molecular formula of copper-zinc-tin-selenium absorbed layer is Cu
2znSnSe
4, conduction type is p-type, and film thickness is 1.5-2 μm; Cadmium sulfide resilient coating conduction type be N-shaped, thickness is 45-50nm; Transparent window layer comprises high resistant native oxide zinc film and low-resistance zinc oxide aluminum film, and conduction type is N-shaped, and the thickness of native oxide zinc film is 50-100nm, and the thickness of zinc oxide aluminum film is 0.4-0.6 μm; The thickness of aluminium upper electrode film is 0.8-1.5 μm.
A kind of preparation method of described copper-zinc-tin-selenium solar cell device, first polyimides glue is applied to soda glass surface, be solidified into polyimide film-soda glass compound substrate, secondly molybdenum back contact, copper-zinc-tin-selenium absorbed layer, cadmium sulfide resilient coating, transparent window layer and top electrode is prepared successively on its surface, after prepared by complete copper-zinc-tin-selenium solar cell, by itself and soda glass substrate separation, obtaining take polyimide film as the flexible copper-zinc-tin-selenium solar cell of substrate.
The preparation method of described polyimide film-soda glass compound substrate, step is as follows:
1) carry out surface clean to soda glass, cleaning method is:
First the soda glass of 10cm × 10cm is put into potassium bichromate solution and soak 2h, potassium bichromate solution is by 300 grammes per square metre potassium chromates, 3 liters of concentrated sulfuric acids and the configuration of 300 ml deionized water form, it is in the acetone soln of 99.5w% that soda glass taking-up deionized water rinsing is placed on concentration, put into supersonic wave cleaning machine to clean, ultrasonic frequency is 20-30kHz, time is 20-25min, then soda glass is taken out from acetone soln, being placed on concentration with deionized water rinsing is in the alcohol of 99.7w%, putting into supersonic wave cleaning machine, to clean ultrasonic frequency be 20-30kHz, time is 20-25min, finally soda glass is taken out from alcohol, put into the beaker filling deionized water, put into supersonic wave cleaning machine cleaning 3 times, ultrasonic frequency is 20-30kHz, time is 20-25min,
2) polyimides glue is coated on soda glass surface, adopt spin processes to carry out even glue, technological parameter is: rotating speed is 1300-1500r/min, and the time is 35-45s;
3) sample after even glue is put into baking oven to be cured, polyimide film-soda glass compound substrate can be obtained, the heating and heat preservation program of described curing process is: oven temperature is warming up to 125-135 DEG C, and the heating-up time is 10-15min, and maintains 25-30min at 125-135 DEG C; Oven temperature is warming up to 150-160 DEG C, and the heating-up time is 5-10min, and maintains 10-15min at 150-160 DEG C; Oven temperature is warming up to 200-210 DEG C, and the heating-up time is 5-10min, and maintains 15-20min at 200-210 DEG C; Oven temperature is warming up to 250-260 DEG C, and the heating-up time is 5-10min, and maintains 15-20min at 250-260 DEG C; Oven temperature is warming up to 340-350 DEG C, and the heating-up time is 5-10min, and maintains 10-15min at 340-350 DEG C, and then slow cooling is to 18-25 DEG C, can obtain polyimide film-soda glass compound substrate.。
The preparation method of described molybdenum back contact film, prepared by employing DC magnetron sputtering system, sample to be prepared is placed in the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the molybdenum of 99.99% be target, rf magnetron sputtering technique is adopted to deposit high resistant molybdenum film and low-resistance molybdenum film respectively successively at substrate surface, wherein:
1) depositing high resistant molybdenum film technological parameter is: base vacuum 3.0 × 10
-4pa, operating air pressure 1-2Pa, underlayer temperature 25-50 DEG C, radio-frequency power 500-700W, Ar throughput 30-50sccm, base target speed of travel 4-6mm/s, sedimentation time is counted 2-4 time with the reciprocal time of base target;
2) technological parameter depositing low-resistance film is: base vacuum 3.0 × 10
-4pa, operating air pressure is 0-0.5Pa, and underlayer temperature is room temperature 25-50 DEG C, and radio-frequency power is 1500-2000W, Ar throughput is 15-20sccm, and the base target speed of travel is 4-6mm/s, and sedimentation time is counted 4-6 time with the reciprocal time of base target.
The preparation method of described copper-zinc-tin-selenium absorbed layer film, adopt selenizing stove film preparing system and electro-deposition method of fractional steps preparation technology, step is as follows:
1) copper sulphate is prepared respectively, zinc sulfate, stannous chloride, citric acid, the tartaric aqueous solution.
2) prepare Cu, Zn, Sn unit solution respectively, tin take citric acid as ligand, and copper, zinc, with citric acid and tartaric acid mixed ligand body, prepare the solution that stable unit can deposit.In each solution, the concentration of component and PH are respectively: 0.2M copper sulphate, 1.2M citric acid, 0.1M tartaric acid, PH=10.7; 0.2M stannous chloride, 0.6 citric acid, PH=5; 0.2M zinc sulfate, 0.6M citric acid, 0.1M tartaric acid.Place after one hour, treat that solution coordination is complete, start to carry out electro-deposition.
