CN104934304B - A kind of method that mixed solvent induction regulating controlling by under room temperature obtains black cubic system perovskite thin film - Google Patents
A kind of method that mixed solvent induction regulating controlling by under room temperature obtains black cubic system perovskite thin film Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000012046 mixed solvent Substances 0.000 title claims abstract description 30
- 239000010409 thin film Substances 0.000 title claims abstract description 28
- 230000006698 induction Effects 0.000 title claims abstract description 20
- 230000001276 controlling effect Effects 0.000 title claims abstract description 18
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 26
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- -1 o-dichlorohenzene Natural products 0.000 claims description 6
- 238000004528 spin coating Methods 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- KZDTZHQLABJVLE-UHFFFAOYSA-N 1,8-diiodooctane Chemical class ICCCCCCCCI KZDTZHQLABJVLE-UHFFFAOYSA-N 0.000 claims description 3
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical class O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical class C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- AJXBTRZGLDTSST-UHFFFAOYSA-N amino 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ON AJXBTRZGLDTSST-UHFFFAOYSA-N 0.000 claims 1
- QXAITBQSYVNQDR-ZIOPAAQOSA-N amitraz Chemical compound C=1C=C(C)C=C(C)C=1/N=C/N(C)\C=N\C1=CC=C(C)C=C1C QXAITBQSYVNQDR-ZIOPAAQOSA-N 0.000 claims 1
- 229960002587 amitraz Drugs 0.000 claims 1
- HRHBQGBPZWNGHV-UHFFFAOYSA-N azane;bromomethane Chemical compound N.BrC HRHBQGBPZWNGHV-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims 1
- 229960002796 polystyrene sulfonate Drugs 0.000 claims 1
- 239000011970 polystyrene sulfonate Substances 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 32
- 238000000137 annealing Methods 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- AJRXEXGVDMEBCT-UHFFFAOYSA-M [NH4+].[I-].C[N+]1=CC=CC=C1.[I-] Chemical compound [NH4+].[I-].C[N+]1=CC=CC=C1.[I-] AJRXEXGVDMEBCT-UHFFFAOYSA-M 0.000 description 2
- IKUCKMMEQAYNPI-UHFFFAOYSA-N [Pb].CN.[I] Chemical group [Pb].CN.[I] IKUCKMMEQAYNPI-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-N iodic acid Chemical compound OI(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- RQQRAHKHDFPBMC-UHFFFAOYSA-L lead(ii) iodide Chemical compound I[Pb]I RQQRAHKHDFPBMC-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- LLWRXQXPJMPHLR-UHFFFAOYSA-N methylazanium;iodide Chemical compound [I-].[NH3+]C LLWRXQXPJMPHLR-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/20—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy
- H01L21/208—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy using liquid deposition
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
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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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- 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
Abstract
The invention discloses a kind of method that mixed solvent induction regulating controlling by under room temperature obtains black cubic system perovskite thin film.Specifically, the method for the present invention includes following steps：1）Perovskite precursor solution is prepared by mixing two kinds of donors in a solvent；2）Perovskite precursor solution is spin-coated in substrate under room temperature, obtains the substrate with perovskite active layer；And 3）Closed atmosphere is built using mixed solvent, and the substrate with perovskite active layer is placed in one and is made annealing treatment, until substrate is changed into black, up to black cubic system perovskite thin film.The method of the present invention carries out at normal temperatures, reduces the energy consumption in preparation process；Smooth, the measured perovskite crystal of crystalline can be quickly prepared at the same time, there is good homogeneity in large area, make it that there is good application prospect in the preparation of large area perovskite solar cell.
Description
Technical field
The invention belongs to solar cell material field, is related to a kind of mixed solvent induction regulating controlling by under room temperature and obtains
The method of black cubic system perovskite thin film, and the black cubic system perovskite thin film obtained by this method.
