CN105742508B - The preparation method of tetramino ZnPc organic cavity transmission layer perovskite solar cell - Google Patents

The preparation method of tetramino ZnPc organic cavity transmission layer perovskite solar cell Download PDF

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CN105742508B
CN105742508B CN201610221077.0A CN201610221077A CN105742508B CN 105742508 B CN105742508 B CN 105742508B CN 201610221077 A CN201610221077 A CN 201610221077A CN 105742508 B CN105742508 B CN 105742508B
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znpc
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solar cell
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CN105742508A (en
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沈悦
朱尧
朱尧一
陈祥
皇甫民赞
曹萌
顾峰
王林军
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University of Shanghai for Science and Technology
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/311—Phthalocyanine
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • 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 preparation method of tetramino ZnPc organic cavity transmission layer perovskite solar cell, tetranitro ZnPc is prepared using microwave method first, reduced to obtain tetramino ZnPc again, using this derivative as organic cavity transmission layer, be spin-coated on the TiO coated with perovskite2On film, perovskite solar cell is prepared for.The present invention has synthesized a kind of phthalocyanine derivates dyestuff-tetramino Phthalocyanine Zinc, as perovskite TiO2Solar cell organic cavity transmission layer, the reaction time can be reduced significantly using microwave synthesis, improve reaction yield, and reduced environmental pollution, and be prepared for the green based on the organic material hole transmission layer, environmental protection, efficient perovskite solar cell.

Description

The preparation method of tetramino ZnPc organic cavity transmission layer perovskite solar cell
Technical field
The present invention relates to a kind of preparation method of solar cell, more particularly to a kind of Ca-Ti ore type solar cell, Applied to solar cell preparation technology field.
Background technology
At present, the silica-based solar cell preparation cost for accounting for leading market status is greatly reduced, and will ensure that following big rule Mould turns into inevitable using photovoltaic cell.According to nearest prediction, from now to the year two thousand thirty, it is newly-increased that photovoltaic power generation quantity will occupy the whole world / 3rd of generating capacity.It is if just organic however, possess very high photoelectric transformation efficiency or cheap preparation cost Traditional solar cell can be substituted to turn into new and effective solar cell of future generation.
In the recent period, the Cenozoic mixes organic inorganic halide element lead perovskite（CH3NH3PbX3, X=Cl, Br, I）, just possess both Characteristic, show wide application prospect.Organic-inorganic halogen lead perovskite has the outstanding absorption coefficient of light, direct band The advantages that gap, suitable energy gap, high charge mobility and longer electric charge diffusion length, has attracted numerous concerns.Except this Outside, element rich content and the easily use simple low temperature solution polycondensation preparation on earth of perovskite material composition.But This perovskite also has shortcoming, such as lead is part essential in all perovskite batteries efficient so far, and causes Preparation in solar cell, the waste procedures for being worked into material all have certain toxicity.And perovskite exposed to moist and Easily degraded under ultraviolet light.Although the stability of perovskite solar cell is improved to a certain extent, distance Long-term practical application is also far from enough.Therefore, it is further to both material and device especially on modular assembly in laboratory It is essential to improve stability.
Ca-Ti ore type solar cell is usually by anode（Electro-conductive glass）, N-type electron transfer layer（Compacted zone）, perovskite Absorbed layer, p-type hole transmission layer and the part such as gold, silver or aluminium negative electrode form；When sunshine excites, calcium titanium ore bed can produce Raw light induced electron and hole, wherein electronics reach anode through electron transfer layer, are then transferred to gold electrode negative electrode by external circuit； Meanwhile hole reaches gold electrode negative electrode through hole transmission layer, is combined here with free electron, a loop is completed.It is but existing Ca-Ti ore type solar cell preparation efficiency it is not high, also there is a certain degree of pollution in preparation process, this all limits calcium Titanium ore type manufacture of solar cells and application.
The content of the invention
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind The preparation method of tetramino ZnPc organic cavity transmission layer perovskite solar cell, a kind of phthalocyanine derivates dye is synthesized Material-tetramino Phthalocyanine Zinc, as perovskite TiO2Solar cell organic cavity transmission layer, and be prepared for being based on organic material The green of material hole transmission layer, environmental protection, efficient perovskite solar cell.
