CN110484963A - A kind of method that pressure-driven ion diffusion growth prepares inorganic perovskite monocrystal thin films - Google Patents
A kind of method that pressure-driven ion diffusion growth prepares inorganic perovskite monocrystal thin films Download PDFInfo
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- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/12—Single-crystal growth directly from the solid state by pressure treatment during the growth
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- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
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Abstract
The present invention relates to the methods that a kind of diffusion growth of pressure-driven ion prepares inorganic perovskite monocrystal thin films.Inorganic perovskite semiconductor polycrystal film is prepared with conventional solution spin coating method first, is then fitted closely with the cover plate of surface polishing and polycrystal film surface, and with flexible high-temperature resistant film coated.Then, sample is put into the high pressure autoclave full of liquid pressure transmission heat transfer medium, applies high pressure in autoclave after sealing kettle, and setting value is warming up to the speed of setting.After constant temperature and pressure handles a period of time, it is slowly cooled to room temperature autoclave.After shedding pressure, opening autoclave can be obtained the inorganic perovskite semiconductor single crystal thin film of high quality that crystallite size is big, crystallinity is high, crystal boundary height merges.Inorganic perovskite monocrystal thin films prepared by the present invention can be used for developing high performance solar cells, electroluminescent device, photodetector etc., have important application value in new energy technology, the display fields such as device fabrication and automatic control.
Description
Technical field
The present invention relates to the methods that a kind of diffusion growth of pressure-driven ion prepares inorganic perovskite monocrystal thin films, belong to new
Field of material technology.
Background technique
Perovskite semiconductor is due to the absorption coefficient of light is big, absorbing wavelength range is wide, exciton binding energy is small, carrier moves
The series of advantages such as shifting rate is high and diffusion length is long, in the photoelectric functionals device such as solar battery, luminescent device, photodetector
It is widely applied in the development of part.
Currently, perovskite semiconductor material is mostly to be applied in above-mentioned various devices in the form of a film, therefore the matter of film
Amount just directly decides the performance of device.In order to obtain high performance photoelectric functional device, just must try to reduce in film
Various defects increase substantially the quality of film.But the film of the solution spin coating method preparation generallyd use now, crystal grain
Granularity is small, crystal boundary bonding state is poor, film layer causes the problems such as coverage is low and surface roughness is high, seriously damages the light of device
Electrical property.Therefore, big crystallite size, crystalline order combination, surface smoothness height and fine and close, continuous perovskite semiconductor are prepared
Film is to increase substantially the only way of photoelectric device performance, while being also a huge challenge facing at present.
In addition, a kind of sky for preparing organic-inorganic composite semiconductor monocrystal thin films of Chinese patent document CN107634141A
Between limit solvent assisting growth method.Organic-inorganic composite semiconductor polycrystal film is adsorbed into a certain amount of solvent vapo(u)r first,
The cover plate of polishing is placed in film surface again, is put into high pressure hot pressing after polycrystal film and cover plate one are reinstated fexible film encapsulating
It in kettle, seals after filling up autoclave with liquid pressure transmission heat transfer medium, and is begun to warm up after applying high pressure in autoclave.In constant temperature
Constant pressure processing after a certain period of time, is gradually cooled to room temperature, lays down pressure slowly up to by large scale, the crystal grain group of high-crystallinity
The Organic-inorganic composite semiconductor single crystal thin film being well combined at, crystal grain boundary.This method is first will be inferior brilliant using solvent
Grain dissolution, reuse high hydrostatic pressure heat treatment, limitation crystal grain carry out three-dimensional island growth, to greatest extent in two-dimensional surface into
Row diauxic growth finally obtains the monocrystal thin films of uniformly continuous, smooth surface.However, this method is not particularly suited for entirely
The improvement of inorganic perovskite semiconductive thin film, because the heat treatment temperature of full-inorganic perovskite semiconductor material is relatively high, no
The effect of good solvent is failed at high temperature, and film is caused seriously to destroy, to cannot achieve the diauxic growth of crystal grain.
Summary of the invention
For it is existing prepare inorganic perovskite thin film method therefor there are the shortcomings that, the present invention propose utilize high hydrostatic pressure
It drives the ion in inorganic perovskite thin film to transport, realizes the quick diffusion of ion in film, and sink again in grain boundary area
Long-pending and crystal grain diauxic growth.Meanwhile being combined with space position-limiting action, effectively eliminate the three-dimensional island growth mould in film
Formula, preparation is made of super large crystal grain, crystal boundary orderly combines, even film layer is fine and close and the inorganic perovskite semiconductor list of surfacing
Brilliant film.
