CN105470338A - Flexible stacked solar cell and preparation method - Google Patents
Flexible stacked solar cell and preparation method Download PDFInfo
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- CN105470338A CN105470338A CN201511014726.1A CN201511014726A CN105470338A CN 105470338 A CN105470338 A CN 105470338A CN 201511014726 A CN201511014726 A CN 201511014726A CN 105470338 A CN105470338 A CN 105470338A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000758 substrate Substances 0.000 claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 239000010408 film Substances 0.000 claims description 68
- 238000000034 method Methods 0.000 claims description 57
- 238000004528 spin coating Methods 0.000 claims description 42
- 238000004544 sputter deposition Methods 0.000 claims description 37
- 238000001704 evaporation Methods 0.000 claims description 30
- 230000008020 evaporation Effects 0.000 claims description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 22
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 20
- 210000001142 back Anatomy 0.000 claims description 17
- 230000005540 biological transmission Effects 0.000 claims description 17
- 239000010409 thin film Substances 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229910052738 indium Inorganic materials 0.000 claims description 14
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 14
- 229920001721 polyimide Polymers 0.000 claims description 14
- 238000007738 vacuum evaporation Methods 0.000 claims description 14
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 238000000137 annealing Methods 0.000 claims description 12
- 239000010931 gold Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 11
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 239000004571 lime Substances 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 9
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 8
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 229910052733 gallium Inorganic materials 0.000 claims description 8
- 239000011669 selenium Substances 0.000 claims description 8
- 229910052711 selenium Inorganic materials 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 6
- 239000005695 Ammonium acetate Substances 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229940043376 ammonium acetate Drugs 0.000 claims description 6
- 235000019257 ammonium acetate Nutrition 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- 229940065287 selenium compound Drugs 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229920000109 alkoxy-substituted poly(p-phenylene vinylene) Polymers 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000012459 cleaning agent Substances 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 230000005525 hole transport Effects 0.000 abstract 3
- 230000031700 light absorption Effects 0.000 abstract 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/068—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
- H01L31/0687—Multiple junction or tandem solar cells
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- 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
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
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- 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
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
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- 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
- H01L31/1876—Particular processes or apparatus for batch treatment of the devices
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- 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
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- Y02E10/541—CuInSe2 material PV cells
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- Y02E10/544—Solar cells from Group III-V materials
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- 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
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Abstract
The invention discloses a flexible stacked solar cell and a preparation method, and relates to the technical field of solar cells. The flexible stacked solar cell sequentially comprises a transparent substrate, a back electrode layer, a copper indium gallium selenide active layer, a CdS buffer layer, a window layer, an intermediate layer, an electron transport layer, a perovskite absorption layer, a hole transport layer and an electrode, wherein the back electrode layer is located on the transparent conductive substrate; the copper indium gallium selenide active layer is located on the back electrode layer; the CdS buffer layer is located on the copper indium gallium selenide active layer; the window layer is located on the CdS buffer layer; the intermediate layer is located on the window layer; the electron transport layer is located on the intermediate layer; the perovskite absorption layer is located on the electron transport layer; the hole transport layer is located on the perovskite absorption layer; and the electrode is located on the hole transport layer. The stacked solar cell adopts copper indium gallium selenide/perovskite as a light absorption layer, so that absorption of light can be improved to the maximal extent; the cell efficiency is improved; furthermore, a roll-to-roll technology can be achieved by a flexible substrate; mass production is achieved; and the prospect in commercial application is improved.
Description
Technical field
The present invention relates to technical field of solar cells, particularly relate to a kind of flexible overlapping solar cell and preparation method.
Background technology
In recent years, due to the exhaustion increasingly of fossil fuel, Energy situation growing tension is caused.In addition the environmental pollution that the combustion of fossil fuel grown with each passing day causes, brings serious harm to the existence of the earth ecological balance and the mankind.Develop renewable new forms of energy and become a global problem.Photovoltaic generation is a kind of clean energy resource of zero discharge, be also a kind of can the real energy of large-scale application, can carrying out Independent Power Generation and generate electricity by way of merging two or more grid systems, is the first-selection in various regenerative resource.
The development of solar battery technology generally can be divided into three generations in general: the first generation take monocrystalline silicon as the monocrystalline type photovoltaic cell of representative; The inorganic thin film solar cell that the second generation is then is representative with cadmium telluride (CdTe) and Copper indium gallium selenide (CIGS); The third generation is the novel solar cell (comprising organic thin film solar cell (OPV), dye-sensitized solar cells (DSSC), perovskite solar cell (PSC) etc.) based on nanometer technology and new material.First, second in generation solar cell technique comparative maturity, its battery efficiency all more than 15%, and achieves and commercially produces.The third generation solar cell technology have less energy consumption, raw material extensively, environmental friendliness, low cost and other advantages show the application and development prospect being rich in potentiality.
