CN105470338B - A kind of flexible overlapping solar cell and preparation method - Google Patents
A kind of flexible overlapping solar cell and preparation method Download PDFInfo
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- 239000010408 film Substances 0.000 claims description 57
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- 239000010409 thin film Substances 0.000 claims description 32
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000001704 evaporation Methods 0.000 claims description 22
- 230000008020 evaporation Effects 0.000 claims description 22
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 20
- 229910052738 indium Inorganic materials 0.000 claims description 16
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000007738 vacuum evaporation Methods 0.000 claims description 14
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- 239000010931 gold Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 10
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 9
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 9
- 239000004571 lime Substances 0.000 claims description 9
- 229920001721 polyimide Polymers 0.000 claims description 9
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 8
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 8
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 8
- 229910052733 gallium Inorganic materials 0.000 claims description 8
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 claims description 8
- 239000002243 precursor Substances 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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 229940043376 ammonium acetate Drugs 0.000 claims description 6
- 235000019257 ammonium acetate Nutrition 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
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- 239000000203 mixture Substances 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- 229940065287 selenium compound Drugs 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000003756 stirring Methods 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
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 238000005530 etching Methods 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000012459 cleaning agent Substances 0.000 claims description 3
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- 239000007864 aqueous solution Substances 0.000 claims 2
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- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 31
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229920000109 alkoxy-substituted poly(p-phenylene vinylene) Polymers 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
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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
- H01L31/04—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
- Y02E10/50—Photovoltaic [PV] energy
- 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 kind of flexible overlapping solar cell and preparation method, it is related to technical field of solar cells, flexible overlapping solar cell includes successively：Transparent substrates；Dorsum electrode layer in above-mentioned transparent conductive substrate；CIGS active layer on above-mentioned dorsum electrode layer；CdS cushion on above-mentioned CIGS active layer；Window layer on above-mentioned CdS cushion；Intermediate layer in above-mentioned Window layer；Electron transfer layer on above-mentioned intermediate layer；Perovskite absorbed layer on above-mentioned electron transfer layer；Hole transmission layer on above-mentioned perovskite absorbed layer；Electrode on above-mentioned hole transmission layer.This builds up solar cell and adopts CIGS/perovskite as light absorbing zone, can improve the absorption to light to greatest extent, improve battery efficiency；In addition, roll to roll technique can be realized using flexible substrate being possibly realized so that producing in enormous quantities, improve prospect in commercial applications.
Description
Technical field
The present invention relates to technical field of solar cells, more particularly to a kind of flexible overlapping solar cell and preparation method.
Background technology
In recent years, due to the exhaustion increasingly of Fossil fuel, cause Energy situation growing tension.In addition the fossil growing with each passing day
Environmental pollution caused by fuel combustion, the existence to earth ecological balance and the mankind brings serious harm.Exploitation is renewable
New forms of energy have become as a global problem.Photovoltaic generation is a kind of clean energy resource of zero-emission, is also that one kind can be big
The real energy of sizable application, can carry out Independent Power Generation and generate electricity by way of merging two or more grid systems, be the first-selection in various regenerative resources.
The development of solar battery technology can generally be divided into three generations in general：The first generation is the list with monocrystal silicon as representative
Crystal formation photovoltaic cell；The second filial generation is then the inorganic thin film sun with cadmium telluride (CdTe) and Copper indium gallium selenide (CIGS) as representative
Battery；The third generation is that the new solar cell based on nanotechnology and new material (includes organic thin film solar cell (OPV), dye
Material sensitization solar cell (DSSC), perovskite solar cell (PSC) etc.).The technique of first, second generation solar cell has compared
Maturation, its battery efficiency is all more than 15%, and achieves and commercially produce.The third generation solar cell technology have less energy consumption,
Raw material is extensive, environmental friendliness, low cost and other advantages show the application being rich in potentiality and development prospect.
At present, broken through by the Laboratory efficiencies of the perovskite solar cell of Perovskite Phase organic metal halogenide preparation
20%, there is very high industrialization prospect.Meanwhile, the existing commercialization of the CIGS solar cell in the third generation solar cell fortune
Battalion, its Laboratory efficiencies also alreadys exceed 20%.CIGS and perovskite material are made by solar cell by stack technology
Spectral absorption scope can be improved, significantly improve the conversion efficiency of solar cell.Prepare CIGS thin-film in liquid phase method to compare,
Prepare thin film using vacuum vapour deposition and can effectively optimize film morphology, improve cell conversion efficiency；With use glass as lining
The solar cell at bottom is compared, and flexible solar cell can reduce production cost using roll-to-roll technique large-scale production,
It is beneficial to commercialized running.
