CN110518130A - A kind of method of electric field regulation perovskite crystal grain diauxic growth - Google Patents

A kind of method of electric field regulation perovskite crystal grain diauxic growth Download PDF

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CN110518130A
CN110518130A CN201910802239.3A CN201910802239A CN110518130A CN 110518130 A CN110518130 A CN 110518130A CN 201910802239 A CN201910802239 A CN 201910802239A CN 110518130 A CN110518130 A CN 110518130A
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electric field
crystal grain
amine
poly
diauxic growth
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CN110518130B (en
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沈文忠
程振东
刘洪�
丁东
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Shanghai Jiaotong University
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    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/54—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C30B29/64—Flat crystals, e.g. plates, strips or discs
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B30/00—Production of single crystals or homogeneous polycrystalline material with defined structure characterised by the action of electric or magnetic fields, wave energy or other specific physical conditions
    • C30B30/02—Production of single crystals or homogeneous polycrystalline material with defined structure characterised by the action of electric or magnetic fields, wave energy or other specific physical conditions using electric fields, e.g. electrolysis
    • 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
    • H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
    • 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
    • H10K30/40—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a p-i-n structure, e.g. having a perovskite absorber between p-type and n-type charge transport layers
    • 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
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • 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
    • 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

Abstract

The invention discloses a kind of methods of electric field regulation perovskite crystal grain diauxic growth, it is related to solar cell field, it is characterized in that, on the basis of the heat treatment of existing step spin-coating method, the autonomous Design device of one added electric field, this device, which can according to need, regulates and controls electric field strength by the distance for adjusting two electrodes, to realize the diauxic growth of regulation film crystal grain.The present invention realizes the visualization during electric field treatment, and be lossless to sample thin film using the electroconductive ITO face of probe contact film.The present invention is more environmentally-friendly without using chemical method, simple and easy.By the bigger crystallite dimension of the perovskite thin film of electric field treatment, more perovskite components, the perovskite solar cell of preparation has bigger open-circuit voltage, short-circuit current density, and then has higher photoelectric conversion efficiency, and has preferably stability.

Description

A kind of method of electric field regulation perovskite crystal grain diauxic growth
Technical field
The present invention relates to solar cell field more particularly to a kind of methods of electric field regulation perovskite crystal grain diauxic growth.
Background technique
Metal halide perovskite solar cell (PSC) causes global concern in the past 10 years, and has become recently For most promising third generation photovoltaic cell, mainly since they have a long carrier diffusion length, high absorption coefficient, relatively Higher defect tolerance.The power conversion efficiency (PCE) of perovskite solar cell from the 3.8% of Miyasaka et al. increase sharply to The 24.2% of Korea Research Inst. of Chemical Technology (KRICT/MIT), currently, the peak efficiency of PSC is close to the theoretical prediction limit 31%, it is suitable with crystalline silicon (c-Si) solar cell.
The form (including crystallite dimension, defect, continuity etc.) of perovskite thin film is to be inverted plane (p-i-n) solar cell Photovoltaic performance in parameter more prior than the crystallinity of perovskite thin film.So far, in order to improve the performance of PSC, research Great trial has been made to control nucleation and promote the improvement of film crystal quality in personnel, and such as interface engineering adulterates, adds Add agent, solvent engineering etc..In general, these strategies are based on the chemical modification method for growing thin-film crystal.Wherein, molten in precursor It is one of most effective strategy that additive is added in liquid.For example, passing through H2At O additive and dimethylformamide (DMF) steam The synergistic effect of reason is prepared for the MAPbI of high quality3(CH3NH3PbI3) film, solar cell transfer efficiency is up to 20.1%.Two Dimethyl sulfide (DS) additive makes crystallite dimension become larger by slowing down crystalline rate, makes flexible perovskite solar cell (F-PSC) Efficiency be increased to 18.4%.Control MAPbI3The amount of thiocarbamide (TU) is brilliant with the perovskite for obtaining smooth and big granularity in precursor Body, which enhance the stability and efficiency of device under ambient air.
