CN104934304A - Method for obtaining black cubic crystal system perovskite film through inductive regulation and control of mixed solvent at normal temperature - Google Patents
Method for obtaining black cubic crystal system perovskite film through inductive regulation and control of mixed solvent at normal temperature Download PDFInfo
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- CN104934304A CN104934304A CN201510299389.9A CN201510299389A CN104934304A CN 104934304 A CN104934304 A CN 104934304A CN 201510299389 A CN201510299389 A CN 201510299389A CN 104934304 A CN104934304 A CN 104934304A
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- perovskite
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- 238000000034 method Methods 0.000 title claims abstract description 61
- 239000012046 mixed solvent Substances 0.000 title claims abstract description 30
- 239000013078 crystal Substances 0.000 title abstract description 35
- 230000001939 inductive effect Effects 0.000 title abstract 2
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 238000000137 annealing Methods 0.000 claims abstract description 9
- 239000002904 solvent 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 60
- 239000010409 thin film Substances 0.000 claims description 26
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- 230000006698 induction Effects 0.000 claims description 18
- 230000001276 controlling effect Effects 0.000 claims description 16
- 230000001105 regulatory effect Effects 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 7
- KZDTZHQLABJVLE-UHFFFAOYSA-N 1,8-diiodooctane Chemical compound ICCCCCCCCI KZDTZHQLABJVLE-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000004528 spin coating Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- 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 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 claims description 3
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 3
- 229960002796 polystyrene sulfonate Drugs 0.000 claims description 3
- 239000011970 polystyrene sulfonate Substances 0.000 claims description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 2
- AJXBTRZGLDTSST-UHFFFAOYSA-N amino 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ON AJXBTRZGLDTSST-UHFFFAOYSA-N 0.000 claims description 2
- 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 description 2
- 229960002587 amitraz Drugs 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- HRHBQGBPZWNGHV-UHFFFAOYSA-N azane;bromomethane Chemical compound N.BrC HRHBQGBPZWNGHV-UHFFFAOYSA-N 0.000 claims description 2
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 2
- LLWRXQXPJMPHLR-UHFFFAOYSA-N methylazanium;iodide Chemical compound [I-].[NH3+]C LLWRXQXPJMPHLR-UHFFFAOYSA-N 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
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- 238000009987 spinning Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 5
- 229920000144 PEDOT:PSS Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000007704 transition Effects 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- OAAKZKGKPMPJIF-UHFFFAOYSA-N [Cl].[I] Chemical compound [Cl].[I] OAAKZKGKPMPJIF-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
- 230000005540 biological transmission Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 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
- 238000002474 experimental method Methods 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
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 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
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- H01L21/208—
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
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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
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- Condensed Matter Physics & Semiconductors (AREA)
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- Engineering & Computer Science (AREA)
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- Microelectronics & Electronic Packaging (AREA)
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Abstract
The invention discloses a method for obtaining a black cubic crystal system perovskite film through inductive regulation and control of a mixed solvent at a normal temperature. The method specifically comprises the following steps: 1, preparing a perovskite precursor solution through mixing two donors in a solvent; 2, coating the perovskite precursor solution on a substrate by spinning at the normal temperature to obtain the substrate with a perovskite active layer; and 3, creating an enclosed atmosphere by use of the mixed solvent and placing the substrate with the perovskite active layer into the atmosphere for annealing processing until the substrate becomes black so as to obtain the black cubic crystal system perovskite film. According to the invention, the method is carried out at the normal temperature so that energy consumption in a preparation process is reduced; and at the same time, flat perovskite crystals with good crystallization quality can be rapidly prepared, the uniformity is good in a large area, and the method has quite good application prospect in preparation of a large-area perovskite solar battery.
Description
Technical field
The invention belongs to solar cell material field, relate to a kind of method being obtained black cubic system perovskite thin film by the mixed solvent induction regulating controlling under normal temperature, and by the black cubic system perovskite thin film that this method obtains.