Purpose is created to reach foregoing invention, using following technical proposals：
A kind of preparation method of tetramino ZnPc organic cavity transmission layer perovskite solar cell, it is characterised in that Comprise the following steps：
1）The preparation of tetramino ZnPc：
A. tetranitro ZnPc is prepared using microwave method：By mole of zinc acetate, 4- nitrophthalic acids acid anhydride and urea Than for 1:4:25 ratio measures reactant feed respectively, then according to reactant feed gross mass and the molybdic acid hydrate of catalyst four The mass ratio of ammonium is（200~260）：1 mass ratio, reactant feed and Ammonium Molybdate Tetrahydrate are mixed to form reaction system thing Material, it is ground uniformly after, then reaction system material is added in beaker, then puts beaker in the lump together with reaction system material Enter to be stirred half an hour in 140 DEG C of oil bath, then beaker is taken out from oil bath, then beaker is put into micro-wave oven, lead to Adjustment microwave power is crossed, and by the way of intermittent-heating, the power for controlling irradiated heat is 300 ~ 380W, in beaker Reaction system material carries out 350 ~ 500s irradiated heat, is reacted the reaction system material in beaker, is obtained after reaction Product mass percent concentration be 5% NaOH solution 200ml soak and be heated to boiling formation the first mixture, then It is filtered by vacuum and removes the filtrate in the first mixture, obtained filtration product is molten with the HCl that mass percent concentration is 5% again Liquid 200ml, which soaks and is heated to boiling, forms the second mixture, then is filtered by vacuum and removes filtrate in the second mixture, obtains Filtration product is soaked with the NaCl solution 200ml that mass percent concentration is 10% and is heated to boiling again forms the 3rd mixture, Then it is filtered by vacuum and removes the filtrate in the 3rd mixture, then the filtration product for cleaning to obtain with deionized water is incited somebody to action to neutrality Tetranitro ZnPc is obtained after filtration product drying；By adjusting microwave power, by the way of intermittent-heating, to beaker In reaction system material when carrying out irradiated heat, it is 15~30 times preferably to control the number that heats repeatedly, or preferred control Adjacent heating process time interval is 30~50s；
B. the synthesis of tetramino ZnPc：It is 1 in molar ratio by tetranitro ZnPc and nine hydrated sodium sulfides:10 amount, Add in flask, then stirred with appropriate dimethyl methyl phthalein amine solvent, uniform mixed solution is formed, then in logical hydrogen Under conditions of oil bath heating to 60 DEG C, stirred with magnetic stirrer, then condensing reflux, after reduction reaction 5 hours, carry out it is cold But reaction product is obtained in flask, excessive distilled water is then added into reaction product, reaction product is cleaned repeatedly, Filtering and drying, obtained solid product ZnPc bisphenol epoxy derivatives are tetramino ZnPc；
2）CH3NH3PbI3−xClxPerovskite TiO2Film preparation：Using the function substrate in anode combination compacted zone, the cause Close layer prepares TiO as electron transfer layer on the compacted zone2Mesoporous layer, by CH3NH3PbI3−xClxPerovskite has unit Divide and inorganic component is mixed into solvent, obtain CH3NH3PbI3−xClxPerovskite solution, perovskite solution is then spun to cause TiO on close layer2On mesoporous layer, after the solvent in perovskite solution is fallen by heating evaporation, i.e., in TiO2Made on mesoporous layer It is standby to form CH3NH3PbI3−xClxPerovskite film；The TiO2Mesoporous layer is preferably by the spin coating P25 emulsions on compacted zone, then Half an hour annealing is carried out at 500 DEG C to be prepared；In CH3NH3PbI3−xClxDuring perovskite solution, it is preferred to use dimethyl First phthalein amine is as solvent；
3）The preparation of tetramino ZnPc and perovskite solar cell：Will be in the step 1）In step b in prepare The normal propyl alcohol solution of ZnPc bisphenol epoxy derivatives be spin-coated in the step 2）The CH of middle preparation3NH3PbI3−xClxCalcium titanium On ore deposit film, it is dried under 90 DEG C of vacuum condition, i.e., in CH3NH3PbI3−xClxZnPc bis-phenol ring is prepared in perovskite film Oxygen derivative layer, the organic cavity transmission layer using ZnPc bisphenol epoxy derivatives layer as perovskite solar cell, then Negative electrode layer is prepared on ZnPc bisphenol epoxy derivatives layer, i.e. assembling obtains perovskite solar cell；
4）Will be in the step 3）The calcium titanium with ZnPc bisphenol epoxy derivatives organic cavity transmission layer of middle preparation Ore deposit heat-sealing polymeric membrane used for solar batteries is packaged, the final solar cell for forming solid-state heterojunction structure.The present invention Perovskite solar cell is assembled by the use of tetramino ZnPc as organic cavity transmission layer, tetranitro is prepared using microwave method first ZnPc, then reduced to obtain tetramino ZnPc, using this derivative as organic cavity transmission layer, it is spin-coated on coated with calcium On the TiO2 films of titanium ore, perovskite solar cell is prepared for.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage：
Battery of the present invention using tetramino ZnPc as new organic cavity transmission layer, and using gold as to electrode, Form solid-state hetero-junctions perovskite solar cell.The present invention can reduce the reaction time significantly using microwave synthesis, improve reaction Yield, and reduce environmental pollution, the tetramino ZnPc of green syt is applied in perovskite solar cell, and is obtained Preferable electricity conversion.