In addition, perovskite crystalline process can pass through chemically and physically technical controlling.Shen Wenzhong et al. (Adv.Funct.Mater.2017,1606156) successfully prepares more compact MAPbI by electrochemical method for the first time3Calcium Titanium ore.He'nan Normal University Ma Heng (J.Mater.Chem.A, 2018,6,1161) devises a power-up field device, this device It needs to contact with film sample, has damage to sample, and spacing is bigger.
Therefore, those skilled in the art, which is dedicated to developing one kind, can preferably control MAPbI3The knot of perovskite thin film Brilliant process, and to the method for sample nondestructive.
Summary of the invention
In view of the above drawbacks of the prior art, the technical problem to be solved by the present invention is to develop a kind of reduction chemistry examination The use of agent, and the method for the increase perovskite crystal grain to sample nondestructive.
To achieve the above object, special the present invention provides a kind of method of electric field regulation perovskite crystal grain diauxic growth Sign is, includes the following steps:
Step 1, by two identical small-sized ito glass placements spaced apart, put on each small-sized ito glass A micron order crystal silicon is set, one large-scale ito glass is placed on the micron order crystal silicon, outer signal source is built into electric field dress It sets；
Step 2 will be patterned into after coating ito glass washs, is dry being transferred to after a certain period of time with UV-ozone processing filling In the glove box of full air；
Step 3, by tetra- cyanogen dimethyl-parabenzoquinone of 2,3,5,6- tetra- fluoro- 7,7', 8,8'- doping it is poly- [bis- (4- phenyl) (2, 4,6- trimethylphenyls) amine] it is dissolved in formation mixed solution in chlorobenzene (CB), it stirs and is heated overnight, filter institute with filter The solution of preparation is then applied on patterning coating ito glass described in step 2, and then annealing is prepared poly- [double (4- phenyl) (2,4,6- trimethylphenyl) amine]/ito substrate；
N,N-dimethylformamide is coated on poly- [bis- (4- phenyl) (2,4,6- trimethylbenzenes described in step 3 by step 4 Base) amine] on/ito substrate, to improve poly- described [bis- (4- phenyl) (2,4,6- trimethylphenyl) amine] film on perovskite precursor Wetability；
Step 5, by lead iodide (PbI2) and methylpyridinium iodide amine (MAI) to be dissolved in N,N-dimethylformamide/dimethyl sub- The perovskite precursor solution formed in the mixing anhydrous solvent of sulfone is filtered after being stirred overnight at a certain temperature with filter, then It is coated on [bis- (4- phenyl) (2,4,6- trimethylphenyl) amine]/ito substrate poly- described in step 3, by chlorobenzene in coating process (CB) it on fast drop to poly- [bis- (4- phenyl) (2,4, the 6- trimethylphenyl) amine] film, is subsequently transferred to described in step 1 In electric field arrangement, coating is placed centrally in the interval of the described two small-sized ito glasses of step 1 upwardly, not with described two A small-sized ito glass contact, and the uncoated area of the patterning coating ito glass is being passed through into probe outer signal source just Pole, and the large-scale ito glass lower surface outer signal source cathode being placed on carry out electric field post-processing, are heating at the same time It anneals on plate, calcium titanium ore bed is prepared；
Calcium titanium ore bed described in step 5 is cooled to room temperature by step 6, then by fullerene derivate PCBM in glove box Liquid deposition is at the top of the calcium titanium ore bed；
Step 7 passes through mask plate thermal evaporation Al (100nm) electricity on the fullerene derivate PCBM under a high vacuum Pole.
Further, the thickness of micron order crystal silicon described in step 1 can be adjusted according to the needs, so regulate and control electric field strength with Realize the diauxic growth of adjusting seed size.