Background technology
Material for perovskite solar cell is the metal halide that a class meets that (1) chemical general formula is ABX3, (2) hybrid inorganic-organic and (3) have the conditions such as perovskite configuration, and wherein A represents methylamine (CH
3nH
3 +), first narrows (NH
2-CH=NH
2 +) etc. monovalent cation, B represents the plumbous bivalent metal ion such as (Pb), tin (Sn), and X represents the monovalence halide ions such as chlorine (Cl), bromine (Br), iodine (I), and to study more be at present the plumbous iodine (CH of methylamine
3nH
3pbI
3) and the plumbous iodine chlorine of methylamine (CH
3nH
3pbI
xcl
3-x) this bi-material.Perovskite material has high absorption coefficient, balanced electronics and the characteristic such as hole migration ability and long transferring charge distance.Just because of have balanced electronics and cavity transmission ability, its perovskite as light absorbent both may be used for p-i-n junction structure, also may be used for the solar cell of p-n junction structure, and this makes perovskite solar cell structurally have very large flexibility.
At present, people mainly concentrate on the following aspects for the research of perovskite solar cell: one is the research for perovskite material composition, namely by replacing and mixing ABX
3effect during first usually research material such as A, B, X in structural formula changes in band gap, energy level, dielectric property and photovoltaic property etc.; Two is for the research on perovskite solar battery structure and interface engineering, namely by the optimization to device architecture and interface, the energy conversion efficiency of device is greatly improved; Three is the research preparing photovoltaic device for perovskite material, the method such as the one-step method such as adopted when preparing perovskite thin film, two-step method, vapour deposition process, mixed solvent dissolving.These processes mainly through the speed that changes perovskite crystal and formed and process, thus obtain that purity is high, crystal particle scale is homogeneous, surfacing, perovskite thin film that coverage rate is high.Usually, perovskite crystal has three kinds of crystal formations: cubic system, tetragonal crystal system and rhombic system.Along with the reduction of temperature, between these three kinds of crystal formations, crystal transition can be there is.In the preparation process of perovskite solar cell device, usually adopt and the way of heating anneal is carried out to impel crystal generation phase in version to the substrate after solution spin coating, thus obtain the black cubic system perovskite crystal with high-energy conversion efficiency.
Given this, seek a kind of easier, easy and effectively obtain the method for black cubic system perovskite thin film, and then significantly improve the energy conversion efficiency of perovskite solar cell, become one of this area problem demanding prompt solution, there is important economic development value and scientific research reference value.
Summary of the invention
In order to solve the problems of the technologies described above, the method that the present invention adopts mixed solvent induction regulating controlling perovskite crystal to grow, impels perovskite material just crystal transition can occur at normal temperatures, and the black cubic system film required for obtaining.The surfacing of the perovskite thin film prepared by the method, the degree of crystallinity of crystal is also higher than the film crystal prepared by common heating method a lot.
Specifically, the invention provides a kind of method being obtained black cubic system perovskite thin film by the mixed solvent induction regulating controlling under normal temperature, it comprises the steps:
1) preparing perovskite precursor solution: under inert gas shielding, is 1:1 ~ 5 by mol ratio, and A donor and the B donor of preferred 1:3 are dissolved in solvent, until the mass concentration of solute reaches 35 ~ 50% in mixed solution, preferably 40%, stir 8 ~ 24 hours under normal temperature, obtain perovskite precursor solution;
2) spin coating perovskite precursor solution: under inert gas shielding, is spin-coated in substrate by the perovskite precursor solution obtained in step 1), obtains the substrate with perovskite active layer under normal temperature;
3) mixed solvent induction regulating controlling: at normal temperatures, mixed solvent is adopted to build closed atmosphere, and by step 2) in the substrate with perovskite active layer that obtains be placed in one and carry out solvent annealing in process, until the described substrate with perovskite active layer becomes black, obtain black cubic system perovskite thin film.
Preferably, in technique scheme, the donor of A described in step 1) is selected from lead chloride (PbCl
2), lead bromide (PbBr
2), lead iodide (PbI
2) in any one, preferred lead chloride or lead iodide, more preferably lead chloride.
Preferably, in technique scheme, the donor of B described in step 1) is selected from ammonio methacrylate (CH
3nH
3cl), amitraz hydrochloride (NH
2-CH=NHHCl), methyl bromide ammonium (CH
3nH
3br), carbonamidine hydrobromate (NH
2-CH=NHHBr), methylpyridinium iodide ammonium (CH
3nH
3i), carbonamidine hydriodate (NH
2-CH=NHHI) in any one, preferable methyl ammonium iodide or carbonamidine hydriodate, more preferably methylpyridinium iodide ammonium.
Preferably, in technique scheme, the described solvent for dissolving A donor and B donor in step 1) be selected from dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), gamma-butyrolacton any one, preferred dimethyl formamide.