Brief description of the drawings
Fig. 1 is tetramino ZnPc perovskite solar battery structure schematic diagram prepared by the preferred embodiment of the present invention.
Fig. 2 be the preferred embodiment of the present invention X ray diffracting spectrum, wherein Fig. 2（A）Spread out for tetramino ZnPc X ray Penetrate collection of illustrative plates, Fig. 2（B）For CH3NH3PbI3−xClxPerovskite and PbI2X ray diffracting spectrum.
Fig. 3 is the CH of the preferred embodiment of the present invention3NH3PbI3−xClxPerovskite UV-vis DRS collection of illustrative plates and fluorogram Spectrum.
Fig. 4 be the preferred embodiment of the present invention scanning electron microscope image, wherein Fig. 4（A）For TiO2Scanning electron microscope image, Fig. 2 （B）For CH3NH3PbI3−xClxPerovskite scanning electron microscope image.
Fig. 5 is the tetramino ZnPc perovskite solar cell J-V curve maps of the preferred embodiment of the present invention.
Embodiment
Details are as follows for the preferred embodiments of the present invention：
In the present embodiment, referring to Fig. 1~Fig. 5, a kind of tetramino ZnPc organic cavity transmission layer perovskite solar energy The preparation method of battery, comprises the following steps：
1）The preparation of tetramino ZnPc：
A. tetranitro ZnPc is prepared using microwave method：By rubbing for zinc acetate, 4- nitrophthalic acids acid anhydrides and urea You are than being 1:4:25 ratio measures reactant feed 4.03g zinc acetates, 21.11g 4- nitrophthalic acids and 15g respectively Urea, the catalyst Ammonium Molybdate Tetrahydrate of reactant feed and 0.2g is then mixed to form reaction system material, it is ground equal After even, then reaction system material is added in 500ml beaker, is then put into beaker in the lump together with reaction system material Half an hour is stirred in 140 DEG C of oil bath, then beaker is taken out from oil bath, then beaker is put into micro-wave oven, passed through Microwave power is adjusted, and by the way of intermittent-heating, high fire heating 20s during micro-wave oven is adjusted, then stop 40s, it is anti-altogether Multiple high fire heats and stopped heating 20 times, adds up to carry out the reaction system material in beaker 400s irradiated heat, makes beaker In reaction system material reacted, the product mass percent concentration obtained after reaction be 5% NaOH solution 200ml Soak and be heated to boiling and form the first mixture, be then filtered by vacuum and remove the filtrate in the first mixture, obtained mistake Filter product is soaked with the HCl solution 200ml that mass percent concentration is 5% and is heated to boiling again forms the second mixture, then very Sky filters and removes filtrate in the second mixture, and obtained filtration product is again with the NaCl solution that mass percent concentration is 10% 200ml, which soaks and is heated to boiling, forms the 3rd mixture, is then filtered by vacuum and removes the filtrate in the 3rd mixture, then uses The filtration product that deionized water cleans to obtain obtains tetranitro ZnPc to neutrality after filtration product is dried；