Content of the invention
The technical problem to be solved in the present invention is：The flexible overlapping sun that provide a kind of efficient and light weight, can be mass-produced
Battery and preparation method.
The present invention is adopted the technical scheme that by solving technical problem present in known technology：
A kind of flexible overlapping solar cell, at least includes：
Transparent substrate (1), described transparent substrate (1) is with receiving the polyimides of lime glass or flexible substrate
Film；The thickness range of wherein polyimide film is 25 μm～100 μm；
It is dorsum electrode layer (2) in described transparent substrate (1) upper surface, the thickness range of described dorsum electrode layer (2) is
100nm～1000nm；
It is CIGS active layer (3) in the upper surface of described dorsum electrode layer (2), described CIGS active layer (3)
Thickness range is 1 μm～3 μm；
It is CdS cushion (4) in the upper surface of described CIGS active layer (3), the thickness of described CdS cushion (4)
Scope is 30nm～100nm；
It is Window layer (5) in the upper surface of described CdS cushion (4), the thickness range of described Window layer (5) is 100nm
～500nm；
It is intermediate layer (6) in the upper surface of described Window layer (5), when described intermediate layer (6) are N-shaped LiF, CsCO3,
C6H5When one of COOLi, ZnO, the thickness range of intermediate layer (6) is 10nm～120nm；When described intermediate layer (6) are p-type
When molybdenum oxide, one of MEH-PPV, PEDOT, the thickness range of intermediate layer (6) is 30nm～150nm；
Upper surface in described intermediate layer (6) is electron transfer layer (7), and described electron transfer layer (7) is TiO2, ZnO,
Al2O3、SiO2One of, the thickness range of described electron transfer layer (7) is 50nm～300nm；
It is perovskite absorbed layer (8) in the upper surface of described electron transfer layer (7), the thickness of described perovskite absorbed layer (8)
Degree scope is 100nm～1000nm；
It is hole transmission layer (9) in the upper surface of described perovskite absorbed layer (8), the thickness of described hole transmission layer (9)
Scope is 100nm～1000nm；
It is electrode (10) in the upper surface of described hole transmission layer (9).
Further：The material of described dorsum electrode layer (2) is one of molybdenum, nickel, aluminum, gold, silver, copper, titanium.
Further：The material of described Window layer (5) is one of i-ZnO, ZnO-Al, ITO.
A kind of preparation method of flexible overlapping solar cell, comprises the steps：
Step 101, cleaning polyimide film surface：
Using plasma backwash etching machine, operating pressure is 0.3Pa, and sputtering power is 0.2kw, sub- to polyamides by Ar
Amine film performs etching cleaning；Cut out after the completion of cleaning to the square of 3cm*3cm；
Step 102, splash dorsum electrode layer (2)：
Select one of molybdenum, nickel, aluminum, gold, silver, copper, titanium, using d.c. sputtering, target purity is 99.99%, power
For 0.6kw, operating pressure is 1.0Pa；Sputtering two-layer, wherein ground floor thickness are 100nm, and second layer thickness is 400nm；
Step 103, evaporation CIGS active layer (3)：
Prepare CIGS thin-film using three-step approach, pass through 300 DEG C of -1200 DEG C of high temperature specially in vacuum chamber and steam
Send out, make CIGS composition that chemical reaction to be occurred on substrate, generate copper-indium-gallium-selenium compound；First, vacuum chamber vacuum 5 ×
10-4Pa, vacuum evaporation indium gallium selenium thin film preformed layer, temperature is respectively 900 DEG C of indium, 1000 DEG C of gallium, 300 DEG C of selenium；Thickness range is
300-800nm；Then it is deposited with CIGS material again, temperature is respectively 1200 DEG C of copper, 900 DEG C of indium, 1000 DEG C of gallium, 300 DEG C of selenium；
Thickness is about 2 μm；Substrate is held at 450 DEG C；
Step 104, use plated film mode plated film CdS cushion (4)：
Ammonium Acetate, ammonia, thiourea volume ratio are 2:3:1 is configured to 500ml solution, and 70 DEG C of bath temperature, by polyamides Asia
Amine film soaks and reacts 30min in the solution；Prepared CdS film thickness is about 50nm；
Step 105, sputtering Window layer Window layer (5)
The use of radio frequency magnetron sputtering method sputtering i-ZnO thickness is 50nm, operating pressure 0.6Pa, power 0.8kw；Use
DC magnetron sputtering method sputters ZnO:Al, operating pressure 0.8Pa, power 1.0kw, ZnO:Al thickness is about 350nm；
Step 106, prepare intermediate layer (6) using evaporation and the mode of spin coating；
P-type LiF for 1.0nm for the thickness is deposited in Window layer (5)；Specifically preparing environment is：Local vacuum is 5 ×
10-4Pa, is observed using film thickness monitor and stops during 1.0nm, evaporation time is 30min；
