CN105762286A - Methods for preparing perovskite thin film of inverse opal structure and corresponding solar cell - Google Patents
Methods for preparing perovskite thin film of inverse opal structure and corresponding solar cell Download PDFInfo
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- 239000010409 thin film Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 42
- 238000004528 spin coating Methods 0.000 claims abstract description 22
- 239000002356 single layer Substances 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 239000010408 film Substances 0.000 claims abstract description 9
- 239000004005 microsphere Substances 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000002360 preparation method Methods 0.000 claims description 30
- 239000004793 Polystyrene Substances 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 28
- 229920002223 polystyrene Polymers 0.000 claims description 23
- 239000010410 layer Substances 0.000 claims description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000084 colloidal system Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 229960004756 ethanol Drugs 0.000 claims description 11
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 10
- 239000000839 emulsion Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000010276 construction Methods 0.000 claims description 7
- 238000003892 spreading Methods 0.000 claims description 7
- 230000007480 spreading Effects 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 230000004888 barrier function Effects 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 230000005540 biological transmission Effects 0.000 claims description 4
- 238000009792 diffusion process Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000004141 Sodium laurylsulphate Substances 0.000 description 10
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 7
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000000465 moulding Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
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- 230000008569 process Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000005019 vapor deposition process Methods 0.000 description 2
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- -1 diisopropyl titanate esters Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
-
- 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
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention provides methods for preparing a perovskite thin film of an inverse opal structure and a solar cell. The method for preparing the perovskite thin film of the inverse opal structure is characterized by comprising a first step of forming a monolayer colloidal crystal template on a substrate; and a second step of spin coating a perovskite solution of a certain concentration on the colloidal crystal template to form a perovskite film, and afterwards removing the colloidal crystal template to obtain the perovskite thin film of the inverse opal structure. The invention prepares the perovskite thin film having a unique two-dimensional inverse opal structure, and provides the method for preparing the perovskite thin film of a novel structure. The invention requires no complex equipment, and is easy to operate and low in cost and energy consumption.
Description
Technical field
The present invention relates to the perovskite thin film of counter opal structure, be specifically related to the preparation method of the perovskite thin film of counter opal structure and the preparation method of the solaode based on this kind of counter opal structure perovskite thin film.
Background technology
In recent years, organic metal halogenide (organic inorganic hybridization perovskite) light absorbent of a kind of perovskite structure[1]Photo-generated carrier transport property with its good light absorption, photoelectric conversion characteristic and excellence[2,3,4,5]Cause extensive concern.This kind of perovskite material has relatively high extinction coefficient and ideal bandgap width, simple in construction, and preparation cost is low, mild condition, is the novel solar battery material of high comprehensive performance.The method preparing perovskite thin film at present mainly has liquid phase spin-coating method[6]And vapor deposition process[7], liquid phase spin-coating method technical process wherein frequently can lead to surface and cover incomplete, pin hole occurs, and vapor deposition process requires higher vacuum, equipment cost is high, operation energy consumption is high.
List of references:
1.Kojima,A.,etal.,OrganometalHalidePerovskitesasVisible-LightSensitizersforPhotovoltaicCells.JournaloftheAmericanChemicalSociety,2009.131(17):p.6050-6051.
2.Im, J.H., etal., 6.5%efficientperovskitequantum-dot-sensitizedsolarcell.N anoscale, 2011.3 (10): p.4088-4093.
3.Kim, H.S., etal., LeadIodidePerovskiteSensitizedAll-Solid-StateSubmicronTh inFilmMesoscopicSolarCellwithEfficiencyExceeding9%.Scien tificReports, 2012.2.
4.Lee,M.M.,etal.,EfficientHybridSolarCellsBasedonMeso-SuperstructuredOrganometalHalidePerovskites.Science,2012.338(6107):p.643-647.
5.Etgar,L.,etal.,MesoscopicCH3NH3PbI3/TiO2HeterojunctionSolarCells.JournaloftheAmericanChemicalSociety,2012.134(42):p.17396-17399.
6.Burschka,J.,etal.,Sequentialdepositionasaroutetohigh-performanceperovskite-sensitizedsolarcells.Nature,2013.499(7458):p.316-319.