Background technology
Material for perovskite solar cell is a kind of satisfaction（1）Chemical general formula for ABX3,（2）Organic and inorganic is miscellaneous
Change and（3）Metal halide with conditions such as perovskite configurations, wherein A represent methylamine（CH3NH3 +）, first narrows（NH2-CH=
NH2 +）Deng monovalent cation, B represents lead（Pb）, tin（Sn）Deng bivalent metal ion, X represents chlorine（Cl）, bromine（Br）, iodine（I）Deng
Monovalence halide ion, and it is methylamine lead iodine to study at present more（CH3NH3PbI3）With methylamine lead iodine chlorine（CH3NH3PbIxCl3-x）
Both materials.Perovskite material has high absorption coefficient, balanced electronics and the electric charge of hole migration ability and length
The characteristics such as transmission range.Just because of with balanced electronics and cavity transmission ability, it both may be used as the perovskite of light absorbent
For p-i-n structure, the solar cell of p-n structure is can be used for, this causes perovskite solar cell in structure
With very big flexibility.
At present, research of the people for perovskite solar cell is concentrated mainly on the following aspects：First, it is directed to calcium
The research of titanium ore class material composition, i.e., by replacing and mixing ABX3First usually research material such as A, B, X in structural formula is in band
Effect in gap, energy level, dielectric property and photovoltaic property etc. change；Second, for perovskite solar battery structure with
And the research on interface engineering, i.e., by the optimization to device architecture and interface, make device energy conversion efficiency obtain it is very big
Lifting；Third, the research of photovoltaic device is prepared for perovskite material, such as a used step when preparing perovskite thin film
The methods of method, two-step method, vapour deposition process, mixed solvent dissolving.What these processes were mainly formed by varying perovskite crystal
Speed and process, so as to obtain the perovskite thin film that purity is high, crystal particle scale is homogeneous, surfacing, coverage rate are high.In general, calcium
Titanium ore crystal has three kinds of crystal forms：Cubic system, tetragonal crystal system and rhombic system.With the reduction of temperature, these three crystal forms it
Between crystal transition can occur.In the preparation process of perovskite solar cell device, after generally use is to solution spin coating
Substrate carry out heating anneal method come promote crystal occur phase in version, stood so as to obtain the black with high-energy conversion efficiency
Prismatic crystal system perovskite crystal.
In consideration of it, seek a kind of easier, easy and method for effectively obtaining black cubic system perovskite thin film,
And then the energy conversion efficiency of perovskite solar cell is significantly improved, have become one of this area urgent problem to be solved,
With important economic development value and scientific research reference value.
The content of the invention
In order to solve the above-mentioned technical problem, the method that the present invention is grown using mixed solvent induction regulating controlling perovskite crystal,
Promote perovskite material that crystal transition can occur at normal temperatures, and obtain required black cubic system film.Pass through
The surfacing of perovskite thin film prepared by this method, the film of the crystallinity of crystal also than being prepared by common heating method are brilliant
Body is much higher.
Specifically, the present invention provides a kind of mixed solvent induction regulating controlling by under room temperature to obtain black cubic system
The method of perovskite thin film, it includes the following steps：
1）Prepare perovskite precursor solution：It is 1 by molar ratio under inert gas shielding:1 ~ 5, preferably 1:3 A donors
It is dissolved in solvent with B donors, until the mass concentration of solute reaches 35 ~ 50%, preferably 40% in mixed solution, is stirred under room temperature
Mix 8 ~ 24 it is small when, obtain perovskite precursor solution；
2）Spin coating perovskite precursor solution：Under inert gas shielding, by step 1）In obtained perovskite precursor solution
It is spin-coated under room temperature in substrate, obtains the substrate with perovskite active layer；
3）Mixed solvent induction regulating controlling：At normal temperatures, closed atmosphere is built using mixed solvent, and by step 2）In obtain
The substrate with perovskite active layer be placed in one and carry out solvent anneal processing, until the base for carrying perovskite active layer
Bottom is changed into black, obtains black cubic system perovskite thin film.