PEDOT is prepared using spin-coating method after the completion of LiF preparation；Spin coating rotating speed 4000r/min, working time 15s, obtain
LiF thickness is about 100nm；
Step 107, using magnetron sputtering method manufacture electron transfer layer (7)；
Prepare TiO2 thin film using the mode of magnetron sputtering；It is specially the TiO the use of purity being 99.99%2Target, work
The vacuum of environment is 5 × 10-4Pa, operating pressure 0.5Pa, sputtering power 0.5kw, sputtering time 2h, gained TiO2Film thickness
For 100nm；
Step 108, one-step method prepare perovskite absorbed layer (8)；Detailed process is：
CH3NH3The preparation of I：The HI solution that 30mL mass percent is 57% and 30mL mass percent is taken to be 40% respectively
Methylamine solution, mixed in three neck round bottom flask be incorporated in stirring reaction in ice-water bath；After 5h, reaction products therefrom is placed in
In 100mL single-necked flask, by Rotary Evaporators under the conditions of 50 DEG C revolving, products therefrom by ether clean three times；Subsequently
Make product recrystallization with the mixed solvent of methanol and ether, generate a kind of white crystal, be finally dried in vacuum drying oven；
The PbI of quality such as take respectively2With CH3NH3I be dissolved in a certain amount of DMF solvent prepare 1.5mM/mL presoma molten
Liquid；Take the precursor solution of 200 μ L, the spin coating rotating speed of setting sol evenning machine is 5000r/15s spin-coating film, finally at 120 DEG C
Annealing 90min process obtains perovskite absorbed layer (8)；
Step 109, spin-coating method prepare hole transmission layer (9)；
200 μ L Spiro-OMETAD solution are dropped in perovskite absorb on layer film, spin coating rotating speed 4000r/min are set,
Time 30s, 150 annealing 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 making
Become photovoltaic cell device.
A kind of preparation method of flexible overlapping solar cell, comprises the steps：
Step 201, it is used and receives lime glass as substrate：
3cm*3cm received after lime glass cleans in cleaning agent repeatedly, more respectively through isopropanol, acetone and chloroformic solution
Soak and be cleaned by ultrasonic, finally dried for standby in infrared baking oven；
Step 202, splash dorsum electrode layer (2)：
Select one of molybdenum, nickel, aluminum, gold, silver, copper, titanium, using d.c. sputtering, target purity is 99.99%, power
For 0.6kw, operating pressure is 1.0Pa；Sputtering two-layer, wherein ground floor thickness are 100nm, and second layer thickness is 400nm；
Step 203, evaporation CIGS active layer (3)：
Prepare CIGS thin-film using three-step approach, pass through 300 DEG C of -1200 DEG C of high temperature specially in vacuum chamber and steam
Send out, make CIGS composition that chemical reaction to be occurred on substrate, generate copper-indium-gallium-selenium compound；First, vacuum chamber vacuum 5 ×
10-4Pa, vacuum evaporation indium gallium selenium thin film preformed layer, temperature is respectively 900 DEG C of indium, 1000 DEG C of gallium, 300 DEG C of selenium；Thickness range is
300-800nm；Then it is deposited with CIGS material again, temperature is respectively 1200 DEG C of copper, 900 DEG C of indium, 1000 DEG C of gallium, 300 DEG C of selenium；
Thickness is about 2 μm；Substrate is held at 450 DEG C；
Step 204, use plated film mode plated film CdS cushion (4)：
Ammonium Acetate, ammonia, thiourea volume ratio are 2:3:1 is configured to 500ml solution, and 70 DEG C of bath temperature, by polyamides Asia
Amine film soaks and reacts 30min in the solution；Prepared CdS film thickness is about 50nm；
Step 205, sputtering Window layer Window layer (5)
The use of radio frequency magnetron sputtering method sputtering i-ZnO thickness is 50nm, operating pressure 0.6Pa, power 0.8kw；Use
DC magnetron sputtering method sputters ZnO:Al, operating pressure 0.8Pa, power 1.0kw, ZnO:Al thickness is about 350nm；
Step 206, prepare intermediate layer (6) using evaporation and the mode of spin coating；
P-type LiF for 1.0nm for the thickness is deposited in Window layer (5)；Specifically preparing environment is：Local vacuum is 5 ×
10-4Pa, is observed using film thickness monitor and stops during 1.0nm, evaporation time is 30min；
PEDOT is prepared using spin-coating method after the completion of LiF preparation；Spin coating rotating speed 4000r/min, working time 15s, obtain
LiF thickness is about 100nm；
Step 207, using magnetron sputtering method manufacture electron transfer layer (7)；
Prepare TiO2 thin film using the mode of magnetron sputtering；It is specially the TiO the use of purity being 99.99%2Target, work
The vacuum of environment is 5 × 10-4Pa, operating pressure 0.5Pa, sputtering power 0.5kw, sputtering time 2h, gained TiO2Film thickness