7.Mingzhen,L.,M.B.Johnston,andH.J.Snaith,Efficientplanarheterojunctionperovskitesolarcellsbyvapourdeposition.Nature,2013.501(7467):p.395-398.
Summary of the invention
It is blank that the present invention has filled up current techniques, and the method preparation being specifically designed colloidal crystal auxiliary has the large area perovskite thin film of two-dimentional counter opal structure, it is provided that the preparation method of a kind of new structure perovskite thin film.This membrane structure is novel, in bright gay color, and preparation method is simple, has better absorbing ability, can be applied in perovskite battery as new and effective light-absorption layer compared with the perovskite thin film of the ordinary construction of same quality.
In order to achieve the above object, the preparation method that the invention provides a kind of counter opal structure perovskite thin film, it is characterised in that including:
Step 1: form colloid monolayer crystal template on substrate；
Step 2: the certain density perovskite solution of spin coating forms perovskite thin film on colloidal crystal template, removes colloidal crystal template afterwards, obtains counter opal structure perovskite thin film.
Preferably, substrate in described step 1 is microscope slide, first carry out pretreatment before use, concrete steps include: first microscope slide uses deionized water and each ultrasonic cleaning of dehydrated alcohol 5～20 minutes, finally microscope slide is immersed in dehydrated alcohol standby, needs during use to dry up with nitrogen air gun.
Preferably, the thickness of the perovskite thin film in described step 2 is 50nm-1000nm.
Preferably, in described step 1, the concrete steps forming colloid monolayer crystal template on substrate include:
Step a: polystyrene (PS) microsphere that particle diameter is 100～2000nm is diluted to the aqueous solution that concentration is 2～3vol%, afterwards it is mixed according to volume ratio 1:1 with spreading agent ethanol, obtain the polystyrene microsphere emulsion that concentration is 1～1.5vol%；
Step b: adopt gas-liquid interface construction from part, first dropping mass fraction is that sodium lauryl sulphate (SDS) solution of 1～5wt% is as surfactant in equipped with the circular culture dish of deionized water, afterwards polystyrene microsphere emulsion is dropwise added drop-wise in described circular culture dish, polystyrene microsphere spreads on gas-liquid interface under the effect of spreading agent ethanol and surfactant SDS, microsphere is partly submerged in below liquid level, surface tension due to the diffusion of ethanol and water, microsphere is made to form single layer structure, adelphotaxy between microsphere makes it spontaneously form ordered arrangement, form colloid monolayer crystal template, it is transferred into again on substrate.
It is highly preferred that the mass ratio of described SDS solution and polystyrene microsphere emulsion is 1:5～1:40.
Preferably, the perovskite in described step 2 is MAPbI3、MAPbBr3And FAPbI3Middle at least one, the solvent of described perovskite solution is dimethyl sulfoxide (DMSO).
Preferably, when the particle diameter of described polystyrene microsphere is 100nm, 250nm, 500nm, 750nm, 1000nm, 1700nm and 2000nm, the concentration respectively 0.1M of described perovskite solution, 0.3M, 0.6M, 0.7M, 0.8M, 0.9M and 1.0M.
Preferably, the particle diameter of described polystyrene microsphere is 500nm.
Preferably, the concrete steps of the described certain density perovskite solution of spin coating on colloidal crystal template include: drip on the colloidal crystal template of 15mm × 15mm size by the 40 certain density perovskite solution of μ L, with the rotating speed spin coating 15s of 4000rpm, afterwards microscope slide is heated at 100 DEG C 60s.
Preferably, in described step 2, the concrete steps removing colloidal crystal template include: soaking to remove colloidal crystal template in toluene solvant by substrate and colloidal crystal template thereon and perovskite film, soak time is 3～10min, are taken out by substrate afterwards and dry.
Preferably, the thickness of described counter opal structure perovskite thin film is 50nm～1000nm.
The preparation method that present invention also offers a kind of solaode, it is characterized in that, concrete steps include: with light anode for substrate, the preparation method adopting above-mentioned counter opal structure perovskite thin film prepares counter opal structure perovskite thin film, spin coating hole transmission layer (HTM), evaporation metal electrode, obtains solaode.