It, can grinding for solution for high-performance photovoltaic device, electroluminescent device, photoelectric detector etc. using method of the invention
System provides the inorganic perovskite semiconductor single crystal thin film of high quality.
Technical scheme is as follows:
A kind of method that pressure-driven ion diffusion growth prepares inorganic perovskite monocrystal thin films, includes the following steps:
By inorganic perovskite semiconductor polycrystal film without adsorption solvent steam course, space limit is directly carried out, then
High hydrostatic pressure heat treatment is carried out in liquid pressure transmission heat transfer medium to get inorganic perovskite monocrystal thin films are arrived.
, according to the invention it is preferred to, the space limits process are as follows: inorganic perovskite thin film and polishing cover plate is close
Fitting, then cladding sealing；It is further preferred that carrying out cladding sealing using fexible film；
Preferably, the polishing cover plate be silicon wafer, Group III-V semiconductor single-chip, II-VI group semiconductor monocrystal piece,
Alumina wafer, sheet glass；
Preferably, the fexible film is polytetrafluoroethylene film, goldleaf or silver foil.
, according to the invention it is preferred to, when carrying out high hydrostatic pressure heat treatment, pressure is 25~500MPa, and heat treatment temperature is
100~400 DEG C, the processing time is 3~360 hours；It is further preferred that high hydrostatic pressure be heat-treated when heating rate be 0.01~
5 DEG C/min.
, according to the invention it is preferred to, after high hydrostatic pressure is heat-treated, in the case where keeping pressure constant, by temperature
It is reduced to room temperature and sheds pressure again, inorganic perovskite monocrystal thin films can be obtained.
, according to the invention it is preferred to, the inorganic perovskite semiconductor is CsBX3-xYx；Wherein, B is Pb or Sn；X and
Y is halogen, further preferred Cl, Br or I；0≤x≤3.
, according to the invention it is preferred to, in high hydrostatic pressure heat treatment process, the liquid pressure transmission heat transfer medium be silicone oil,
Benzene homologues, alkane, alcohol；
It is further preferred that the silicone oil are as follows: dimethicone, diethyl silicone oil, methyl-silicone oil, aminomethyl phenyl silicon
Oil, methyl vinyl silicon oil, methyl trifluoro propyl silicone oil；
The benzene homologues are benzene, toluene, chlorobenzene, dimethylbenzene；
The alkane are as follows: octane, cyclooctane, nonane, decane, hendecane or dodecane；
The alcohol are as follows: ethylene glycol, triethylene glycol, diethylene glycol (DEG) or triphenylcarbinol.
According to the present invention, the inorganic perovskite semiconductor polycrystal film can be prepared by existing method, can refer to
Document: Rebecca J.Sutton, Giles E.Eperon, Laura Miranda et al., Adv.Energ.Mater.,
2016,6,1502458.Typical preparation CsPbI3-xBrxThe process of polycrystal film includes: by 0.21 mM of PbBr2With 1.19
MM PbI2It is dissolved in the mixed solution of 1mL DMF/DMSO and stirs at normal temperature 3h, then with the filter membrane in 0.22 μm of aperture
Filtering；The ito glass of surface cleaning is placed in 70 DEG C of thermal station and heats 5min, then the 40 above-mentioned mixed solutions of μ L are added drop-wise to
On ito glass substrate, and with 2000 revs/min of revolving speed spin coating 30s, the film obtained in this way is in 70 DEG C of annealing 5min；
Then, a certain amount of CsBr is dissolved into the CsBr solution for obtaining that concentration is 15mg/mL in the methanol of 4.9mL, so
The DMSO of 100 μ L is added in CsBr solution again afterwards, obtains CsBr precursor solution；(about by a drop CsBr precursor solution
10 μ L) it is added drop-wise to PbI prepared above2/PbBr2Film surface, and with the rotation of 2500 revs/min of speed until solvent volatilizees
It is complete, this spin coating process repeat 8-9 times, then by obtained film sample 100 DEG C preannealing 10 minutes.The above whole operation
Process carries out in the glove box full of nitrogen.By the way that Pb is replaced with Sn, and change the molar ratio of mixed halogen, use is above-mentioned
Same method can prepare CsPbI3、CsPbBr3、CsPbCl3、CsSnI3、CsSnBr3、CsSnCl3、CsSnI3-xBrx、
CsPbI3-xBrxEtc. a variety of inorganic perovskite semiconductor polycrystal films.