For 100nm；
Step 208, one-step method prepare perovskite absorbed layer (8)；Detailed process is：
CH3NH3The preparation of I：The HI solution that 30mL mass percent is 57% and 30mL mass percent is taken to be 40% respectively
Methylamine solution, mixed in three neck round bottom flask be incorporated in stirring reaction in ice-water bath；After 5h, reaction products therefrom is placed in
In 100mL single-necked flask, by Rotary Evaporators under the conditions of 50 DEG C revolving, products therefrom by ether clean three times；Subsequently
Make product recrystallization with the mixed solvent of methanol and ether, generate a kind of white crystal, be finally dried in vacuum drying oven；
The PbI of quality such as take respectively2With CH3NH3I be dissolved in a certain amount of DMF solvent prepare 1.5mM/mL presoma molten
Liquid；Take the precursor solution of 200 μ L, the spin coating rotating speed of setting sol evenning machine is 5000r/15s spin-coating film, finally at 120 DEG C
Annealing 90min process obtains perovskite absorbed layer (8)；
Step 209, spin-coating method prepare hole transmission layer (9)；
200 μ L Spiro-OMETAD solution are dropped in perovskite absorb on layer film, spin coating rotating speed 4000r/min are set,
Time 30s, 150 annealing 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 making light
Volt battery device.
The present invention has the advantages and positive effects that：
This flexible overlapping solar cell adopts CIGS/perovskite as light absorbing zone, and it is right to improve to greatest extent
The absorption of light, improves battery efficiency；In addition, roll-to-roll technique can be realized using flexible substrate so that high-volume is raw
Product is possibly realized, and improves prospect in commercial applications；Finally, prepare CIGS thin film using the mode of vacuum evaporation can improve
Film morphology, improves battery efficiency.
Brief description：
Fig. 1 is the layer structure figure of the flexible overlapping solar cell of the preferred embodiment of the present invention.
Wherein：1st, transparent substrate；2nd, dorsum electrode layer；3rd, CIGS active layer；4th, CdS cushion；5th, Window layer；6、
Intermediate layer；7th, electron transfer layer；8th, perovskite absorbed layer；9th, hole transmission layer；10th, electrode.
Specific embodiment
For content of the invention, feature and effect of the present invention can be further appreciated that, hereby enumerate following examples, and coordinate accompanying drawing
Describe in detail as follows：
Refer to Fig. 1, a kind of flexible overlapping solar cell, include successively from bottom to top transparent substrate 1, dorsum electrode layer 2,
CIGS active layer 3, CdS cushion 4, Window layer 5, intermediate layer 6, electron transfer layer 7, perovskite absorbed layer 8, hole transport
Layer 9, electrode 10 totally ten Rotating fields, wherein：
Transparent substrate 1, described transparent substrate 1 is with receiving the polyimide film of lime glass or flexible substrate；Its
The thickness range of middle polyimide film is 25 μm～100 μm；Receive lime glass thickness in 1～4mm；
Be dorsum electrode layer 2 in described transparent substrate 1 upper surface, the thickness range of described dorsum electrode layer 2 be 100nm～
1000nm；
It is CIGS active layer 3 in the upper surface of described dorsum electrode layer 2, the thickness model of described CIGS active layer 3
Enclose is 1 μm～3 μm；
It is CdS cushion 4 in the upper surface of described CIGS active layer 3, the thickness range of described CdS cushion 4 is
30nm～100nm；
Be Window layer 5 in the upper surface of described CdS cushion 4, the thickness range of described Window layer 5 be 100nm～
500nm；
It is intermediate layer 6 in the upper surface of described Window layer 5, when described intermediate layer 6 is N-shaped LiF, CsCO3, C6H5COOLi,
During one of ZnO, the thickness range in intermediate layer 6 is 10nm～120nm；When described intermediate layer 6 is p-type molybdenum oxide, MEH-
When one of PPV, PEDOT, the thickness range in intermediate layer 6 is 30nm～150nm；
Upper surface in described intermediate layer 6 is electron transfer layer 7, and described electron transfer layer 7 is TiO2, ZnO, Al2O3、
SiO2One of, the thickness range of described electron transfer layer 7 is 50nm～300nm；
It is perovskite absorbed layer 8 in the upper surface of described electron transfer layer 7, the thickness range of described perovskite absorbed layer 8
For 100nm～1000nm；
It is hole transmission layer 9 in the upper surface of described perovskite absorbed layer 8, the thickness range of described hole transmission layer 9 is
100nm～1000nm；
It is electrode 10 in the upper surface of described hole transmission layer 9.
