CN104393109A - Chemical vapor deposition preparation method for perovskite solar cell - Google Patents
Chemical vapor deposition preparation method for perovskite solar cell Download PDFInfo
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- CN104393109A CN104393109A CN201410586978.0A CN201410586978A CN104393109A CN 104393109 A CN104393109 A CN 104393109A CN 201410586978 A CN201410586978 A CN 201410586978A CN 104393109 A CN104393109 A CN 104393109A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000005229 chemical vapour deposition Methods 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 37
- 230000005540 biological transmission Effects 0.000 claims abstract description 24
- 239000011521 glass Substances 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 76
- 239000000376 reactant Substances 0.000 claims description 54
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 49
- 238000001556 precipitation Methods 0.000 claims description 43
- 239000000243 solution Substances 0.000 claims description 33
- 239000007790 solid phase Substances 0.000 claims description 32
- 235000019441 ethanol Nutrition 0.000 claims description 29
- 238000004528 spin coating Methods 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 23
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 20
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 15
- RAJISUUPOAJLEQ-UHFFFAOYSA-N chloromethanamine Chemical compound NCCl RAJISUUPOAJLEQ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000967 suction filtration Methods 0.000 claims description 12
- QEZYDNSACGFLIC-UHFFFAOYSA-N CN.[I] Chemical compound CN.[I] QEZYDNSACGFLIC-UHFFFAOYSA-N 0.000 claims description 10
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 10
- 238000007669 thermal treatment Methods 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 8
- 150000002220 fluorenes Chemical class 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 8
- 239000011630 iodine Substances 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- XPOLVIIHTDKJRY-UHFFFAOYSA-N acetic acid;methanimidamide Chemical compound NC=N.CC(O)=O XPOLVIIHTDKJRY-UHFFFAOYSA-N 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 7
- 238000002207 thermal evaporation Methods 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- GBMPPHPJKKUMPS-UHFFFAOYSA-N [Br].CN Chemical compound [Br].CN GBMPPHPJKKUMPS-UHFFFAOYSA-N 0.000 claims description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- RYTLGWCJESCDMY-UHFFFAOYSA-N carbamimidoyl chloride Chemical compound NC(Cl)=N RYTLGWCJESCDMY-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052745 lead Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 4
- 238000005137 deposition process Methods 0.000 claims description 4
- 230000005525 hole transport Effects 0.000 claims description 4
- 125000001905 inorganic group Chemical group 0.000 claims description 4
- 125000000962 organic group Chemical group 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical group 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 2
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- -1 diisopropyl titanate esters Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000010409 thin film Substances 0.000 abstract description 12
- 239000000758 substrate Substances 0.000 abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 4
- 230000031700 light absorption Effects 0.000 abstract 3
- 239000010408 film Substances 0.000 description 99
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 229960002358 iodine Drugs 0.000 description 5
- JTDNNCYXCFHBGG-UHFFFAOYSA-L tin(ii) iodide Chemical compound I[Sn]I JTDNNCYXCFHBGG-UHFFFAOYSA-L 0.000 description 4
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 3
- 238000007738 vacuum evaporation Methods 0.000 description 3
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical compound NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229940108184 stannous iodide Drugs 0.000 description 2
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XFJRVKQTVNCACZ-UHFFFAOYSA-N ac1l9fmv Chemical compound NC.NC XFJRVKQTVNCACZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000002365 hybrid physical--chemical vapour deposition Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
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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
- Y02E10/549—Organic PV cells
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Electromagnetism (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a chemical vapor deposition preparation method for a perovskite solar cell. The preparation method is characterized in that a compact layer TiO2 thin film is deposited on a surface on which the FTO thin film of FTO conductive glass is positioned so as to act as an electron transmission layer; a perovskite light absorption layer thin film is prepared on the electron transmission layer via a chemical vapor deposition method; a hole transmission layer is prepared on the perovskite light absorption layer thin film; and an Ag electrode or an Au electrode is vapor-deposited on the hole transmission layer to act as a top electrode so that the perovskite solar cell is obtained. The preparation method is simple and low in cost. The prepared perovskite light absorption layer thin film is high in quality, excellent in substrate coverage and great in stability and repeatability. Preliminary conversion efficiency of the prepared planar heterojunction perovskite solar cell can be 11%.
Description
Technical field
The present invention relates to a kind of preparation method of perovskite solar cell, belong to the preparation technology field of thin film solar cell photovoltaic device.
Background technology
At present, hybrid inorganic-organic perovskite solar cell causes the extensive concern of photovoltaic circle due to the photoelectric characteristic of its excellence, due to its have that conversion efficiency is high, low cost of manufacture and the feature such as preparation technology is simple, and be considered to the solar cell of new generation having development prospect.The novel solar battery that perovskite battery is is light absorbing zone with perovskite thin film material, generally can be expressed as AMX
3, wherein A represents cation radius at the organic of 0.164nm ~ 0.259nm and inorganic group, and common is methylamine Methylammonium (Ma), carbonamidine Formamidinium (Fa) and caesium Cs etc.; M is Pb, Sn and Pb
xsn
1-xalloy; X is halogen.Decades in the past, hydridization perovskite material is used as field-effect transistor FET, LED and photodetector etc. more.Until 2009, Kojima uses it for dye-sensitized solar cells first, and obtains the photoelectric conversion efficiency of 3.8%; Subsequently only within short 5 years, perovskite obtains fast development in the application of photovoltaic art, its conversion efficiency is risen to nearly 20% by Yang etc., perovskite solar cell has become the hot subject that current academia falls over each other to study, Quantity of Papers exponentially increases fast, and industrial quarters also starts the study on the industrialization exploitation carrying out being correlated with.
