CN108023017A - A kind of monocrystal thin films of organo-mineral complexing perovskite material and its preparation method and application - Google Patents
A kind of monocrystal thin films of organo-mineral complexing perovskite material and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of monocrystal thin films of organo-mineral complexing perovskite material and its preparation method and application, the method be using two-dimensional confinement induction solution to prepare the monocrystal thin films of organo-mineral complexing large area perovskite, this method is to ABX3Type perovskite structural material is effective, can obtain the monocrystal thin films of the perovskite material of high quality large area.The thickness of the film is adjustable in 10 nanometers to 10 micrometer ranges, adapts to the thickness requirements to light absorbing layer in different photoelectric devices.The film can be prepared in different substrates, and the method for this growth in situ makes have good contact between monocrystal thin films and base, adapts to the interface requirements to light absorbing layer in different photoelectric devices.The preparation condition of the preparation method is gentle, and possesses many advantages, such as step is simple, operation is convenient, cost is low, and energy consumption is small, is adapted for use in the photoelectric device large-scale industrial production application of different purposes.
Description
Technical field
The invention belongs to optoelectronic materials technology, and in particular to a kind of monocrystalline of organo-mineral complexing perovskite material is thin
Film and its preparation method and application.
Background technology
Organo-mineral complexing perovskite material is widely paid close attention to due to its remarkable photoelectric properties in recent years, is based on
The thin film solar cell of such material is broken through again and again in the few years in efficiency, fast less than 4% by 2009
Speed is promoted to this year just the 22.1% of NREL certifications, has been over the efficiency record of polycrystal silicon cell.Due to perovskite electricity
Pond is of low cost, and preparation process is simple, it is considered to be one of contenders of solar cell of future generation.In addition, calcium
Before the excellent photoelectric properties of titanium ore material also allow it to have very big application in laser, light emitting diode, photoelectric sensor etc.
Scape.
The typical structure molecular formula of perovskite-type material is ABX3, wherein A is usually CH3NH3 +、CH3CH2NH3 +、NH2CH=
NH2 +And replace element Cs as full-inorganic perovskite material+；B is usually Pb2+、Sn2+、Ge2+Deng X is halide ion.This
The material of kind of structure have the advantages that abundant raw material, it is cheap, be easily-synthesized, while this kind of ABX3The organo-mineral complexing of structure
Perovskite material has good crystallinity, absorption coefficient of light height, bipolar semiconductor is functional, carrier mobility is high, carrier
The remarkable photoelectric properties such as recombination lifetime length.
In order to probe into the performance boundary of perovskite material and the mechanism of action, and also to more preferable device is prepared, it is related
Also receive much concern in the research of perovskite material monocrystalline, only Huang, Sargent, Yang in 2015 et al. are just on SCIENCE
3 papers probed into relation to perovskite material crystal growth and performance have been published, while at other with the miscellaneous of tremendous influence power
Also many growth synthesis on perovskite material crystal and the paper applied have been delivered in will.Perovskite material monocrystalline at present
Research be also concentrated mainly in the nanocrystalline research of perovskite body phase crystal and various forms, perovskite body phase monocrystal by
Prove that there is the low defect density of states, the outstanding photoelectric properties such as high carrier mobility and long carrier recombination lifetime, but because
For its extremely strong crystal property, conventional method for monocrystal growth is difficult the monocrystal thin films for growing two dimension, so related two dimension is thin
The research of film perovskite monocrystalline is also without too many achievement.
Up to the present, prepare the process of perovskite photoelectric device light absorbing layer mainly have spin coating, spraying, blade coating,
Double source hot evaporation etc..The perovskite photoelectric device light absorbing layer prepared by various processes is all perovskite polycrystal film,
And polycrystal film inevitably has substantial amounts of grain boundary and surface defect and causes trap states level density to become higher, so as to lead
The decline of the important parameters such as carrier mobility, service life and diffusion length is caused, thereby reduces the performance of photoelectric device.Therefore,
In order to further improve the performance of perovskite photoelectric device, it is necessary to prepare a kind of high quality, large area, preparation condition temperature
The high perovskite monocrystal thin films with, controllability.
The content of the invention
An object of the present invention is to provide a kind of preparation method of the monocrystal thin films of organo-mineral complexing perovskite material.