A kind of preparation method of flexible overlapping solar cell includes following two embodiment：
Embodiment 1.
(1) clean PI film surface：
Using plasma backwash etching machine, operating pressure 0.3Pa, sputtering power 0.2kw, by Ar, PI film is carved
Erosion cleaning.Cut out after the completion of cleaning to 3cm*3cm size.
(2) sputter back electrode：
We select Mo herein.Using d.c. sputtering, target purity 99.99%, power 0.6kw, operating pressure 1.0Pa；
Sputtering two-layer Mo electrode, wherein ground floor thickness 100nm, second layer thickness 400nm.
(3) it is deposited with CIGS thin-film
We prepare CIGS thin-film using traditional three-step approach.Pass through high temperature evaporation in vacuum chamber, make copper and indium
There is chemical reaction in gallium selenium composition on substrate, generate copper-indium-gallium-selenium compound.First, local vacuum 5.0e- of vacuum chamber
4Pa, vacuum evaporation indium gallium selenium thin film preformed layer, temperature is respectively 900 DEG C, 1000 DEG C, 300 DEG C.Thickness is about 500nm.Then
It is deposited with CIGS material again, temperature is respectively 1200 DEG C, 900 DEG C, 1000 DEG C, 300 DEG C.Thickness is about 2 μm.In all evaporations
During, substrate is held at 450 DEG C.
(4) use plated film mode plated film CdS
Ammonium Acetate, ammonia, thiourea ratio are 2:3:1 (volume ratio) is configured to 500ml solution, and 70 DEG C of bath temperature, by PI
Film soaks and reacts 30min in the solution.Prepared film thickness is about 50nm.
(5) sputter Window layer
The use of radio frequency magnetron sputtering method sputtering i-ZnO thickness is 50nm, operating pressure 0.6Pa, power 0.8kw；Use
DC magnetron sputtering method sputters ZnO：Al, operating pressure 0.8Pa, power 1.0kw, thickness 350nm.
(6) intermediate layer is prepared using the mode of evaporation/spin coating.
1.0nm thickness p-type LiF is deposited in Window layer.Local vacuum 5*e-4Pa, is observed using film thickness monitor
Stop during 1.0nm, evaporation time about 30min.
PEDOT is prepared using spin-coating method after the completion of LiF preparation.Spin coating rotating speed 4000r/min, time 15s, thickness is about
100nm.
(7) electron transfer layer TiO2
Mode using magnetron sputtering prepares TiO2Thin film.The TiO the use of purity being 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.
CH3NH3The preparation of I：Take the HI solution that 30mL mass fraction is 57% (2.27mmol) and 30mL mass fraction respectively
Methylamine solution (being dissolved in methanol) for 40% (2.73mmol), is sufficiently mixed in three neck round bottom flask and stirs in ice-water bath
Reaction.After 5h by reaction products therefrom be placed in 100mL single-necked flask, by Rotary Evaporators under the conditions of 50 DEG C revolving, institute
Obtain product to clean three times by ether.Subsequently make product recrystallization with the mixed solvent of methanol and ether, generate a kind of white brilliant
Body, is finally dried in vacuum drying oven.
The PbI of quality such as take respectively2With CH3NH3I be dissolved in a certain amount of DMF solvent prepare 1.5mM/mL presoma molten
Liquid.Take the precursor solution of 200 μ L, the spin coating rotating speed of setting sol evenning machine is 5000r/15s spin-coating film, finally at 120 DEG C
Annealing 90min process obtains perovskite thin film.
(9) spin-coating method prepares hole transmission layer.
200 μ L Spiro-OMETAD solution are dropped on thin film, spin coating rotating speed 4000r/min, time 30s, 150 are set
Annealing 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 making photovoltaic electric
Pond device.With similar method preparation comparative device.
Embodiment 2.