Preferably, the method that pressure-driven ion diffusion growth prepares inorganic perovskite monocrystal thin films are as follows:
The cover plate of surface polishing is fitted closely in inorganic perovskite semiconductor polycrystal film surface, fexible film is then used
Cladding is got up and is transferred in the high pressure autoclave full of liquid pressure transmission heat transfer medium；Apply 25~500MPa high in autoclave
Pressure, and temperature is increased to 100~400 DEG C of constant temperature for a period of time, the speed for then making the temperature of autoclave again to set reduces
To room temperature；After shedding pressure, opening high pressure autoclave can be obtained the inorganic perovskite semiconductor single crystal thin film of high quality.
The principle of the present invention:
Use space position-limiting action of the present invention effectively eliminates the three-dimensional island growth mode in film, makes it in two dimension
It is grown in plane.Due to not using solvent vapo(u)r to adsorb, numerous spotty crystal grain, this hair are contained in polycrystal film surface
It is bright to drive ion to transport by the way of high hydrostatic pressure heat treatment, realize the quick diffusion of ion in film, and in crystal boundary area
The redeposited diauxic growth with crystal grain in domain.Finally obtain be made of super large crystal grain, crystal boundary orderly combines, even film layer is fine and close and
The inorganic perovskite semiconductor single crystal thin film of surfacing.
Beneficial effects of the present invention:
1, the method for the present invention eliminates crystal grain inferior without using the mode of adsorption solvent steam, but directlys adopt high quiet
The mode of autoclaving drives ion to transport, realize film in ion quick diffusion, and grain boundary area it is redeposited and
The diauxic growth of crystal grain.The defects of film is effectively eliminated, acquisition crystallite size is big, crystallinity is high, crystal boundary orderly combines；Film
The inorganic perovskite semiconductive thin film of high quality of layer uniformly, fine and close.
2, across the scale growth of the crystal grain in film may be implemented in the method for the present invention, and the number of grain boundaries in film is greatly lowered
The performance of photoelectric device is significantly improved to improve carrier mobility with defect state density is reduced.
3, the method for the present invention can be obviously improved the planarization of film and improve coverage, to prepare complete optoelectric device mistake
Subsequent technique in journey creates favorable conditions.In addition, the reduction of defect concentration is conducive to eliminate nocuousness in photovoltaic device in film
Hysteresis, improve device photoelectric conversion efficiency and improve its stability.
Detailed description of the invention
Fig. 1 is the method for the present invention operating process schematic diagram.
Fig. 2 is CsPbI before and after treatment in embodiment 13-xBrxThe XRD spectra of film.
Fig. 3 is CsPbI before and after treatment in embodiment 13-xBrx(200) of film/(110) crystal face diffracted intensity
Ratio.
Fig. 4 is CsPbI before and after treatment in embodiment 13-xBrxThe optical photograph and SEM photograph of film.Wherein:
(a) and (b) is CsPbI before handling3-xBrxThe surface topography and cross-section morphology of film are (c) CsPbI before handling3-xBrxOptics
Photo；(d) and (e) is CsPbI after processing3-xBrxThe surface topography and cross-section morphology of film are (f) CsPbI after handling3-xBrx
Optical photograph.
Fig. 5 is CsPbI before and after treatment in embodiment 13-xBrxAbsorption spectrum and emission spectrum.
Fig. 6 is CsPbI before and after treatment in embodiment 13-xBrxThe photoelectric response performance test result of film.Its
In: (a) the I-V characteristic curve for film before and after treatment under the excitation of 60 milliwatt, 532 nanometer laser is (b) processing
I-V characteristic curve of the film afterwards under different wave length laser irradiation, (c) for treated, film is excited in 532 nanometer lasers
Under photoelectric current-laser power between relationship, be (d) treated light of the film under 532 nm laser irradiation of different capacity
Electric performance stablity test result.
Fig. 7 is the SEM figure for the film that the mode of increase isopropanol solvent vapor sorption in comparative example 1 is handled.