Preferably, in the above-mentioned technical solutions, step 1）Described in A donors be selected from lead chloride（PbCl2）, lead bromide
（PbBr2）, lead iodide（PbI2）In any one, preferably lead chloride or lead iodide, more preferably lead chloride.
Preferably, in the above-mentioned technical solutions, step 1）Described in B donors be selected from ammonio methacrylate（CH3NH3Cl）, carbonamidine
Hydrochloride（NH2-CH=NH·HCl）, methyl bromide ammonium（CH3NH3Br）, carbonamidine hydrobromate（NH2-CH=NH·HBr）, methyl
Ammonium iodide（CH3NH3I）, carbonamidine hydriodate（NH2-CH=NH·HI）In any one, preferably methylpyridinium iodide ammonium or carbonamidine hydrogen
Iodate, more preferably methylpyridinium iodide ammonium.
Preferably, in the above-mentioned technical solutions, step 1）In be used to dissolve the solvent of A donors and B donors and be selected from two
Methylformamide（DMF）, dimethyl sulfoxide (DMSO)（DMSO）, any one in gamma-butyrolacton, preferably dimethylformamide.
Preferably, in the above-mentioned technical solutions, in step 1）Described in stirring start before, into the mixed solution plus
Enter and be calculated as 0.5 ~ 5% with percent by volume, preferably 1% additive；The additive is selected from methyl pyrrolidone（NMP）、1,8-
Pungent two mercaptan（OT）, 1,8- diiodo-octanes（DIO）, 1- chloronaphthalenes（CN）In any one, preferably 1,8- diiodo-octanes or methyl
Pyrrolidones, more preferably 1,8- diiodo-octanes.
Preferably, in the above-mentioned technical solutions, in step 1）Described in stirring complete after, by extra filtration step
Obtain perovskite precursor solution；The filtration step is preferably by means of filter, more preferably polytetrafluoroethylene (PTFE) filter, most preferably 0.45
The polytetrafluoro filter in μm aperture is completed.
Preferably, in the above-mentioned technical solutions, step 2）Described in the speed of spin coating be 2000 ~ 5000rpm, preferably
3000rpm。
Preferably, in the above-mentioned technical solutions, step 2）Described in substrate be by poly- 3,4- ethylenedioxy thiophenes/polyphenyl second
Alkene sulfonate（PEDOT:PSS）It is spin-coated on ITO electro-conductive glass obtained；The poly- 3,4- ethylenedioxy thiophenes/polystyrene
The thickness of sulfonate is 20 ~ 40nm, its structure is as follows：
。
Preferably, in the above-mentioned technical solutions, step 3）Described in mixed solvent be dimethylformamide（DMF）Or two
First sulfoxide（DMSO）With the mixture of any one in chlorobenzene, o-dichlorohenzene, paraxylene, chloroform, preferably dimethyl formyl
The mixture of amine and chlorobenzene, and the volume ratio of dimethylformamide and chlorobenzene is 1:10~1:30.
Preferably, in the above-mentioned technical solutions, inert gas described in the above method is selected from nitrogen（N2）, neon（Ne）、
Argon gas（Ar）In any one, preferred nitrogen.
On the other hand, the black cubic system perovskite thin film obtained according to the above method is claimed in the present invention.
Another further aspect, the present invention are also claimed above-mentioned black cubic system perovskite thin film and are preparing photovoltaic device, special
It is not the purposes in perovskite solar cell.