Among the research boom of perovskite battery, mainly report two large class preparation technologies: vacuum thermal evaporation technique and solwution method technique.Vacuum thermal evaporation can obtain high-quality perovskite thin film undoubtedly, but vacuum evaporation apparatus is expensive, processing procedure is complicated, be difficult to accurate control element ratio, and some evaporation source is difficult to the large area preparation realizing homogeneous film.And solwution method technological operation is simple, but cause due to the ultrafast reaction rate of material that film is coarse, porous and the not problem such as covering completely.Meanwhile, the poor perovskite thin film material of film quality is general very unstable in atmosphere, thus needs to operate under the environment of glove box or ultralow humidity, thus further limit the industrialization large-area applications of perovskite solar cell.
Summary of the invention
The invention provides a kind of chemical gas-phase deposition process for preparing of perovskite solar cell, perovskite light absorbing zone film in battery is adopted the method preparation of chemical vapour deposition (CVD), to densification, even and stable high-quality perovskite thin film material can be prepared, and then obtain high efficiency perovskite solar cell.
Perovskite solar cell of the present invention is planar heterojunction structure, be with FTO electro-conductive glass for substrate, deposit electron transfer layer, perovskite light absorbing zone film, hole transmission layer and top electrode from bottom to up successively in the face, FTO film place of described FTO electro-conductive glass;
Described electron transfer layer is compacted zone TiO
2film;
Described perovskite light absorbing zone film is the AMX with perovskite crystal structure
3film, wherein A is the organic or inorganic group of cation radius at 0.164nm ~ 0.259nm, preferred methylamine CH
3nH
3or carbonamidine HC (NH
2)
2; M is Pb, Sn or Pb
xsn
1-xalloy; X is halogen.
Described hole transmission layer is 2,2', 7,7'-tetra-[N, N-bis-(4-methoxyphenyl) is amino]-9,9'-spiral shell two fluorenes (spiro-OMeTAD) layers.
Described top electrode is Ag electrode or Au electrode.
Wherein said electric transmission layer thickness is 20 ~ 100nm; Described perovskite light absorbing zone film thickness is 100 ~ 3000nm; Described thickness of hole transport layer is 20 ~ 500nm; Described top electrode thickness is 50 ~ 150nm.
Technical solution problem of the present invention, adopts following technical scheme:
The chemical gas-phase deposition process for preparing of perovskite solar cell of the present invention, its feature is to carry out as follows:
A, FTO film institute deposition compact layer TiO on the whole at FTO electro-conductive glass
2film is as electron transfer layer;
B, on the electron transport layer by chemical vapor deposition perovskite light absorbing zone film;
C, on described perovskite light absorbing zone film, prepare 2,2', 7,7'-tetra-[N, N-bis-(4-methoxyphenyl) is amino]-9,9'-spiral shell two fluorenes layers as hole transmission layer;
D, on the hole transport layer evaporation Ag electrode or Au electrode, as top electrode, obtain perovskite solar cell.
The perovskite light absorbing zone film of perovskite solar cell of the present invention adopts chemical vapour deposition (CVD) (Chemical VaporDeposition, CVD) method preparation, comprise aumospheric pressure cvd (Atmospheric Pressure CVD, APCVD), low-pressure chemical vapor deposition (Low-pressure CVD, LPCVD), high-pressure chemical vapor deposition (High-pressure CVD, HPCVD), plasma enhanced chemical vapor deposition (Plasma enhanced CVD, and single warm area PECVD), two warm area and many temperature-area tubular furnaces CVD etc., preferably two temperature-area tubular furnace CVD.
Step a is at the FTO film institute deposition compact layer TiO on the whole of FTO electro-conductive glass
2film as the method for electron transfer layer is:
Method one: FTO electro-conductive glass FTO film spin coating concentration be on the whole the isopropyl titanate ethanolic solution of 0.24mol/L, at 450 ~ 500 DEG C, sinter 30 ~ 60min in air, be then soaked in the TiCl of 40mM
4in the aqueous solution, 70 DEG C of process 30min, finally sinter 30 ~ 60min again, obtain compacted zone TiO at 450 ~ 500 DEG C of temperature
2film;
Method two: by TiCl
4be added drop-wise in absolute ethyl alcohol, and then add phenmethylol and obtain yellow solution, described TiCl
4, absolute ethyl alcohol and phenmethylol volume ratio be 1:4:20; Described yellow solution water-bath 8h at 80 DEG C is obtained milky white solution, in described milky white solution, adds extracted with diethyl ether go out TiO to be cleaned
2precipitation, successively with ethanol and the described TiO to be cleaned of ether cleaning
2precipitation, then centrifugal acquisition TiO
2precipitation;
By described TiO
2in ethanol, obtaining concentration is 3 ~ 15mg/ml TiO in precipitation dispersion
2alcohol dispersion liquid, then TiO described in 10ml
2alcohol dispersion liquid in add two (acetylacetone based) diisopropyl titanate esters of 0.1 ~ 0.3ml as stabilizer, obtain TiO
2spin coating liquid;
At the FTO film institute TiO described in spin coating on the whole of FTO electro-conductive glass
2spin coating liquid, namely the 30min that then anneals at 150 DEG C obtains compacted zone TiO
2film.