3) adopt electrochemistry station, Princeton, electro-deposition Cu/Sn/Zn tri-layers of monometallic precursor layer, prepare for preparing copper-zinc-tin-selenium.At room temperature 20 DEG C, adopting three-electrode system, is work electrode, reference electrode and auxiliary electrode respectively.Constant current process accurately can determine each tenor of deposition.Therefore, take galvanostatic deposition, deposition current, determine the time deposited.The quality of the Copper thin film of deposition directly determines the quality of subsequent metal layer, so the deposition current of copper is less than normal.Finally deposit Cu/ (Zn+Sn)=0.8, Zn/Sn=1.15, the ternary alloy three-partalloy precursor layer of the Cu-Zn-Sn that composition is suitable.
4) rear selenizing is carried out to precursor layer.Progressively heat up to substrate and selenium source, underlayer temperature rises to 500 DEG C, toasts substrate, selenium source is risen to 270 DEG C, flapper closure, after substrate bake 45min, open baffle plate selenizing 30min before baking.Fully reacted by Se and Cu/Zn/Sn, generate quaternary compound copper-zinc-tin-selenium.
5) lowered the temperature by substrate, cooling, drops to 25 DEG C, after 10min by selenium source simultaneously, closes selenium source.
The preparation method of described cadmium sulfide resilient coating, adopt chemical bath method preparation technology, step is as follows:
1) preparation feedback liquid: first configuration concentration is 0.01mol/L thiourea solution 1L, configuration cadmium acetate and Ammonium Acetate mixed solution 1L, wherein cadmium acetate solution concentration is 0.001mol/L, and liquor ammonii acetatis concentration is 0.003mol/L, and ammonia spirit concentration is 1.3 × 10
-3mol/L, then mixes thiourea solution 25mL, cadmium acetate and Ammonium Acetate mixed solution 25mL and ammonia spirit 4 and stirs, obtained reactant liquor;
2) being added by reactant liquor in the beaker being placed with sample and beaker is put into water-bath, bath temperature is set to 78-80 DEG C, and the reaction time is 50-60min;
3), after having reacted, the cadmium sulfide particle of the unreacted film forming of sample cadmium sulfide buffer-layer surface is totally residued in deionized water rinsing.
The high resistant native oxide zinc film of described transparent window layer and the preparation method of low-resistance zinc oxide aluminum film, adopt rf magnetron sputtering system and DC magnetron sputtering system preparation respectively, step is as follows:
1) preparation of high resistant native oxide zinc film
Sample to be prepared being placed in the settling chamber of r. f. magnetron sputtering system, take purity as the i-ZnO of 99.99% is target, and adopt rf magnetron sputtering technique at substrate surface deposition intrinsic zinc-oxide film, technological parameter is: base vacuum 3.0 × 10
-4pa, underlayer temperature 25-50 DEG C, radio-frequency power 800-1000W, Ar throughput 10-20sccm, O
2throughput 2-6sccm, the base target speed of travel is 2-6mm/s, and sedimentation time is counted 6-10 time with the reciprocal time of base target;
2) preparation of low-resistance zinc oxide aluminum film
Being placed at by sample to be prepared in the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the ZnO:Al of 99.99% is target, and adopt DC magnetron sputtering process at substrate surface deposition ZnO:Al film, technological parameter is: base vacuum 3.0 × 10
-4pa, underlayer temperature 25-50 DEG C, direct current power 1000-1200W, Ar throughput 12-18sccm, base target speed of travel 2-6mm/s, sedimentation time is counted 10-15 time with the reciprocal time of base target.
The preparation method of described aluminium top electrode, adopt the preparation of coevaporation system, step is as follows:
1) sample to be prepared is placed in coevaporation system, at base vacuum 3.0 × 10
-4under Pa, give heater strip 20A electric current successively, continue 1-2min, give heater strip 50A electric current, continue 1-2min, give heater strip 80A electric current, continue 1-2min; Give heater strip 120A electric current, continue 5-8min;
2) after glass pane to be seen is covered completely by aluminium film, stop heating, slowly reduce giving heater strip electric current, then cool.
Know-why analysis of the present invention:
In order to meet the requirement preparing the copper-zinc-tin-selenium flexible thin-film solar cell that crystalline quality is better, crystal grain is comparatively large, defect is less, the substrate that substrate is soft, light, thermal coefficient of expansion comparatively mates with copper-zinc-tin-selefilm film must be selected.Polyimide film-soda glass compound substrate can rely on soda glass and the comparatively close feature of the copper-zinc-tin-selenium absorbed layer film thermal coefficient of expansion, and compound substrate is prepared copper-zinc-tin-selefilm film solar cell.Be that substrate is separated from soda glass surface afterwards again with polyimides by thin film solar cell, obtain flexible copper zinc-tin selenium film solar battery, realize the design preparing flexible solar cell with rigidity substrate.
The technical advantage of the described copper-zinc-tin-selenium solar cell based on polyimide film-soda glass compound substrate:
1) polyimides glue is applied to glass surface, better can improves the roughness of substrate;
2) thermal coefficient of expansion of polyimides itself is larger, can not itself mate with copper-zinc-tin-selenium material well, easily be out of shape at relatively high temperatures, film is caused to loosen, very easily come off, and be grown on the polyimides of glass surface, rely on the adhesive force between glass, make it that comparatively large deformation not easily occur, more mate with copper-zinc-tin-selenium material;
3) due to glass contact, not easily there is deformation, polyimides can be given comparatively close to the temperature of its heatproof upper limit, contribute to copper-zinc-tin-selefilm film and better grow;
4) its epontic copper-zinc-tin-selefilm film crystalline quality is good, crystal grain is large, defect is few; .