At present, the Laboratory efficiencies of the perovskite solar cell prepared by Perovskite Phase organic metal halide breaks through 20%, has very high industrialization prospect.Meanwhile, the CIGS solar cell in the third generation solar cell has commercial operation, and its Laboratory efficiencies is also more than 20%.By stack technology, Copper Indium Gallium Selenide and perovskite material are made solar cell and can improve spectral absorption scope, significantly improve the conversion efficiency of solar cell.Compare in Liquid preparation methods CIGS thin-film, using vacuum vapour deposition to prepare film effectively can optimize film morphology, improves cell conversion efficiency; With use glass as substrate solar cell compared with, flexible solar cell can use the large-scale production of roll-to-roll technique reduce production cost, be of value to commercialized running.
Summary of the invention
The technical problem to be solved in the present invention is: provide a kind of efficient and light weight, the flexible overlapping solar cell that can be mass-produced and preparation method.
The technical scheme that the present invention takes for the technical problem existed in solution known technology is:
A kind of flexible overlapping solar cell, at least comprises:
Transparent substrate (1), described transparent substrate (1) is with receiving the polyimide film of lime glass or flexible substrate; Wherein the thickness range of polyimide film is 25 μm ~ 100 μm;
Be dorsum electrode layer (2) at described transparent substrate (1) upper surface, the thickness range of described dorsum electrode layer (2) is 100nm ~ 1000nm;
Be Copper Indium Gallium Selenide active layer (3) at the upper surface of described dorsum electrode layer (2), the thickness range of described Copper Indium Gallium Selenide active layer (3) is 1 μm ~ 3 μm;
Be CdS resilient coating (4) at the upper surface of described Copper Indium Gallium Selenide active layer (3), the thickness range of described CdS resilient coating (4) is 30nm ~ 100nm;
Be Window layer (5) at the upper surface of described CdS resilient coating (4), the thickness range of described Window layer (5) is 100nm ~ 500nm;
Be intermediate layer (6) at the upper surface of described Window layer (5), when described intermediate layer (6) are N-shaped LiF, CsCO
3, C
6h
5during a kind of in COOLi, ZnO, the thickness range of intermediate layer (6) is 10nm ~ 120nm; When described intermediate layer (6) are for a kind of in p-type molybdenum oxide, MEH-PPV, PEDOT, the thickness range of intermediate layer (6) is 30nm ~ 150nm;
Be electron transfer layer (7) at the upper surface of described intermediate layer (6), described electron transfer layer (7) is TiO2, ZnO, Al
2o
3, SiO
2in one, the thickness range of described electron transfer layer (7) is 50nm ~ 300nm;
Be perovskite absorbed layer (8) at the upper surface of described electron transfer layer (7), the thickness range of described perovskite absorbed layer (8) is 100nm ~ 1000nm;
Be hole transmission layer (9) at the upper surface of described perovskite absorbed layer (8), the thickness range of described hole transmission layer (9) is 100nm ~ 1000nm;
Be electrode (10) at the upper surface of described hole transmission layer (9).
Further: the material of described dorsum electrode layer (2) is the one in molybdenum, nickel, aluminium, gold, silver, copper, titanium.
Further: the material of described Window layer (5) is the one in i-ZnO, ZnO-Al, ITO.
A preparation method for flexible overlapping solar cell, comprises the steps:
Step 101, clean polyimide film surface:
Use plasma backwash etching machine, operating pressure is 0.3Pa, and sputtering power is 0.2kw, carries out etched clean by Ar to polyimide film; The square to 3cm*3cm is cut out after having cleaned;
Step 102, spatter dorsum electrode layer (2):
Select the one in molybdenum, nickel, aluminium, gold, silver, copper, titanium, use direct current sputtering, target purity is 99.99%, and power is 0.6kw, and operating pressure is 1.0Pa; Sputter two-layer, wherein ground floor thickness is 100nm, and second layer thickness is 400nm;
Step 103, evaporation Copper Indium Gallium Selenide active layer (3):
Use three-step approach to prepare CIGS thin-film, to be specially in vacuum chamber by 300 DEG C of-1200 DEG C of high temperature evaporations, to make Copper Indium Gallium Selenide composition, on substrate, chemical reaction occur, generate copper-indium-gallium-selenium compound; First, vacuum chamber vacuum 5 × 10
-4pa, vacuum evaporation indium gallium selenium film preformed layer, temperature is respectively indium 900 DEG C, gallium 1000 DEG C, 300 DEG C, selenium; Thickness range is 300-800nm; And then evaporation Copper Indium Gallium Selenide material, temperature is respectively copper 1200 DEG C, indium 900 DEG C, gallium 1000 DEG C, 300 DEG C, selenium; Thickness is about 2 μm; At substrate all remains on 450 DEG C;
Step 104, use plated film mode plated film CdS resilient coating (4):
Ammonium Acetate, ammoniacal liquor, thiocarbamide volume ratio are that 2:3:1 is configured to 500ml solution, bath temperature 70 DEG C, are soaked by polyimide film and react 30min in the solution; Obtained CdS film thickness is about 50nm;
Step 105, sputtering Window layer Window layer (5)