(1) it is used and receive lime glass as substrate：
3cm*3cm received after lime glass cleans in cleaning agent repeatedly, more respectively through isopropanol, acetone and chloroformic solution
Soak and be cleaned by ultrasonic, finally dried for standby in infrared baking oven；
(2) sputter back electrode：
We select Mo herein.Using d.c. sputtering, target purity 99.99%, power 0.6kw, operating pressure 1.0Pa；
Sputtering two-layer Mo electrode, wherein ground floor thickness 100nm, second layer thickness 400nm.
(3) it is deposited with CIGS thin-film
We prepare CIGS thin-film using traditional three-step approach.Pass through high temperature evaporation in vacuum chamber, make copper and indium
There is chemical reaction in gallium selenium composition on substrate, generate copper-indium-gallium-selenium compound.First, local vacuum 5.0e- of vacuum chamber
4Pa, vacuum evaporation indium gallium selenium thin film preformed layer, temperature is respectively 900 DEG C, 1000 DEG C, 300 DEG C.Thickness is about 500nm.Then
It is deposited with CIGS material again, temperature is respectively 1200 DEG C, 900 DEG C, 1000 DEG C, 300 DEG C.Thickness is about 2 μm.In all evaporations
During, substrate is held at 450 DEG C.
(4) use plated film mode plated film CdS
Ammonium Acetate, ammonia, thiourea ratio are 2:3:1 (volume ratio) is configured to 500ml solution, and 70 DEG C of bath temperature, by PI
Film soaks and reacts 30min in the solution.Prepared film thickness is about 50nm.
(5) sputter Window layer
The use of radio frequency magnetron sputtering method sputtering i-ZnO thickness is 50nm, operating pressure 0.6Pa, power 0.8kw；Use
DC magnetron sputtering method sputters ZnO：Al, operating pressure 0.8Pa, power 1.0kw, thickness 350nm.
(6) intermediate layer is prepared using the mode of evaporation/spin coating.
1.0nm thickness p-type LiF is deposited in Window layer.Local vacuum 5*e-4Pa, is observed using film thickness monitor
Stop during 1.0nm, evaporation time about 30min.
PEDOT is prepared using spin-coating method after the completion of LiF preparation.Spin coating rotating speed 4000r/min, time 15s, thickness is about
100nm.
(7) electron transfer layer TiO2
Mode using magnetron sputtering prepares TiO2Thin film.The TiO the use of purity being 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.
CH3NH3The preparation of I：Take the HI solution that 30mL mass fraction is 57% (2.27mmol) and 30mL mass fraction respectively
Methylamine solution (being dissolved in methanol) for 40% (2.73mmol), is sufficiently mixed in three neck round bottom flask and stirs in ice-water bath
Reaction.After 5h by reaction products therefrom be placed in 100mL single-necked flask, by Rotary Evaporators under the conditions of 50 DEG C revolving, institute
Obtain product to clean three times by ether.Subsequently make product recrystallization with the mixed solvent of methanol and ether, generate a kind of white brilliant
Body, is finally dried in vacuum drying oven.
The PbI of quality such as take respectively2With CH3NH3I be dissolved in a certain amount of DMF solvent prepare 1.5mM/mL presoma molten
Liquid.Take the precursor solution of 200 μ L, the spin coating rotating speed of setting sol evenning machine is 5000r/15s spin-coating film, finally at 120 DEG C
Annealing 90min process obtains perovskite thin film.
(9) spin-coating method prepares hole transmission layer.
200 μ L Spiro-OMETAD solution are dropped on thin film, spin coating rotating speed 4000r/min, time 30s, 150 are set
Annealing 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 making photovoltaic electric
Pond device.
Technique scheme advantage is：This builds up solar cell and adopts CIGS/perovskite as light absorbing zone, can
To improve the absorption to light to greatest extent, improve battery efficiency；In addition, roll-to-roll work can be realized using flexible substrate
Skill is possibly realized so that producing in enormous quantities, improves prospect in commercial applications；Finally, prepared using the mode of vacuum evaporation
CIGS thin film can improve film morphology, improves battery efficiency.
Above embodiments of the invention are described in detail, but described content have been only presently preferred embodiments of the present invention,
It is not to be regarded as the practical range for limiting the present invention.All impartial changes made according to the present patent application scope and improvement etc.,
All should still belong within the patent covering scope of the present invention.