Wherein, method two compacted zone TiO
2the preparation of film, without the need to high-temperature process, achieves the full low temperature process of perovskite solar cell.And can once prepare a large amount of TiO
2spin coating liquid, is convenient to later stage use.
Step b by the method for chemical vapor deposition perovskite light absorbing zone film is on the electron transport layer:
Prepare PbI on the electron transport layer
2, SnI
2film or PbCl
2film, as reactant, is positioned over the thermal treatment zone place of two temperature-area tubular furnace; With iodine methylamine CH
3nH
3i, chloromethane amine CH
3nH
3cl, bromine methylamine CH
3nH
3br, iodine carbonamidine HC (NH
2)
2i, chloromethane amidine HC (NH
2)
2cl, bromine carbonamidine HC (NH
2)
2described gaseous sources, as gaseous sources, is positioned over another thermal treatment zone place of two temperature-area tubular furnace by Br; Described gaseous sources position is heated to 100 ~ 300 DEG C, described reactant position is heated to 50 ~ 300 DEG C simultaneously, namely isothermal reaction 10 ~ 300min obtains perovskite light absorbing zone film.
Wherein:
Iodine methylamine CH
3nH
3i is prepared as follows: the hydriodic acid aqueous solution mixing of to be the methylamine alcohol solution of 33wt% and 10mL mass concentration by 24mL mass concentration be 45wt%, reaction 2h obtains reactant liquor, 60 DEG C of precipitations obtained after drying described reactant liquor are dissolved in 80mL ethanol, add 300mL ether more wherein to extract as extractant, collect solid phase, carry out centrifugal or suction filtration to solid phase to be precipitated, to precipitation vacuumize 24h, obtain iodine methylamine CH
3nH
3i powder;
Chloromethane amine CH
3nH
3cl powder is prepared as follows: the HCl aqueous solution of to be the methylamine alcohol solution of 33wt% and 10mL mass concentration by 24mL mass concentration be 45wt%, reaction 2h obtains reactant liquor, 60 DEG C of precipitations obtained after drying described reactant liquor are dissolved in 80mL ethanol, add 300mL ether more wherein to extract as extractant, collect solid phase, carry out centrifugal or suction filtration to solid phase to be precipitated, to precipitation vacuumize 24h, obtain chloromethane amine CH
3nH
3cl powder;
Bromine methylamine CH
3nH
3br powder is prepared as follows: the HBr aqueous solution of to be the methylamine alcohol solution of 33wt% and 10mL mass concentration by 24mL mass concentration be 45wt%, reaction 2h obtains reactant liquor, 60 DEG C of precipitations obtained after drying described reactant liquor are dissolved in 80mL ethanol, add 300mL ether more wherein to extract as extractant, collect solid phase, carry out centrifugal or suction filtration to solid phase to be precipitated, to precipitation vacuumize 24h, obtain bromine methylamine CH
3nH
3br powder;
Iodine carbonamidine HC (NH
2)
2i is prepared as follows: the hydriodic acid aqueous solution mixing by 4g formamidine acetate and 13.2g mass concentration being 45wt%, reaction 2h obtains reactant liquor, 60 DEG C of precipitations obtained after drying described reactant liquor are dissolved in 80mL ethanol, add 300mL ether more wherein to extract as extractant, collect solid phase, carry out centrifugal or suction filtration to solid phase to be precipitated, to precipitation vacuumize 24h, obtain iodine carbonamidine HC (NH
2)
2i powder;
Chloromethane amidine HC (NH
2)
2cl is prepared as follows: the HCl aqueous solution by 4g formamidine acetate and 13.2g mass concentration being 45wt%, reaction 2h obtains reactant liquor, 60 DEG C of precipitations obtained after drying described reactant liquor are dissolved in 80mL ethanol, add 300mL ether more wherein to extract as extractant, collect solid phase, carry out centrifugal or suction filtration to solid phase to be precipitated, to precipitation vacuumize 24h, obtain chloromethane amidine HC (NH
2)
2cl powder
Bromine carbonamidine HC (NH
2)
2br is prepared as follows: the HBr aqueous solution by 4g formamidine acetate and 13.2g mass concentration being 45wt%, reaction 2h obtains reactant liquor, 60 DEG C of precipitations obtained after drying described reactant liquor are dissolved in 80mL ethanol, add 300mL ether more wherein to extract as extractant, collect solid phase, carry out centrifugal or suction filtration to solid phase to be precipitated, to precipitation vacuumize 24h, obtain bromine carbonamidine HC (NH
2)
2br powder
PbI
2the preparation method of film is: spin coating concentration is on the electron transport layer the PbI of 1M
2dMF solution or PbI
2dMSO solution, at 70 DEG C anneal 10 ~ 30min, obtain PbI
2film;
Described PbCl
2film and described SnI
2film takes the method for thermal evaporation plated film to obtain, and is using lead chloride or stannous iodide as evaporation source, is positioned in crucible, substrate is positioned over plated film position, the vacuum degree of thermal evaporation deposition system is being down to 10
-4during Pa, start plated film, the plated film time is 10 ~ 30min.