5) after prepared by complete copper-zinc-tin-selenium solar cell, it is separated from glass, just can prepares the flexible copper-zinc-tin-selenium solar cell with larger columnar grain.
Advantage of the present invention is: this kind is good based on the film of absorbing layer of copper zinc tin selenium (CZTS) solar cell crystalline quality of polyimide film-soda glass compound substrate, crystal grain is large, defect is few, utilizes rigidity substrate to prepare flexible solar cell; Its preparation method is simple, easy to implement, is conducive to applying on a large scale, especially in space and special occasions, has extremely important application prospect.
Accompanying drawing explanation
Accompanying drawing is the structural representation of this copper-zinc-tin-selenium solar cell.
Embodiment
In order to make those skilled in the art person understand the present invention program better, below in conjunction with drawings and embodiments, the present invention is described in further detail.
Embodiment 1:
A kind of copper-zinc-tin-selenium solar cell device, for the copper-zinc-tin-selenium solar cell based on polyimide film-soda glass compound substrate, as shown in Figure 1, formed by glass, polyimides, molybdenum back contact, copper-zinc-tin-selenium absorbed layer, cadmium sulfide resilient coating, transparent window layer high resistant native oxide zinc film, transparent window layer low-resistance zinc oxide aluminum film and aluminium top electrode and formed laminated construction, wherein substrate is made up of soda glass and the polyimide film that is grown on its surface, the thickness of soda glass is 2mm, and polyimides film thickness is 25 μm; Molybdenum back contact comprises resistive formation film and low resistivity layer film, and wherein the thickness of resistive formation film is 100nm, and the thickness of low resistivity layer film is 600nm; The chemical molecular formula of copper-zinc-tin-selenium absorbed layer is Cu
2znSnSe
4, type is p-type, and film thickness is 1.5 μm; Cadmium sulfide resilient coating conduction type be N-shaped, thickness is 45nm; Transparent window layer comprises high resistant native oxide zinc film and low-resistance zinc oxide aluminum film, and conduction type is N-shaped, and the thickness of native oxide zinc film is 70nm, and the thickness of zinc oxide aluminum film is 0.6 μm; The thickness of aluminium upper electrode film is 1 μm.
The preparation method of described copper-zinc-tin-selenium solar cell device, first polyimides glue is applied to soda glass surface, be solidified into polyimide film-soda glass compound substrate, secondly molybdenum back contact, copper-zinc-tin-selenium absorbed layer, cadmium sulfide resilient coating, transparent window layer and top electrode is prepared successively on its surface, after prepared by complete copper-zinc-tin-selenium solar cell, by itself and soda glass substrate separation, obtaining take polyimide film as the flexible copper-zinc-tin-selenium solar cell of substrate.
The preparation method of described polyimide film-soda glass compound substrate, step is as follows:
1) carry out surface clean to soda glass, cleaning method is:
First the soda glass of 10cm × 10cm is put into potassium bichromate solution and soak 2h, potassium bichromate solution is by 300 grammes per square metre potassium chromates, 3 liters of concentrated sulfuric acids and the configuration of 300 ml deionized water form, it is in the acetone soln of 99.5w% that soda glass taking-up deionized water rinsing is placed on concentration, put into supersonic wave cleaning machine to clean, ultrasonic frequency is 20kHz, time is 25min, then soda glass is taken out from acetone soln, being placed on concentration with deionized water rinsing is in the alcohol of 99.7w%, putting into supersonic wave cleaning machine, to clean ultrasonic frequency be 20kHz, time is 25min, finally soda glass is taken out from alcohol, put into the beaker filling deionized water, put into supersonic wave cleaning machine cleaning 3 times, ultrasonic frequency is 20kHz, time is 25min,
2) polyimides glue is coated on soda glass surface, adopt spin processes to carry out even glue, technological parameter is: rotating speed is 1300r/min, and the time is 45s;
3) sample after even glue is put into baking oven to be cured, polyimide film-soda glass compound substrate can be obtained, the heating and heat preservation program of described curing process is: oven temperature is warming up to 125 DEG C, and the heating-up time is 15min, and maintains 30min at 125 DEG C; Oven temperature is warming up to 150 DEG C, the heating-up time is 5min, and maintains 15min at 150 DEG C; Oven temperature is warming up to 200 DEG C, the heating-up time is 5min, and maintains 20min at 200 DEG C; Oven temperature is warming up to 250 DEG C, the heating-up time is 5min, and maintains 20min at 250 DEG C; Oven temperature is warming up to 350 DEG C, the heating-up time is 10min, and maintains 10min at 350 DEG C, then slow cooling to 22 DEG C, can obtain polyimide film-soda glass compound substrate.