Preferably, in technique scheme, before stirring described in step 1) starts, add in described mixed solution and count 0.5 ~ 5% with percent by volume, the preferably additive of 1%; Described additive be selected from methyl pyrrolidone (NMP), 1,8-pungent two mercaptan (OT), 1,8-diiodo-octane (DIO), 1-chloronaphthalene (CN) any one, preferably 1,8-diiodo-octane or methyl pyrrolidone, more preferably 1,8-diiodo-octane.
Preferably, in technique scheme, after having stirred described in step 1), obtain perovskite precursor solution through extra filtration step; Described filtration step is preferably by means of filter, and more preferably polytetrafluoroethylene filter, most preferably the polytetrafluoro filter in 0.45 μm of aperture has come.
Preferably, in technique scheme, step 2) described in the speed of spin coating be 2000 ~ 5000rpm, preferred 3000rpm.
Preferably, in technique scheme, step 2) described in substrate poly-3,4-ethylene dioxythiophene/poly styrene sulfonate (PEDOT:PSS) is spin-coated on ITO electro-conductive glass obtained; The thickness of described poly-3,4-ethylene dioxythiophene/poly styrene sulfonate is 20 ~ 40nm, and its structure is as follows:
。
Preferably, in technique scheme, mixed solvent described in step 3) is dimethyl formamide (DMF) or methyl-sulfoxide (DMSO) and any one the mixture in chlorobenzene, o-dichlorohenzene, paraxylene, chloroform, the mixture of preferred dimethyl formamide and chlorobenzene, and the volume ratio of dimethyl formamide and chlorobenzene is 1:10 ~ 1:30.
Preferably, in technique scheme, inert gas described in said method is selected from nitrogen (N
2), any one in neon (Ne), argon gas (Ar), preferred nitrogen.
On the other hand, request protection of the present invention is according to the black cubic system perovskite thin film of said method acquisition.
Again on the one hand, the present invention also asks to protect above-mentioned black cubic system perovskite thin film preparing photovoltaic device, the purposes particularly in perovskite solar cell.
Compared with prior art, the tool of the present invention of technique scheme is adopted to have the following advantages:
1, traditional heating anneal phase in version method needs to be heated to about 100 DEG C, and needs continuous heating more than 1 hour; Method of the present invention is then carried out at normal temperatures, and can prepare smooth, the measured perovskite crystal of crystalline fast, whole transition process only needs to complete for 1 ~ 30 minute, and manufacturing cycle shortens greatly;
The degree of crystallinity of the perovskite crystal 2, obtained by method of the present invention is very high, compared with common heating method for annealing, the intensity being positioned at the diffraction maximum of (110), (220) diffraction direction (2 θ=110 ° and 220 ° of places) in its XRD spectra will exceed more than four times;
3, compared with the conventional method impelling calcium titanium ore bed generation phase in version with heating, heating when the present invention prepares calcium titanium ore bed, is not needed; On the one hand, for perovskite material provides possibility in the suprabasil application of plastic flexible, on the other hand, the energy consumption in preparation process is also reduced;
4, the perovskite crystal that prepared by the present invention has good homogeneity in large area, makes this kind of method in the preparation of large area perovskite solar cell, have good application;
5, under same solar cell device structure, during the device of the perovskite thin film prepared by the mixed solvent induction regulating controlling method under normal temperature as active layer, its open circuit voltage and fill factor, curve factor are all higher, are obviously better than the solar cell preparing perovskite thin film based on common heating method.
Accompanying drawing explanation
The XRD spectra of perovskite thin film of Fig. 1 for preparing based on two kinds of distinct methods (induction of heating/mixed solvent).
The J-V performance diagram of solar cell of Fig. 2 for preparing based on two kinds of distinct methods (induction of heating/mixed solvent).
Fig. 3 is large area (1.21cm
2) the J-V performance diagram of perovskite solar cell.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment, further explanation and explanation are made to the present invention.If no special instructions, material, reagent etc. used in following embodiment all can obtain from commercial channels.
Embodiment 1: obtain black cubic system perovskite crystal by the mixed solvent induction regulating controlling under normal temperature.