Compared with prior art, using above-mentioned technical proposal the invention has the advantages that：
1st, traditional heating anneal phase in version method needs to be heated to 100 DEG C or so, and when needing continuous heating 1 small with
On；And the method for the present invention then carries out at normal temperatures, smooth, the measured perovskite crystal of crystalline can be quickly prepared, it is whole
A transition process only needs to complete for 1 ~ 30 minute, and manufacturing cycle greatly shortens；
2nd, the crystallinity of the perovskite crystal obtained by the method for the present invention is very high, with common heating method for annealing phase
Than being located in its XRD spectra（110）、（220）Diffraction direction（At 2 θ=110 ° and 220 °）The intensity of diffraction maximum to be higher by four
More than times；
3rd, compared with the conventional method that heating promotes calcium titanium ore bed that phase in version occurs, the present invention is not required to when preparing calcium titanium ore bed
Heat；On the one hand, the application for being perovskite material in plastic flexible substrate provides possibility, and another aspect, also reduces
Energy consumption in preparation process；
4th, perovskite crystal prepared by the present invention has good homogeneity in large area so that such a method is in big face
There is application well in the preparation of product perovskite solar cell；
5th, under same solar cell device structure, prepared by the mixed solvent induction regulating controlling method under room temperature
During device of the perovskite thin film as active layer, its open-circuit voltage and fill factor, curve factor are all higher, hence it is evident that better than based on common heating
Method prepares the solar cell of perovskite thin film.
Brief description of the drawings
Fig. 1 is based on two kinds of distinct methods（Heating/mixed solvent induction）The XRD spectra of the perovskite thin film of preparation.
Fig. 2 is based on two kinds of distinct methods（Heating/mixed solvent induction）The J-V characteristic curves of the solar cell of preparation
Figure.
Fig. 3 is large area（1.21cm2）The J-V performance diagrams of perovskite solar cell.
Embodiment
Further explanation and explanation are made to the present invention with specific embodiment below in conjunction with the accompanying drawings.Such as without special theory
Bright, the materials, reagents and the like used in the following examples commercially obtains.
Embodiment 1：Black cubic system perovskite crystal is obtained by the mixed solvent induction regulating controlling under room temperature.
（1）In N2Under protection, by PbCl2（198.0mg, 0.7mmol）With CH3NH3I（339.6mg, 2.1mmol）Dissolving
In DMF（0.85mL）In（Mass concentration is 40%）, then add DIO（8.5μL）, and 12h is stirred under room temperature, until solute
It is completely dissolved, obtains perovskite precursor solution；
（2）In N2In glove box, above-mentioned precursor solution is spin-coated on PEDOT under room temperature with the speed of 3000rpm:
In the ITO electro-conductive glass substrates of PSS, thickness is about 350nm, obtains the substrate with perovskite active layer；
（3）At normal temperatures, the above-mentioned substrate with calcium titanium ore bed is placed in by DMF/ chlorobenzene mixed solvents（1:10, v/v）
Annealing 6min is carried out in the closed atmosphere of construction, obtains black cubic system perovskite crystal.
Test and find compared with carrying out XRD by crystal made from traditional heating anneal method, have successfully been obtained required
The black cubic system perovskite thin film wanted, the results are shown in Figure 1 for it.As seen from the figure, two methods prepare crystal 2 θ=
All occur diffraction maximum at 110 ° and 220 °, and pass through the diffraction maximum of perovskite crystal made from mixed solvent induction regulating controlling method
Intensity is higher（It is more than six times higher than the diffraction peak intensity of common crystal）, illustrate that it has very high crystalline order degree, and it is higher
Crystalline order degree be then the necessary condition for realizing efficient perovskite solar cell.
Embodiment 2：Black cubic system perovskite crystal is obtained by the mixed solvent induction regulating controlling under room temperature.
（1）In N2Under protection, by PbCl2（198.0mg, 0.7mmol）With CH3NH3I（339.6mg, 2.1mmol）It is dissolved in
DMF（0.85mL）In（Mass concentration is 40%）, in stirring at normal temperature 12h, until solute is completely dissolved, it is molten to obtain perovskite precursor
Liquid；
（2）Experimental procedure is the same as the step in embodiment 1（2）；
（3）At normal temperatures, the above-mentioned substrate with calcium titanium ore bed is placed in by DMF/ chlorobenzene mixed solvents（1:30, v/v）
Annealing 10min is carried out in the closed atmosphere of construction, obtains black cubic system perovskite crystal.