Radio frequency magnetron sputtering method sputtering i-ZnO thickness is used to be 50nm, operating pressure 0.6Pa, power 0.8kw; Use DC magnetron sputtering method sputtering ZnO:Al, operating pressure 0.8Pa, power 1.0kw, ZnO:Al thickness is about 350nm;
Step 106, the mode of evaporation and spin coating is used to prepare intermediate layer (6);
Be that the P type LiF of 1.0nm is deposited on (5) in Window layer by thickness; Specifically preparing environment is: local vacuum degree is 5 × 10
-4pa, stop when using film thickness monitor to observe 1.0nm, evaporation time is 30min;
LiF has prepared rear use spin-coating method and has prepared PEDOT; Spin coating rotating speed 4000r/min, operating time 15s, the LiF thickness obtained is about 100nm;
Step 107, utilize magnetron sputtering method manufacture electron transfer layer (7);
The mode of magnetron sputtering is utilized to prepare TiO2 film; Be specially and use purity to be the TiO of 99.99%
2target, the vacuum of operational environment is 5 × 10
-4pa, operating pressure 0.5Pa, sputtering power 0.5kw, sputtering time 2h, gained TiO
2film thickness is 100nm;
Step 108, one-step method prepare perovskite absorbed layer (8); Detailed process is:
CH
3nH
3the preparation of I: get respectively 30mL mass percent be 57% HI solution and 30mL mass percent be the methylamine solution of 40%, mixedly in three mouthfuls of round-bottomed flasks being incorporated in stirring reaction in ice-water bath; After 5h, reaction products therefrom is placed in 100mL single port flask, steamed at 50 DEG C of condition backspins by Rotary Evaporators, products therefrom cleans three times by ether; Make product recrystallization with the mixed solvent of methyl alcohol and ether subsequently, generate a kind of white crystal, finally dry in vacuum drying chamber;
The PbI of quality such as to get respectively
2with CH
3nH
3i is dissolved in the precursor solution that 1.5mM/mL prepared by a certain amount of DMF solvent; Get the precursor solution of 200 μ L, the spin coating rotating speed arranging sol evenning machine is 5000r/15s spin-coating film, and 90min process of finally annealing at 120 DEG C obtains perovskite absorbed layer (8);
Step 109, spin-coating method prepare hole transmission layer (9);
200 μ LSpiro-OMETAD solution are dropped on perovskite absorbed layer film, spin coating rotating speed 4000r/min is set, time 30s, 150 annealing in process 1h; Gained Spiro-OMETAD film thickness is 100nm;
Step 110, utilize striped-shaped mask plate, the Au of vacuum evaporation 100nm purity 99.999% does electrode, thus system
Become photovoltaic cell device.
A preparation method for flexible overlapping solar cell, comprises the steps:
Step 201, use receive lime glass as substrate:
By 3cm*3cm receive lime glass in cleaning agent repeatedly cleaning after, more respectively through isopropyl alcohol, acetone and chloroformic solution soak and ultrasonic cleaning, finally dried for standby in IR bake;
Step 202, spatter dorsum electrode layer (2):
Select the one in molybdenum, nickel, aluminium, gold, silver, copper, titanium, use direct current sputtering, target purity is 99.99%, and power is 0.6kw, and operating pressure is 1.0Pa; Sputter two-layer, wherein ground floor thickness is 100nm, and second layer thickness is 400nm;
Step 203, evaporation Copper Indium Gallium Selenide active layer (3):
Use three-step approach to prepare CIGS thin-film, to be specially in vacuum chamber by 300 DEG C of-1200 DEG C of high temperature evaporations, to make Copper Indium Gallium Selenide composition, on substrate, chemical reaction occur, generate copper-indium-gallium-selenium compound; First, vacuum chamber vacuum 5 × 10
-4pa, vacuum evaporation indium gallium selenium film preformed layer, temperature is respectively indium 900 DEG C, gallium 1000 DEG C, 300 DEG C, selenium; Thickness range is 300-800nm; And then evaporation Copper Indium Gallium Selenide material, temperature is respectively copper 1200 DEG C, indium 900 DEG C, gallium 1000 DEG C, 300 DEG C, selenium; Thickness is about 2 μm; At substrate all remains on 450 DEG C;
Step 204, use plated film mode plated film CdS resilient coating (4):
Ammonium Acetate, ammoniacal liquor, thiocarbamide volume ratio are that 2:3:1 is configured to 500ml solution, bath temperature 70 DEG C, are soaked by polyimide film and react 30min in the solution; Obtained CdS film thickness is about 50nm;
Step 205, sputtering Window layer Window layer (5)
Radio frequency magnetron sputtering method sputtering i-ZnO thickness is used to be 50nm, operating pressure 0.6Pa, power 0.8kw; Use DC magnetron sputtering method sputtering ZnO:Al, operating pressure 0.8Pa, power 1.0kw, ZnO:Al thickness is about 350nm;
Step 206, the mode of evaporation and spin coating is used to prepare intermediate layer (6);
Be that the P type LiF of 1.0nm is deposited on (5) in Window layer by thickness; Specifically preparing environment is: local vacuum degree is 5 × 10
-4pa, stop when using film thickness monitor to observe 1.0nm, evaporation time is 30min;
LiF has prepared rear use spin-coating method and has prepared PEDOT; Spin coating rotating speed 4000r/min, operating time 15s, the LiF thickness obtained is about 100nm;
Step 207, utilize magnetron sputtering method manufacture electron transfer layer (7);