The preparation method is that the monocrystalline of organo-mineral complexing perovskite material is prepared by way of two-dimensional confinement induced growth
Film, the preparation method have many advantages, such as simple, cost is low, energy consumption is small and operation is convenient.
The second object of the present invention is to provide the organo-mineral complexing perovskite material that above-mentioned preparation method is prepared
Monocrystal thin films, the monocrystal thin films have the characteristics that high quality, large area, controllability are high, and its thickness can be within the specific limits
Controllably adjust, to preparing substrate non-selectivity, can adapt to the preparation requirement of various photoelectric devices.
The third object of the present invention is to provide the application of the monocrystal thin films of above-mentioned organo-mineral complexing perovskite material, it can
It is adapted to the large-scale industrial production application of photoelectric device (particularly solar cell).
To achieve these goals, the present invention provides following technical solution：
A kind of preparation method of the monocrystal thin films of organo-mineral complexing perovskite material, the preparation method include following step
Suddenly：
(1) precursor solution of organo-mineral complexing perovskite material is prepared, processing is envisaged for the base of growth monocrystal thin films
Bottom；
(2) will processing obtains in step (1) substrate combination into two-dimensional confinement structure, and with before the perovskite material
Liquid solution contact is driven, forms the film of the precursor solution through capillary action；
(3) under certain condition, precursor in situ is grown to monocrystalline, obtains the organo-mineral complexing perovskite material
Monocrystal thin films.
According to the present invention, the preparation method still further comprises following steps：
(4) the presoma solvent in the monocrystal thin films for the organo-mineral complexing perovskite material that step (3) is prepared
Remove, obtain the monocrystal thin films of final organo-mineral complexing perovskite material.
According to the present invention, in step (1), the presoma of the organo-mineral complexing perovskite material includes at least one tie
The compound and at least one structural formula that structure formula is AX are BX2Compound, wherein, A is selected from CH3NH3 +, CH3CH2NH3 +, NH2CH
=NH2 +, CH3(CH2)2NH3 +, CH3(CH2)3NH3 +, C6H5(CH2)2NH3 +One kind or its mixture in；B is selected from Pb2+, Sn2 +, Ge2+One kind or its mixture in；X is selected from Cl-, Br-, I-In one kind or its mixture.
According to the present invention, in step (1), compound and structural formula that the structural formula is AX are BX2Compound rub
You are than being 1:1~10, it is preferably 1:1~3.
According to the present invention, in step (1), the solvent of the precursor solution be selected from tetrahydrofuran, gamma-butyrolacton (GBL),
One or more in acetonitrile, aniline, dimethyl sulfoxide (DMSO) (DMSO), N,N-dimethylformamide (DMF) etc.；Preferably γ-fourth
One or more in lactone (GBL), dimethyl sulfoxide (DMSO) (DMSO) and N,N-dimethylformamide (DMF).
According to the present invention, in step (1), the concentration of the precursor solution can be 0.01~5mol/L, preferably 0.5~
2.5mol/L。
According to the present invention, in step (1), the substrate for being used to grow monocrystal thin films includes but not limited to silicon chip, quartz
Piece, sheet glass, high molecular polymer (PET) substrate, indium tin oxide-coated glass (ITO) piece, the tin dioxide conductive for adulterating fluorine
Glass (FTO) piece, graphene-based bottom, mica sheet and all kinds of metallic substrates etc..
According to the present invention, in step (2), the substrate can be combined into two-dimensional confinement structure in any way.
According to the present invention, in step (2), the way of contact of the substrate and the precursor solution includes but not limited to will
The precursor solution penetrated into by way of dropwise addition the substrate combination into two-dimensional confinement structure in, form the forerunner
Liquid solution film；Or by the base part or be entirely within the precursor solution, form the precursor solution film.
According to the present invention, in step (3), the temperature of growth in situ can be 0~200 DEG C, be preferably 50~150 DEG C, more excellent
Elect 80~110 DEG C as.
According to the present invention, in step (3), the time of growth in situ is 6h~5d, is preferably 24h~48h.
According to the present invention, in step (3), the thickness of the monocrystal thin films can by apply pressure on the substrate come
Regulated and controled.
