CN106058060A - Method for preparing high-quality perovskite crystal thin film - Google Patents
Method for preparing high-quality perovskite crystal thin film Download PDFInfo
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- CN106058060A CN106058060A CN201610431212.4A CN201610431212A CN106058060A CN 106058060 A CN106058060 A CN 106058060A CN 201610431212 A CN201610431212 A CN 201610431212A CN 106058060 A CN106058060 A CN 106058060A
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- H—ELECTRICITY
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- 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
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Abstract
The invention discloses a method for simply and quickly preparing a high-quality perovskite crystal thin film, and belongs to the technical field of solar cells. The method comprises the main steps of firstly forming a flat lead iodide thin film on a substrate through a film forming technology; and then processing a PbI2 thin film through a mixed solution of CH<3>NH<3>X and HC(NH<2>)<2>X and carrying out thermal treatment to obtain the high-quality perovskite crystal thin film. Under the condition of not adopting the equipment of vacuum equipment, a glove box and the like, the perovskite crystal thin film which is controllable in thickness, good in crystallinity, high in coverage rate, flat and smooth in surface and good in light absorption performance can also be prepared by the method disclosed by the invention; the technology is simple in operation; and the preparation cycle is short. The perovskite crystal thin film prepared through the method is applied to the solar cell as a light absorption material; and the prepared cell device is high in efficiency and good in stability, and has important reference value for implementation of low-cost manufacturing of the high-efficiency perovskite solar cell.
Description
Technical field
The invention belongs to photoelectric device (especially solaode or photodetector) thin film technique field, mainly relate to
And a kind of simple and quick method preparing high-quality perovskite crystal thin film.
Background technology
For realizing the sustainable development of human society, current energy crisis and the big outstanding problem of environmental pollution two, need badly
Countries in the world are responded actively, and development new theory, new technique seek solution, wherein, and development and utilization renewable energy
Just can yet be regarded as a good plan in source.Solar energy, wind energy, biomass energy, tide energy etc. are all the regenerative resources of inexpensive clean, wherein
Solar energy because of have inexhaustible, without geographical restrictions, the advantage such as Land use systems is versatile and flexible, be undoubtedly not
Carry out in global energy systems one of regenerative resource with development potentiality most.At present, to Solar use most effective way
It is to carry out opto-electronic conversion by solar photovoltaic device.As a kind of novel third generation solar cell, the perovskite sun
Can battery (Perovskite Solar Cells, PSCs) development swift and violent, battery efficiency is from 3.81% in 2009
(ref.A.Kojima,T.MiyasakaJ,et al."Organometal Halide Perovskites as Visible-
Light Sensitizers for Photovoltaic Cells."Journal of The American Chemical
Society 131.17 (2009): 6050-6051.) bring up to 20.1% nearest (ref.W.S.Yang, J.H.Noh and
S.Seok,et al."High-performance Photovoltaic Perovskite Layers Fabricated
through Intramolecular Exchange."Journal of Science 348.6240(2015):1234-
1237.), PSCs has become as a research hot topic of current photovoltaic art, and it is also chosen as by authority's magazine " Science "
One of the world ten big science breakthrough in 2013.
Why perovskite solaode can by leaps and bounds develop, and largely has benefited from as photoactive layer
Perovskite material.Hybrid inorganic-organic perovskite material is the heterocomplex on a kind of molecular scale, has Organic substance and inorganic matter concurrently
Properties, its molecular formula is ABX3, wherein A is generally CH3NH3 +、CH3CH2NH3 +、NH2CH=NH2 +, B is generally Pb2 +Or
Sn2 +, X is typically I-、Br-、Cl-, A, B, X connect the formation center of area-body-centered cubic lattic structure by chemical bond.Organic and inorganic is miscellaneous
Change perovskite material preparation method for material is various and cost is relatively low, and its band structure can be by changing inorganic constituent element and the group of organic constituent element
One-tenth is adjusted, and the most this material has that exciton bind energy is little, carrier diffusion speed fast and diffusion length length, absorbing light
The characteristics such as spectral limit is wide, thus have broad application prospects in area of solar cell.