The mode of magnetron sputtering is utilized to prepare TiO2 film; Be specially and use purity to be the TiO of 99.99%
2target, the vacuum of operational environment is 5 × 10
-4pa, operating pressure 0.5Pa, sputtering power 0.5kw, sputtering time 2h, gained TiO
2film thickness is 100nm;
Step 208, one-step method prepare perovskite absorbed layer (8); Detailed process is:
CH
3nH
3the preparation of I: get respectively 30mL mass percent be 57% HI solution and 30mL mass percent be the methylamine solution of 40%, mixedly in three mouthfuls of round-bottomed flasks being incorporated in stirring reaction in ice-water bath; After 5h, reaction products therefrom is placed in 100mL single port flask, steamed at 50 DEG C of condition backspins by Rotary Evaporators, products therefrom cleans three times by ether; Make product recrystallization with the mixed solvent of methyl alcohol and ether subsequently, generate a kind of white crystal, finally dry in vacuum drying chamber;
The PbI of quality such as to get respectively
2with CH
3nH
3i is dissolved in the precursor solution that 1.5mM/mL prepared by a certain amount of DMF solvent; Get the precursor solution of 200 μ L, the spin coating rotating speed arranging sol evenning machine is 5000r/15s spin-coating film, and 90min process of finally annealing at 120 DEG C obtains perovskite absorbed layer (8);
Step 209, spin-coating method prepare hole transmission layer (9);
200 μ LSpiro-OMETAD solution are dropped on perovskite absorbed layer film, spin coating rotating speed 4000r/min is set, time 30s, 150 annealing in process 1h; Gained Spiro-OMETAD film thickness is 100nm;
Step 210, utilize striped-shaped mask plate, the Au of vacuum evaporation 100nm purity 99.999% does electrode, thus makes photovoltaic cell device.
The advantage that the present invention has and good effect are:
This flexible overlapping solar cell adopts Copper Indium Gallium Selenide/perovskite as light absorbing zone, can improve the absorption to light to greatest extent, improves battery efficiency; In addition, use flexible substrate can realize roll-to-roll technique, make production in enormous quantities become possibility, improve prospect in commercial applications; Finally, using the mode of vacuum evaporation to prepare CIGS thin film can improve film morphology, improves battery efficiency.
Accompanying drawing illustrates:
Fig. 1 is the layer structure figure of the flexible overlapping solar cell of the preferred embodiment of the present invention.
Wherein: 1, transparent substrate; 2, dorsum electrode layer; 3, Copper Indium Gallium Selenide active layer; 4, CdS resilient coating; 5, Window layer; 6, intermediate layer; 7, electron transfer layer; 8, perovskite absorbed layer; 9, hole transmission layer; 10, electrode.
Embodiment
For summary of the invention of the present invention, Characteristic can be understood further, hereby exemplify following examples, and coordinate accompanying drawing to be described in detail as follows:
Refer to Fig. 1, a kind of flexible overlapping solar cell, comprise transparent substrate 1, dorsum electrode layer 2, Copper Indium Gallium Selenide active layer 3, CdS resilient coating 4, Window layer 5, intermediate layer 6, electron transfer layer 7, perovskite absorbed layer 8, hole transmission layer 9, electrode 10 totally ten Rotating fields from bottom to top successively, wherein:
Transparent substrate 1, described transparent substrate 1 is with receiving the polyimide film of lime glass or flexible substrate; Wherein the thickness range of polyimide film is 25 μm ~ 100 μm; Receive lime glass thickness at 1 ~ 4mm;
Be dorsum electrode layer 2 at described transparent substrate 1 upper surface, the thickness range of described dorsum electrode layer 2 is 100nm ~ 1000nm;
Be Copper Indium Gallium Selenide active layer 3 at the upper surface of described dorsum electrode layer 2, the thickness range of described Copper Indium Gallium Selenide active layer 3 is 1 μm ~ 3 μm;
Be CdS resilient coating 4 at the upper surface of described Copper Indium Gallium Selenide active layer 3, the thickness range of described CdS resilient coating 4 is 30nm ~ 100nm;
Be Window layer 5 at the upper surface of described CdS resilient coating 4, the thickness range of described Window layer 5 is 100nm ~ 500nm;
Be intermediate layer 6 at the upper surface of described Window layer 5, when described intermediate layer 6 is N-shaped LiF, CsCO
3, C
6h
5during a kind of in COOLi, ZnO, the thickness range in intermediate layer 6 is 10nm ~ 120nm; When described intermediate layer 6 is a kind of in p-type molybdenum oxide, MEH-PPV, PEDOT, the thickness range in intermediate layer 6 is 30nm ~ 150nm;
Be electron transfer layer 7 at the upper surface in described intermediate layer 6, described electron transfer layer 7 is TiO2, ZnO, Al
2o
3, SiO
2in one, the thickness range of described electron transfer layer 7 is 50nm ~ 300nm;
Be perovskite absorbed layer 8 at the upper surface of described electron transfer layer 7, the thickness range of described perovskite absorbed layer 8 is 100nm ~ 1000nm;
Be hole transmission layer 9 at the upper surface of described perovskite absorbed layer 8, the thickness range of described hole transmission layer 9 is 100nm ~ 1000nm;
Be electrode 10 at the upper surface of described hole transmission layer 9.