The preparation method of described molybdenum back contact film, prepared by employing DC magnetron sputtering system, sample to be prepared is placed in the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the molybdenum of 99.99% be target, rf magnetron sputtering technique is adopted to deposit high resistant molybdenum film and low-resistance molybdenum film respectively successively at substrate surface, wherein:
1) depositing high resistant molybdenum film technological parameter is: base vacuum 3.0 × 10
-4pa, operating air pressure 1Pa, underlayer temperature 25 DEG C, radio-frequency power 600W, Ar throughput 40sccm, base target speed of travel 4mm/s, sedimentation time counts 2 times with the reciprocal time of base target;
2) technological parameter depositing low-resistance film is: base vacuum 3.0 × 10
-4pa, operating air pressure is 0.1Pa, and underlayer temperature is 25 DEG C, and radio-frequency power is 1500W, Ar throughput is 15sccm, and the base target speed of travel is 4mm/s, and sedimentation time counts 6 times with the reciprocal time of base target.
The preparation method of described copper-zinc-tin-selenium absorbed layer film, adopt selenizing stove film preparing system and electro-deposition one-step preparation process, step is as follows:
1) prepare Cu, Zn, Sn unit solution respectively, tin take citric acid as ligand, and copper, zinc, with citric acid and tartaric acid mixed ligand body, prepare the solution that stable unit can deposit.In each solution, the concentration of component and PH are respectively: 0.2M copper sulphate, 1.2M citric acid, 0.1M tartaric acid, PH=10.7; 0.2M stannous chloride, 0.6 citric acid, PH=5; 0.2M zinc sulfate, 0.6M citric acid, 0.1M tartaric acid.
2) adopt electrochemistry station, Princeton, at room temperature 20 DEG C, deposition current and sedimentation time are respectively, Cu, 40mA, 125s; Sn, 100mA, 31.15s; Zn, 100mA, 52.45s.Obtain Cu/ (Zn+Sn)=0.8, Zn/Sn=1.15, three layers of monometallic precursor layer of the Cu/Zn/Sn that composition is suitable.
3) adopt selenizing stove film preparing system, rear selenizing is carried out to precursor layer.Sample is placed in selenizing stove film preparing system, vacuum is 3.0 × 10
-4pa, substrate flapper closure, underlayer temperature is increased to 500 DEG C, carries out baking 45min, selenium source temperature is increased to 270 DEG C simultaneously, opens baffle plate and carries out selenizing, after 30min.The composition of control Se, reaches suitable stoichiometric proportion.
4) lowered the temperature by substrate, cooling, drops to 25 DEG C, after 10min by selenium source simultaneously, closes selenium source.
The preparation method of described cadmium sulfide resilient coating, adopt chemical bath method preparation technology, step is as follows:
1) preparation feedback liquid: first configuration concentration is 0.01mol/L thiourea solution 1L, configuration cadmium acetate and Ammonium Acetate mixed solution 1L, wherein cadmium acetate solution concentration is 0.001mol/L, and liquor ammonii acetatis concentration is 0.003mol/L, and ammonia spirit concentration is 1.3 × 10
-3mol/L, then mixes thiourea solution 25mL, cadmium acetate and Ammonium Acetate mixed solution 25mL and ammonia spirit 4 and stirs, obtained reactant liquor;
2) reactant liquor is put into beaker and beaker is put into water-bath, bath temperature is set to 78 DEG C, and the reaction time is 60min;
3), after having reacted, the cadmium sulfide particle of the unreacted film forming of sample cadmium sulfide buffer-layer surface is totally residued in deionized water rinsing.
The high resistant native oxide zinc film of described transparent window layer and the preparation method of low-resistance zinc oxide aluminum film, adopt rf magnetron sputtering system and DC magnetron sputtering system preparation respectively, step is as follows:
1) preparation of high resistant native oxide zinc film
Sample to be prepared being placed in the settling chamber of r. f. magnetron sputtering system, take purity as the i-ZnO of 99.99% is target, and adopt rf magnetron sputtering technique at substrate surface deposition intrinsic zinc-oxide film, technological parameter is: base vacuum 3.0 × 10
-4pa, underlayer temperature 35 DEG C, radio-frequency power 800W, Ar throughput 10sccm, O
2throughput 3sccm, the base target speed of travel is 4mm/s, and sedimentation time counts 8 times with the reciprocal time of base target;
2) preparation of low-resistance zinc oxide aluminum film
Being placed at by sample to be prepared in the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the ZnO:Al of 99.99% is target, and adopt DC magnetron sputtering process at substrate surface deposition ZnO:Al film, technological parameter is: base vacuum 3.0 × 10
-4pa, underlayer temperature 25 DEG C, direct current power 1000W, Ar throughput 15sccm, base target speed of travel 6mm/s, sedimentation time counts 10 times with the reciprocal time of base target.
The preparation method of described aluminium top electrode, adopt the preparation of coevaporation system, step is as follows:
1) sample to be prepared is placed in coevaporation system, at base vacuum 3.0 × 10
-4under Pa, give heater strip 20A electric current successively, continue 2min, give heater strip 50A electric current, continue 2min, give heater strip 80A electric current, continue 2min; Give heater strip 120A electric current, continue 6min;
2) after glass pane to be seen is covered completely by aluminium film, stop heating, slowly reduce giving heater strip electric current, then cool.
Shown by test, prepared copper-zinc-tin-selenium solar cell device can form good PN junction, produces photovoltaic effect, can produce electric energy under solar light irradiation.