Preferably, the monocrystal thin films thickness non-linear reduction with the pressure increase applied on the substrate, such as
Monocrystal thin films can be formed when pressure is more than 1kPa；When pressure is more than 200kPa, the thickness of the monocrystal thin films, which can reach, to be received
Meter level, pressure continue increase and are then difficult to accurately measure, and 10nm thickness can be reached after great pressure is increased to.
According to the present invention, in step (3), the organo-mineral complexing perovskite material includes at least one structural formula and is
ABX3Organo-mineral complexing perovskite material, wherein, A is selected from CH3NH3 +, CH3CH2NH3 +, NH2CH=NH2 +, CH3(CH2)2NH3 +, CH3(CH2)3NH3 +, C6H5(CH2)2NH3 +One kind or its mixture in；B is selected from Pb2+, Sn2+, Ge2+One kind in or
Its mixture；X is selected from Cl-, Br-, I-In one kind or its mixture.
According to the present invention, in step (4), the presoma solvent in the monocrystal thin films can pass through thermal station, baking oven, drying box
One or more modes such as baking remove.
According to the present invention, in step (4), different depending on perovskite component, the removal time of the presoma solvent can be 12h
~5d；The removal temperature of the presoma solvent can be 50~150 DEG C, be preferably 80~110 DEG C.
A kind of monocrystal thin films for the organo-mineral complexing perovskite material being prepared the present invention also provides above method, institute
State that the thickness of monocrystal thin films is adjustable between micron dimension and nanometer scale, i.e., the thickness of described monocrystal thin films is at 10 nanometers to 10
It is adjustable in micrometer range, and uniform film thickness.
In the present invention, the big (film of monocrystal thin films quality height, area for the organo-mineral complexing perovskite material being prepared
Area diameter length is at least 500 μm), thickness it is controllable, to substrate non-selectivity.Wherein, for growing the substrates of monocrystal thin films
Including but not limited to silicon chip, quartz plate, sheet glass, high molecular polymer (PET) substrate, indium tin oxide-coated glass (ITO) piece,
Adulterate tin dioxide conductive glass (FTO) piece, graphene-based bottom, mica sheet and all kinds of metallic substrates of fluorine etc..
In the present invention, crystal defect is few in the monocrystal thin films for the organo-mineral complexing perovskite material being prepared, quality
Height, its photoelectric properties are suitable with the body phase monocrystal of corresponding perovskite material.
The present invention also provides the application of the monocrystal thin films of above-mentioned organo-mineral complexing perovskite material, it can be adapted to phototube
The large-scale industrial production application of part, particularly solar cell.
Beneficial effects of the present invention：
1. the present invention provides a kind of preparation method of the monocrystal thin films of organo-mineral complexing perovskite material, the method
It is that this method is to ABX using two-dimensional confinement inducing solution to prepare the monocrystal thin films of organo-mineral complexing large area perovskite3Type
Perovskite structural material is effective, can obtain high quality, the calcium of large area (such as film size diameter length is at least 500 μm)
The monocrystal thin films of titanium ore material.The preparation condition of the preparation method is gentle, and preparation process is simple and convenient to operate, cost is low,
Many advantages, such as energy consumption is small, is suitable for industrialized production.
2. the monocrystal thin films for the organo-mineral complexing perovskite material being prepared the present invention also provides the above method, described
Organo-mineral complexing perovskite material monocrystal thin films thickness it is adjustable in 10 nanometers to 10 micrometer ranges, adapt in not
Thickness requirements with photoelectric device to light absorbing layer.The monocrystal thin films of the organo-mineral complexing perovskite material are different
It can be prepared in substrate, and the method for this growth in situ makes have good contact between monocrystal thin films and substrate, adapts to
Interface requirements in different photoelectric devices to light absorbing layer.The monocrystal thin films of the organo-mineral complexing perovskite material have
High crystal quality, proves that it has the photoelectric properties suitable with perovskite body phase monocrystal by testing, adapts to phototube
Requirement of the part to monocrystal material light absorbing layer.The monocrystal thin films of the organo-mineral complexing perovskite material have well steady
Qualitative, in 1 atmospheric pressure, room temperature, does not have significant change after placing 5 months under the air conditional of 20% humidity, can be greatly
The service life of photoelectric device is improved, reduces device manufacturing cost.