Further, patterning coating ito glass described in step 2 is identical as small-sized ito glass thickness described in step 1, greatly Small is 0.7 inch × 0.7 inch, sheet resistance≤10 Ω/, light transmittance >=83%, and the washing process is to wash respectively diluted It washs ultrasonic treatment in agent, deionized water, acetone and isopropanol (IPA) to be kept for 20 minutes, the drying process is in vacuum drying oven Middle drying, the UV-ozone processing time is 15 minutes.
Further, 2,3,5,6- tetra- fluoro- 7,7' described in step 3,8,8'- tetra- cyanogen dimethyl-parabenzoquinones are adulterated poly- [double (4- phenyl) (2,4,6- trimethylphenyl) amine] in tetra- cyanogen dimethyl-parabenzoquinone's mass ratio of 2,3,5,6- tetra- fluoro- 7,7', 8,8'- It is 25%, the mixed solution concentration is 1mg/ml.
Further, filter described in step 3 be 0.45 μm of polytetrafluoroethylene filter, the coating process be with 5000rpm revolving speed is spun on ito substrate 30 seconds, and the annealing process is to anneal 10 minutes at 150 DEG C in glove box.
Further, n,N-Dimethylformamide volume described in step 4 is 60 μ l, and the coating process is with 4000rpm Speed be spin-coated on poly- [bis- (4- phenyl) (2,4,6- trimethylphenyl) the amine]/ito substrate 10 seconds.
Further, n,N-Dimethylformamide described in step 5/dimethyl sulfoxide volume ratio is 9:1, and the lead iodide is dense Degree is 1.20M, and the methylpyridinium iodide amine concentration is 1M, and the temperature of the whipping process is 60-70 DEG C, and the filter is 0.45 μm polytetrafluoroethylene filter, the coating process be spin-coated on the revolving speed of 4000rpm it is described it is poly- [bis- (4- phenyl) (2,4, 6- trimethylphenyl) amine] 30 seconds on/ito substrate, the chlorobenzene (CB) is added on the 5th second the coating process.
Further, the post-processing of electric field described in step 5 voltage is 0-40V, frequency 0-100Hz, and the annealing process is It anneals 10 minutes at 100 DEG C on hot plate.
Further, deposition process described in step 6 is to be deposited 60 seconds with the revolving speed of 1000rpm.
Further, high vacuum described in step 7 is less than 6E10-4Pa.
The present invention has the following technical effect that
1, electric field proposed by the invention increases crystal grain preparation method, and unused chemical method is more environmentally-friendly, simple and easy；
2, using the electroconductive ITO face of probe contact film, the visualization during electric field treatment is realized, and thin to sample Film is lossless；
3, the bigger crystallite dimension of perovskite thin film through electric field treatment of the present invention, more perovskite components, preparation Perovskite solar cell have bigger open-circuit voltage, short-circuit current density, and then have higher photoelectric conversion efficiency, and With preferably stability.
It is described further below with reference to technical effect of the attached drawing to design of the invention, specific structure and generation, with It is fully understood from the purpose of the present invention, feature and effect.
Detailed description of the invention
Fig. 1 is the equipment schematic diagram of the extra electric field of a preferred embodiment of the invention,
Wherein, the small-sized ito glass of 1-, perovskite thin film 2- to be processed, 3- micron order crystal silicon, 4- large size ito glass, 5- Metal probe, 6- conducting wire, 7- signal source, 8- patterning coating ito glass；
Fig. 2 is the scanning electron microscope diagram of present pre-ferred embodiments；
Fig. 3 is the crystallite dimension statistical chart of present pre-ferred embodiments；
Fig. 4 is the efficiency curve for being assembled into solar cell of present pre-ferred embodiments.
Specific embodiment
Multiple preferred embodiments of the invention are introduced below with reference to Figure of description, keep its technology contents more clear and just In understanding.The present invention can be emerged from by many various forms of embodiments, and protection scope of the present invention not only limits The embodiment that Yu Wenzhong is mentioned.