(1) at N
2under protection, by PbCl
2(198.0mg, 0.7mmol) and CH
3nH
3i(339.6mg, 2.1mmol) be dissolved in DMF(0.85mL) in (mass concentration is 40%), then add DIO(8.5 μ L), and stir 12h under normal temperature, until solute dissolves completely, obtain perovskite precursor solution;
(2) at N
2in glove box, be spin-coated in the ITO electro-conductive glass substrate with PEDOT:PSS with the speed of 3000rpm under normal temperature by above-mentioned precursor solution, 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 the closed atmosphere of being built by DMF/ chlorobenzene mixed solvent (1:10, v/v) and carries out annealing in process 6min, obtain black cubic system perovskite crystal.
Carry out XRD compare test discovery with the crystal obtained by traditional heating anneal method, have successfully been obtained required black cubic system perovskite thin film, its result as shown in Figure 1.As seen from the figure, the crystal prepared of two kinds of methods in 2 θ=110 ° and 220 ° of places all there is diffraction maximum, and the diffraction peak intensity higher (higher than the diffraction peak intensity of common crystal more than six times) of the perovskite crystal obtained by mixed solvent induction regulating controlling method, illustrate that it has very high crystalline order degree, higher crystalline order degree is then the necessary condition realizing efficient calcium titanium ore solar cell.
Embodiment 2: obtain black cubic system perovskite crystal by the mixed solvent induction regulating controlling under normal temperature.
(1) at N
2under protection, by PbCl
2(198.0mg, 0.7mmol) and CH
3nH
3i(339.6mg, 2.1mmol) be dissolved in DMF(0.85mL) in (mass concentration is 40%), in stirring at normal temperature 12h, until solute dissolves completely, obtain perovskite precursor solution;
(2) experimental procedure is with the step (2) in embodiment 1;
(3) at normal temperatures, the above-mentioned substrate with calcium titanium ore bed is placed in the closed atmosphere of being built by DMF/ chlorobenzene mixed solvent (1:30, v/v) and carries out annealing in process 10min, obtain black cubic system perovskite crystal.
Found by XRD test, have successfully been obtained required black cubic system perovskite thin film.
Embodiment 3: obtain black cubic system perovskite crystal by the mixed solvent induction regulating controlling under normal temperature.
(1) at N
2under protection, by PbCl
2(115.0mg, 0.4mmol) and CH
3nH
3i(201.2mg, 1.2mmol) be dissolved in DMF(0.5mL) in (mass concentration is 40%), then add DIO(5 μ L), and stir 12h under normal temperature, and filter with the polytetrafluoro filter in 0.45 μm of aperture, obtain perovskite precursor solution;
(2) at N
2in glove box, above-mentioned precursor solution is spin-coated in the ITO electro-conductive glass substrate with PEDOT:PSS with the speed of 3000rpm under normal temperature, until 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 the closed atmosphere of being built by DMF/ chlorobenzene mixed solvent (1:10, v/v) and carries out annealing in process 10min, obtain black cubic system perovskite crystal.
Found by XRD test, have successfully been obtained the perovskite thin film of required black cubic system.
Embodiment 4: obtain black cubic system perovskite crystal by the mixed solvent induction regulating controlling under normal temperature.
(1) at N
2under protection, by PbCl
2(198.0mg, 0.7mmol) and CH
3nH
3i(226.4mg, 1.4mmol) be dissolved in DMF(0.64mL) in (mass concentration is 40%), then add OT(19.2 μ L), and stir 12h under normal temperature, and filter with the polytetrafluoro filter in 0.45 μm of aperture, obtain perovskite precursor solution.
(2) at N
2in gas glove box, above-mentioned precursor solution is spin-coated in the ITO electro-conductive glass substrate with PEDOT:PSS with the speed of 3000rpm under normal temperature, until thickness is 350nm, obtains the substrate with perovskite active layer;
(3) the above-mentioned substrate with calcium titanium ore bed is placed in the closed atmosphere of being built by DMF/ chlorobenzene mixed solvent (1:10, v/v) and carries out annealing in process 10min, obtain black cubic system perovskite crystal.
The perovskite crystal successfully obtaining required black cubic system is found by XRD test.
Embodiment 5: the perovskite crystal obtained by mixed solvent induction regulating controlling is applied in solar cells.
Using perovskite thin film obtained in the perovskite thin film prepared by common heating method for annealing and embodiment 1 as solar cell (active area 0.04cm
2) in photoactive layer, compare the photoelectric properties of the two whereby, quantitative relationship between its current density (J) and voltage (V) (
j-Vcharacteristic curve) as shown in Figure 2.As shown in Figure 2, compared with common perovskite thin film, the photoelectric conversion efficiency of the perovskite thin film prepared based on mixed solvent induction regulating controlling method increases, and its most high-photoelectric transformation efficiency is about 15 ~ 16%.