Fig. 8 is that substrate does not heat the film for preparing treated SEM figure in comparative example 2.
Specific embodiment
Technical solution of the present invention is described further below by specific embodiment and in conjunction with attached drawing.
Embodiment 1: a kind of pressure-driven ion transport growing method preparing inorganic perovskite monocrystal thin films, comprising as follows
Step:
By 0.21 mM of PbBr2With 1.19 mMs of PbI2It is dissolved in the mixed solution of 1mL DMF/DMSO and in room temperature
Lower stirring 3h, then with the membrane filtration in 0.22 μm of aperture；The ito glass of surface cleaning is placed in 70 DEG C of thermal station and is heated
5min, then the 40 above-mentioned mixed solutions of μ L are added drop-wise on ito glass substrate, and with 2000 revs/min of revolving speed spin coating 30s.This
The film that sample obtains is in 70 DEG C of annealing 5min.Then, a certain amount of CsBr is dissolved into the methanol of 0.98mL and obtains concentration and is
The CsBr solution of 15mg/mL, is then added to the DMSO of 0.02mL in CsBr solution again, obtains CsBr precursor solution.It will
One drop CsBr precursor solution (about 10 μ L) is added drop-wise to PbI prepared above2/PbBr2Film surface, and with 2500 revs/min
Speed rotation is until solvent is evaporated completely.This spin coating process repeats 8-9 times, then moves back obtained film sample in advance at 100 DEG C
Fire 10 minutes, obtains CsPbI3-xBrxPolycrystal film.The above whole operation process carries out in the glove box full of nitrogen.
In the glove box full of nitrogen, silicon wafer and the polycrystal film surface of clean surface are fitted closely, then with poly-
They are coated, are sealed by tetrafluoroethene film, are subsequently transferred to fill in the high pressure autoclave of dimethicone.Seal hot high pressure
The constant high-pressure for applying a 100MPa after pressure kettle, is then warming up to 280 for the temperature of autoclave with 0.08 DEG C/min of speed
DEG C constant temperature 3 hours.Then, it keeps pressure constant and the temperature of autoclave is made to be reduced to 180 DEG C with 0.2 DEG C/min of speed, so
After naturally cool to room temperature.High quality CsPbI can be obtained after shedding pressure3-xBrxMonocrystal thin films.
Fig. 1 is the method for the present invention operating process schematic diagram.
Fig. 2 is CsPbI before and after treatment in the present embodiment3-xBrxThe XRD spectra of film, Fig. 3 are before handling and places
Manage the ratio of (200) and (110) crystal face diffracted intensity of rear film.It is not difficult to find out from Fig. 2,3, method of the invention is utilized to handle
Afterwards, the crystalline quality of film and orientation are all significantly improved.
Fig. 4 is CsPbI before and after treatment in the present embodiment3-xBrxThe optical microscope photograph and scanning electron of film
Microscope (SEM) photo.Wherein: (a), (b) be respectively handle before CsPbI3-xBrxThe surface of film and cross-section morphology are (c)
CsPbI before handling3-xBrxOptical photograph；(d), (e) is respectively CsPbI after handling3-xBrxThe surface of film and cross-section morphology,
It (f) is CsPbI after handling3-xBrxOptical photograph.Fig. 4 shows: the film of high quality can be obtained using method of the invention:
Crystallite dimension significantly increases, defect concentration significantly reduces；Crystal boundary well merges, film entirety connectivity improves, film surface
Flatness improves.Since defect is reduced in film, so that film light transmittance improves.
Fig. 5 is CsPbI before and after treatment in the present embodiment3-xBrxThe Absorption and emission spectra of film.It can by Fig. 5
Know, significantly reduced through trailing phenomenon in the method for the present invention treated film absorption map, illustrate the quality of film significantly improve,
Defect level is reduced.Blue shift occurs for the emission peak of film, illustrates that the defect state density in film near band edge is substantially reduced, this has
Conducive to greatly reducing the compound of photo-generated carrier.