Tested and found by XRD, have successfully been obtained required black cubic system perovskite thin film.
Embodiment 3：Black cubic system perovskite crystal is obtained by the mixed solvent induction regulating controlling under room temperature.
（1）In N2Under protection, by PbCl2（115.0mg, 0.4mmol）With CH3NH3I（201.2mg, 1.2mmol）It is dissolved in
DMF（0.5mL）In（Mass concentration is 40%）, then add DIO（5μL）, and 12h is stirred under room temperature, and with 0.45 μm of aperture
Polytetrafluoro filter filtering, obtain perovskite precursor solution；
（2）In N2In glove box, above-mentioned precursor solution is spin-coated on PEDOT under room temperature with the speed of 3000rpm:
In the ITO electro-conductive glass substrates of PSS, until thickness is about 350nm, the substrate with perovskite active layer is obtained；
（3）At normal temperatures, the above-mentioned substrate with calcium titanium ore bed is placed in by DMF/ chlorobenzene mixed solvents（1:10, v/v）
Annealing 10min is carried out in the closed atmosphere of construction, obtains black cubic system perovskite crystal.
Tested and found by XRD, have successfully been obtained the perovskite thin film of required black cubic system.
Embodiment 4：Black cubic system perovskite crystal is obtained by the mixed solvent induction regulating controlling under room temperature.
（1）In N2Under protection, by PbCl2（198.0mg, 0.7mmol）With CH3NH3I（226.4mg, 1.4mmol）It is dissolved in
DMF（0.64mL）In（Mass concentration is 40%）, then add OT（19.2μL）, and 12h is stirred under room temperature, and with 0.45 μm
The polytetrafluoro filter filtering in aperture, obtains perovskite precursor solution.
（2）In N2In gas glove box, above-mentioned precursor solution is spin-coated under room temperature with the speed of 3000rpm and is carried
PEDOT:In the ITO electro-conductive glass substrates of PSS, until thickness is 350nm, the substrate with perovskite active layer is obtained；
（3）The above-mentioned substrate with calcium titanium ore bed is placed in by DMF/ chlorobenzene mixed solvents（1:10, v/v）That builds is closed
Annealing 10min is carried out in atmosphere, obtains black cubic system perovskite crystal.
Find to successfully obtain the perovskite crystal of required black cubic system by XRD tests.
Embodiment 5：The perovskite crystal obtained by mixed solvent induction regulating controlling is applied in solar cells.
By obtained perovskite thin film difference in the perovskite thin film prepared by common heating method for annealing and embodiment 1
As solar cell（Active area 0.04cm2）In photoactive layer, compare the photoelectric properties of the two whereby, its current density
（J）With voltage（V）Between quantitative relationship（J-VCharacteristic curve）As shown in Figure 2.As shown in Figure 2, with common perovskite thin film phase
Than the photoelectric conversion efficiency of the perovskite thin film prepared based on mixed solvent induction regulating controlling method is increased, its highest photoelectricity
Transfer efficiency is about 15 ~ 16%.
In addition, the present inventor also attempts to prepare the perovskite solar cell of large area in the same way（Active area
1.21cm2）, itsJ-VCharacteristic curve is as shown in Figure 3.By calculating, the photoelectric conversion efficiency of the solar energy in large area battery
About 9% ~ 11%.
The above results show, can be prepared by the method for the growth of mixed solvent induction regulating controlling perovskite crystal and phase in version
It is good to go out crystalline quality（Crystallinity is high）And homogeneous perovskite thin film in large area, can be effective for preparing with higher
The perovskite solar cell of photoelectric conversion efficiency.