Step c prepares 2 on described perovskite light absorbing zone film, 2', 7, 7'-tetra-[N, N-bis-(4-methoxyphenyl) is amino]-9, 9'-spiral shell two fluorenes layer as the method for hole transmission layer is: by 72.3mg 2, 2', 7, 7'-tetra-[N, N-bis-(4-methoxyphenyl) is amino]-9, 9'-spiral shell two fluorenes (Spiro-MeTAD) is dissolved in 1mL chlorobenzene, add the acetonitrile solution that 17.5 μ L concentration are two trifluoromethanesulfonimide lithiums (LiFSFI) of 520mg/mL, add 28.8 μ L 4-tert .-butylpyridine (4-tBP) again, obtain hole transmission layer spin coating liquid, hole transmission layer spin coating liquid described in spin coating on described perovskite light absorbing zone film, each dropping 30 μ L, and 30s is rotated with the speed of 4000rpm after each dropping, obtain hole transmission layer.
Compared with the prior art, beneficial effect of the present invention is embodied in:
The perovskite light absorbing zone film of perovskite solar cell of the present invention adopt simple to operate, with low cost, can large area industrialization chemical vapour deposition (CVD) (CVD) method of amplifying, replace current expensive vacuum evaporation technology and be difficult to amplify solution spin coating proceeding, adopt gas phase-solid phase (G-S) reaction slowly, effectively to overcome in solwution method organic group (as CH
3nH
3i etc.) and inorganic thin film (as TiO
2deng) between ultrafast intercalation problem rate, the defects such as coarse, the porous avoiding film to occur and not exclusively covering, and then prepare that film quality is high, substrate spreadability is good, stability and reproducible perovskite light absorbing zone film, the efficiency of the planar heterojunction perovskite battery of first trial-production is up to 12%.The invention still further relates to compacted zone titanium dioxide TiO
2the low-temperature fabrication of film, can prepare perovskite solar cell under whole 200 DEG C of low temperature.
In sum, the loaded down with trivial details glove box operation that the present invention can effectively avoid current perovskite solar cell to prepare and expensive vacuum evaporation apparatus drop into, and under the non-vacuum condition of complete atmospheric environment, realize the low-cost and high-quality preparation of perovskite solar cell.Perovskite light absorbing zone thin-film material prepared by the method is very fine and close, highly stable, is also applicable to the preparation of the perovskite solar cell of meso-porous nano structure.And this chemical vapor deposition method can be amplified easily in industrialization, thus vital effect is served to the commercial applications promoting perovskite solar cell.
In addition, the present invention, by using the mixed-powder of iodine methylamine and chloromethane amine as gaseous sources, compared with doing gaseous sources, improves degree of crystallinity and the surface coverage of prepared perovskite light absorbing zone film with single iodine methylamine or chloromethane amine; And the chlorine Elements C l of trace, the carrier lifetime of perovskite light absorbing zone film can be made elongated, and the diffusion length of charge carrier is also increased to more than 1000nm by 100nm, thus the greatly very high conversion efficiency of gained perovskite solar cell.
Accompanying drawing explanation
Fig. 1 is the structural representation of perovskite solar cell of the present invention;
Fig. 2 is two temperature-area tubular furnace CVD precipitation equipment schematic diagrames of perovskite light absorbing zone film of the present invention;
The CH of Fig. 3 prepared by the embodiment of the present invention 1
3nH
3pbI
3xRD figure (Fig. 3 (a)) of film and SEM figure (Fig. 3 (b));
The J-V curve of the perovskite solar cell of Fig. 4 prepared by the embodiment of the present invention 1;
Number in the figure: 1 quartz ampoule; 2 pairs of temperature-area tubular furnaces; The 3 gaseous sources thermals treatment zone; The 4 reactant thermals treatment zone; 5 valves and vacuum meter; 6 mechanical pump evacuation passageway; 7 gaseous sources; 8 reactants.
Embodiment
Embodiment 1
The structural representation of the perovskite solar cell of the present embodiment as shown in Figure 1, for substrate with FTO electro-conductive glass, deposit electron transfer layer, perovskite light absorbing zone film, hole transmission layer and top electrode from bottom to up successively in the face, FTO film place of FTO electro-conductive glass, concrete preparation method is:
A, FTO film institute deposition compact layer TiO on the whole at FTO electro-conductive glass
2film is as electron transfer layer: FTO electro-conductive glass FTO film on the whole with the isopropyl titanate ethanolic solution that the speed spin coating 50 μ L concentration of 2000rpm/30s is 0.24mol/L, then at 450 DEG C, sinter 30min in air, be then soaked in the TiCl of 40mM
4in the aqueous solution, 70 DEG C of process 30min, finally sinter 30min again, obtain the compacted zone TiO that thickness is 100nm at 450 DEG C of temperature
2film.