3. the present invention also provides a kind of purposes of the monocrystal thin films of organo-mineral complexing perovskite material, for different purposes
Photoelectric device large-scale industrial production application.
Brief description of the drawings
Fig. 1 is the scanning electron microscopy of the monocrystal thin films for the organo-mineral complexing perovskite material that embodiment 1 is prepared
Mirror figure (SEM).
Fig. 2 is the monocrystal thin films for the organo-mineral complexing perovskite material that embodiment 1 is prepared under standard x RD light sources
MABr powder (the wherein MA measured+For CH3NH3 +)、PbBr2Powder and MAPbBr3Monocrystalline abrasive flour (wherein MA+For CH3NH3 +) XRD diffraction patterns, synchrotron radiation diffraction pattern and after synchrotron radiation light source signal is converted to standard x RD light signals
XRD diffraction patterns.
Fig. 3 is the original of the different thickness of the monocrystal thin films for the organo-mineral complexing perovskite material that embodiment 1 is prepared
Sub- force microscope sectional view (Fig. 3 .a) and 3D illustratons of model (Fig. 3 .b).
Fig. 4 is the steady-state fluorescence transmitting of the monocrystal thin films for the organo-mineral complexing perovskite material that embodiment 1 is prepared
Spectrum and Ultraviolet visible absorption spectrum figure.
Fig. 5 is respectively the organo-mineral complexing perovskite CH that embodiment 2 and embodiment 3 are prepared3NH3PbI3(Fig. 5 .a)
And CH3NH3PbCl3The scanning electron microscope diagram (SEM) of the monocrystal thin films of (Fig. 5 .b) material.
Fig. 6 is respectively the monocrystal thin films for the organo-mineral complexing perovskite material that embodiment 4-6 is prepared in macromolecule
Polymer (PET) substrate (Fig. 6 .a), sheet glass (Fig. 6 .b), adulterate on tin dioxide conductive glass (FTO) piece (Fig. 6 .c) of fluorine
The optical microscope of growth.
Embodiment
As described above, the present invention provides a kind of preparation method of organo-mineral complexing perovskite material monocrystal thin films, institute
Preparation method is stated to include the following steps：
(1) precursor solution of organo-mineral complexing perovskite material is prepared, processing is envisaged for the base of growth monocrystal thin films
Bottom；
(2) will processing obtains in step (1) substrate combination into two-dimensional confinement structure, and with before the perovskite material
Liquid solution contact is driven, forms the precursor solution film through capillary action；
(3) under certain condition, precursor in situ is grown to monocrystalline, obtains the organo-mineral complexing perovskite material
Monocrystal thin films.
In one preferred embodiment, the preparation method still further comprises following steps：
(4) the presoma solvent in the monocrystal thin films for the organo-mineral complexing perovskite material that step (3) is prepared
Remove, obtain the monocrystal thin films of final organo-mineral complexing perovskite material.
In an embodiment of the invention, in step (1), the processing side of the substrate for monocrystal thin films growth
Method is：The substrate is sequentially placed into deionized water, absolute ethyl alcohol, acetone soln and distinguishes 15~30min of ultrasound, nitrogen is blown
It is dry, 0~20min of oxygen is passed through under ultraviolet light.It is unrestricted, it is possible the reason for needed for the growth of large area monocrystal thin films
Nucleating point is reduced to the greatest extent, it is necessary to substrate surface is very clean, can be gone by the cleaning of deionized water, absolute ethyl alcohol, acetone
Except the pollution of substrate surface, pass through UV-O3Further cleaning and hydrophilic treated, the leaching of perovskite precursor solution can be improved
Lubricant nature, makes perovskite precursor solution uniformly spread over substrate surface.
In an embodiment of the invention, in step (2), the substrate can be that any-mode is combined into two-dimentional limit
Domain structure.The way of contact of the substrate and the precursor solution includes but not limited to the precursor solution passing through dropwise addition
Mode penetrate into the two-dimensional confinement structure of the substrate combination, form the precursor solution film；Or by the basal part
Divide or be entirely within the precursor solution, form the precursor solution film.It is unrestricted, it is possible the reason for pass through
Perovskite precursor solution film in substrate can be connected by the mode of contact with a large amount of precursor solutions, thin in precursor solution
While constantly growth monocrystal thin films consume raw material in film, constantly supplemented by small concentration difference from solution into liquid film
Raw material, is conducive to the perovskite monocrystal thin films of growing large-area.