Claims (2)
1. a kind of preparation method of flexible overlapping solar cell it is characterised in that：Comprise the steps：
Step 101, cleaning polyimide film surface：
Using plasma backwash etching machine, operating pressure is 0.3Pa, and sputtering power is 0.2kw, by Ar to polyimide film
Perform etching cleaning；Cut out after the completion of cleaning to the square of 3cm*3cm；
Step 102, splash dorsum electrode layer (2)：
Select one of molybdenum, nickel, aluminum, gold, silver, copper, titanium, using d.c. sputtering, target purity is 99.99%, and power is
0.6kw, operating pressure is 1.0Pa；Sputtering two-layer, wherein ground floor thickness are 100nm, and second layer thickness is 400nm；
Step 103, evaporation CIGS active layer (3)：
Prepare CIGS thin-film using three-step approach, pass through 300 DEG C of -1200 DEG C of high temperature evaporations specially in vacuum chamber, make
There is chemical reaction in CIGS composition on substrate, generate copper-indium-gallium-selenium compound；First, vacuum chamber vacuum 5 × 10- 4Pa, vacuum evaporation indium gallium selenium thin film preformed layer, temperature is respectively 900 DEG C of indium, 1000 DEG C of gallium, 300 DEG C of selenium；Thickness range is
300-800nm；Then it is deposited with CIGS material again, temperature is respectively 1200 DEG C of copper, 900 DEG C of indium, 1000 DEG C of gallium, 300 DEG C of selenium；
Thickness is 2 μm；Substrate is held at 450 DEG C；
Step 104, use plated film mode plated film CdS cushion (4)：
Ammonium Acetate, ammonia, thiourea volume ratio are 2:3:1 is configured to 500ml solution, and 70 DEG C of bath temperature, by polyimide film
Soak and react 30min in the solution；Prepared CdS film thickness is 50nm；
Step 105, sputtering Window layer Window layer (5)
The use of radio frequency magnetron sputtering method sputtering i-ZnO thickness is 50nm, operating pressure 0.6Pa, power 0.8kw；Using direct current
Magnetically controlled sputter method sputters ZnO:Al, operating pressure 0.8Pa, power 1.0kw, ZnO:Al thickness is 350nm；
Step 106, prepare intermediate layer (6) using evaporation and the mode of spin coating；
The N-shaped LiF for 1.0nm for the thickness is deposited in Window layer (5)；Specifically preparing environment is：Local vacuum is 5 × 10- 4Pa, is observed using film thickness monitor and stops during 1.0nm, evaporation time is 30min；
PEDOT is prepared using spin-coating method after the completion of LiF preparation；Spin coating rotating speed 4000r/min, working time 15s, the LiF obtaining
Thickness is 100nm；
Step 107, using magnetron sputtering method manufacture electron transfer layer (7)；
Prepare TiO2 thin film using the mode of magnetron sputtering；It is specially the TiO the use of purity being 99.99%2Target, working environment
Vacuum be 5 × 10-4Pa, operating pressure 0.5Pa, sputtering power 0.5kw, sputtering time 2h, gained TiO2Film thickness is
100nm；
Step 108, one-step method prepare perovskite absorbed layer (8)；Detailed process is：
CH3NH3The preparation of I：Take the HI solution that 30mL mass percent is 57% respectively and first that 30mL mass percent is 40%
Amine aqueous solution, mixes in three neck round bottom flask and is incorporated in stirring reaction in ice-water bath；After 5h, reaction products therefrom is placed in 100mL mono-
In mouthful flask, by Rotary Evaporators under the conditions of 50 DEG C revolving, products therefrom passes through ether cleaning three times；Subsequently use methanol and
The mixed solvent of ether makes product recrystallization, generates a kind of white crystal, is finally dried in vacuum drying oven；
The PbI of quality such as take respectively2With CH3NH3I is dissolved in the precursor solution that a certain amount of DMF solvent prepares 1.5mM/mL；
Take the precursor solution of 200 μ L, the spin coating rotating speed of setting sol evenning machine is 5000r/15s spin-coating film, finally anneals at 120 DEG C
90min process obtains perovskite absorbed layer (8)；
Step 109, spin-coating method prepare hole transmission layer (9)；
200 μ L Spiro-OMETAD solution are dropped in perovskite absorb on layer film, spin coating rotating speed 4000r/min, time are set
30s, 150 annealing 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 making photovoltaic electric
Pond device.