At present, the preparation method of perovskite crystal thin film is broadly divided into two big classes: physical vacuum vapour deposition method and chemical deposition
Method.Physical vacuum vapour deposition method is high by the perovskite thin film quality obtained by common source evaporation mode, thickness controllable precise, but needs
Wanting expensive vacuum equipment, preparation process is more complicated, and process costs energy consumption is high, still suffers from challenge in reality is promoted.Chemistry is heavy
Area method, can be divided into the most again according to processing step: one-step method and two-step method.Wherein, one-step method, utilize the perovskite prepared in advance
Precursor solution, directly prepares perovskite thin film through spin coating or blade coating mode on substrate.The method processing step is the simplest
Single, but owing to perovskite precursor solution generally uses DMF (N, N-dimethylformamide, DMF)
As solvent, its evaporation during spin coating or blade coating quickly, causes perovskite thin film rapid crystallization, and film coverage is relatively
Low, often in netted, defect is more；Although the anti-solvent method improved on this basis largely improves the film forming of perovskite
Property, but technical process need to use such as the organic solvent such as toluene, ether, and these solvents have toxicity, inflammable, explosive, to environment
All there is certain threat with production safety, and concrete processing procedure requires the dropping when perovskite precursor solution spin coating is carried out
Solvent process, dropping opportunity, dropping volume, action time etc. parameter more, easily affected by manual operation uncertain factor, experiment
Result repeatability is poor.And two-step method, mainly first pass through spin coating mode on substrate, prepare PbI2Thin film, then by methyl
Iodate amine (methylammonium iodide, MAI) solution soaks or processes in MAI steam, thus by PbI2Thin film is
Change into perovskite thin film eventually.The perovskite crystal film quality that two-step method prepares is typically good than one-step method, but two-step method is also deposited
PbI is converted completely more difficult2Drawback for perovskite.The two-step method of immersion way, converts completely to lead iodide and need to soak number
As long as hour, but even come off along with soak time prolongation calcium titanium ore bed can dissolve again；The two-step method of steam processing mode, equally
Need the longer response time, and still have PbI2Residual.So, seek one the most simple and quick and effectively prepare high-quality
The method of perovskite crystal thin film, and then improve energy conversion efficiency and the device stability of perovskite solaode, still
There is highly important significance of scientific research and using value.
Summary of the invention
It is an object of the invention to provide a kind of simple and quick method preparing high-quality perovskite crystal thin film, i.e. first exist
PbI2Solution adds dimethyl sulfoxide (dimethyl sulfoxide, DMSO), it is not necessary to heat treatment i.e. can form surface and put down
Whole fine and close PbI2Thin film, then at PbI2Fast drop spin coating CH on thin film3NH3X Yu HC (NH2)2The mixed solution of X, passes through
Change the two ratio and regulate and control perovskite crystallite dimension and surface topography, eventually pass short time heat treatment and can be prepared by high-quality
Perovskite crystal thin film.Under conditions of need not use the instrument such as vacuum equipment, glove box, this method utilizes an equal glue
Machine just can prepare high-quality perovskite crystal thin film quickly and easily, its have better crystallinity degree, grain size distribution uniformly,
The plurality of advantages such as coverage rate height, smooth, the good stability of surfacing, apply it in perovskite solaode prepared
Device photoelectric performance is good, good stability.
Technical scheme is as follows:
A kind of simple and quick method preparing high-quality perovskite crystal thin film, it is characterised in that comprise the steps:
(1) PbI is scribbled on surface2Fast drop CH in the transparent conductive substrate of thin film3NH3X Yu HC (NH2)2The mixing of X is molten
Liquid, X is halogen iodine ion I-, chloride ion Cl-, bromide ion Br-In any one, form perovskite forerunner by spin coating mode
Body film；(2) heat treatment forms high-quality perovskite crystal thin film；
Wherein, CH described in step (1)3NH3X Yu HC (NH2)2The compound method of the mixed solution of X is as follows: first will
CH3NH3X Yu HC (NH2)2X x:(1-x in molar ratio) or (1-x): x mixing, then it is molten that this mixture is dissolved completely in isopropanol
In agent；Wherein, 0.1≤x≤0.4, the concentration of mixture solute is 0.37～0.46mM.