A kind of preparation method of flexible overlapping solar cell comprises two embodiments below:
Embodiment 1.
(1) clean PI film surface:
Use plasma backwash etching machine, operating pressure 0.3Pa, sputtering power 0.2kw, carry out etched clean by Ar to PI film.Cut out after having cleaned to 3cm*3cm size.
(2) back electrode is sputtered:
We select Mo herein.Use direct current sputtering, target purity 99.99%, power 0.6kw, operating pressure 1.0Pa; Sputter two-layer Mo electrode, wherein ground floor thickness 100nm, second layer thickness 400nm.
(3) evaporation CIGS thin-film
We use traditional three-step approach to prepare CIGS thin-film.By high temperature evaporation in vacuum chamber, make Copper Indium Gallium Selenide composition, on substrate, chemical reaction occur, generate copper-indium-gallium-selenium compound.First, the local vacuum 5.0e-4Pa of vacuum chamber, vacuum evaporation indium gallium selenium film preformed layer, temperature is respectively 900 DEG C, 1000 DEG C, 300 DEG C.Thickness is about 500nm.And then evaporation Copper Indium Gallium Selenide material, temperature is respectively 1200 DEG C, 900 DEG C, 1000 DEG C, 300 DEG C.Thickness is about 2 μm.In all evaporate process, at substrate all remains on 450 DEG C.
(4) plated film mode plated film CdS is used
Ammonium Acetate, ammoniacal liquor, thiocarbamide ratio are that 2:3:1 (volume ratio) is configured to 500ml solution, bath temperature 70 DEG C, are soaked by PI film and react 30min in the solution.Obtained film thickness is about 50nm.
(5) Window layer is sputtered
Radio frequency magnetron sputtering method sputtering i-ZnO thickness is used to be 50nm, operating pressure 0.6Pa, power 0.8kw; Use DC magnetron sputtering method sputtering ZnO:Al, operating pressure 0.8Pa, power 1.0kw, thickness 350nm.
(6) intermediate layer uses the mode of evaporation/spin coating to prepare.
Thick for 1.0nm P type LiF is deposited in Window layer.Local vacuum 5*e-4Pa, stop when using film thickness monitor to observe 1.0nm, evaporation time is about 30min.
LiF has prepared rear use spin-coating method and has prepared PEDOT.Spin coating rotating speed 4000r/min, time 15s, thickness is about 100nm.
(7) electron transfer layer TiO
2
The mode of magnetron sputtering is utilized to prepare TiO
2film.Purity is used to be the TiO of 99.99%
2target, base vacuum 5*e-4Pa, operating pressure 0.5Pa, sputtering power 0.5kw, sputtering time 2h, gained film thickness is about 100nm.
(8) one-step method prepares perovskite thin film.
CH
3nH
3the preparation of I: get the methylamine solution (being dissolved in methyl alcohol) that HI solution that 30mL mass fraction is 57% (2.27mmol) and 30mL mass fraction are 40% (2.73mmol) respectively, fully mixedly in three mouthfuls of round-bottomed flasks is incorporated in stirring reaction in ice-water bath.After 5h, reaction products therefrom is placed in 100mL single port flask, steamed at 50 DEG C of condition backspins by Rotary Evaporators, products therefrom cleans three times by ether.Make product recrystallization with the mixed solvent of methyl alcohol and ether subsequently, generate a kind of white crystal, finally dry in vacuum drying chamber.
The PbI of quality such as to get respectively
2with CH
3nH
3i is dissolved in the precursor solution that 1.5mM/mL prepared by a certain amount of DMF solvent.Get the precursor solution of 200 μ L, the spin coating rotating speed arranging sol evenning machine is 5000r/15s spin-coating film, and 90min process of finally annealing at 120 DEG C obtains perovskite thin film.
(9) spin-coating method prepares hole transmission layer.
200 μ LSpiro-OMETAD solution are dropped on film, spin coating rotating speed 4000r/min is set, time 30s, 150 annealing in process 1h.Gained film thickness is about 100nm.
(10) by striped-shaped mask plate, the Au of vacuum evaporation 100nm purity 99.999% does electrode, thus makes photovoltaic cell device.Comparative device is prepared by similar way.
Embodiment 2.
(1) use receives lime glass as substrate:
By 3cm*3cm receive lime glass in cleaning agent repeatedly cleaning after, more respectively through isopropyl alcohol, acetone and chloroformic solution soak and ultrasonic cleaning, finally dried for standby in IR bake;
(2) back electrode is sputtered:
We select Mo herein.Use direct current sputtering, target purity 99.99%, power 0.6kw, operating pressure 1.0Pa; Sputter two-layer Mo electrode, wherein ground floor thickness 100nm, second layer thickness 400nm.
(3) evaporation CIGS thin-film
We use traditional three-step approach to prepare CIGS thin-film.By high temperature evaporation in vacuum chamber, make Copper Indium Gallium Selenide composition, on substrate, chemical reaction occur, generate copper-indium-gallium-selenium compound.First, the local vacuum 5.0e-4Pa of vacuum chamber, vacuum evaporation indium gallium selenium film preformed layer, temperature is respectively 900 DEG C, 1000 DEG C, 300 DEG C.Thickness is about 500nm.And then evaporation Copper Indium Gallium Selenide material, temperature is respectively 1200 DEG C, 900 DEG C, 1000 DEG C, 300 DEG C.Thickness is about 2 μm.In all evaporate process, at substrate all remains on 450 DEG C.