In an embodiment of the invention, in step (3), the growth temperature of the perovskite material monocrystal thin films can
It is preferably 50~150 DEG C for 0~200 DEG C, more preferably 80~110 DEG C.It is unrestricted, it is possible the reason for for monocrystal thin films
Growth temperature and evaporation rate of solvent are all critically important crystal growth Control factors：Temperature is excessive, the shape meeting of monocrystal thin films
Become irregular, crystallinity reduces；Temperature is too low, and the crystal growth cycle is too long to be unfavorable for conventional efficient, and temperature is too low to be caused
Non- photoelectricity crystalline phase generation；Evaporation rate is too fast, emulative can generate a large amount of body phase monocrystals, waste raw material, while increase crystal
Defect, reduces crystal quality；Evaporation rate is excessively slow, and the crystal growth cycle is too long to be unfavorable for conventional efficient.
In an embodiment of the invention, perovskite monocrystal thin films can be baked by including and being not limited in step (4)
The modes such as glue machine, baking oven, vacuum drying chamber baking remove presoma solvent.It is unrestricted, it is possible the reason for be not through overcharging
Divide removal solvent to cause to show to grow a large amount of little crystal grains in monocrystal thin films, influence monocrystalline film quality.
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments with attached drawing pair
The present invention is further described.It is to be understood that these embodiments are merely to illustrate the model of the present invention rather than the limitation present invention
Enclose.Furthermore, it is to be understood that after described content of the invention has been read, those skilled in the art can make the present invention each
Kind change or modification, such equivalent forms equally fall within limited range of the present invention.
Experimental method used in following embodiments is conventional method unless otherwise specified.Institute in following embodiments
Material, reagent etc., are commercially available unless otherwise specified.
Embodiment 1
Prepare perovskite monocrystal thin films
(1) PbBr is selected2And CH3NH3Br is the precursor material of perovskite-type material, in molar ratio 1：1 amount is dissolved in
In n,N-Dimethylformamide (DMF), configuration obtains the precursor solution of 0.7mol/L；Selected monocrystalline silicon piece substrate is distinguished
The ultrasound 15min in deionized water, absolute ethyl alcohol, acetone, UV-O after nitrogen drying3Handle 20min.
(2) by two panels monocrystalline silicon piece substrate with the force combination more than 1kPa together, then by one end of monocrystalline silicon piece
It is immersed in above-mentioned prepared perovskite precursor solution.
(3) at 100 DEG C, the substrate solution system containing precursor solution film is placed in thermal station and heats 48h, carried out
Growth in situ, obtains the organo-mineral complexing perovskite material monocrystal thin films.
(4) substrate is transferred in vacuum drying oven together with film, dry 48h, obtains final organic nothing at 100 DEG C
Machine composite perofskite material monocrystal thin films.
The organo-mineral complexing perovskite CH that embodiment 1 is prepared3NH3PbBr3Material monocrystal thin films.
Fig. 1 is the organo-mineral complexing perovskite CH that embodiment 1 is prepared3NH3PbBr3The scanning of material monocrystal thin films
Electron microscope picture (SEM).As seen from the figure, the perovskite monocrystal thin films obtained using the technique have very high crystal matter
Amount, the smooth zero defect in surface, the very sharp crystallization degree in side is very high, and area is big, and film size diameter length can reach
500μm.This flawless monocrystal thin films will greatly reduce the trap density of states of film, improve the carrier lifetime of film
And diffusion length, and then improve the device performance to prepare.