B, prepare perovskite light absorbing zone film by chemical vapour deposition technique on the electron transport layer
B1, preparation CH
3h
3i powder is as gaseous sources: the hydriodic acid aqueous solution of to be the methylamine alcohol solution (directly buy from Chemical Reagent Co., Ltd., Sinopharm Group) of 33wt% and 10mL mass concentration by 24mL mass concentration be 45wt% mixes, reaction 2h obtains reactant liquor, then the precipitation obtained after drying reactant liquor at 60 DEG C is dissolved in 80mL ethanol, add 300mL ether again to extract as extractant, collect solid phase, now still contain a small amount of ether in solid phase, therefore to the dry 24h of the precipitation obtained after solid phase centrifugal segregation ether, namely CH is obtained
3nH
3i powder;
B2, preparation PbI
2film: compound concentration is the PbI of 1M
2dMF solution, and be heated to 70 DEG C, obtain PbI for subsequent use
2spin coating liquid; On the electron transport layer with the speed spin coating 50 μ L PbI for subsequent use of 2000rpm/30s
2spin coating liquid, then has PbI by spin coating
2substrate to anneal at 70 DEG C 30min, obtain PbI
2film;
B3, by PbI
2film is positioned over the thermal treatment zone place (being the reactant thermal treatment zone) of two temperature-area tubular furnace, by CH as reactant
3nH
3i powder is positioned over another thermal treatment zone place (being the gaseous sources thermal treatment zone) of two temperature-area tubular furnace as gaseous sources, gaseous sources position place is heated to 250 DEG C, reactant position place is heated 150 DEG C, and reaction 60min, obtains the CH as perovskite light absorbing zone film
3nH
3pbI
3film;
As shown in Figure 2, for two temperature-area tubular furnace CVD precipitation equipment schematic diagrames of perovskite light absorbing zone film, 1 be quartz ampoule, 2 be two temperature-area tubular furnace in figure, 3 be the gaseous sources thermal treatment zone, 4 be the reactant thermal treatment zone, 5 be mechanical pump evacuation passageway, 7 be gaseous sources, 8 be reactant for valve and vacuum meter, 6.
Fig. 3 a is prepared CH
3nH
3pbI
3the XRD of film, Fig. 3 b is the CH of preparation
3nH
3pbI
3the SEM figure of film.CH can be found out from Fig. 3 a
3nH
3pbI
3the peak of film is 14.07 °, 28.36 °, 31.82 ° and 43.14 °, PbI
2all change into CH
3nH
3pbI
3.As can be seen from Fig. 3 b, prepared CH
3nH
3pbI
3film quality is high, substrate spreadability is good.
C, preparation 2 on perovskite light absorbing zone film, 2', 7,7'-tetra-[N, N-bis-(4-methoxyphenyl) is amino]-9,9'-spiral shell two fluorenes layers are as hole transmission layer: 72.3mg Spiro-MeTAD are dissolved in 1mL chlorobenzene, add the acetonitrile solution that 17.5 μ L concentration are the LiFSFI of 520mg/mL, add 28.8 μ L 4-tBP again, obtain hole transmission layer spin coating liquid; Perovskite light absorbing zone film drips 30 μ L hole transmission layer spin coating liquid, then rotates 30s with the speed of 2000rpm, obtain hole transmission layer.
D, on hole transmission layer, evaporation 100nm Ag electrode, as top electrode, obtains perovskite solar cell.
After tested, the present embodiment gained perovskite solar cell J-V curve as shown in Figure 4, calculates the conversion efficiency of acquisition the present embodiment gained perovskite solar cell up to 11%.
Embodiment 2
The present embodiment prepares perovskite solar cell by the mode that embodiment 1 is identical, and difference is:
1, step a adopts and prepares compacted zone TiO with the following method
2film:
By 0.5ml TiCl
4be added drop-wise in 2ml absolute ethyl alcohol, and then add 10ml phenmethylol and obtain yellow solution; Yellow solution water-bath 8h at 80 DEG C is obtained milky white solution, in milky white solution, adds extracted with diethyl ether go out TiO to be cleaned
2precipitation, cleans TiO to be cleaned with ethanol and ether successively
2precipitate 3 times, then centrifugal go out TiO
2precipitation;
By TiO
2in ethanol, obtaining concentration is 8mg/ml TiO in precipitation dispersion
2alcohol dispersion liquid, then at 10ml TiO
2alcohol dispersion liquid in add two (acetylacetone based) diisopropyls titanate esters (TiAcac) of 0.2ml as stabilizer, obtain TiO
2spin coating liquid;
50 μ LTiO are dripped on the whole at the FTO film of FTO electro-conductive glass
2spin coating liquid, and rotate 30s with the speed of 2000rpm, namely the 30min that then anneals at 150 DEG C obtains compacted zone TiO
2film.
2, in step b3, gaseous sources position place is heated to 250 DEG C, and reactant position place is heated 70 DEG C, and reaction 20min, obtains the CH as perovskite light absorbing zone film
3nH
3pbI
3film;
Calculating the conversion efficiency obtaining the present embodiment gained perovskite solar cell is 7%.