Fig. 6 is CsPbI before and after treatment in the present embodiment3-xBrxThe photoelectric response performance test result of film.Its
In: it is (a) 532 nanometers in wavelength for film before and after treatment, the I-V curve under the laser excitation of 60 milliwatt of power,
It (b) is treated I-V characteristic curve of the film under the laser irradiation of different wave length, (c) for treated, film is received 532
Photoelectric current-laser power dynamic response curve under rice laser excitation is (d) treated film at 532 nanometers of different capacity
Photoelectric respone stability test result under laser irradiation.The photoelectric current of treated film is mentioned than the photoelectric current of film before handling
It is more than ten times high, and have apparent photoelectric response performance, and wave to the laser of multi-wavelength's (405,465 and 532 nanometers)
Longer photoelectric current is bigger.With the increase of power, the changing value of photoelectric current is more obvious, and is recycled by multiple light on-off
Afterwards, the photoelectric current of film does not significantly decrease, and illustrates that the photoelectric device of the film preparation has certain photostability.
Embodiment 2: a kind of method that pressure-driven ion diffusion growth prepares inorganic perovskite monocrystal thin films, operating procedure
It is same as Example 1, except that: polishing cover plate uses the sheet glass of polishing instead, and heat transfer transmission medium is triethylene glycol, at hot pressing
Reason pressure is 25MPa, and hot pressing temperature is 300 DEG C, and the hot-pressing processing time is 60 hours, and heating rate is 5 DEG C/min, processing
Film is CsPbBr3。
Embodiment 3: a kind of method that pressure-driven ion diffusion growth prepares inorganic perovskite monocrystal thin films, operating procedure
It is same as Example 1, except that: polishing cover plate uses gallium arsenide single-crystal wafer instead, and the flexible membrane of cladding sample is goldleaf, passes
Hot transmission medium is triphenylcarbinol, and heat treatment pressure is 500MPa, and hot pressing temperature is 100 DEG C, heat treatment time 360 hours, is risen
Warm speed is 1 DEG C/min, and the film of processing is CsSnCl3。
Embodiment 4: a kind of method that pressure-driven ion diffusion growth prepares inorganic perovskite monocrystal thin films, operating procedure
It is same as Example 1, except that: film has changed CsPbI into3, polish cover plate and use single-crystal sapphire instead, cladding sample is used
Flexible membrane be silver foil, pressure transmission heat transfer medium is changed to benzene, and hot-pressing processing pressure is 350MPa, 400 DEG C of hot pressing temperature, hot-pressing processing
Time 50 hours, 0.5 DEG C/min of heating rate.
Embodiment 5: a kind of method that pressure-driven ion diffusion growth prepares inorganic perovskite monocrystal thin films, operating procedure
It is same as Example 1, except that: polishing cover plate uses zinc selenide single-chip instead, and hot-pressing processing pressure is 150MPa, hot pressing temperature
Degree 150 DEG C, pressure transmission heat transfer medium be ethylene glycol, the hot-pressing processing time 200 hours, 0.10 DEG C/min of heating rate.
Embodiment 6: a kind of method that pressure-driven ion diffusion growth prepares inorganic perovskite monocrystal thin films, operating procedure
It is same as Example 1, except that: composite semiconductor has changed CsSnI into3-xBrx, it polishes cover plate and uses single-crystal sapphire instead,
Hot-pressing processing pressure is 350MPa, and 100 DEG C of hot pressing temperature, pressure transmission heat transfer medium is decane, the hot-pressing processing time 100 hours, is risen
0.25 DEG C/min of warm speed.
Embodiment 7: a kind of method that pressure-driven ion diffusion growth prepares inorganic perovskite monocrystal thin films, operating procedure
It is same as Example 1, except that: heat transfer transmission medium is diethyl silicone oil, and hot-pressing processing pressure is 250MPa, hot pressing temperature
220 DEG C, the hot-pressing processing time 80 hours, 0.01 DEG C/min of heating rate of degree.
Embodiment 8: a kind of method that pressure-driven ion diffusion growth prepares inorganic perovskite monocrystal thin films, operating procedure
Same as Example 1, heat transfer transmission medium is methyl phenyl silicone oil, and hot-pressing processing pressure is 450MPa, 80 DEG C of hot pressing temperature, hot
The pressure processing time extends to 300 hours, and 0.2 DEG C/min of heating rate.
Embodiment 9: a kind of method that pressure-driven ion diffusion growth prepares inorganic perovskite monocrystal thin films, operating procedure
Same as Example 1, heat transfer transmission medium is dimethylbenzene, and polishing cover plate uses single-crystal sapphire instead, coats the flexibility of sample
Film is silver foil, and hot-pressing processing pressure is 250MPa, 350 DEG C of hot pressing temperature, the hot-pressing processing time 100 hours, and heating rate 0.02
DEG C/min, the film of processing is CsPbBr3Polycrystal film.