In the preferred embodiment, PbI described in step (1)2Thin film has that surfacing is smooth, compact structure
Feature, its preparation method comprises the steps: PbI2, DMSO join in DMF solvent, wherein PbI2Concentration be 0.8～
1.2M, DMSO and PbI2Mol ratio be 1:(1～2), then stirring is until PbI2It is completely dissolved, obtains reactant liquor A；Preparation
Reactant liquor A drips in transparent conductive substrate, carries out spin coating for the first time, forms PbI2Thin film, wherein, rotating speed be 3000～
5000rpm, spin-coating time is 25～35s, and the consumption of reactant liquor A is 8～14 μ L cm-2。
In the preferred embodiment, transparent conductive substrate described in step (1) is at glass or flexiplast base
Commonly using thoroughly including including indium tin oxide (ITO), fluorine tin-oxide (FTO) or aluminum zinc oxide (AZO) etc. is grown at the end
The conductive substrates that prescribed electrode material is formed.
In the preferred embodiment, it is being coated with PbI described in step (1)2Before thin film, in transparent conductive substrate
First one layer of TiO of spin coating2, with after through 550 DEG C annealing 30 minutes formed compacted zones, thickness range is 30～50nm；Then in densification
Layer one layer of mesoporous TiO of surface spin coating2, with after within 30 minutes, form mesoporous layer through 500 DEG C of annealing, thickness range is 100～250nm.
In the preferred embodiment, the fast drop described in step (1) refers at PbI2After thin film is formed
CH is dripped within 0.5～5 minute3NH3X Yu HC (NH2)2The mixed solution of X.
In the preferred embodiment, described in step (1), the rotating speed of spin coating mode is 3000～5000rpm, time
Between be 20～40s, CH3NH3X Yu HC (NH2)2The mixed solution consumption of X is 40～70 μ L cm-2。
In the preferred embodiment, described in step (2), the concrete operations of heat treatment are as follows: by step (1)
Surface defines the conductive substrates of perovskite precursor film and is placed on warm table, carries out at certain time heating in air atmosphere
Reason, wherein, heating-up temperature is 120～160 DEG C, and heat time heating time is 10～30 minutes.
In the preferred embodiment, the operating environment of described step (1) and (2) is air atmosphere, wherein, and temperature
Degree scope is 18～30 DEG C, and humidity range is≤50%.
As preferably, a kind of simple and quick method preparing high-quality perovskite crystal thin film, step is as follows:
(1) preparation reaction solution
By PbI2, DMSO join DMF (DMF, N, N-dimethylformamide, DMF) solvent
In, wherein PbI2Concentration be 0.8～1.2M, DMSO and PbI2Mol ratio be 1:(1～2), then stirring is until PbI2Completely
Dissolve, obtain reactant liquor A；By CH3NH3X Yu HC (NH2)2X x:(1-x in molar ratio) or (1-x): x mixing, then by this mixture
Being dissolved in isopropanol solvent, mixture solute concentration is 0.37～0.46mM, obtains reactant liquor B；Wherein, X be halogen iodine from
Sub-I-, chloride ion Cl-, bromide ion Br-In any one, 0.1≤x≤0.4.
(2) spin-coating film
A) first one layer of TiO of spin coating in clean FTO conductive substrates2, with after through 550 DEG C annealing 30 minutes formed densification
Layer, thickness is about 30～50nm；Then at one layer of mesoporous TiO of compacted zone surface spin coating2, with after through 500 DEG C anneal 30 minutes shapes
Becoming mesoporous layer, thickness is about 100～250nm.
B) add hot surface and define TiO2Compacted zone and TiO2The FTO conductive substrates of mesoporous layer so that it is temperature maintain 60～
80℃。
C) the reactant liquor A of preparation in step (1) is dripped in the transparent conductive substrate of step b), carry out revolving for the first time
It is coated with, forms PbI2Thin film, wherein, rotating speed is 3000～4500rpm, and spin-coating time is 25～35s, the consumption of reactant liquor A be 8～
14μL·cm-2。
D) then, by reactant liquor B fast drop at the PbI formed2On thin film, carry out second time spin coating, form calcium titanium
Ore deposit precursor film, wherein, rotating speed is 3000～5000rpm, and the time is 20～40s, and the consumption of reactant liquor B is 40～70 μ L
cm-2。
(3) heat treatment
The conductive substrates that surface in step (2) defines perovskite precursor film is placed on warm table, in air atmosphere
In carry out certain time heat treated, wherein, heating-up temperature is 120～160 DEG C, and heat time heating time is 10～30 minutes.