Embodiment 3
The present embodiment prepares perovskite solar cell by the mode that embodiment 2 is identical:
Difference is: in step b3, gaseous sources position place is heated to 250 DEG C, and reactant position place is heated 200 DEG C, and reaction 80min, obtains the CH as perovskite light absorbing zone film
3nH
3pbI
3film;
Calculating the conversion efficiency obtaining the present embodiment gained perovskite solar cell is 8%.
Embodiment 4
The present embodiment prepares perovskite solar cell by the mode that embodiment 2 is identical:
Difference is: in step b3, gaseous sources position place is heated to 200 DEG C, and reactant position place is heated to 100 DEG C, and reaction 120min, obtains the CH as perovskite light absorbing zone film
3nH
3pbI
3film;
Calculating the conversion efficiency obtaining the present embodiment gained perovskite solar cell is 8%.
Embodiment 5
The present embodiment prepares perovskite solar cell by the mode that embodiment 2 is identical:
Difference is: in step b3, gaseous sources position place is heated to 180 DEG C, and reactant position place is heated 100 DEG C, and reaction 40min, obtains the CH as perovskite light absorbing zone film
3nH
3pbI
3film;
Calculating the conversion efficiency obtaining the present embodiment gained perovskite solar cell is 6%.
Embodiment 6
The present embodiment prepares perovskite solar cell by the mode that embodiment 2 is identical:
Difference is:
1, in step b1 with chloromethane amine CH
3h
3cl powder is as gaseous sources, preparation method is: the HCl aqueous solution of to be the methylamine alcohol solution of 33wt% and 10mL mass concentration by 24mL mass concentration be 45wt%, reaction 2h obtains reactant liquor, 60 DEG C of precipitations obtained after drying described reactant liquor are dissolved in 80mL ethanol, add 300mL ether more wherein to extract as extractant, collect solid phase, centrifugal being precipitated is carried out to solid phase, to precipitation vacuumize 24h, obtain chloromethane amine CH
3h
3cl powder;
2, in step b3, gaseous sources position place is heated to 180 DEG C, and reactant position place is heated 70 DEG C, and reaction 80min, obtains the CH as perovskite light absorbing zone film
3nH
3pbI
3and CH
3nH
3pbCl
3mixed film;
Calculating the conversion efficiency obtaining the present embodiment gained perovskite solar cell is 3%.
Embodiment 7
The present embodiment prepares perovskite solar cell by the mode that embodiment 2 is identical:
Difference is: in step b3, gaseous sources position place is heated to 180 DEG C, and reactant position place is heated 100 DEG C, and reaction 150min, obtains the CH as perovskite light absorbing zone film
3nH
3pbI
3and CH
3nH
3pbCl
3mixed film;
Calculating the conversion efficiency obtaining the present embodiment gained perovskite solar cell is 1%.
Embodiment 8:
The present embodiment prepares perovskite solar cell by the mode that embodiment 6 is identical
Difference is:
1, in step b1 with iodine carbonamidine HC (NH
2)
2i powder is as gaseous sources, preparation method is: the hydriodic acid aqueous solution mixing by 4g formamidine acetate and 13.2g mass concentration being 45wt%, reaction 2h obtains reactant liquor, 60 DEG C of precipitations obtained after drying described reactant liquor are dissolved in 80mL ethanol, add 300mL ether more wherein to extract as extractant, collect solid phase, centrifugal being precipitated is carried out to solid phase, to precipitation vacuumize 24h, obtain iodine carbonamidine HC (NH
2)
2i powder;
2, in step b3, gaseous sources position place is heated to 180 DEG C, and reactant position place is heated 70 DEG C, and reaction 40min, obtains the HC (NH as perovskite light absorbing zone film
2)
2pbI
3film;
Calculating the conversion efficiency obtaining the present embodiment gained perovskite solar cell is 3%.
Embodiment 9:
The present embodiment prepares perovskite solar cell by the mode that embodiment 8 is identical:
Difference is: in step b3, gaseous sources position place is heated to 180 DEG C, and reactant position place is heated 100 DEG C, and reaction 40min, obtains the HC (NH as perovskite light absorbing zone film
2)
2pbI
3film; Calculating the conversion efficiency obtaining the present embodiment gained perovskite solar cell is 4%.
Embodiment 10
The present embodiment prepares perovskite solar cell by the method that embodiment 2 is identical, and difference is:
With PbCl in step b2
2film is as reactant, and preparation method is: electron transfer layer substrate being placed in plated film position, thermal evaporation deposition system vacuum chamber top, being placed on as evaporation source in crucible using 1g lead chloride, is 10 in vacuum degree
-4during Pa, start plated film, the plated film time is 10min, then takes out substrate, both obtains PbCl
2film.
In step b3, gaseous sources position place is heated to 180 DEG C, and reactant position place is heated 70 DEG C, and reaction 40min, obtains the CH as perovskite light absorbing zone film
3nH
3pbI
3film;
Calculating the conversion efficiency obtaining the present embodiment gained perovskite solar cell is 10%.
Embodiment 11
The present embodiment prepares perovskite solar cell by the method that embodiment 10 is identical, and difference is:
In step b3, gaseous sources position place is heated to 180 DEG C, and reactant position place is heated 100 DEG C, and reaction 40min, obtains the CH as perovskite light absorbing zone film
3nH
3pbI
3film;
Calculating the conversion efficiency obtaining the present embodiment gained perovskite solar cell is 8%.