In the accompanying drawings, the identical component of structure is indicated with same numbers label, everywhere the similar component of structure or function with Like numeral label indicates.The size and thickness of each component shown in the drawings are to be arbitrarily shown, and there is no limit by the present invention The size and thickness of each component.Apparent in order to make to illustrate, some places suitably exaggerate the thickness of component in attached drawing.
Embodiment 1
Such as Fig. 1, step 1, by two identical small-sized ito glass 1 placements spaced apart, each small-sized ITO A micron order crystal silicon 3 is placed on glass, and one large-scale ito glass 4, outer signal source 7 are placed on the micron order crystal silicon 3 It is built into electric field arrangement；
Step 2, by 0.7 inch × 0.7 inch, the patterning of sheet resistance≤10 Ω/, light transmittance >=83% coats ITO glass Ultrasonic treatment is kept for 20 minutes glass 8 in diluted detergent, deionized water, acetone and isopropanol (IPA) respectively.
Step 3, in vacuum drying oven after dry patterning coating ito glass 8, by its with UV-ozone (Jelight, USA it) handles 15 minutes, is then transferred into the glove box full of air.
The preparation of step 4, hole transmission layer: the tetra- cyanogen dimethyl of 2,3,5,6- tetra- fluoro- 7,7', 8,8'- of mass ratio 25% Poly- [bis- (4- phenyl) (2,4,6- trimethylphenyl) amine] of 1,4-benzoquinone doping is dissolved in chlorobenzene (CB) mixed to form 1mg/ml Solution is closed, then stirs and is heated overnight at 70 DEG C.Before spin coating, with (0.45 μm) filtering institute of polytetrafluoroethylene filter Then mixture is spun to patterning with 5000rpm revolving speed and coats 8 upper 30 second of ito glass, then in gloves by the solution of preparation It anneals 10 minutes at 150 DEG C in case, obtains poly- [bis- (4- phenyl) (2,4,6- trimethylphenyl) amine]/ito substrate.
Step 5, in order to improve poly- [bis- (4- phenyl) (2,4,6- trimethylphenyl) amine] profit of the film on perovskite precursor It is moist, 60 μ l n,N-Dimethylformamide are spin-coated on poly- [bis- (4- phenyl) (2,4,6- trimethylbenzenes with the speed of 4000rpm Base) amine] 10 seconds on/ito substrate.
Step 6 prepares calcium titanium ore bed and electric field treatment: perovskite precursor solution by be dissolved in N,N-dimethylformamide/ Lead iodide (PbI in the mixing anhydrous solvent of dimethyl sulfoxide (volume ratio 9:1)2, 1.20M), methylpyridinium iodide amine (MAI, 1M) form.The solution of preparation is stirred overnight at 60-70 DEG C using preceding.Later with poly- (tetrafluoroethene) filter (0.45 μ M) solution is spin-coated on poly- [bis- (4- phenyl) (2,4,6- trimethylbenzenes with 4000rpm revolving speed by the prepared solution of filtering Base) amine] 30 seconds on/ito substrate.At the 5th second of spin coating process, by 150mL chlorobenzene (CB) fast drop to above-mentioned film, obtain Perovskite thin film 2 to be processed.It is subsequently transferred in electric field arrangement described in step 1, coating is placed centrally upwardly small in two The interval of type ito glass 1, and do not contacted with described two small-sized ito glasses 1, and will be patterned into coating ito glass 8 Uncoated area passes through the anode in 6 outer signal source 7 of metal probe 5 and conducting wire, and under the large-scale ito glass 4 being placed on Surface carries out electric field post-processing by the cathode in 6 outer signal source 7 of conducting wire, anneals 10 at 100 DEG C on hot plate at the same time Minute, calcium titanium ore bed is prepared；
Step 7 is cooled to room temperature, and then in glove box with 1000rpm, 60 seconds conditions are by fullerene derivate PCBM Solution (in CB) is deposited on the top of the calcium titanium ore bed.