B. the synthesis of tetramino ZnPc：3g tetranitros ZnPc and the hydrated sodium sulfides of 9.6g nine are added in flask, then Stirred with 120g dimethyl methyl phthalein amine solvent, form uniform mixed solution, then the oil bath under conditions of logical hydrogen 60 DEG C are heated to, is stirred with magnetic stirrer, then condensing reflux, after reduction reaction 5 hours, is cooled down i.e. in flask Reaction product is obtained, excessive distilled water is then added into reaction product, reaction product is cleaned, filtered and dried repeatedly, Obtained solid product ZnPc bisphenol epoxy derivatives are tetramino ZnPc；
2）CH3NH3PbI3−xClxPerovskite TiO2Film preparation：Using in fluorine doped SnO2Electro-conductive glass (FTO) anode, which combines, to be caused The function substrate of close layer, using compacted zone as electron transfer layer, the spin coating P25 emulsions on compacted zone, then carried out at 500 DEG C Half an hour anneals, and TiO is prepared on compacted zone2Mesoporous layer, lead iodide and chloric acid methylamine salt are pressed 1:1.5 mixed in molar ratio In DMF solvent, the total mass fraction of solute is 50%, in 70 degrees Celsius of lower oil bath heating stirring 24h, is taken Layer clear liquid, is then spun to TiO in glove box by this solution2On mesoporous layer, rotating speed 2000rpm is controlled, passes through 90 degrees Celsius After heating evaporation falls solvent, perovskite film is formed in substrate, i.e., in TiO2Prepared on mesoporous layer and form CH3NH3PbI3−xClx Perovskite film；
3）The preparation of tetramino ZnPc and perovskite solar cell：Will be in the step 1）In step b in prepare The normal propyl alcohol solution of ZnPc bisphenol epoxy derivatives be spin-coated in the step 2）The CH of middle preparation3NH3PbI3−xClxCalcium titanium Ore deposit TiO2On mesoporous layer, it is dried under 90 DEG C of vacuum condition, i.e., in CH3NH3PbI3−xClxZinc phthalein is prepared in perovskite film Cyanines bisphenol epoxy derivatives layer, transmitted using ZnPc bisphenol epoxy derivatives layer as the organic hole of perovskite solar cell Layer, then evaporation metal Au obtains perovskite too as negative electrode layer, i.e. assembling on ZnPc bisphenol epoxy derivatives layer Positive energy battery；
4）Will be in the step 3）The calcium titanium with ZnPc bisphenol epoxy derivatives organic cavity transmission layer of middle preparation Ore deposit heat-sealing polymeric membrane used for solar batteries is packaged, the final solar cell for forming solid-state heterojunction structure.
The present embodiment is by zinc acetate, 4- nitrophthalic acids are matched somebody with somebody and urea, with appropriate catalyst Ammonium Molybdate Tetrahydrate Mixing, oil bath heating stir half an hour, pass through multistep after microwave reaction and wash acquisition tetranitro ZnPc；By tetranitro ZnPc Stirred with nine hydrated sodium sulfides and appropriate dimethyl methyl phthalein amine solvent, oil bath heating reaction, repeatedly cleaning obtains four ammonia Base ZnPc；Lead iodide and chloric acid methylamine salt are mixed in DMF solvent, oil bath heating stirs round the clock, rotation It is applied to TiO2On mesoporous layer；The normal propyl alcohol solution of tetramino ZnPc is spin-coated on CH3NH3PbI3−xClxPerovskite TiO2Mesoporous layer On, obtain CH using gold-plated fluorine doped tin oxide electro-conductive glass (FTO) as to electrode, assembling3NH3PbI3−xClxThe perovskite sun Can battery.