Described high-quality perovskite crystal thin film can be at photovoltaic device, especially perovskite solaode or light electrical resistivity survey
Survey in device and apply.
The present invention has the advantage that:
1. the perovskite crystal film crystal unity prepared by method of the present invention is good, grain size distribution uniformly, cover
Lid rate is high, surfacing is smooth, extinction characteristic good, is applied in perovskite solaode as photoactive layer, it is possible to
Prepare that photoelectric properties are good, the battery device of good stability.
Method the most of the present invention is liquid phase deposition based on spin coating mode, it is not necessary to the costliness such as glove box, vacuum chamber
Equipment, reduces preparation cost；Operational process of craft is simple, from starting spin coating PbI2Thin to finally preparing perovskite crystal
Film, this process can complete in 20～30 minutes, shorten manufacturing cycle.
Accompanying drawing explanation
Fig. 1, the SEM for the embodiment of the present invention 1, embodiment 2 and the prepared perovskite crystal thin film of comparative example 1 scheme, wherein,
Figure a, b are that embodiment 1, embodiment 2 with the addition of a certain proportion of methylpyridinium iodide amine (methylammonium in reactant liquor B
Iodide, MAI) the SEM figure of prepared perovskite crystal thin film, figure c is that comparative example 1 is not added with MAI in reactant liquor B and prepares
The SEM figure of perovskite crystal thin film.
Fig. 2, for the XRD figure spectrum of the perovskite crystal thin film that the embodiment of the present invention 1, embodiment 2 and comparative example 1 prepare.
Fig. 3, for the ultraviolet-visible light of the perovskite crystal thin film that the embodiment of the present invention 1, embodiment 2 and comparative example 1 prepare
Abosrption spectrogram.
Fig. 4, the SEM for the embodiment of the present invention 3, embodiment 4 and the prepared perovskite crystal thin film of comparative example 2 scheme, wherein,
Figure a, b are that embodiment 3, embodiment 4 with the addition of certain proportion carbonamidine hydriodate (formamidinium in reactant liquor B
Iodide, FAI) the SEM figure of prepared perovskite crystal thin film, figure c is that comparative example 2 is not added with FAI in reactant liquor B and prepares
The SEM figure of perovskite crystal thin film.
Fig. 5, for the XRD figure spectrum of the perovskite crystal thin film that the embodiment of the present invention 3, embodiment 4 and comparative example 2 prepare.
Fig. 6, for the ultraviolet-visible light of the perovskite crystal thin film that the embodiment of the present invention 3, embodiment 4 and comparative example 2 prepare
Abosrption spectrogram.
Fig. 7, for the structural representation of the perovskite solar cell device that the present invention makes.1-gold electrode 2-hole passes
Conducting shell 3-perovskite 4-TiO2 mesoporous layer 5-TiO2 compacted zone 6-FTO 7-glass substrate.
Fig. 8, for applying the perovskite crystal thin film that the embodiment of the present invention 1 and comparative example 1 prepare at perovskite solar energy
The IV curve of the surveyed battery of battery.
Detailed description of the invention
With specific embodiment the present invention be further explained below in conjunction with the accompanying drawings and illustrate, but the present invention be not limited to
Lower embodiment.As without if no special instructions, material used in following embodiment, reagent etc. the most commercially obtain.
Embodiment 1
(1) preparation reactant liquor
First by PbI2Join in DMF solvent with DMSO, wherein, PbI2Concentration be 1M, DMSO and PbI2Equimolar
Ratio, the most at room temperature magnetic agitation 1 hour, makes PbI2It is completely dissolved and obtains reactant liquor A；By methylpyridinium iodide amine
(methylammonium iodide, MAI) and carbonamidine hydriodate (formamidinium iodide, FAI) in molar ratio 1:
9 mixing, then this mixture is dissolved in isopropanol solvent, the concentration of mixture solute is 0.41mM, and vibration makes solute complete
Dissolving obtains reactant liquor B.