Embodiment 10: a kind of method that pressure-driven ion diffusion growth prepares inorganic perovskite monocrystal thin films, operation step
It is rapid same as Example 1, except that: polishing cover plate uses the quartz plate of polishing instead, and the flexible membrane of cladding sample is goldleaf,
Heat transfer transmission medium is methyl trifluoro propyl silicone oil, and hot-pressing processing pressure is 300MPa, 150 DEG C of hot pressing temperature, when hot-pressing processing
Between 350 hours, 0.5 DEG C/min of heating rate.
Embodiment 11: a kind of method that pressure-driven ion diffusion growth prepares inorganic perovskite monocrystal thin films, operation step
It is rapid same as Example 1, except that: pressure transmission heat transfer medium is changed to methyl-silicone oil.
Embodiment 12: a kind of method that pressure-driven ion diffusion growth prepares inorganic perovskite monocrystal thin films, operation step
It is rapid same as Example 1, except that: pressure transmission heat transfer medium is changed to methyl vinyl silicon oil.
Embodiment 13: a kind of method that pressure-driven ion diffusion growth prepares inorganic perovskite monocrystal thin films, operation step
It is rapid same as Example 1, except that: pressure transmission heat transfer medium is changed to toluene.
Embodiment 14: a kind of method that pressure-driven ion diffusion growth prepares inorganic perovskite monocrystal thin films, operation step
It is rapid same as Example 1, except that: pressure transmission heat transfer medium is changed to chlorobenzene.
Embodiment 15: a kind of method that pressure-driven ion diffusion growth prepares inorganic perovskite monocrystal thin films, operation step
It is rapid same as Example 1, except that: pressure transmission heat transfer medium is changed to octane.
Embodiment 16: a kind of method that pressure-driven ion diffusion growth prepares inorganic perovskite monocrystal thin films, operation step
It is rapid same as Example 1, except that: pressure transmission heat transfer medium is changed to nonane.
Embodiment 17: a kind of method that pressure-driven ion diffusion growth prepares inorganic perovskite monocrystal thin films, operation step
It is rapid same as Example 1, except that: pressure transmission heat transfer medium is changed to dodecane.
Embodiment 18: a kind of method that pressure-driven ion diffusion growth prepares inorganic perovskite monocrystal thin films, operation step
It is rapid same as Example 1, except that: pressure transmission heat transfer medium is changed to diethylene glycol (DEG).
Comparative example 1
A kind of method that pressure-driven ion diffusion growth prepares inorganic perovskite monocrystal thin films, operating procedure and embodiment
1 is identical, except that: increase the mode of isopropanol solvent vapor sorption.
Fig. 7 is the shape appearance figure for the film that the mode of increase isopropanol solvent vapor sorption is handled, and the crystallite dimension of film does not have
There is apparent increase, and there is many fine particles for the surface of film and crystal boundary connectivity part, this will extremely be unfavorable for film
Application in the opto-electronic device.
Comparative example 2
A kind of method that pressure-driven ion diffusion growth prepares inorganic perovskite monocrystal thin films, operating procedure and embodiment
1 is identical, except that: CsPbI3-xBrxIn polycrystal film preparation process, substrate is not heated.
Fig. 8 is that substrate does not heat the film for preparing treated shape appearance figure.It can be found that film from Fig. 8
There is close to micron-sized gap between single crystal grain.In thin film growth process, the thickness of crystallite dimension and film reaches one
When determining ratio, in order to reduce the surface energy of film, crystal grain is intended to form individual particle.But from the carrier of photoelectric device
From the aspect of transmission, the grain boundaries of film be occur non-radiative recombination main region, crystal boundary healing it is more good be conducive to carry
Flow the transmission of son.So needing to heat substrate during preparing film to obtain more nucleus to prepare vertical thickness
Biggish film.
Claims (10)
1. a kind of method that pressure-driven ion diffusion growth prepares inorganic perovskite monocrystal thin films, includes the following steps:
By inorganic perovskite semiconductor polycrystal film without adsorption solvent steam course, directly progress space limit, then in liquid
High hydrostatic pressure heat treatment is carried out in state pressure transmission heat transfer medium to get inorganic perovskite monocrystal thin films are arrived.