The detection of perovskite solar cell and sign：
Tetramino ZnPc, the CH for preparing or using to the present embodiment3NH3PbI3−xClxPerovskite and PbI2Carry out X ray Diffraction experiment.Fig. 2 be the preferred embodiment of the present invention X ray diffracting spectrum, wherein Fig. 2（A）Spread out for tetramino ZnPc X ray Penetrate collection of illustrative plates, Fig. 2（B）For CH3NH3PbI3−xClxPerovskite and PbI2X ray diffracting spectrum.PbI in Fig. 22The XRD tests of product As a result PDF cards are corresponded to（JCPDS No.07-0235）It is more intact, show to test resulting PbI2For hexagonal crystal system, P- 3m1 (164) point group.Main diffraction peak is located at 2 θ and is equal at 12.7 °, 25.9 °, 34.3 °, 39.5 ° and 47.8 °, and corresponding crystal face is （001）、（101）、（102）、（110）With（201）.PbI2Crystal exists（001）Preferred orientation on crystal face.CH3NH3PbI3−xClxCalcium Titanium ore belongs to tetragonal crystal system I4cm point groups, and specific diffraction peak is 14.0 ° in 2 θ, 20.0 °, 23.5 °, 24.5 °, 28.4 °, At 31.8 °, 34.9 °, 40.6 °, 43.2 °, 50.3 ° and 59.0 °, corresponding crystal face is（110）,（200）,（211）,（202）, （220）,（310）,（312）,（224）,（314）,（404）With（440）.Also there is CH simultaneously3NH3Cl and PbI2Characteristic peak, Such as 2 θ=38.6 °, 47.8 °, 52.4 °, 53.3 °, 56.5 °, 57.8 ° are PbI2Peak position；2 θ=29.6 ° are CH3NH3Cl peak positions. This is probably because perovskite surface is influenceed by vapor and oxygen in test environment, is decomposed.From UV, visible light Diffusing reflection spectrum detection understands that perovskite, which absorbs, is limited to 770nm, referring to Fig. 3.It is visible in Fig. 4, to TiO2And CH3NH3PbI3− xClxPerovskite is scanned electron microscopy image analysis, the TiO that spin coating obtains2Mesoporous layer SEM figures are it can be seen that form honeycomb knot Structure, aperture size are about 200nm, show that the organic additives such as ethyl cellulose have certain pore-creating effect, heat treated Cheng Zhong, organic additive are oxidized removing and leave many holes, add Film roughness and specific surface area, more to adsorb Organic-inorganic perovskite sensitizer provide structural condition.Perovskite SEM it can be seen from the figure that perovskite crystal grain distributions are uniform, TiO can be completely covered2Mesoporous layer surface；Further amplification is it can be seen that polyhedral structure, crystallite dimension is presented in perovskite crystal grain Heterogeneity, larger crystallite dimension is in 1 microns, compared with little crystallite size in 500nm or so.Referring to Fig. 5, according to J-V data Parameter, open-circuit voltage, short-circuit current density and the photoelectric transformation efficiency of the battery are respectively 0.55V, 0.762mA/cm-2With 0.114%.The present embodiment can reduce the reaction time significantly using microwave synthesis, improve reaction yield, and reduce environmental pollution. The tetramino ZnPc of green syt is applied in perovskite solar cell, and obtains preferable electricity conversion.
The embodiment of the present invention is illustrated above in conjunction with accompanying drawing, but the invention is not restricted to above-described embodiment, can be with A variety of changes are made according to the purpose of the innovation and creation of the present invention, under all Spirit Essence and principle according to technical solution of the present invention Change, modification, replacement, combination or the simplification made, should be equivalent substitute mode, as long as meeting the goal of the invention of the present invention, It is former without departing from the technology of the preparation method of tetramino ZnPc organic cavity transmission layer perovskite solar cell of the present invention Reason and inventive concept, belong to protection scope of the present invention.