Step 8 passes through the mask plate thermal evaporation Al on fullerene derivate PCBM at high vacuum (< 6E10-4Pa) (100nm) electrode.
Such as the Scanning Electron microscopy of Fig. 2, the crystallite dimension ratio of the perovskite thin film through electric field treatment without electric field at That manages is bigger.If the crystallite dimension statistical chart of Fig. 3 is shown, the crystallite dimension normal distribution of the perovskite thin film through electric field treatment exists Near 355nm, than the size offset of the Xiang Geng great of no electric field treatment.The performance test of battery is carried out such as under standard simulator Fig. 4 shows that the perovskite thin film through electric field treatment is bigger than the open-circuit voltage and short-circuit current density of no electric field treatment, thus With higher photoelectric conversion efficiency.
The preferred embodiment of the present invention has been described in detail above.It should be appreciated that the ordinary skill of this field is without wound The property made labour, which according to the present invention can conceive, makes many modifications and variations.Therefore, all technician in the art Pass through the available technology of logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea Scheme, all should be within the scope of protection determined by the claims.

Claims (10)

1. a kind of method of electric field regulation perovskite crystal grain diauxic growth, which comprises the steps of:
Step 1, by two identical small-sized ito glass placements spaced apart, place one on each small-sized ito glass A micron order crystal silicon places one large-scale ito glass on the micron order crystal silicon, and outer signal source is built into electric field arrangement；
Step 2 is transferred to after a certain period of time with UV-ozone processing full of sky after will be patterned into the washing of coating ito glass, drying In the glove box of gas；
Step 3, poly- [bis- (4- the phenyl) (2,4,6- for adulterating tetra- cyanogen dimethyl-parabenzoquinone of 2,3,5,6- tetra- fluoro- 7,7', 8,8'- Trimethylphenyl) amine] be dissolved in chlorobenzene (CB) and form mixed solution, stir and be heated overnight, filtered with filter prepared by Solution, be then applied to described in step 2 on patterning coating ito glass, then poly- [bis- (4- benzene are prepared in annealing Base) (2,4,6- trimethylphenyl) amine]/ito substrate；
N,N-dimethylformamide is coated on poly- [bis- (4- phenyl) (2,4,6- trimethylphenyl) described in step 3 by step 4 Amine] on/ito substrate, to improve poly- described [bis- (4- phenyl) (2,4,6- trimethylphenyl) amine] film on perovskite precursor Wetability；
Step 5, by lead iodide (PbI2) and methylpyridinium iodide amine (MAI) to be dissolved in N,N-dimethylformamide/dimethyl sulfoxide mixed The perovskite precursor solution that forms in anhydrous solvent is closed to be filtered after being stirred overnight at a certain temperature with filter, be coated in It is in coating process that chlorobenzene (CB) is fast on [bis- (4- phenyl) (2,4,6- trimethylphenyl) amine]/ito substrate poly- described in step 3 Speed is added drop-wise on poly- [bis- (4- phenyl) (2,4, the 6- trimethylphenyl) amine] film, is subsequently transferred to the dress of electric field described in step 1 In setting, coating upwardly be placed centrally in the interval of the described two small-sized ito glasses of step 1, not with it is described two small-sized Ito glass contact, and the uncoated area of the patterning coating ito glass is positive by metal probe outer signal source, And the large-scale ito glass lower surface outer signal source cathode being placed on, electric field post-processing is carried out, at the same time on hot plate Annealing, is prepared calcium titanium ore bed；
Calcium titanium ore bed described in step 5 is cooled to room temperature by step 6, then by fullerene derivate PCBM solution in glove box It is deposited on the top of the calcium titanium ore bed；
Step 7 passes through mask plate thermal evaporation Al (100nm) electrode on the fullerene derivate PCBM under a high vacuum.