(2) spin-coating film
A) hot surface is added already formed with fine and close TiO2 layer and mesoporous TiO2The FTO conductive substrates of layer so that it is temperature maintains
At 65 DEG C.
B) the reactant liquor A of preparation in step (1) is dripped at above-mentioned a) in preparation substrate on, carry out spin coating for the first time,
Form PbI2Thin film, wherein, rotating speed is 4000rpm, and spin-coating time is 25s, and the consumption of reactant liquor A is 12 μ L cm-2。
C) then, by reactant liquor B fast drop at the PbI formed2On thin film, carry out second time spin coating, form calcium titanium
Ore deposit precursor film, wherein, rotating speed is 4000rpm, and spin-coating time is 30s, and the consumption of reactant liquor B is 50 μ L cm-2。
(3) heat treatment
The FTO conductive substrates that surface defines perovskite precursor film is placed on warm table, carries out in air atmosphere
Certain time heat treated, wherein, heating-up temperature is 150 DEG C, and heat time heating time is 15 minutes.
Embodiment 2
(1) preparation reactant liquor
First by PbI2Join in DMF solvent with DMSO, wherein, PbI2Concentration be 1M, DMSO and PbI2Equimolar
Ratio, the most at room temperature magnetic agitation 1 hour, makes PbI2It is completely dissolved and obtains reactant liquor A；By MAI Yu FAI 3:7 in molar ratio
Mixing, then this mixture is dissolved in isopropanol solvent, the concentration of mixture solute is 0.41mM, and vibration makes solute the most molten
Solution obtains reactant liquor B.
(2) spin-coating film
Identical with the step (2) in embodiment 1.
(3) heat treatment
Identical with the step (3) in embodiment 1.
Embodiment 3
(1) preparation reactant liquor
First by PbI2Join in DMF solvent with DMSO, wherein, PbI2Concentration be 0.8M, DMSO and PbI2Equimolar
Ratio, the most at room temperature magnetic agitation 1 hour, makes PbI2It is completely dissolved and obtains reactant liquor A；By MAI and FAI 9:1 in molar ratio
Mixing, then this mixture is dissolved in isopropanol solvent, the concentration of mixture solute is 0.43mM, and vibration makes solute the most molten
Solution obtains reactant liquor B.
(2) spin-coating film
A) hot surface is added already formed with fine and close TiO2Layer and mesoporous TiO2The FTO conductive substrates of layer so that it is temperature maintains
65℃。
B) the reactant liquor A of preparation in step (1) is dripped at above a) the middle mesoporous TiO formed2On layer, carry out for the first time
Spin coating, forms PbI2Thin film, wherein, rotating speed is 3500rpm, and spin-coating time is 30s, and the consumption of reactant liquor A is 12 μ L cm-2。
C) then, by reactant liquor B fast drop at the PbI formed2On thin film, carry out second time spin coating, form calcium titanium
Ore deposit precursor film, wherein, rotating speed is 4000rpm, and spin-coating time is 25s, and the consumption of reactant liquor B is 60 μ L cm-2。
(3) heat treatment
The FTO conductive substrates that surface defines perovskite precursor film is placed on warm table, carries out in air atmosphere
Certain time heat treated, wherein, heating-up temperature is 130 DEG C, and heat time heating time is 20 minutes.
Embodiment 4
(1) preparation reactant liquor
First by PbI2Join in DMF solvent with DMSO, wherein, PbI2Concentration be 0.8M, DMSO and PbI2Equimolar
Ratio, the most at room temperature magnetic agitation 1 hour, makes PbI2It is completely dissolved and obtains reactant liquor A；By MAI and FAI 7:3 in molar ratio
Mixing, then this mixture is dissolved in isopropanol solvent, the concentration of mixture solute is 0.43mM, and vibration makes solute the most molten
Solution obtains reactant liquor B.
(2) spin-coating film
Identical with the step (2) in embodiment 3.
(3) heat treatment
Identical with the step (3) in embodiment 3.