Preferably, the preparation method of described light anode includes: etching electro-conductive glass conductive layer, sprays electronic barrier layer, spin coating electron transfer layer, obtains light anode.
The present invention is on the microscope slide that hydrophilic treated is crossed, utilize gas-liquid interface self-assembly method deposition monolayer polystyrene colloid crystal template, the method of recycling spin coating, perovskite solution deposition is filled space therein in template, remove template afterwards, obtain the perovskite thin film of respective two-dimensional ordered big hole structure.The present invention is prepared for the solaode based on two dimension counter opal structure perovskite thin film simultaneously, and tests the photovoltaic performance of battery.
Compared with prior art, the invention has the beneficial effects as follows:
The characteristics such as the present invention is a kind of new structure perovskite thin film by the two-dimentional counter opal structure perovskite thin film that colloidal crystal template grows, and has a novel structure, in bright gay color.Have voidage height, pore structure periodic arrangement, hole dimension is uniformly adjustable and the characteristic such as long-range order, has better absorbing ability compared with the perovskite thin film of the ordinary construction of equal in quality simultaneously.Two dimension counter opal structure perovskite thin film can be used as new and effective light-absorption layer and is applied in perovskite battery, at the same time as catalyst, function carrier, adsorbing material, has very wide application prospect in catalysis, chemical industry and electronics industry.The present invention prepares the perovskite thin film with unique two dimension counter opal structure, it is provided that the preparation method of a kind of new structure perovskite thin film.The present invention is without complex device, easy and simple to handle, and cost, energy consumption are low.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of polystyrene two-dimensional colloidal crystal template；
Fig. 2 is the scanning electron microscope (SEM) photograph of two dimension counter opal structure perovskite thin film；
Fig. 3 is the VA characteristic curve of counter opal structure perovskite battery.
A)-g in Fig. 1) corresponding embodiment 2,3,1,4,5,6,7 respectively.A)-f in Fig. 2) corresponding embodiment 3,1,4,5,6,7 respectively.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate the present invention rather than restriction the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, the present invention can be made various changes or modifications by those skilled in the art, and these equivalent form of values fall within the application appended claims limited range equally.
Embodiment 1
The preparation method of a kind of counter opal structure perovskite thin film, concretely comprises the following steps:
One, microscope slide is carried out pretreatment:
First microscope slide is used deionized water and dehydrated alcohol (AR, Chemical Reagent Co., Ltd., Sinopharm Group) each ultrasonic cleaning 10 minutes, finally microscope slide is immersed in dehydrated alcohol standby, needs during use to dry up with nitrogen air gun.
Two, on microscope slide, colloid monolayer crystal template is formed:
By polystyrene (PS) microsphere (DS050 that particle diameter is 500nm, peptide bio tech ltd, Shanghai hundred) it is diluted to the aqueous solution that concentration is 3vol%, afterwards it is mixed according to volume ratio 1:1 with dehydrated alcohol, obtain the PS microsphere emulsion that concentration is 1.5vol%.
nullAdopt gas-liquid interface construction from part，First the circular culture dish that a diameter is 8.5cm is taken，Load 35mL deionized water，Sodium lauryl sulphate (the SDS that mass fraction is 2wt% of 50 μ L is dripped in culture dish，AR，Aladdin biochemical technology limited company) aqueous solution is as surfactant，Afterwards 400 μ LPS microsphere emulsions are dropwise added drop-wise in described circular culture dish，Polystyrene microsphere spreads on gas-liquid interface under the effect of spreading agent ethanol and surfactant SDS，Microsphere is partly submerged in below liquid level，Surface tension due to the diffusion of ethanol and water，Microsphere is made to form single layer structure，Adelphotaxy between microsphere makes it spontaneously form ordered arrangement，Form colloid monolayer crystal film，It is transferred on microscope slide again and obtains colloid monolayer crystal template，See accompanying drawing 1c).