Embodiment 2:
A kind of copper-zinc-tin-selenium solar cell device, for the copper-zinc-tin-selenium solar cell based on polyimide film-soda glass compound substrate, as shown in Figure 1, formed by glass, polyimides, molybdenum back contact, copper-zinc-tin-selenium absorbed layer, cadmium sulfide resilient coating, transparent window layer high resistant native oxide zinc film, transparent window layer low-resistance zinc oxide aluminum film and aluminium top electrode and formed laminated construction, wherein substrate is made up of soda glass and the polyimide film that is grown on its surface, the thickness of soda glass is 2mm, and polyimides film thickness is 30 μm; Molybdenum back contact comprises resistive formation film and low resistivity layer film, and wherein the thickness of resistive formation film is 100nm, and the thickness of low resistivity layer film is 700nm; The chemical molecular formula of copper-zinc-tin-selenium absorbed layer is CuIn
1-xga
xse
2, in formula, x is 0.28, and conduction type is p-type, and film thickness is 1.8 μm; Cadmium sulfide resilient coating conduction type be N-shaped, thickness is 50nm; Transparent window layer comprises high resistant native oxide zinc film and low-resistance zinc oxide aluminum film, and conduction type is N-shaped, and the thickness of native oxide zinc film is 80nm, and the thickness of zinc oxide aluminum film is 0.5 μm; The thickness of aluminium upper electrode film is 1.2 μm.
The preparation method of described copper-zinc-tin-selenium solar cell device is identical with embodiment 1.
The preparation method of described polyimide film-soda glass compound substrate, step is as follows:
1) carry out surface clean to soda glass, cleaning method is:
First the soda glass of 10cm × 10cm is put into potassium bichromate solution and soak 2h, potassium bichromate solution is by 300 grammes per square metre potassium chromates, 3 liters of concentrated sulfuric acids and the configuration of 300 ml deionized water form, it is in the acetone soln of 99.5w% that soda glass taking-up deionized water rinsing is placed on concentration, put into supersonic wave cleaning machine to clean, ultrasonic frequency is 30kHz, time is 20min, then soda glass is taken out from acetone soln, being placed on concentration with deionized water rinsing is in the alcohol of 99.7w%, putting into supersonic wave cleaning machine, to clean ultrasonic frequency be 30kHz, time is 20min, finally soda glass is taken out from alcohol, put into the beaker filling deionized water, put into supersonic wave cleaning machine cleaning 3 times, ultrasonic frequency is 30kHz, time is 20min,
2) polyimides glue is coated on soda glass surface, adopt spin processes to carry out even glue, technological parameter is: rotating speed is 1400r/min, and the time is 40s;
3) sample after even glue is put into baking oven to be cured, polyimide film-soda glass compound substrate can be obtained, the heating and heat preservation program of described curing process is: oven temperature is warming up to 130 DEG C, and the heating-up time is 20min, and maintains 25min at 130 DEG C; Oven temperature is warming up to 160 DEG C, the heating-up time is 10min, and maintains 10min at 160 DEG C; Oven temperature is warming up to 210 DEG C, the heating-up time is 10min, and maintains 20min at 210 DEG C; Oven temperature is warming up to 260 DEG C, the heating-up time is 10min, and maintains 20min at 260 DEG C; Oven temperature is warming up to 345 DEG C, the heating-up time is 10min, and maintains 15min at 345 DEG C, then slow cooling to 22 DEG C, can obtain polyimide film-soda glass compound substrate.
The preparation method of described molybdenum back contact film, prepared by employing DC magnetron sputtering system, sample to be prepared is placed in the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the molybdenum of 99.99% be target, rf magnetron sputtering technique is adopted to deposit high resistant molybdenum film and low-resistance molybdenum film respectively successively at substrate surface, wherein:
1) depositing high resistant molybdenum film technological parameter is: base vacuum 3.0 × 10
-4pa, operating air pressure 1.5Pa, underlayer temperature 25 DEG C, radio-frequency power 700W, Ar throughput 50sccm, base target speed of travel 5mm/s, sedimentation time counts 4 times with the reciprocal time of base target;
2) technological parameter depositing low-resistance film is: base vacuum 3.0 × 10
-4pa, operating air pressure is 0.5Pa, and underlayer temperature is 25 DEG C, and radio-frequency power is 1800W, Ar throughput is 20sccm, and the base target speed of travel is 6mm/s, and sedimentation time counts 6 times with the reciprocal time of base target.
The preparation method of described copper-zinc-tin-selenium absorbed layer film, adopt selenizing stove film preparing system and electro-deposition three-step approach preparation technology, step is as follows:
1) prepare Cu, Zn, Sn unit solution respectively, tin take citric acid as ligand, and copper, zinc, with citric acid and tartaric acid mixed ligand body, prepare the solution that stable unit can deposit.In each solution, the concentration of component and PH are respectively: 0.2M copper sulphate, 1.2M citric acid, 0.1M tartaric acid, PH=10.7; 0.2M stannous chloride, 0.6 citric acid, PH=5; 0.2M zinc sulfate, 0.6M citric acid, 0.1M tartaric acid.