(4) plated film mode plated film CdS is used
Ammonium Acetate, ammoniacal liquor, thiocarbamide ratio are that 2:3:1 (volume ratio) is configured to 500ml solution, bath temperature 70 DEG C, are soaked by PI film and react 30min in the solution.Obtained film thickness is about 50nm.
(5) Window layer is sputtered
Radio frequency magnetron sputtering method sputtering i-ZnO thickness is used to be 50nm, operating pressure 0.6Pa, power 0.8kw; Use DC magnetron sputtering method sputtering ZnO:Al, operating pressure 0.8Pa, power 1.0kw, thickness 350nm.
(6) intermediate layer uses the mode of evaporation/spin coating to prepare.
Thick for 1.0nm P type LiF is deposited in Window layer.Local vacuum 5*e-4Pa, stop when using film thickness monitor to observe 1.0nm, evaporation time is about 30min.
LiF has prepared rear use spin-coating method and has prepared PEDOT.Spin coating rotating speed 4000r/min, time 15s, thickness is about 100nm.
(7) electron transfer layer TiO
2
The mode of magnetron sputtering is utilized to prepare TiO
2film.Purity is used to be the TiO of 99.99%
2target, base vacuum 5*e-4Pa, operating pressure 0.5Pa, sputtering power 0.5kw, sputtering time 2h, gained film thickness is about 100nm.
(8) one-step method prepares perovskite thin film.
CH
3nH
3the preparation of I: get the methylamine solution (being dissolved in methyl alcohol) that HI solution that 30mL mass fraction is 57% (2.27mmol) and 30mL mass fraction are 40% (2.73mmol) respectively, fully mixedly in three mouthfuls of round-bottomed flasks is incorporated in stirring reaction in ice-water bath.After 5h, reaction products therefrom is placed in 100mL single port flask, steamed at 50 DEG C of condition backspins by Rotary Evaporators, products therefrom cleans three times by ether.Make product recrystallization with the mixed solvent of methyl alcohol and ether subsequently, generate a kind of white crystal, finally dry in vacuum drying chamber.
The PbI of quality such as to get respectively
2with CH
3nH
3i is dissolved in the precursor solution that 1.5mM/mL prepared by a certain amount of DMF solvent.Get the precursor solution of 200 μ L, the spin coating rotating speed arranging sol evenning machine is 5000r/15s spin-coating film, and 90min process of finally annealing at 120 DEG C obtains perovskite thin film.
(9) spin-coating method prepares hole transmission layer.
200 μ LSpiro-OMETAD solution are dropped on film, spin coating rotating speed 4000r/min is set, time 30s, 150 annealing in process 1h.Gained film thickness is about 100nm.
(10) by striped-shaped mask plate, the Au of vacuum evaporation 100nm purity 99.999% does electrode, thus makes photovoltaic cell device.
Technique scheme advantage is: this builds up solar cell and adopts Copper Indium Gallium Selenide/perovskite as light absorbing zone, can improve the absorption to light to greatest extent, improve battery efficiency; In addition, use flexible substrate can realize roll-to-roll technique, make production in enormous quantities become possibility, improve prospect in commercial applications; Finally, using the mode of vacuum evaporation to prepare CIGS thin film can improve film morphology, improves battery efficiency.
Above embodiments of the invention have been described in detail, but described content being only preferred embodiment of the present invention, can not being considered to for limiting practical range of the present invention.All equalizations done according to the present patent application scope change and improve, and all should still belong within patent covering scope of the present invention.
Claims (5)
1. a flexible overlapping solar cell, is characterized in that: at least comprise:
Transparent substrate (1), described transparent substrate (1) is with receiving the polyimide film of lime glass or flexible substrate; Wherein the thickness range of polyimide film is 25 μm ~ 100 μm;
Be dorsum electrode layer (2) at described transparent substrate (1) upper surface, the thickness range of described dorsum electrode layer (2) is 100nm ~ 1000nm;
Be Copper Indium Gallium Selenide active layer (3) at the upper surface of described dorsum electrode layer (2), the thickness range of described Copper Indium Gallium Selenide active layer (3) is 1 μm ~ 3 μm;
Be CdS resilient coating (4) at the upper surface of described Copper Indium Gallium Selenide active layer (3), the thickness range of described CdS resilient coating (4) is 30nm ~ 100nm;
Be Window layer (5) at the upper surface of described CdS resilient coating (4), the thickness range of described Window layer (5) is 100nm ~ 500nm;
Be intermediate layer (6) at the upper surface of described Window layer (5), when described intermediate layer (6) are N-shaped LiF, CsCO
3, C
6h
5during a kind of in COOLi, ZnO, the thickness range of intermediate layer (6) is 10nm ~ 120nm; When described intermediate layer (6) are for a kind of in p-type molybdenum oxide, MEH-PPV, PEDOT, the thickness range of intermediate layer (6) is 30nm ~ 150nm;
Be electron transfer layer (7) at the upper surface of described intermediate layer (6), described electron transfer layer (7) is TiO2, ZnO, Al
2o
3, SiO
2in one, the thickness range of described electron transfer layer (7) is 50nm ~ 300nm;
Be perovskite absorbed layer (8) at the upper surface of described electron transfer layer (7), the thickness range of described perovskite absorbed layer (8) is 100nm ~ 1000nm;
Be hole transmission layer (9) at the upper surface of described perovskite absorbed layer (8), the thickness range of described hole transmission layer (9) is 100nm ~ 1000nm;
Be electrode (10) at the upper surface of described hole transmission layer (9).