Fig. 2 is that the organo-mineral complexing perovskite material monocrystal thin films that embodiment 2 is prepared are surveyed under standard x RD light sources
MABr powder (the wherein MA obtained+For CH3NH3 +), PbBr2Powder and MAPbBr3Monocrystalline abrasive flour (wherein MA+For CH3NH3 +)
XRD diffraction patterns, synchrotron radiation diffraction pattern and synchrotron radiation light source signal is converted to the XRD after standard x RD light signals
Diffraction pattern.As seen from the figure, two origins in synchrotron radiation diffraction pattern represent (100) and (300) of monocrystal thin films respectively
Crystal face signal.There was only the signal of (l00) family of crystal planes in figure, it was demonstrated that monocrystal thin films have fabulous (l00) high preferred orientation, scheme at the same time
It is middle without any polycrystalline ring, it was demonstrated that film is perfect monocrystal thin films.Changed by Bragg equation in XRD diffraction patterns, be in 2 θ
Corresponding diffraction represents the characteristic diffraction peak of (100) and (300) crystal face of perovskite crystal respectively at 14.9 ° and 45.9 °, with
Perovskite body phase monocrystal and the x-ray diffractogram of powder of raw material prepared by same solution condition is compared, and illustrates prepared by this method
Perovskite monocrystal thin films have good crystallinity and crystal orientation.
Fig. 3 is the atom of the different thickness for the organo-mineral complexing perovskite material monocrystal thin films that embodiment 1 is prepared
Force microscope sectional view and 3D models.As seen from the figure, the perovskite monocrystal thin films that the present embodiment is prepared are in 10nm to 5 μm of model
Enclose it is interior can obtain, and film surface flat smooth zero defect has very high crystal quality, can adapt in various devices for
The demand of different thickness.
Fig. 4 is that the steady-state fluorescence for the organo-mineral complexing perovskite material monocrystal thin films that embodiment 1 is prepared launches light
Spectrum, Ultraviolet visible absorption spectrum figure.Fluorescence emission peak is very sharp as we can see from the figure, does not have position relative to body phase monocrystal
Move, photoabsorption cross-section is very sharp, and does not have magnetic tape trailer state, illustrates the perovskite monocrystal thin films crystallinity of this method preparation very
It is good, there is very high crystal quality.
The defects of organo-mineral complexing perovskite material monocrystal thin films that embodiment 1 is prepared the density of states and carrier move
Shifting rate is respectively 4.8 × 1010cm-3And 15.7cm2V-1s-1, and body phase monocrystal is suitable, illustrates it with good crystal quality.
Embodiment 2
The preparation method is differed only in embodiment 1：In step (1), PbI is used2And CH3NH3I is perovskite
The precursor material of section bar material, and 1.2mol/L solution is prepared for presoma solvent with gamma-butyrolacton (GBL).
The organo-mineral complexing perovskite CH that embodiment 2 is prepared3NH3PbI3The monocrystal thin films of material.
Fig. 5 .a are the organo-mineral complexing perovskite CH that embodiment 2 is prepared3NH3PbI3The monocrystal thin films of material are swept
Retouch electron microscope picture (SEM).As seen from the figure, the perovskite monocrystal thin films obtained using the technique have very high crystal matter
Amount, the smooth zero defect in surface, the very sharp crystallization degree in side is very high, and area is big, and film size diameter length can reach
500μm.This flawless monocrystal thin films will greatly reduce the trap density of states of film, improve the carrier lifetime of film
And diffusion length, and then improve the device performance to prepare.
Embodiment 3
The preparation method is differed only in embodiment 1：In step (1), PbCl is used2And CH3NH3Cl is calcium titanium
The precursor material of ore deposit section bar material, and 2.0mol/L solution is prepared for presoma solvent with dimethyl sulfoxide (DMSO) (DMSO).
The organo-mineral complexing perovskite CH that embodiment 3 is prepared3NH3PbCl3The monocrystal thin films of material.
Fig. 5 .b are the organo-mineral complexing perovskite CH that embodiment 3 is prepared3NH3PbCl3The monocrystal thin films of material
Scanning electron microscope diagram (SEM).As seen from the figure, the monocrystal thin films of the perovskite material obtained using the technique have very high
Crystal quality, the smooth zero defect in surface, the very sharp crystallization degree in side is very high, and area is big, film size diameter length
Degree can reach 500 μm.This flawless monocrystal thin films will greatly reduce the trap density of states of film, improve the load of film
Sub- service life and diffusion length are flowed, and then improves the device performance to prepare.
Embodiment 4
The preparation method is differed only in embodiment 1：In step (1), high molecular polymer (PET) base is used
Monocrystal thin films growth substrate of the bottom as perovskite material.
The organo-mineral complexing perovskite CH that embodiment 4 is prepared3NH3PbBr3The monocrystal thin films of material.