Claims (14)
1. a kind of method that mixed solvent induction regulating controlling by under room temperature obtains black cubic system perovskite thin film, it includes
Following steps：
1）Prepare perovskite precursor solution：It is 1 by molar ratio under inert gas shielding:1 ~ 5 A donors are dissolved in B donors
In solvent, until the mass concentration of solute reaches 35 ~ 50% in mixed solution, when stirring 8 ~ 24 is small under room temperature, perovskite is obtained
Precursor solution；
2）Spin coating perovskite precursor solution：Under inert gas shielding, by step 1）In obtained perovskite precursor solution in normal
It is spin-coated under temperature in substrate, obtains the substrate with perovskite active layer；
3）Mixed solvent induction regulating controlling：At normal temperatures, closed atmosphere is built using mixed solvent, and by step 2）In obtained band
The substrate for having perovskite active layer, which is placed in one, carries out solvent anneal processing, until the substrate with perovskite active layer becomes
For black, black cubic system perovskite thin film is obtained；
Step 1）Described in any one of A donors in lead chloride, lead bromide, lead iodide；
Step 1）Described in B donors be selected from ammonio methacrylate, amitraz hydrochloride, methyl bromide ammonium, carbonamidine hydrobromate, methyl iodide
Change any one in ammonium, carbonamidine hydriodate；
Step 1）In be used to dissolve the solvent of A donors and B donors and be selected from dimethylformamide, dimethyl sulfoxide (DMSO), γ-Ding Nei
Any one in ester；
Step 3）Described in mixed solvent be dimethylformamide or dimethyl sulfoxide and chlorobenzene, o-dichlorohenzene, paraxylene, chlorine
The volume ratio of the mixture of any one in imitative, dimethylformamide and chlorobenzene is 1:10~1:30；
Step 3）The time of middle solvent anneal processing is 6 ~ 10 minutes.
2. according to the method described in claim 1, it is characterized in that：
Step 1）It is middle by molar ratio be 1:3 A donors are dissolved in solvent with B donors, up to the quality of solute in mixed solution
Concentration reaches 40%.
3. according to the method described in claim 1, it is characterized in that：
In step 1）Described in before stirring starts, add into the mixed solution and be calculated as 0.5 ~ 5% with percent by volume and add
Add agent；
Any one of the additive in methyl pyrrolidone, pungent two mercaptan of 1,8-, 1,8- diiodo-octanes, 1- chloronaphthalenes.
4. according to the method described in claim 3, it is characterized in that：
In step 1）Described in stirring start before, into the mixed solution add be calculated as with percent by volume 1% addition
Agent.
5. according to the method described in claim 1, it is characterized in that：
In step 1）Described in stirring complete after, obtain perovskite precursor solution by extra filtration step.
6. according to the method described in claim 5, it is characterized in that：
The filtration step is completed preferably by means of filter.
7. according to the method described in claim 6, it is characterized in that：
The filtration step is completed preferably by means of polytetrafluoroethylene (PTFE) filter.
8. according to the method described in claim 7, it is characterized in that：
The filtration step is completed preferably by means of the polytetrafluoro filter in 0.45 μm of aperture.
9. according to the method described in claim 1, it is characterized in that：
Step 2）Described in the speed of spin coating be 2000 ~ 5000rpm.
10. according to the method described in claim 9, it is characterized in that：
Step 2）Described in the speed of spin coating be 3000rpm.
11. according to the method described in claim 1, it is characterized in that：
Step 2）Described in substrate be that poly- 3,4- ethylenedioxy thiophenes/poly styrene sulfonate is spin-coated on ITO electro-conductive glass
It is obtained.
12. according to the method described in claim 1, it is characterized in that：
Any one of the inert gas in nitrogen, neon, argon gas.
13. the black cubic system perovskite thin film that method according to any one of claim 1 to 12 obtains.
14. purposes of the black cubic system perovskite thin film according to claim 13 in photovoltaic device is prepared.
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Inventor after: Song Bo Inventor after: Zhou Dai Inventor after: Li Yongfang Inventor after: Yu Hao Inventor after: Liu Xiaodong Inventor before: Zhou Dai Inventor before: Song Bo Inventor before: Li Yongfang Inventor before: Yu Hao Inventor before: Liu Xiaodong |