Three, on colloidal crystal template, the certain density perovskite solution of spin coating forms perovskite film, removes colloidal crystal template afterwards, obtains counter opal structure perovskite thin film:
The MAPbI of preparation 0.6M concentration3(> 99%, Ningbo Bo Run new material Science and Technology Ltd.) solution, the solvent used is dimethyl sulfoxide (DMSO, anhydrous solvent level, Aladdin biochemical technology limited company).
By 40 μ LMAPbI3Solution drips on the colloidal crystal template of 1.5cm × 1.5cm size, with the rotating speed spin coating 15s of 4000rpm, microscope slide heats at 100 DEG C 60s afterwards.After treating microscope slide cooling, microscope slide and colloidal crystal template thereon and perovskite film (thickness is 500nm) are soaked in toluene solvant removal polystyrene moulding, soak time is 3～10min, take out afterwards and dry, obtain the corresponding counter opal structure perovskite thin film that thickness is 250nm, see accompanying drawing 2b)
Embodiment 2-7
It is similar to embodiment 1, is distinctive in that the particle diameter of the embodiment 2-7 polystyrene microsphere used is followed successively by 100nm, 250nm, 750nm, 1000nm, 1700nm and 2000nm, corresponding MAPbI3The concentration of solution respectively 0.1M, 0.3M, 0.7M, 0.8M, 0.9M, 1.0M.For colloid monolayer crystal template see accompanying drawing 1a), b), d), e), f), g), the counter opal structure perovskite thin film that embodiment 3-7 obtains is shown in accompanying drawing 2a successively), c), d), e), f).
Embodiment 8
The preparation method of a kind of solaode, concretely comprises the following steps:
One, the preparation of light anode:
Adopt the SnO of F doping2Transparent conductive oxide (FTO, NSG10) glass is as substrate, it is sized to 15mm × 15mm, first 0.2g zinc powder (AR is taken, Chemical Reagent Co., Ltd., Sinopharm Group) and 1mL hydrochloric acid (AR, Tai Tan Science and Technology Co., Ltd.) it is etched removing conductive oxide layer by solution (concentrated hydrochloric acid of mass fraction 37wt% 1:1 by volume with water dilution), and etching area is 15mm × 4mm.FTO substrate after etching is rinsed well, more successively with deionized water and dehydrated alcohol ultrasonic cleaning respectively, standby after drying.
By the double; two aqueous isopropanol (Sigma-Aldrich) of (acetylacetone based) diisopropyl titanate esters, acetylacetone,2,4-pentanedione (AR that mass fraction is 75wt%, Chemical Reagent Co., Ltd., Sinopharm Group) and dehydrated alcohol (AR, Chemical Reagent Co., Ltd., Sinopharm Group) 3:2:45 mix homogeneously by volume as electronic barrier layer solution.Adopt the fine and close TiO of spray pyrolysis preparation2Layer.FTO substrate etch processes crossed is heated slowly to 450 DEG C, to the electronic barrier layer solution that its spraying is above-mentioned, afterwards substrate is incubated 10min, obtains fine and close TiO2Thin film is as electronic barrier layer (bl-TiO2)。
By porous TiO2Slurry (18NR-T, Dyesol) and dehydrated alcohol are configured to mesoporous TiO according to weight ratio 1:3.52(meso-TiO2) slurry, drip 60 μ Lmeso-TiO2To above-mentioned bl-TiO2On thin film, with the rotating speed spin coating 30s of 5000rpm, then anneal 30min at 500 DEG C, obtains thickness and is about the mesoporous TiO of 300nm2Layer, as electron transfer layer, obtains light anode.
Two, on light anode, colloid monolayer crystal template is formed: polystyrene (PS) microsphere that particle diameter is 500nm is diluted to the aqueous solution that concentration is 2～3vol%, afterwards it is mixed according to volume ratio 1:1 with spreading agent ethanol, obtain polystyrene (PS) the microsphere emulsion that concentration is 1.5vol%；
nullAdopt gas-liquid interface construction from part，First the circular culture dish that a diameter is 8.5cm is taken，Load 35mL deionized water，Sodium lauryl sulphate (the SDS that mass fraction is 2wt% of 50 μ L is dripped in culture dish，AR，Aladdin biochemical technology limited company) aqueous solution is as surfactant，Afterwards 400 μ L polystyrene (PS) microsphere emulsions are dropwise added drop-wise in described circular culture dish，Polystyrene microsphere spreads on gas-liquid interface under the effect of spreading agent ethanol and surfactant SDS，Microsphere is partly submerged in below liquid level，Surface tension due to the diffusion of ethanol and water，Microsphere is made to form single layer structure，Adelphotaxy between microsphere makes it spontaneously form ordered arrangement，Form colloid monolayer crystal film，It is transferred on light anode again and obtains colloid monolayer crystal template.