Claims (5)

  1. A kind of 1. preparation method of tetramino ZnPc organic cavity transmission layer perovskite solar cell, it is characterised in that bag Include following steps：
    1）The preparation of tetramino ZnPc：
    A. tetranitro ZnPc is prepared using microwave method：Mol ratio by zinc acetate, 4- nitrophthalic acids acid anhydride and urea is 1:4:25 ratio measures reactant feed respectively, then according to reactant feed gross mass and catalyst Ammonium Molybdate Tetrahydrate Mass ratio is（200~260）：1 mass ratio, reactant feed and Ammonium Molybdate Tetrahydrate are mixed to form reaction system material, It is ground uniformly after, then reaction system material is added in beaker, is then put into beaker in the lump together with reaction system material Half an hour is stirred in 140 DEG C of oil bath, then beaker is taken out from oil bath, then beaker is put into micro-wave oven, passed through Microwave power is adjusted, and by the way of intermittent-heating, the power for controlling irradiated heat is 300 ~ 380W, to anti-in beaker Answer system material to carry out 350 ~ 500s irradiated heat, reacted the reaction system material in beaker, obtained after reaction The NaOH solution 200ml that product mass percent concentration is 5%, which soaks and is heated to boiling, forms the first mixture, then It is filtered by vacuum and removes the filtrate in the first mixture, obtained filtration product is molten with the HCl that mass percent concentration is 5% again Liquid 200ml, which soaks and is heated to boiling, forms the second mixture, then is filtered by vacuum and removes filtrate in the second mixture, obtains Filtration product again with mass percent concentration be 10% NaCl solution 200ml soak and be heated to boiling formed the 3rd mix Compound, then it is filtered by vacuum and removes the filtrate in the 3rd mixture, then the filtration product for cleaning to obtain with deionized water is into Property, tetranitro ZnPc is obtained after filtration product is dried；
    B. the synthesis of tetramino ZnPc：It is 1 in molar ratio by tetranitro ZnPc and nine hydrated sodium sulfides:10 amount, add In flask, then stirred with appropriate dimethyl methyl phthalein amine solvent, form uniform mixed solution, then in the bar of logical hydrogen Oil bath heating is stirred, then condensing reflux to 60 DEG C with magnetic stirrer under part, after reduction reaction 5 hours, is cooled down Reaction product is obtained in flask, excessive distilled water is then added into reaction product, reaction product is cleaned repeatedly, mistake Filter and drying, obtained solid product ZnPc bisphenol epoxy derivatives are tetramino ZnPc；
    2）CH3NH3PbI3 xClx perovskite TiO2 film preparations：Using on the basis of anode combination compacted zone, the densification Layer makees electron transfer layer, and the mesoporous layers of TiO2 are prepared on the compacted zone, CH3NH3PbI3 xClx perovskites are had into unit Divide and inorganic component is mixed into solvent, CH3NH3PbI3 xClx perovskite solution is obtained, then by perovskite solution spin coating On the mesoporous layers of TiO2 on to compacted zone, after the solvent in perovskite solution is fallen by heating evaporation, i.e., it is situated between in TiO2 Prepared in aperture layer and form CH3NH3PbI3 xClx perovskite films；
    3）The preparation of tetramino ZnPc and perovskite solar cell：Will be in the step 1）In step b in the zinc for preparing The normal propyl alcohol solution of phthalocyanine bisphenol epoxy derivatives is spin-coated in the step 2）The CH3NH3PbI3 xClx calcium titaniums of middle preparation On ore deposit film, it is dried under 90 DEG C of vacuum condition, i.e., it is double that ZnPc is prepared in CH3NH3PbI3 xClx perovskite films Phenol epoxides layer, the organic cavity transmission layer using ZnPc bisphenol epoxy derivatives layer as perovskite solar cell, Negative electrode layer is prepared on ZnPc bisphenol epoxy derivatives layer again, i.e. assembling obtains perovskite solar cell；
    4）Will be in the step 3）The perovskite with ZnPc bisphenol epoxy derivatives organic cavity transmission layer of middle preparation is too Positive energy battery is packaged with heat-sealing polymeric membrane, the final solar cell for forming solid-state heterojunction structure.
  2. 2. the preparation method of tetramino ZnPc organic cavity transmission layer perovskite solar cell according to claim 1, It is characterized in that：In the step 2）In, the mesoporous layers of TiO2 are by the spin coating P25 emulsions on compacted zone, then 500 Half an hour annealing is carried out at DEG C to be prepared.
  3. 3. according to the preparation of the tetramino ZnPc organic cavity transmission layer perovskite solar cell of claim 1 or 2 Method, it is characterised in that：In the step 2）In, in CH3NH3PbI3 xClx perovskite solution, the solvent used is two Methyl first phthalein amine.
  4. 4. according to the preparation of the tetramino ZnPc organic cavity transmission layer perovskite solar cell of claim 1 or 2 Method, it is characterised in that：In the step 1）Step a in, by adjusting microwave power, by the way of intermittent-heating, When carrying out irradiated heat to the reaction system material in beaker, it is 15~30 times to control the number heated repeatedly.
  5. 5. according to the preparation of the tetramino ZnPc organic cavity transmission layer perovskite solar cell of claim 1 or 2 Method, it is characterised in that：In the step 1）Step a in, by adjusting microwave power, by the way of intermittent-heating, When carrying out irradiated heat to the reaction system material in beaker, it is 30~50s to control adjacent heating process time interval.
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