Embodiment 12
The present embodiment prepares perovskite solar cell by the method that embodiment 10 is identical, and difference is:
With SnI in step b2
2film is as reactant, and preparation method is: described electron transfer layer substrate being placed in plated film position, thermal evaporation deposition system vacuum chamber top, being placed on as evaporation source in crucible using 1g stannous iodide, is 10 in vacuum degree
-4during Pa, start plated film, the plated film time is 10min, then takes out substrate, both obtains SnI
2film.
In step b3, gaseous sources position place is heated to 180 DEG C, and reactant position place is heated 70 DEG C, and reaction 40min, obtains the CH as perovskite light absorbing zone film
3nH
3snI
3film;
Calculating the conversion efficiency obtaining the present embodiment gained perovskite solar cell is 2%.
Embodiment 13
The present embodiment prepares perovskite solar cell by the mode that embodiment 2 is identical:
Difference is: with chloromethane amine CH in step b1
3h
3cl powder and iodine methylamine CH
3h
3i powder in mass ratio 1:1 mixes as gaseous sources.
Calculating the conversion efficiency obtaining the present embodiment gained perovskite solar cell is 12%.
Claims (8)
1. a chemical gas-phase deposition process for preparing for perovskite solar cell, is characterized in that carrying out as follows:
A, FTO film institute deposition compact layer TiO on the whole at FTO electro-conductive glass
2film is as electron transfer layer;
B, prepare perovskite light absorbing zone film by chemical vapour deposition technique on the electron transport layer;
C, on described perovskite light absorbing zone film, prepare 2,2', 7,7'-tetra-[N, N-bis-(4-methoxyphenyl) is amino]-9,9'-spiral shell two fluorenes layers as hole transmission layer;
D, on the hole transport layer evaporation Ag electrode or Au electrode, as top electrode, obtain perovskite solar cell.
2. preparation method according to claim 1, is characterized in that: described perovskite light absorbing zone film is the AMX with perovskite crystal structure
3film, wherein A is the organic or inorganic group of cation radius at 0.164nm ~ 0.259nm; M is Pb, Sn or Pb
xsn
1-xalloy; X is halogen.
3. preparation method according to claim 2, is characterized in that: described cation radius is methylamine CH at the organic or inorganic group of 0.164nm ~ 0.259nm
3nH
3or carbonamidine HC (NH
2)
2.
4. preparation method according to claim 1, is characterized in that: described electric transmission layer thickness is 20 ~ 100nm; Described perovskite light absorbing zone film thickness is 100 ~ 3000nm; Described thickness of hole transport layer is 20 ~ 500nm; Described top electrode thickness is 50 ~ 150nm.
5. preparation method according to claim 1, is characterized in that:
Step a is at the FTO film institute deposition compact layer TiO on the whole of FTO electro-conductive glass
2film as the method for electron transfer layer is:
Method one: FTO electro-conductive glass FTO film spin coating concentration be on the whole the isopropyl titanate ethanolic solution of 0.24mol/L, at 450 ~ 500 DEG C, sinter 30 ~ 60min in air, be then soaked in the TiCl of 40mM
4in the aqueous solution, 70 DEG C of process 30min, finally sinter 30 ~ 60min again, obtain compacted zone TiO at 450 ~ 500 DEG C of temperature
2film;
Method two: by TiCl
4be added drop-wise in absolute ethyl alcohol, and then add phenmethylol and obtain yellow solution, described TiCl
4, absolute ethyl alcohol and phenmethylol volume ratio be 1:4:20; Described yellow solution water-bath 8h at 80 DEG C is obtained milky white solution, in described milky white solution, adds extracted with diethyl ether go out TiO to be cleaned
2precipitation, successively with ethanol and the described TiO to be cleaned of ether cleaning
2precipitation, then centrifugal acquisition TiO
2precipitation;
By described TiO
2in ethanol, obtaining concentration is 3 ~ 15mg/ml TiO in precipitation dispersion
2alcohol dispersion liquid, then TiO described in 10ml
2alcohol dispersion liquid in add two (acetylacetone based) diisopropyl titanate esters of 0.1 ~ 0.3ml as stabilizer, obtain TiO
2spin coating liquid;
At the FTO film institute TiO described in spin coating on the whole of FTO electro-conductive glass
2spin coating liquid, namely the 30min that then anneals at 150 DEG C obtains compacted zone TiO
2film.
6. the preparation method according to claim 1,2 or 3, is characterized in that:
The method that step b prepares perovskite light absorbing zone film by chemical vapour deposition technique is on the electron transport layer:
Prepare PbI on the electron transport layer
2film, SnI
2film or PbCl
2film, as reactant, is positioned over the thermal treatment zone place of two temperature-area tubular furnace;
With iodine methylamine CH
3nH
3i, chloromethane amine CH
3nH
3cl, bromine methylamine CH
3nH
3br, iodine carbonamidine HC (NH
2)
2i, chloromethane amidine HC (NH
2)
2cl or bromine carbonamidine HC (NH
2)
2br as gaseous sources, or with iodine methylamine CH
3nH
3i and chloromethane amine CH
3nH
3described gaseous sources, as gaseous sources, is positioned over another thermal treatment zone place of two temperature-area tubular furnace by the mixture of Cl;
Described gaseous sources position is heated to 100 ~ 300 DEG C, described reactant position is heated to 50 ~ 300 DEG C simultaneously, namely isothermal reaction 10 ~ 300min obtains perovskite light absorbing zone film.