Three, on colloidal crystal template, the certain density perovskite solution of spin coating forms perovskite film, removes colloidal crystal template afterwards, obtains counter opal structure perovskite thin film:
The MAPbI of preparation 0.6M concentration3Solution, the solvent used is dimethyl sulfoxide (DMSO).
By 40 μ LMAPbI3Solution drips on the colloidal crystal template of 1.5cm × 1.5cm size, with the rotating speed spin coating 15s of 4000rpm, thin film heats at 100 DEG C 60s afterwards.After to be cooled, light anode and colloidal crystal template thereon and perovskite thin film (thickness is 250nm) are soaked in toluene solvant removal polystyrene moulding, soak time is 3～10min, take out afterwards and dry, obtaining corresponding counter opal structure perovskite thin film, thickness is 250nm.
Four, spin coating hole transport layer material and evaporation metal electrode on the perovskite thin film of two dimension counter opal structure:
9.1mg bis-trifluoromethylsulfoandimide lithium (Li-TFSI, 99.95%, Sigma-Aldrich) is dissolved in 17.5 μ L anhydrous acetonitriles (99.8%, Sigma-Aldrich).By the 1-tetra-[N of 72.3mg, N-bis-(4-methoxyphenyl) amino]-9,9, and-spiral shell two fluorenes (Spiro-OMeTAD, >=99.7%, Ningbo Bo Run new material Science and Technology Ltd.) it is dissolved in 1mL chlorobenzene (99.8%, Sigma-Aldrich), mix homogeneously with above-mentioned Li-TFSI solution afterwards, and be added thereto to 28.8 μ L tetra-tert pyridine (tBP, 96%, Sigma-Aldrich) as hole transmission layer (HTM) solution.Spin coating HTM solution on counter opal structure perovskite thin film, with the rotating speed spin coating 15s of 2000rpm, obtains the HTM that thickness is about 200nm.
Finally on hole transmission layer, the Ag metallic film of hot evaporation thickness 80nm, as back electrode, obtains solaode.
Embodiment 9
Being similar to embodiment 8, be distinctive in that the particle diameter of the polystyrene microsphere that embodiment 9 uses is 1000nm, the concentration of perovskite solution is 1.0M, and the thickness of the corresponding counter opal structure perovskite thin film obtained is 500nm.
Battery C-V characteristic (I-V) curve can reflect the open-circuit voltage (V of solaodeoc), short circuit current (Jsc), the characteristic parameter such as fill factor, curve factor (FF) and photoelectric transformation efficiency (PCE).The above-mentioned counter opal structure perovskite battery based on 500nm, 1000nm polystyrene moulding is carried out I-V curve test, adopt xenon source (CEL-S500, Zhong Jiaojin source, Beijing Science and Technology Ltd.) and electrochemical workstation (CHI660E, Shanghai Chen Hua Instrument Ltd.), the light intensity used in test is AM1.5 (100mW/cm2).Owing to electric current I is relevant with cell active area, generally converting electric current I to current density, J in actually used, obtained J-V curve is shown in Fig. 3.Curve IOP500 represents the perovskite thin film solaode based on 500nm polystyrene moulding, and its open-circuit voltage is 0.84V, and short circuit current is 11.1mA/cm2, fill factor, curve factor is 61%, and photoelectric transformation efficiency is 5.7%.Curve IOP1000 represents the perovskite thin film solaode based on 1000nm polystyrene moulding, and its open-circuit voltage is 0.91V, and short circuit current is 15.7mA/cm2, fill factor, curve factor is 66.6%, and photoelectric transformation efficiency is 9.5%.This is the peak efficiency that the counter opal structure perovskite battery reported in the world at present obtains.