2) adopt electrochemistry station, Princeton, at room temperature 20 DEG C, deposition current and sedimentation time are respectively, Cu, 45mA, 111s; Sn, 80mA, 38.94s; Zn, 100mA, 52.45s.Obtain Cu/ (Zn+Sn)=0.8, Zn/Sn=1.15, three layers of monometallic precursor layer of the Cu/Zn/Sn that composition is suitable.
3) adopt selenizing stove film preparing system, rear selenizing is carried out to precursor layer.Sample is placed in selenizing stove film preparing system, vacuum is 3.0 × 10
-4pa, substrate flapper closure, underlayer temperature is increased to 500 DEG C, carries out baking 45min, selenium source temperature is increased to 270 DEG C simultaneously, opens baffle plate and carries out selenizing, after 30min.The composition of control Se, reaches suitable stoichiometric proportion.
4) lowered the temperature by substrate, cooling, drops to 25 DEG C, after 10min by selenium source simultaneously, closes selenium source.
The preparation method of described cadmium sulfide resilient coating, adopt chemical bath method preparation technology, step is as follows:
1) preparation feedback liquid: first configuration concentration is 0.01mol/L thiourea solution 1L, configuration cadmium acetate and Ammonium Acetate mixed solution 1L, wherein cadmium acetate solution concentration is 0.001mol/L, and liquor ammonii acetatis concentration is 0.003mol/L, and ammonia spirit concentration is 1.3 × 10
-3mol/L, then mixes thiourea solution 25mL, cadmium acetate and Ammonium Acetate mixed solution 25mL and ammonia spirit 4 and stirs, obtained reactant liquor;
2) reactant liquor is put into beaker and beaker is put into water-bath, bath temperature is set to 80 DEG C, and the reaction time is 50min;
3) after having reacted, with the cadmium sulfide particle of the clean sample carryover of deionized water rinsing in the unreacted film forming of cadmium sulfide buffer-layer surface.
The high resistant native oxide zinc film of described transparent window layer and the preparation method of low-resistance zinc oxide aluminum film, adopt rf magnetron sputtering system and DC magnetron sputtering system preparation respectively, step is as follows:
1) preparation of high resistant native oxide zinc film
Sample to be prepared being placed in the settling chamber of r. f. magnetron sputtering system, take purity as the i-ZnO of 99.99% is target, and adopt rf magnetron sputtering technique at substrate surface deposition intrinsic zinc-oxide film, technological parameter is: base vacuum 3.0 × 10
-4pa, underlayer temperature 50 DEG C, radio-frequency power 1000W, Ar throughput 15sccm, O
2throughput 4sccm, the base target speed of travel is 6mm/s, and sedimentation time counts 8 times with the reciprocal time of base target;
2) preparation of low-resistance zinc oxide aluminum film
Being placed at by sample to be prepared in the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the ZnO:Al of 99.99% is target, and adopt DC magnetron sputtering process at substrate surface deposition ZnO:Al film, technological parameter is: base vacuum 3.0 × 10
-4pa, underlayer temperature 25 DEG C, direct current power 1200W, Ar throughput 17sccm, base target speed of travel 4mm/s, sedimentation time counts 12 times with the reciprocal time of base target.
The preparation method of described aluminium top electrode, adopt the preparation of coevaporation system, step is as follows:
1) sample to be prepared is placed in coevaporation system, at base vacuum 3.0 × 10
-4under Pa, give heater strip 20A electric current successively, continue 21min, give heater strip 50A electric current, continue 1min, give heater strip 80A electric current, continue 2min; Give heater strip 120A electric current, continue 5min;
2) after glass pane to be seen is covered completely by aluminium film, stop heating, slowly reduce giving heater strip electric current, then cool.
Testing result is identical with embodiment 1.
In sum, for preparing the flexible copper zinc-tin selenium cell of high conversion efficiency, the invention provides a kind of preparation method of the copper-zinc-tin-selenium solar cell device based on polyimide film-soda glass compound substrate, polyimides glue is applied to soda glass surface, be solidified into polyimide film-soda glass compound substrate, and prepare copper-zinc-tin-selenium solar cell on its surface, after prepared by complete copper-zinc-tin-selenium solar cell, it is separated with soda glass, formation take polyimide film as the flexible copper-zinc-tin-selenium solar cell of substrate, realize preparing flexible battery with rigidity substrate.These preparation method's process conditions are convenient and easy, are conducive to applying on a large scale, especially in space and special occasions, have extremely important application prospect.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (8)
1. a copper-zinc-tin-selenium solar cell device, it is characterized in that: be the copper-zinc-tin-selenium solar cell based on polyimide film-soda glass compound substrate, formed by glass, polyimides, molybdenum back contact, copper-zinc-tin-selenium absorbed layer, cadmium sulfide resilient coating, transparent window layer high resistant native oxide zinc film, transparent window layer low-resistance zinc oxide aluminum film and aluminium top electrode and formed laminated construction, wherein substrate is made up of soda glass and the polyimide film that is grown on its surface, the thickness of soda glass is 1.5-2mm, and polyimides film thickness is 25-30 μm; Molybdenum back contact comprises resistive formation film and low resistivity layer film, and wherein the thickness of resistive formation film is 80-120nm, and the thickness of low resistivity layer film is 600-700nm; The chemical molecular formula of copper-zinc-tin-selenium absorbed layer is Cu
2znSnSe
4, conduction type is p-type, and film thickness is 1.5-2 μm; Cadmium sulfide resilient coating conduction type be N-shaped, thickness is 45-50nm; Transparent window layer comprises high resistant native oxide zinc film and low-resistance zinc oxide aluminum film, and conduction type is N-shaped, and the thickness of native oxide zinc film is 50-100nm, and the thickness of zinc oxide aluminum film is 0.4-0.6 μm; The thickness of aluminium upper electrode film is 0.8-1.5 μm.