2. flexible overlapping solar cell according to claim 1, is characterized in that: the material of described dorsum electrode layer (2) is the one in molybdenum, nickel, aluminium, gold, silver, copper, titanium.
3. flexible overlapping solar cell according to claim 2, is characterized in that: the material of described Window layer (5) is the one in i-ZnO, ZnO-Al, ITO.
4. a preparation method for flexible overlapping solar cell as claimed in claim 3, is characterized in that: comprise the steps:
Step 101, clean polyimide film surface:
Use plasma backwash etching machine, operating pressure is 0.3Pa, and sputtering power is 0.2kw, carries out etched clean by Ar to polyimide film; The square to 3cm*3cm is cut out after having cleaned;
Step 102, spatter dorsum electrode layer (2):
Select the one in molybdenum, nickel, aluminium, gold, silver, copper, titanium, use direct current sputtering, target purity is 99.99%, and power is 0.6kw, and operating pressure is 1.0Pa; Sputter two-layer, wherein ground floor thickness is 100nm, and second layer thickness is 400nm;
Step 103, evaporation Copper Indium Gallium Selenide active layer (3):
Use three-step approach to prepare CIGS thin-film, to be specially in vacuum chamber by 300 DEG C of-1200 DEG C of high temperature evaporations, to make Copper Indium Gallium Selenide composition, on substrate, chemical reaction occur, generate copper-indium-gallium-selenium compound; First, vacuum chamber vacuum 5 × 10
-4pa, vacuum evaporation indium gallium selenium film preformed layer, temperature is respectively indium 900 DEG C, gallium 1000 DEG C, 300 DEG C, selenium; Thickness range is 300-800nm; And then evaporation Copper Indium Gallium Selenide material, temperature is respectively copper 1200 DEG C, indium 900 DEG C, gallium 1000 DEG C, 300 DEG C, selenium; Thickness is about 2 μm; At substrate all remains on 450 DEG C;
Step 104, use plated film mode plated film CdS resilient coating (4):
Ammonium Acetate, ammoniacal liquor, thiocarbamide volume ratio are that 2:3:1 is configured to 500ml solution, bath temperature 70 DEG C, are soaked by polyimide film and react 30min in the solution; Obtained CdS film thickness is about 50nm;
Step 105, sputtering Window layer Window layer (5)
Radio frequency magnetron sputtering method sputtering i-ZnO thickness is used to be 50nm, operating pressure 0.6Pa, power 0.8kw; Use DC magnetron sputtering method sputtering ZnO:Al, operating pressure 0.8Pa, power 1.0kw, ZnO:Al thickness is about 350nm;
Step 106, the mode of evaporation and spin coating is used to prepare intermediate layer (6);
Be that the P type LiF of 1.0nm is deposited on (5) in Window layer by thickness; Specifically preparing environment is: local vacuum degree is 5 × 10
-4pa, stop when using film thickness monitor to observe 1.0nm, evaporation time is 30min;
LiF has prepared rear use spin-coating method and has prepared PEDOT; Spin coating rotating speed 4000r/min, operating time 15s, the LiF thickness obtained is about 100nm;
Step 107, utilize magnetron sputtering method manufacture electron transfer layer (7);
The mode of magnetron sputtering is utilized to prepare TiO2 film; Be specially and use purity to be the TiO of 99.99%
2target, the vacuum of operational environment is 5 × 10
-4pa, operating pressure 0.5Pa, sputtering power 0.5kw, sputtering time 2h, gained TiO
2film thickness is 100nm;
Step 108, one-step method prepare perovskite absorbed layer (8); Detailed process is:
CH
3nH
3the preparation of I: get respectively 30mL mass percent be 57% HI solution and 30mL mass percent be the methylamine solution of 40%, mixedly in three mouthfuls of round-bottomed flasks being incorporated in stirring reaction in ice-water bath; After 5h, reaction products therefrom is placed in 100mL single port flask, steamed at 50 DEG C of condition backspins by Rotary Evaporators, products therefrom cleans three times by ether; Make product recrystallization with the mixed solvent of methyl alcohol and ether subsequently, generate a kind of white crystal, finally dry in vacuum drying chamber;
The PbI of quality such as to get respectively
2with CH
3nH
3i is dissolved in the precursor solution that 1.5mM/mL prepared by a certain amount of DMF solvent; Get the precursor solution of 200 μ L, the spin coating rotating speed arranging sol evenning machine is 5000r/15s spin-coating film, and 90min process of finally annealing at 120 DEG C obtains perovskite absorbed layer (8);
Step 109, spin-coating method prepare hole transmission layer (9);
200 μ LSpiro-OMETAD solution are dropped on perovskite absorbed layer film, spin coating rotating speed 4000r/min is set, time 30s, 150 annealing in process 1h; Gained Spiro-OMETAD film thickness is 100nm;
Step 110, utilize striped-shaped mask plate, the Au of vacuum evaporation 100nm purity 99.999% does electrode, thus makes photovoltaic cell device.