Claims (10)
1. the preparation method of a counter opal structure perovskite thin film, it is characterised in that including:
Step 1: form colloid monolayer crystal template on substrate；
Step 2: the certain density perovskite solution of spin coating forms perovskite thin film on colloidal crystal template, removes colloidal crystal template afterwards, obtains counter opal structure perovskite thin film.
2. the preparation method of counter opal structure perovskite thin film as claimed in claim 1, it is characterized in that, substrate in described step 1 is microscope slide, first carry out pretreatment before use, concrete steps include: first microscope slide uses deionized water and each ultrasonic cleaning of dehydrated alcohol 5～20 minutes, finally microscope slide is immersed in dehydrated alcohol standby, needs during use to dry up with nitrogen air gun.
3. the preparation method of counter opal structure perovskite thin film as claimed in claim 1, it is characterised in that in described step 1, the concrete steps forming colloid monolayer crystal template on substrate include:
Step a: the polystyrene microsphere that particle diameter is 100～2000nm is diluted to the aqueous solution that concentration is 2～3vol%, it is mixed according to volume ratio 1: 1 with spreading agent ethanol afterwards, obtains the polystyrene microsphere emulsion that concentration is 1～1.5vol%；
Step b: adopt gas-liquid interface construction from part, first in equipped with the circular culture dish of deionized water, sodium dodecyl sulfate solution is dripped as surfactant, afterwards polystyrene microsphere emulsion is dropwise added drop-wise in described circular culture dish, polystyrene microsphere spreads on gas-liquid interface under the effect of spreading agent ethanol and surfactant SDS, microsphere is partly submerged in below liquid level, surface tension due to the diffusion of ethanol and water, microsphere is made to form single layer structure, adelphotaxy between microsphere makes it spontaneously form ordered arrangement, form colloid monolayer crystal template, it is transferred into again on substrate.
4. the preparation method of counter opal structure perovskite thin film as claimed in claim 1, it is characterised in that the perovskite in described step 2 is MAPbI3、MAPbBr3And FAPbI3Middle at least one, the solvent of described perovskite solution is dimethyl sulfoxide.
5. the preparation method of counter opal structure perovskite thin film as claimed in claim 1, it is characterized in that, when the particle diameter of described polystyrene microsphere is 100nm, 250nm, 500nm, 750nm, 1000nm, 1700nm and 2000nm, the concentration respectively 0.1M of described perovskite solution, 0.3M, 0.6M, 0.7M, 0.8M, 0.9M and 1.0M.
6. the preparation method of counter opal structure perovskite thin film as claimed in claim 1, it is characterized in that, the concrete steps of the described certain density perovskite solution of spin coating on colloidal crystal template include: drip on the colloidal crystal template of 15mm × 15mm size by the 40 certain density perovskite solution of μ L, with the rotating speed spin coating 15s of 4000rpm, afterwards microscope slide is heated at 100 DEG C 60s.
7. the preparation method of counter opal structure perovskite thin film as claimed in claim 1, it is characterized in that, in described step 2, the concrete steps removing colloidal crystal template include: soak to remove colloidal crystal template in toluene solvant by substrate and colloidal crystal template thereon and perovskite film, soak time is 3～10min, is taken out by substrate afterwards and dries.
8. the preparation method of counter opal structure perovskite thin film as claimed in claim 1, it is characterised in that the thickness of described counter opal structure perovskite thin film is 50nm～1000nm.
9. the preparation method of a solaode, it is characterized in that, concrete steps include: with light anode for substrate, the preparation method adopting the counter opal structure perovskite thin film according to any one of claim 1-8 prepares counter opal structure perovskite thin film, spin coating hole transmission layer, evaporation metal electrode, obtains solaode.
10. the preparation method of solaode as claimed in claim 9, it is characterised in that the preparation method of described light anode includes: etching electro-conductive glass conductive layer, sprays electronic barrier layer, the mesoporous electron transfer layer of spin coating, obtains light anode.
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