In addition, the present inventor also attempts preparing large-area perovskite solar cell (active area 1.21cm in the same way
2), its
j-Vcharacteristic curve as shown in Figure 3.Known by calculating, the photoelectric conversion efficiency of this solar energy in large area battery is about 9% ~ 11%.
The above results shows, crystalline quality good (degree of crystallinity is high) can be prepared and perovskite thin film homogeneous in large area by the method for the growth of mixed solvent induction regulating controlling perovskite crystal and phase in version, can be effective to prepare the perovskite solar cell with higher photoelectric conversion efficiency.
Claims (10)
1. obtained a method for black cubic system perovskite thin film by the mixed solvent induction regulating controlling under normal temperature, it comprises the steps:
1) preparing perovskite precursor solution: under inert gas shielding, is 1:1 ~ 5 by mol ratio, and A donor and the B donor of preferred 1:3 are dissolved in solvent, until the mass concentration of solute reaches 35 ~ 50% in mixed solution, preferably 40%, stir 8 ~ 24 hours under normal temperature, obtain perovskite precursor solution;
2) spin coating perovskite precursor solution: under inert gas shielding, is spin-coated in substrate by the perovskite precursor solution obtained in step 1), obtains the substrate with perovskite active layer under normal temperature;
3) mixed solvent induction regulating controlling: at normal temperatures, mixed solvent is adopted to build closed atmosphere, and by step 2) in the substrate with perovskite active layer that obtains be placed in one and carry out solvent annealing in process, until the described substrate with perovskite active layer becomes black, obtain black cubic system perovskite thin film.
2. method according to claim 1, is characterized in that:
The donor of A described in step 1) be selected from lead chloride, lead bromide, lead iodide any one, preferred lead chloride or lead iodide, more preferably lead chloride;
The donor of B described in step 1) be selected from ammonio methacrylate, amitraz hydrochloride, methyl bromide ammonium, carbonamidine hydrobromate, methylpyridinium iodide ammonium, carbonamidine hydriodate any one, preferable methyl ammonium iodide or carbonamidine hydriodate, more preferably methylpyridinium iodide ammonium;
Described solvent for dissolving A donor and B donor in step 1) be selected from dimethyl formamide, dimethyl sulfoxide (DMSO), gamma-butyrolacton any one, preferred dimethyl formamide.
3. method according to claim 1, is characterized in that:
Before stirring described in step 1) starts, add in described mixed solution and count 0.5 ~ 5% with percent by volume, the preferably additive of 1%;
Described additive be selected from methyl pyrrolidone, 1,8-pungent two mercaptan, 1,8-diiodo-octane, 1-chloronaphthalene any one, preferably 1,8-diiodo-octane or methyl pyrrolidone, more preferably 1,8-diiodo-octane.
4. method according to claim 1, is characterized in that:
After having stirred described in step 1), obtain perovskite precursor solution through extra filtration step;
Described filtration step is preferably by means of filter, and more preferably polytetrafluoroethylene filter, most preferably the polytetrafluoro filter in 0.45 μm of aperture has come.
5. method according to claim 1, is characterized in that:
Step 2) described in the speed of spin coating be 2000 ~ 5000rpm, preferred 3000rpm.
6. method according to claim 1, is characterized in that:
Step 2) described in substrate poly-3,4-ethylene dioxythiophene/poly styrene sulfonate to be spin-coated on ITO electro-conductive glass obtained.
7. method according to claim 1, is characterized in that:
Mixed solvent described in step 3) is any one the mixture in dimethyl formamide or methyl-sulfoxide and chlorobenzene, o-dichlorohenzene, paraxylene, chloroform, the mixture of preferred dimethyl formamide and chlorobenzene, and the volume ratio of dimethyl formamide and chlorobenzene is 1:10 ~ 1:30.
8. method according to claim 1, is characterized in that:
Described inert gas be selected from nitrogen, neon, argon gas any one, preferred nitrogen.
9. the black cubic system perovskite thin film of method acquisition according to any one of claim 1 to 8.
10. black cubic system perovskite thin film according to claim 9 is preparing photovoltaic device, the purposes particularly in perovskite solar cell.
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