5. a preparation method for flexible overlapping solar cell as claimed in claim 3, is characterized in that: comprise the steps:
Step 201, use receive lime glass as substrate:
By 3cm*3cm receive lime glass in cleaning agent repeatedly cleaning after, more respectively through isopropyl alcohol, acetone and chloroformic solution soak and ultrasonic cleaning, finally dried for standby in IR bake;
Step 202, spatter dorsum electrode layer (2):
Select the one in molybdenum, nickel, aluminium, gold, silver, copper, titanium, use direct current sputtering, target purity is 99.99%, and power is 0.6kw, and operating pressure is 1.0Pa; Sputter two-layer, wherein ground floor thickness is 100nm, and second layer thickness is 400nm;
Step 203, evaporation Copper Indium Gallium Selenide active layer (3):
Use three-step approach to prepare CIGS thin-film, to be specially in vacuum chamber by 300 DEG C of-1200 DEG C of high temperature evaporations, to make Copper Indium Gallium Selenide composition, on substrate, chemical reaction occur, generate copper-indium-gallium-selenium compound; First, vacuum chamber vacuum 5 × 10
-4pa, vacuum evaporation indium gallium selenium film preformed layer, temperature is respectively indium 900 DEG C, gallium 1000 DEG C, 300 DEG C, selenium; Thickness range is 300-800nm; And then evaporation Copper Indium Gallium Selenide material, temperature is respectively copper 1200 DEG C, indium 900 DEG C, gallium 1000 DEG C, 300 DEG C, selenium; Thickness is about 2 μm; At substrate all remains on 450 DEG C;
Step 204, use plated film mode plated film CdS resilient coating (4):
Ammonium Acetate, ammoniacal liquor, thiocarbamide volume ratio are that 2:3:1 is configured to 500ml solution, bath temperature 70 DEG C, are soaked by polyimide film and react 30min in the solution; Obtained CdS film thickness is about 50nm;
Step 205, sputtering Window layer Window layer (5)
Radio frequency magnetron sputtering method sputtering i-ZnO thickness is used to be 50nm, operating pressure 0.6Pa, power 0.8kw; Use DC magnetron sputtering method sputtering ZnO:Al, operating pressure 0.8Pa, power 1.0kw, ZnO:Al thickness is about 350nm;
Step 206, the mode of evaporation and spin coating is used to prepare intermediate layer (6);
Be that the P type LiF of 1.0nm is deposited on (5) in Window layer by thickness; Specifically preparing environment is: local vacuum degree is 5 × 10
-4pa, stop when using film thickness monitor to observe 1.0nm, evaporation time is 30min;
LiF has prepared rear use spin-coating method and has prepared PEDOT; Spin coating rotating speed 4000r/min, operating time 15s, the LiF thickness obtained is about 100nm;
Step 207, utilize magnetron sputtering method manufacture electron transfer layer (7);
The mode of magnetron sputtering is utilized to prepare TiO2 film; Be specially and use purity to be the TiO of 99.99%
2target, the vacuum of operational environment is 5 × 10
-4pa, operating pressure 0.5Pa, sputtering power 0.5kw, sputtering time 2h, gained TiO
2film thickness is 100nm;
Step 208, one-step method prepare perovskite absorbed layer (8); Detailed process is:
CH
3nH
3the preparation of I: get respectively 30mL mass percent be 57% HI solution and 30mL mass percent be the methylamine solution of 40%, mixedly in three mouthfuls of round-bottomed flasks being incorporated in stirring reaction in ice-water bath; After 5h, reaction products therefrom is placed in 100mL single port flask, steamed at 50 DEG C of condition backspins by Rotary Evaporators, products therefrom cleans three times by ether; Make product recrystallization with the mixed solvent of methyl alcohol and ether subsequently, generate a kind of white crystal, finally dry in vacuum drying chamber;
The PbI of quality such as to get respectively
2with CH
3nH
3i is dissolved in the precursor solution that 1.5mM/mL prepared by a certain amount of DMF solvent; Get the precursor solution of 200 μ L, the spin coating rotating speed arranging sol evenning machine is 5000r/15s spin-coating film, and 90min process of finally annealing at 120 DEG C obtains perovskite absorbed layer (8);
Step 209, spin-coating method prepare hole transmission layer (9);
200 μ LSpiro-OMETAD solution are dropped on perovskite absorbed layer film, spin coating rotating speed 4000r/min is set, time 30s, 150 annealing in process 1h; Gained Spiro-OMETAD film thickness is 100nm;
Step 210, utilize striped-shaped mask plate, the Au of vacuum evaporation 100nm purity 99.999% does electrode, thus makes photovoltaic cell device.
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