Comparative example 1
(1) preparation reactant liquor
First by PbI2Join in DMF solvent with DMSO, wherein, PbI2Concentration be 1M, DMSO and PbI2Equimolar
Ratio, the most at room temperature magnetic agitation 1 hour, makes PbI2It is completely dissolved and obtains reactant liquor A；FAI is dissolved in isopropanol solvent
In, the concentration of solute is 0.41mM, and vibration makes solute be completely dissolved to obtain reactant liquor B.
(2) spin-coating film
Identical with the step (2) in embodiment 1.
(3) heat treatment
Identical with the step (3) in embodiment 1.
The SEM photograph of the perovskite crystal thin film that embodiment 1, embodiment 2 and comparative example 1 prepare respectively as Fig. 1 (a),
Shown in (b), (c)；XRD figure spectrum and uv-visible absorption spectroscopy figure are then the most as shown in Figure 2 and Figure 3.As seen from Figure 1,
The smooth densification of perovskite crystal thin film that embodiment 1, embodiment 2, comparative example 1 prepare, and crystallite dimension relatively big (500～
1000nm)；As seen from Figure 2, the perovskite thin film prepared by embodiment 1, embodiment 2, the perovskite feature of its correspondence is spread out
Penetrate peak intensity all ratio being obviously enhanced in comparative example 1, and PbI2Residual significantly reduces, and illustrates that embodiment 1, embodiment 2 prepare
The degree of crystallinity of perovskite crystal thin film is more preferable；As seen from Figure 3, embodiment 1, embodiment 2 prepare perovskite crystal thin film phase
For comparative example 1, the absorbing ability in 400～550nm wave-length coverages is remarkably reinforced.
Comparative example 2
(1) preparation reactant liquor
First by PbI2Join in DMF solvent with DMSO, wherein, PbI2Concentration be 0.8M, DMSO and PbI2Equimolar
Ratio, the most at room temperature magnetic agitation 1 hour, makes PbI2It is completely dissolved and obtains reactant liquor A；MAI is dissolved in isopropanol solvent
In, the concentration of solute is 0.43mM, and vibration makes solute be completely dissolved to obtain reactant liquor B.
(2) spin-coating film
Identical with the step (2) in embodiment 3.
(3) heat treatment
Identical with the step (3) in embodiment 3.
The SEM photograph of the perovskite crystal thin film that embodiment 3, embodiment 4 and comparative example 2 prepare respectively as Fig. 4 (a),
B, shown in (), (c), XRD figure spectrum and uv-visible absorption spectroscopy figure are then the most as shown in Figure 5, Figure 6.As seen from Figure 4,
The smooth densification of perovskite crystal thin film that embodiment 3, embodiment 4, comparative example 2 prepare, crystallite dimension relatively big (500～
1000nm)；As seen from Figure 5, the perovskite thin film prepared by embodiment 3, embodiment 4, the perovskite feature of its correspondence is spread out
Penetrate peak intensity all ratio being obviously enhanced in comparative example 2, embodiment 3, the crystallization of the prepared perovskite crystal thin film of embodiment 4 are described
Degree is more preferably；As seen from Figure 6, the perovskite crystal thin film that embodiment 3, embodiment 4 prepare, not only at 400～600nm wavelength
In the range of absorbing ability be remarkably reinforced, simultaneously in the range of 750～800nm longer wavelengths, absorbing ability has strengthened, and inhales
Receive border and there occurs red shift, more preferable as the light absorbing material effect in solaode.
In order to the perovskite crystal thin film prepared according to the inventive method is described, it is applied to too as light absorbing material
In sun energy battery, obtained device has transformation efficiency height, the advantage of good stability, has made perovskite solar energy further
Battery, as it is shown in fig. 7, its structure is from top to bottom followed successively by: gold electrode/hole-conductive layer/calcium titanium ore bed/mesoporous TiO 2
Layer/compact titanium dioxide layer/FTO glass substrate.Except calcium titanium ore bed respectively according in embodiment 1,2,3,4 and comparative example 1,2
Described step and parameter make, and other structure sheafs of the battery of all making all use identical making step and technological parameter.