2. the preparation method of a copper-zinc-tin-selenium solar cell device as claimed in claim 1, it is characterized in that: first polyimides glue is applied to soda glass surface, be solidified into polyimide film-soda glass compound substrate, secondly molybdenum back contact, copper-zinc-tin-selenium absorbed layer, cadmium sulfide resilient coating, transparent window layer and top electrode is prepared successively on its surface, after prepared by complete copper-zinc-tin-selenium solar cell, by itself and soda glass substrate separation, obtaining take polyimide film as the flexible copper-zinc-tin-selenium solar cell of substrate.
3. the preparation method of copper-zinc-tin-selenium solar cell device according to claim 2, it is characterized in that: the preparation method of described polyimide film-soda glass compound substrate, step is as follows:
1) carry out surface clean to soda glass, cleaning method is:
First the soda glass of 10cm × 10cm is put into potassium bichromate solution and soak 2h, potassium bichromate solution is by 300 grammes per square metre potassium chromates, 3 liters of concentrated sulfuric acids and the configuration of 300 ml deionized water form, it is in the acetone soln of 99.5w% that soda glass taking-up deionized water rinsing is placed on concentration, put into supersonic wave cleaning machine to clean, ultrasonic frequency is 20-30kHz, time is 20-25min, then soda glass is taken out from acetone soln, being placed on concentration with deionized water rinsing is in the alcohol of 99.7w%, putting into supersonic wave cleaning machine, to clean ultrasonic frequency be 20-30kHz, time is 20-25min, finally soda glass is taken out from alcohol, put into the beaker filling deionized water, put into supersonic wave cleaning machine cleaning 3 times, ultrasonic frequency is 20-30kHz, time is 20-25min,
2) polyimides glue is coated on soda glass surface, adopt spin processes to carry out even glue, technological parameter is: rotating speed is 1300-1500r/min, and the time is 35-45s;
3) sample after even glue is put into baking oven to be cured, polyimide film-soda glass compound substrate can be obtained, the heating and heat preservation program of described curing process is: oven temperature is warming up to 125-135 DEG C, and the heating-up time is 10-15min, and maintains 25-30min at 125-135 DEG C; Oven temperature is warming up to 150-160 DEG C, and the heating-up time is 5-10min, and maintains 10-15min at 150-160 DEG C; Oven temperature is warming up to 200-210 DEG C, and the heating-up time is 5-10min, and maintains 15-20min at 200-210 DEG C; Oven temperature is warming up to 250-260 DEG C, and the heating-up time is 5-10min, and maintains 15-20min at 250-260 DEG C; Oven temperature is warming up to 340-350 DEG C, and the heating-up time is 5-10min, and maintains 10-15min at 340-350 DEG C, and then slow cooling is to 18-25 DEG C, can obtain polyimide film-soda glass compound substrate.
4. the preparation method of copper-zinc-tin-selenium solar cell device according to claim 2, it is characterized in that: the preparation method of described molybdenum back contact film, prepared by employing DC magnetron sputtering system, sample to be prepared is placed in the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the molybdenum of 99.99% be target, rf magnetron sputtering technique is adopted to deposit high resistant molybdenum film and low-resistance molybdenum film respectively successively at substrate surface, wherein:
1) depositing high resistant molybdenum film technological parameter is: base vacuum 3.0 × 10
-4pa, operating air pressure 1-2Pa, underlayer temperature 25-50 DEG C, radio-frequency power 500-700W, Ar throughput 30-50sccm, base target speed of travel 4-6mm/s, sedimentation time is counted 2-4 time with the reciprocal time of base target;
2) technological parameter depositing low-resistance film is: base vacuum 3.0 × 10
-4pa, operating air pressure is 0-0.5Pa, and underlayer temperature is room temperature 25-50 DEG C, and radio-frequency power is 1500-2000W, Ar throughput is 15-20sccm, and the base target speed of travel is 4-6mm/s, and sedimentation time is counted 4-6 time with the reciprocal time of base target.