Fig. 6 .a are the organo-mineral complexing perovskite CH that embodiment 4 is prepared3NH3PbBr3The monocrystal thin films of material exist
The optical microscope grown in high molecular polymer (PET) substrate.As seen from the figure, the perovskite material obtained using the technique
The monocrystal thin films of material have very high crystal quality, and the smooth zero defect in surface, the very sharp crystallization degree in side is very high, face
Product is big, and film size diameter length can reach 500 μm.This flawless monocrystal thin films will greatly reduce the trap of film
The density of states, improves the carrier lifetime and diffusion length of film, and then improves the device performance to prepare.
Embodiment 5
The preparation method is differed only in embodiment 1：In step (1), perovskite material is used as using sheet glass
Monocrystal thin films growth substrate.
The organo-mineral complexing perovskite CH that embodiment 5 is prepared3NH3PbBr3The monocrystal thin films of material.
Fig. 6 .b are the organo-mineral complexing perovskite CH that embodiment 5 is prepared3NH3PbBr3The monocrystal thin films of material exist
The optical microscope grown on sheet glass.As seen from the figure, the monocrystal thin films tool of the perovskite material obtained using the technique
There is very high crystal quality, the smooth zero defect in surface, the very sharp crystallization degree in side is very high, and area is big, film size
Diameter length can reach 500 μm.This flawless monocrystal thin films will greatly reduce the trap density of states of film, improve thin
The carrier lifetime and diffusion length of film, and then improve the device performance to prepare.
Embodiment 6
The preparation method is differed only in embodiment 1：In step (1), the tin dioxide conductive of doping fluorine is used
Monocrystal thin films growth substrate of the glass (FTO) as perovskite material.
The organo-mineral complexing perovskite CH that embodiment 6 is prepared3NH3PbBr3The monocrystal thin films of material.
Fig. 6 .c are the organo-mineral complexing perovskite CH that embodiment 6 is prepared3NH3PbBr3The monocrystal thin films of material exist
Adulterate the optical microscope grown on the tin dioxide conductive glass (FTO) of fluorine.As seen from the figure, obtained using the technique
The monocrystal thin films of perovskite material have very high crystal quality, and the smooth zero defect in surface, side sharply crystallizes journey very much
Degree is very high, and area is big, and film size diameter length can reach 500 μm.This flawless monocrystal thin films will greatly reduce
The trap density of states of film, improves the carrier lifetime and diffusion length of film, and then improves the device performance to prepare.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to the above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done, should be included in the guarantor of the present invention
Within the scope of shield.
Claims (10)
- A kind of 1. preparation method of the monocrystal thin films of organo-mineral complexing perovskite material, it is characterised in that the preparation method Include the following steps：(1) precursor solution of organo-mineral complexing perovskite material is prepared, processing is envisaged for the substrate of growth monocrystal thin films；(2) will processing obtains in step (1) substrate combination into two-dimensional confinement structure, and with the presoma of the perovskite material Solution contacts, and forms the film of the precursor solution through capillary action；(3) under certain condition, precursor in situ is grown to monocrystalline, obtains the monocrystalline of the organo-mineral complexing perovskite material Film.
- 2. preparation method according to claim 1, it is characterised in that the preparation method still further comprises following step Suddenly：(4) the presoma solvent in the monocrystal thin films for the organo-mineral complexing perovskite material that step (3) is prepared removes, Obtain the monocrystal thin films of final organo-mineral complexing perovskite material.