2. a kind of method of electric field regulation perovskite crystal grain diauxic growth as described in claim 1, which is characterized in that step 1 The thickness of the micron order crystal silicon can be adjusted according to the needs, and then it is secondary with realize adjusting seed size two to regulate and control electric field strength It is long.
3. a kind of method of electric field regulation perovskite crystal grain diauxic growth as described in claim 1, which is characterized in that step 2 The patterning coating ito glass is identical as small-sized ito glass thickness described in step 1, and size is 0.7 inch × 0.7 inch, side ≤ 10 Ω/, light transmittance >=83% are hindered, the washing process is respectively in diluted detergent, deionized water, acetone and isopropyl Ultrasonic treatment is kept for 20 minutes in alcohol (IPA), and the drying process is to dry in vacuum drying oven, the UV-ozone processing Time is 15 minutes.
4. a kind of method of electric field regulation perovskite crystal grain diauxic growth as described in claim 1, which is characterized in that step 3 Poly- [bis- (4- phenyl) (2,4,6- trimethylbenzenes of tetra- cyanogen dimethyl-parabenzoquinone of 2,3,5,6- tetra- fluoro- 7,7', the 8,8'- doping Base) amine] in 2,3,5,6- tetra- fluoro- 7,7', 8,8'- tetra- cyanogen dimethyl-parabenzoquinone's mass ratioes be 25%, the mixed solution concentration For 1mg/ml.
5. a kind of method of electric field regulation perovskite crystal grain diauxic growth as described in claim 1, which is characterized in that step 3 The filter is 0.45 μm of polytetrafluoroethylene filter, and the coating process is to be spun on ito substrate with 5000rpm revolving speed 30 seconds, the annealing process was to anneal 10 minutes at 150 DEG C in glove box.
6. a kind of method of electric field regulation perovskite crystal grain diauxic growth as described in claim 1, which is characterized in that step 4 The n,N-Dimethylformamide volume is 60 μ l, and the coating process is described poly- [double to be spin-coated on the speed of 4000rpm (4- phenyl) (2,4,6- trimethylphenyl) amine] 10 seconds on/ito substrate.
7. a kind of method of electric field regulation perovskite crystal grain diauxic growth as described in claim 1, which is characterized in that step 5 The n,N-Dimethylformamide/dimethyl sulfoxide volume ratio is 9:1, and the iodate lead concentration is 1.20M, the methylpyridinium iodide Amine concentration is 1M, and the temperature of the whipping process is 60-70 DEG C, and the filter is 0.45 μm of polytetrafluoroethylene filter, institute Stating coating process is to be spin-coated on poly- [bis- (4- phenyl) (2,4,6- trimethylphenyl) the amine]/ITO base with the revolving speed of 4000rpm 30 seconds on plate, the chlorobenzene (CB) is added on the 5th second the coating process.
8. a kind of method of electric field regulation perovskite crystal grain diauxic growth as described in claim 1, which is characterized in that step 5 Electric field post-processing voltage is 0-40V, frequency 0-100Hz, and the annealing process is to anneal 10 at 100 DEG C on hot plate Minute.
9. a kind of method of electric field regulation perovskite crystal grain diauxic growth as described in claim 1, which is characterized in that step 6 The deposition process is to be deposited 60 seconds with the revolving speed of 1000rpm.
10. a kind of method of electric field regulation perovskite crystal grain diauxic growth as described in claim 1, which is characterized in that step 7 The high vacuum is less than 6E10-4Pa.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111211224A (en) * 2020-01-09 2020-05-29 上海交通大学 Method for quickly preparing commercial perovskite film at low cost
CN112349847A (en) * 2020-10-12 2021-02-09 上海交通大学 Automatic production equipment for perovskite solar cell
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CN112349847A (en) * 2020-10-12 2021-02-09 上海交通大学 Automatic production equipment for perovskite solar cell
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CN115036430A (en) * 2022-08-09 2022-09-09 中国华能集团清洁能源技术研究院有限公司 Method for preparing perovskite film with assistance of external electric field and photoelectric device

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