5. the preparation method of copper-zinc-tin-selenium solar cell device according to claim 2, is characterized in that: the preparation method of described copper-zinc-tin-selenium absorbed layer film, and adopt selenizing stove film preparing system and coevaporation three-step approach preparation technology, step is as follows:
1) prepare Cu, Zn, Sn unit solution respectively, tin take citric acid as ligand, and copper, zinc, with citric acid and tartaric acid mixed ligand body, prepare the solution that stable unit can deposit.In each solution, the concentration of component and PH are respectively: 0.2M copper sulphate, 1.2M citric acid, 0.1M tartaric acid, PH=10.7; 0.2M stannous chloride, 0.6 citric acid, PH=5; 0.2M zinc sulfate, 0.6M citric acid, 0.1M tartaric acid;
2) adopt electrochemistry station, Princeton, at room temperature 20 DEG C, deposition current and sedimentation time are respectively, Cu, 40-45mA, 111s-125s; Sn, 80-100mA, 31.15s-38.94s; Zn, 100mA, 52.45s, obtain Cu/ (Zn+Sn)=0.8, Zn/Sn=1.15, three layers of monometallic precursor layer of the Cu/Zn/Sn that composition is suitable;
3) adopt selenizing stove film preparing system, rear selenizing is carried out to precursor layer.Sample is placed in selenizing stove film preparing system, vacuum is 3.0 × 10
-4pa, substrate flapper closure, underlayer temperature is increased to 500 DEG C, carries out baking 45min, selenium source temperature is increased to 270 DEG C simultaneously, opens baffle plate and carries out selenizing, after 30min.The composition of control Se, reaches suitable stoichiometric proportion;
4) lowered the temperature by substrate, cooling, drops to 25 DEG C, after 10min by selenium source simultaneously, closes selenium source.
6. the preparation method of copper-zinc-tin-selenium solar cell device according to claim 2, is characterized in that: the preparation method of described cadmium sulfide resilient coating, and adopt chemical bath method preparation technology, step is as follows:
1) preparation feedback liquid: first configuration concentration is 0.01mol/L thiourea solution 1L, configuration cadmium acetate and Ammonium Acetate mixed solution 1L, wherein cadmium acetate solution concentration is 0.001mol/L, and liquor ammonii acetatis concentration is 0.003mol/L, and ammonia spirit concentration is 1.3 × 10
-3mol/L, then mixes thiourea solution 25mL, cadmium acetate and Ammonium Acetate mixed solution 25mL and ammonia spirit 4 and stirs, obtained reactant liquor;
2) being added by reactant liquor in the beaker being placed with sample and beaker is put into water-bath, bath temperature is set to 78-80 DEG C, and the reaction time is 50-60min;
3), after having reacted, the cadmium sulfide particle of the unreacted film forming of sample cadmium sulfide buffer-layer surface is totally residued in deionized water rinsing.
7. the preparation method of copper-zinc-tin-selenium solar cell device according to claim 2, it is characterized in that: the high resistant native oxide zinc film of described transparent window layer and the preparation method of low-resistance zinc oxide aluminum film, adopt rf magnetron sputtering system and DC magnetron sputtering system preparation respectively, step is as follows:
1) preparation of high resistant native oxide zinc film
Sample to be prepared being placed in the settling chamber of r. f. magnetron sputtering system, take purity as the i-ZnO of 99.99% is target, and adopt rf magnetron sputtering technique at substrate surface deposition intrinsic zinc-oxide film, technological parameter is: base vacuum 3.0 × 10
-4pa, underlayer temperature 25-50 DEG C, radio-frequency power 800-1000W, Ar throughput 10-20sccm, O
2throughput 2-6sccm, the base target speed of travel is 2-6mm/s, and sedimentation time is counted 6-10 time with the reciprocal time of base target;
2) preparation of low-resistance zinc oxide aluminum film
Being placed at by sample to be prepared in the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the ZnO:Al of 99.99% is target, and adopt DC magnetron sputtering process at substrate surface deposition ZnO:Al film, technological parameter is: base vacuum 3.0 × 10
-4pa, underlayer temperature 25-50 DEG C, direct current power 1000-1200W, Ar throughput 12-18sccm, base target speed of travel 2-6mm/s, sedimentation time is counted 10-15 time with the reciprocal time of base target.
8. the preparation method of copper-zinc-tin-selenium solar cell device according to claim 2, is characterized in that: the preparation method of described aluminium top electrode, and adopt the preparation of coevaporation system, step is as follows:
1) sample to be prepared is placed in coevaporation system, at base vacuum 3.0 × 10
-4under Pa, give heater strip 20A electric current successively, continue 1-2min, give heater strip 50A electric current, continue 1-2min, give heater strip 80A electric current, continue 1-2min; Give heater strip 120A electric current, continue 5-8min;
2) after glass pane to be seen is covered completely by aluminium film, stop heating, slowly reduce giving heater strip electric current, then cool.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106549082A (en) * | 2015-09-21 | 2017-03-29 | 云南师范大学 | The method that alloys target prepares copper-zinc-tin-sulfur film absorbed layer with sulfide target cosputtering |
| CN113471332A (en) * | 2021-07-01 | 2021-10-01 | 南开大学 | Method for designing P-N junction structure of copper-based thin film solar cell with effectively separated current carriers and solar cell prepared by method |
-
2015
- 2015-04-29 CN CN201510222224.1A patent/CN104779307A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106549082A (en) * | 2015-09-21 | 2017-03-29 | 云南师范大学 | The method that alloys target prepares copper-zinc-tin-sulfur film absorbed layer with sulfide target cosputtering |
| CN106549082B (en) * | 2015-09-21 | 2019-07-05 | 云南师范大学 | The method that alloys target and sulfide target cosputtering prepare copper-zinc-tin-sulfur film absorbed layer |
| CN113471332A (en) * | 2021-07-01 | 2021-10-01 | 南开大学 | Method for designing P-N junction structure of copper-based thin film solar cell with effectively separated current carriers and solar cell prepared by method |
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