7. preparation method according to claim 6, is characterized in that:
Described iodine methylamine CH
3nH
3i is prepared as follows: the hydriodic acid aqueous solution mixing of to be the methylamine alcohol solution of 33wt% and 10mL mass concentration by 24mL mass concentration be 45wt%, reaction 2h obtains reactant liquor, 60 DEG C of precipitations obtained after drying reactant liquor are dissolved in 80mL ethanol, add 300mL ether more wherein to extract as extractant, collect solid phase, carry out centrifugal or suction filtration to solid phase to be precipitated, to precipitation vacuumize 24h, obtain iodine methylamine CH
3nH
3i powder;
Described chloromethane amine CH
3nH
3cl is prepared as follows: the HCl aqueous solution of to be the methylamine alcohol solution of 33wt% and 10mL mass concentration by 24mL mass concentration be 45wt%, reaction 2h obtains reactant liquor, 60 DEG C of precipitations obtained after drying reactant liquor are dissolved in 80mL ethanol, add 300mL ether more wherein to extract as extractant, collect solid phase, carry out centrifugal or suction filtration to solid phase to be precipitated, to precipitation vacuumize 24h, obtain chloromethane amine CH
3nH
3cl powder;
Described bromine methylamine CH
3nH
3br is prepared as follows: the HBr aqueous solution of to be the methylamine alcohol solution of 33wt% and 10mL mass concentration by 24mL mass concentration be 45wt%, reaction 2h obtains reactant liquor, 60 DEG C of precipitations obtained after drying reactant liquor are dissolved in 80mL ethanol, add 300mL ether more wherein to extract as extractant, collect solid phase, carry out centrifugal or suction filtration to solid phase to be precipitated, to precipitation vacuumize 24h, obtain bromine methylamine CH
3nH
3br powder;
Described iodine carbonamidine HC (NH
2)
2i is prepared as follows: the hydriodic acid aqueous solution mixing by 4g formamidine acetate and 13.2g mass concentration being 45wt%, reaction 2h obtains reactant liquor, 60 DEG C of precipitations obtained after drying reactant liquor are dissolved in 80mL ethanol, add 300mL ether more wherein to extract as extractant, collect solid phase, carry out centrifugal or suction filtration to solid phase to be precipitated, to precipitation vacuumize 24h, obtain iodine carbonamidine HC (NH
2)
2i powder;
Described chloromethane amidine HC (NH
2)
2cl is prepared as follows: the HCl aqueous solution by 4g formamidine acetate and 13.2g mass concentration being 45wt%, reaction 2h obtains reactant liquor, 60 DEG C of precipitations obtained after drying reactant liquor are dissolved in 80mL ethanol, add 300mL ether more wherein to extract as extractant, collect solid phase, carry out centrifugal or suction filtration to solid phase to be precipitated, to precipitation vacuumize 24h, obtain chloromethane amidine HC (NH
2)
2cl powder;
Described bromine carbonamidine HC (NH
2)
2br is prepared as follows: the HBr aqueous solution by 4g formamidine acetate and 13.2g mass concentration being 45wt%, reaction 2h obtains reactant liquor, 60 DEG C of precipitations obtained after drying reactant liquor are dissolved in 80mL ethanol, add 300mL ether more wherein to extract as extractant, collect solid phase, carry out centrifugal or suction filtration to solid phase to be precipitated, to precipitation vacuumize 24h, obtain bromine carbonamidine HC (NH
2)
2br powder;
Described PbI
2the preparation method of film is: compound concentration is the PbI of 1M
2dMF solution or PbI
2dMSO solution, and be heated to 70 DEG C, obtain PbI for subsequent use
2spin coating liquid; PbI for subsequent use described in spin coating on the electron transport layer
2spin coating liquid, and then the 10 ~ 30min that anneals at 70 DEG C, obtain PbI
2film;
Described PbCl
2film and described SnI
2film takes the method for thermal evaporation plated film to obtain.
8. preparation method according to claim 4, is characterized in that:
Step c prepares 2 on described perovskite light absorbing zone film, 2', 7,7'-tetra-[N, N-bis-(4-methoxyphenyl) is amino]-9,9'-spiral shell two fluorenes layer as the method for hole transmission layer is: by 72.3mg 2,2', 7,7'-tetra-[N, N-bis-(4-methoxyphenyl) is amino]-9,9'-spiral shell two fluorenes is dissolved in 1mL chlorobenzene, add the acetonitrile solution that 17.5 μ L concentration are two trifluoromethanesulfonimide lithiums of 520mg/mL, then add 28.8 μ L 4-tert .-butylpyridine, obtain hole transmission layer spin coating liquid; On described perovskite light absorbing zone film, hole transmission layer spin coating liquid described in spin coating, obtains hole transmission layer.
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