2. a kind of preparation method of flexible overlapping solar cell it is characterised in that：Comprise the steps：
Step 201, it is used and receives lime glass as substrate：
By 3cm*3cm receive lime glass in cleaning agent repeatedly clean after, more respectively through isopropanol, acetone and chloroformic solution soak
And be cleaned by ultrasonic, finally dried for standby in infrared baking oven；
Step 202, splash dorsum electrode layer (2)：
Select one of molybdenum, nickel, aluminum, gold, silver, copper, titanium, using d.c. sputtering, target purity is 99.99%, and power is
0.6kw, operating pressure is 1.0Pa；Sputtering two-layer, wherein ground floor thickness are 100nm, and second layer thickness is 400nm；
Step 203, evaporation CIGS active layer (3)：
Prepare CIGS thin-film using three-step approach, pass through 300 DEG C of -1200 DEG C of high temperature evaporations specially in vacuum chamber, make
There is chemical reaction in CIGS composition on substrate, generate copper-indium-gallium-selenium compound；First, vacuum chamber vacuum 5 × 10- 4Pa, vacuum evaporation indium gallium selenium thin film preformed layer, temperature is respectively 900 DEG C of indium, 1000 DEG C of gallium, 300 DEG C of selenium；Thickness range is
300-800nm；Then it is deposited with CIGS material again, temperature is respectively 1200 DEG C of copper, 900 DEG C of indium, 1000 DEG C of gallium, 300 DEG C of selenium；
Thickness is 2 μm；Substrate is held at 450 DEG C；
Step 204, use plated film mode plated film CdS cushion (4)：
Ammonium Acetate, ammonia, thiourea volume ratio are 2:3:1 is configured to 500ml solution, and 70 DEG C of bath temperature, by polyimide film
Soak and react 30min in the solution；Prepared CdS film thickness is 50nm；
Step 205, sputtering Window layer Window layer (5)
The use of radio frequency magnetron sputtering method sputtering i-ZnO thickness is 50nm, operating pressure 0.6Pa, power 0.8kw；Using direct current
Magnetically controlled sputter method sputters ZnO:Al, operating pressure 0.8Pa, power 1.0kw, ZnO:Al thickness is 350nm；
Step 206, prepare intermediate layer (6) using evaporation and the mode of spin coating；
The N-shaped LiF for 1.0nm for the thickness is deposited in Window layer (5)；Specifically preparing environment is：Local vacuum is 5 × 10- 4Pa, is observed using film thickness monitor and stops during 1.0nm, evaporation time is 30min；
PEDOT is prepared using spin-coating method after the completion of LiF preparation；Spin coating rotating speed 4000r/min, working time 15s, the LiF obtaining
Thickness is 100nm；
Step 207, using magnetron sputtering method manufacture electron transfer layer (7)；
Prepare TiO2 thin film using the mode of magnetron sputtering；It is specially the TiO the use of purity being 99.99%2Target, working environment
Vacuum be 5 × 10-4Pa, operating pressure 0.5Pa, sputtering power 0.5kw, sputtering time 2h, gained TiO2Film thickness is
100nm；
Step 208, one-step method prepare perovskite absorbed layer (8)；Detailed process is：
CH3NH3The preparation of I：Take the HI solution that 30mL mass percent is 57% respectively and first that 30mL mass percent is 40%
Amine aqueous solution, mixes in three neck round bottom flask and is incorporated in stirring reaction in ice-water bath；After 5h, reaction products therefrom is placed in 100mL mono-
In mouthful flask, by Rotary Evaporators under the conditions of 50 DEG C revolving, products therefrom passes through ether cleaning three times；Subsequently use methanol and
The mixed solvent of ether makes product recrystallization, generates a kind of white crystal, is finally dried in vacuum drying oven；
The PbI of quality such as take respectively2With CH3NH3I is dissolved in the precursor solution that a certain amount of DMF solvent prepares 1.5mM/mL；
Take the precursor solution of 200 μ L, the spin coating rotating speed of setting sol evenning machine is 5000r/15s spin-coating film, finally anneals at 120 DEG C
90min process obtains perovskite absorbed layer (8)；
Step 209, spin-coating method prepare hole transmission layer (9)；
200 μ L Spiro-OMETAD solution are dropped in perovskite absorb on layer film, spin coating rotating speed 4000r/min, time are set
30s, 150 annealing 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 making photovoltaic electric
Pond device.
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| CN104022225A (en) * | 2014-06-20 | 2014-09-03 | 苏州瑞晟纳米科技有限公司 | High-efficiency low-cost copper indium gallium selenium / perovskite double-junction solar photocell prepared through all-solution method |
| CN104362253A (en) * | 2014-10-23 | 2015-02-18 | 河北工业大学 | All solid state perovskite microcrystalline silicon composite solar battery and preparation method thereof |
| CN204315592U (en) * | 2014-12-10 | 2015-05-06 | 北京汉能创昱科技有限公司 | A kind of compound film solar cell |
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