- 3. preparation method according to claim 1 or 2, it is characterised in that in step (1), the organo-mineral complexing calcium It is BX that the presoma of titanium ore material, which includes the compound that at least one structural formula is AX and at least one structural formula,2Compound, Wherein, A is selected from CH3NH3 +, CH3CH2NH3 +, NH2CH=NH2 +, CH3(CH2)2NH3 +, CH3(CH2)3NH3 +, C6H5(CH2)2NH3 +Deng In one kind or its mixture；B is selected from Pb2+, Sn2+, Ge2+One kind or its mixture in；X is selected from Cl-, Br-, I-In one Kind or its mixture.Preferably, in step (1), compound and structural formula that the structural formula is AX are BX2Compound molar ratio be 1:1 ~10, it is preferably 1:1~3.Preferably, in step (1), the solvent of the precursor solution is selected from tetrahydrofuran, gamma-butyrolacton (GBL), acetonitrile, benzene One or more in amine, dimethyl sulfoxide (DMSO) (DMSO), N,N-dimethylformamide (DMF) etc.；Preferably gamma-butyrolacton (GBL), the one or more in dimethyl sulfoxide (DMSO) (DMSO) and N,N-dimethylformamide (DMF).Preferably, in step (1), the concentration of the precursor solution can be 0.01~5mol/L, be preferably 0.5~2.5mol/ L。Preferably, in step (1), the substrate for being used to grow monocrystal thin films includes but not limited to silicon chip, quartz plate, glass Piece, high molecular polymer (PET) substrate, indium tin oxide-coated glass (ITO) piece, the SnO for adulterating fluorine2Electro-conductive glass (FTO) piece, Graphene-based bottom, mica sheet and all kinds of metallic substrates etc..
- 4. according to the preparation method described in any one of claim 1-3 claim, it is characterised in that described in step (1) The processing method of substrate for monocrystal thin films growth is：It is molten that the substrate is sequentially placed into deionized water, absolute ethyl alcohol, acetone 15~30min of ultrasound is distinguished in liquid, nitrogen drying, is passed through 0~20min of oxygen under ultraviolet light.
- 5. according to the preparation method described in any one of claim 1-4 claim, it is characterised in that described in step (2) Substrate can be combined into two-dimensional confinement structure in any way.Preferably, in step (2), the substrate and the way of contact of the precursor solution include but not limited to the forerunner Liquid solution penetrated into by way of dropwise addition the substrate combination into two-dimensional confinement structure in, it is thin to form the precursor solution Film；Or by the base part or be entirely within the precursor solution, form the precursor solution film.
- 6. according to the preparation method described in any one of claim 1-5 claim, it is characterised in that in situ in step (3) The temperature of growth can be 0~200 DEG C, be preferably 50~150 DEG C, more preferably 80~110 DEG C.Preferably, in step (3), the time of growth in situ is 6h~5d, is preferably 24h~48h.Preferably, in step (3), the thickness of the monocrystal thin films can be adjusted by applying pressure on the substrate Control.Preferably, the monocrystal thin films thickness non-linear reduction with the pressure increase applied on the substrate, such as work as pressure Power, which is more than 1kPa, can form monocrystal thin films；When pressure is more than 200kPa, the thickness of the monocrystal thin films can reach nanoscale, Pressure continues increase and is then difficult to accurately measure, and 10nm thickness can be reached after great pressure is increased to.
- 7. according to the preparation method described in any one of claim 1-6 claim, it is characterised in that described in step (3) It is ABX that organo-mineral complexing perovskite material, which includes at least one structural formula,3Organo-mineral complexing perovskite material, wherein, A Selected from CH3NH3 +, CH3CH2NH3 +, NH2CH=NH2 +, CH3(CH2)2NH3 +, CH3(CH2)3NH3 +, C6H5(CH2)2NH3 +One in Kind or its mixture；B is selected from Pb2+, Sn2+, Ge2+One kind or its mixture in；X is selected from Cl-, Br-, I-In one kind or its Mixture.
- 8. according to the preparation method described in any one of claim 1-7 claim, it is characterised in that described in step (4) Presoma solvent in monocrystal thin films can be removed by way of the one or more such as thermal station, baking oven, drying box baking.Preferably, in step (4), different depending on perovskite component, the removal time of the presoma solvent can be 12h~5d；Institute The removal temperature for stating presoma solvent can be 50~150 DEG C, be preferably 80~110 DEG C.
- 9. the organo-mineral complexing perovskite material that the method described in a kind of any one of claim 1-8 claim is prepared The monocrystal thin films of material, it is characterised in that the thickness of the monocrystal thin films is adjustable between micron dimension and nanometer scale, i.e., described The thickness of monocrystal thin films is adjustable in 10 nanometers to 10 micrometer ranges, and uniform film thickness.
- 10. organo-mineral complexing perovskite material described in prepared by the method for any one of claim 1-8 or claim 9 The application of monocrystal thin films, it is characterised in that available for the application in photoelectric device.Preferably, available for the application in solar cell.
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