The perovskite solaode just completed is carried out photoelectric properties test, and it the results are shown in Table one；By these batteries in room temperature
Placing 23 days in air ambient, the most again it is carried out photoelectric properties test, it the results are shown in Table two.Wherein, embodiment 1 and contrast
The I-V curve of the corresponding battery of example 1 is as shown in Figure 8.
Table one
Table two
Claims (10)
1. the simple and quick method preparing high-quality perovskite crystal thin film, it is characterised in that comprise the steps:
(1) PbI is scribbled on surface2Fast drop CH in the transparent conductive substrate of thin film3NH3X Yu HC (NH2)2The mixed solution of X, X
For halogen iodine ion I-, chloride ion Cl-, bromide ion Br-In any one, form perovskite precursor film by spin coating mode；
(2) heat treatment forms high-quality perovskite crystal thin film；
Wherein, CH described in step (1)3NH3X Yu HC (NH2)2The compound method of the mixed solution of X is as follows: first by CH3NH3X with
HC(NH2)2X x:(1-x in molar ratio) or (1-x): x mixing, then this mixture is dissolved completely in isopropanol solvent；Wherein,
0.1≤x≤0.4, the concentration of mixture solute is 0.37～0.46mM.
A kind of simple and quick method preparing high-quality perovskite crystal thin film the most according to claim 1, its feature exists
In: PbI described in step (1)2Thin film has that surfacing is smooth, the feature of compact structure, and its preparation method includes walking as follows
Rapid: by PbI2, DMSO join in DMF solvent, wherein PbI2Concentration be 0.8～1.2M, DMSO and PbI2Mol ratio be 1:
1～2, then stirring is until PbI2It is completely dissolved, obtains reactant liquor A；The reactant liquor A of preparation drips in transparent conductive substrate,
Carry out spin coating for the first time, form PbI2Thin film, wherein, rotating speed is 3000～5000rpm, and spin-coating time is 25～35s, reactant liquor
The consumption of A is 8～14 μ L cm-2。
A kind of simple and quick method preparing high-quality perovskite crystal thin film the most according to claim 1 and 2, its feature
It is:
Transparent conductive substrate described in step (1) includes indium tin oxide, fluorine stannum for growth on glass or flexible plastic substrates
The conductive substrates that oxide or aluminum zinc oxide are formed at interior conventional transparent electrode material.
A kind of simple and quick method preparing high-quality perovskite crystal thin film the most according to claim 2, its feature exists
In: it is being coated with PbI described in step (1)2Before thin film, first one layer of TiO of spin coating in transparent conductive substrate2, formed with after annealing and cause
Close layer, thickness range is 30～50nm；Then at one layer of mesoporous TiO of compacted zone surface spin coating2, thickness range be 100～
250nm。
A kind of simple and quick method preparing high-quality perovskite crystal thin film the most according to claim 1, its feature exists
In: the fast drop described in step (1) is at PbI2Thin film formed after 0.5～5 minute within drip CH3NH3X and HC
(NH2)2The mixed solution of X.
A kind of simple and quick method preparing high-quality perovskite crystal thin film the most according to claim 1, its feature exists
In: described in step (1), the rotating speed of spin coating mode is 3000～5000rpm, and the time is 20～40s, CH3NH3X Yu HC (NH2)2X
Mixed solution consumption be 40～70 μ L cm-2。
A kind of simple and quick method preparing high-quality perovskite crystal thin film the most according to claim 1, its feature exists
In: described in step (2), the concrete operations of heat treatment are as follows: surface in step (1) is defined leading of perovskite precursor film
Electricity substrate is placed on warm table, carries out certain time heat treated in air atmosphere, and wherein, heating-up temperature is 120～160
DEG C, heat time heating time is 10～30 minutes.
A kind of simple and quick method preparing high-quality perovskite crystal thin film the most according to claim 1, its feature exists
In: the operating environment of described step (1) and (2) is air atmosphere, and wherein, temperature range is 18～30 DEG C, and humidity range is
≤ 50%.
9. a high-quality perovskite crystal thin film, it is prepared by the method described in claim 1.
10. the application of the high-quality perovskite crystal thin film described in claim 9, it is used for photoelectric device, described photoelectricity
Device includes perovskite solaode or photodetector.
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