2. the method that pressure-driven ion diffusion growth according to claim 1 prepares inorganic perovskite monocrystal thin films,
It is characterized in that, the space limits process are as follows: inorganic perovskite thin film and polishing cover plate are fitted closely, then coated close
Envelope.
3. the method that pressure-driven ion diffusion growth according to claim 2 prepares inorganic perovskite monocrystal thin films,
It is characterized in that, carries out cladding sealing using fexible film；Preferably, the fexible film is polytetrafluoroethylene film, goldleaf
Or silver foil.
4. the method that pressure-driven ion diffusion growth according to claim 2 prepares inorganic perovskite monocrystal thin films,
It is characterized in that, the polishing cover plate is silicon wafer, Group III-V semiconductor single-chip, II-VI group semiconductor monocrystal piece, aluminium oxide
Piece or sheet glass.
5. the method that pressure-driven ion diffusion growth according to claim 1 prepares inorganic perovskite monocrystal thin films,
It is characterized in that, when carrying out high hydrostatic pressure heat treatment, pressure is 25~500MPa, and heat treatment temperature is 100~400 DEG C, when processing
Between be 3~360 hours；Preferably, heating rate is 0.01~5 DEG C/min when high hydrostatic pressure is heat-treated.
6. the method that pressure-driven ion diffusion growth according to claim 1 prepares inorganic perovskite monocrystal thin films,
It is characterized in that, after high hydrostatic pressure is heat-treated, in the case where keeping pressure constant, temperature is reduced to room temperature and sheds pressure again
Inorganic perovskite monocrystal thin films can be obtained in power.
7. the method that pressure-driven ion diffusion growth according to claim 1 prepares inorganic perovskite monocrystal thin films,
It is characterized in that, the inorganic perovskite semiconductor is CsBX3-xYx；Wherein, B is Pb or Sn；X and Y is halogen, preferably Cl,
Br or I；0≤x≤3.
8. the method that pressure-driven ion diffusion growth according to claim 1 prepares inorganic perovskite monocrystal thin films,
It is characterized in that, in high hydrostatic pressure heat treatment process, the liquid pressure transmission heat transfer medium is silicone oil, benzene homologues, alkane, alcohol；
Preferably, the silicone oil are as follows: dimethicone, diethyl silicone oil, methyl-silicone oil, methyl phenyl silicone oil, ethylene methacrylic
Base silicone oil, methyl trifluoro propyl silicone oil；
The benzene homologues are benzene, toluene, chlorobenzene, dimethylbenzene；
The alkane are as follows: octane, cyclooctane, nonane, decane, hendecane or dodecane；
The alcohol are as follows: ethylene glycol, triethylene glycol, diethylene glycol (DEG) or triphenylcarbinol.
9. the method that pressure-driven ion diffusion growth according to claim 1 prepares inorganic perovskite monocrystal thin films,
It is characterized in that, the inorganic perovskite semiconductor polycrystal film is prepared as follows to obtain:
By 0.21 mM of PbBr2With 1.19 mMs of PbI2It is dissolved in the mixed solution of 1mL DMF/DMSO and stirs at normal temperature
3h is mixed, then with the membrane filtration in 0.22 μm of aperture；The ito glass of surface cleaning is placed in 70 DEG C of thermal station and heats 5min,
The 40 above-mentioned mixed solutions of μ L are added drop-wise on ito glass substrate again, and with 2000 revs/min of revolving speed spin coating 30s, are obtained in this way
Film in 70 DEG C of annealing 5min；
Then, CsBr is dissolved into the CsBr solution for obtaining that concentration is 15mg/mL in the methanol of 4.9mL, then again 100 μ L's
DMSO is added in CsBr solution, obtains CsBr precursor solution；One drop CsBr precursor solution is added drop-wise to prepared above
PbI2/PbBr2Film surface, and with the rotation of 2500 revs/min of speed until solvent is evaporated completely, this spin coating process repeats 8-9
It is secondary, then by obtained film sample 100 DEG C preannealing 10 minutes；The above whole operation process is in the gloves for being full of nitrogen
It is carried out in case.
10. the method that pressure-driven ion diffusion growth according to claim 1 prepares inorganic perovskite monocrystal thin films,
It is characterized in that, preparation process comprises the following steps that
The cover plate of surface polishing is fitted closely in inorganic perovskite semiconductor polycrystal film surface, is then coated with fexible film
Get up and is transferred in the high pressure autoclave full of liquid pressure transmission heat transfer medium；Apply 25~500MPa high pressure in autoclave,
And temperature is increased to 100~400 DEG C of constant temperature for a period of time, then the temperature of autoclave is made to be reduced to room with the speed set again
Temperature；After shedding pressure, opening high pressure autoclave can be obtained the inorganic perovskite semiconductor single crystal thin film of high quality.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111276566A (en) * | 2020-01-21 | 2020-06-12 | 中国海洋大学 | All-inorganic perovskite solar cell prepared based on liquid phase continuous spin coating direct phase transition method and preparation method and application thereof |
| CN111403610A (en) * | 2020-03-19 | 2020-07-10 | 武汉理工大学 | High-performance organic-inorganic hybrid perovskite photoelectric material and preparation method and application thereof |
| CN113026102A (en) * | 2021-02-01 | 2021-06-25 | 中国科学院合肥物质科学研究院 | Inorganic perovskite material, photoelectric detector and preparation method thereof |
| CN113745405A (en) * | 2021-08-31 | 2021-12-03 | 中国科学院上海光学精密机械研究所 | Preparation method of perovskite thin film and solar cell thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008230959A (en) * | 2007-02-22 | 2008-10-02 | Kyushu Univ | Perovskite oxide single crystal and its manufacture process |
| CN104911714A (en) * | 2015-07-01 | 2015-09-16 | 山东大学 | Method for growing organic-inorganic compound semiconductor crystals in higher static pressure |
| CN106058060A (en) * | 2016-06-16 | 2016-10-26 | 厦门大学 | Method for preparing high-quality perovskite crystal thin film |
| CN106676631A (en) * | 2016-11-28 | 2017-05-17 | 昆明理工大学 | Method for preparing ABX3 perovskite single crystal film |
| CN107634141A (en) * | 2017-09-30 | 2018-01-26 | 山东大学 | A kind of spacing solvent assisting growth method in space for preparing organic-inorganic composite semiconductor monocrystal thin films |
-
2019
- 2019-08-13 CN CN201910743625.XA patent/CN110484963B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008230959A (en) * | 2007-02-22 | 2008-10-02 | Kyushu Univ | Perovskite oxide single crystal and its manufacture process |
| CN104911714A (en) * | 2015-07-01 | 2015-09-16 | 山东大学 | Method for growing organic-inorganic compound semiconductor crystals in higher static pressure |
| CN106058060A (en) * | 2016-06-16 | 2016-10-26 | 厦门大学 | Method for preparing high-quality perovskite crystal thin film |
| CN106676631A (en) * | 2016-11-28 | 2017-05-17 | 昆明理工大学 | Method for preparing ABX3 perovskite single crystal film |
| CN107634141A (en) * | 2017-09-30 | 2018-01-26 | 山东大学 | A kind of spacing solvent assisting growth method in space for preparing organic-inorganic composite semiconductor monocrystal thin films |
Non-Patent Citations (2)
| Title |
|---|
| NING DONG 等: "Solvent-Assisted Thermal-Pressure Strategy for Constructing High Quality CH3NH3PbI3−xClx Films as High-Performance Perovskite Photodetectors", 《ACS APPLLIED MATERIALS INTERFACES》 * |
| XIANWEI FU 等: "High-Quality CH3NH3PbI3 F ilms Obtained via a Pressure-Assisted Space-Confined Solvent-Engineering Strategy for Ultrasensitive Photodetectors", 《NANO LETTERS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111276566A (en) * | 2020-01-21 | 2020-06-12 | 中国海洋大学 | All-inorganic perovskite solar cell prepared based on liquid phase continuous spin coating direct phase transition method and preparation method and application thereof |
| CN111403610A (en) * | 2020-03-19 | 2020-07-10 | 武汉理工大学 | High-performance organic-inorganic hybrid perovskite photoelectric material and preparation method and application thereof |
| CN113026102A (en) * | 2021-02-01 | 2021-06-25 | 中国科学院合肥物质科学研究院 | Inorganic perovskite material, photoelectric detector and preparation method thereof |
| CN113745405A (en) * | 2021-08-31 | 2021-12-03 | 中国科学院上海光学精密机械研究所 | Preparation method of perovskite thin film and solar cell thereof |
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