CN106757371A - A kind of organo-mineral complexing perovskite monocrystalline induced conversion method and device based on methylamine atmosphere - Google Patents
A kind of organo-mineral complexing perovskite monocrystalline induced conversion method and device based on methylamine atmosphere Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- 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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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- 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
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
Abstract
The present invention relates to a kind of organo-mineral complexing perovskite monocrystalline induced conversion method and device based on methylamine atmosphere.The method includes：The organo-mineral complexing perovskite monocrystalline is placed under methylamine atmosphere, 3 36h for the treatment of are induced at a temperature of 40 150 DEG C.The present invention also provides the device that methylamine gas induce single crystal transition.After broad-band gap perovskite material induced conversion, its optical absorption ranges is significantly extended, and photoelectric properties are increased substantially, and can be applied to the fields such as solar cell, photodetector；This method equipment is simple, cheap, prepares efficient.
Description
Technical field
It is based on the present invention relates to a kind of method of converting of organo-mineral complexing perovskite monocrystalline to monocrystalline, more particularly to one kind
The organo-mineral complexing perovskite monocrystalline induced conversion method and device of methylamine atmosphere, belongs to semiconductor crystalline material technology neck
Domain.
Background technology
2009, Japanese Tong Yin Yokohama university Miyasaka etc. was first by perovskite material CH3NH3PbBr3With
CH3NH3PbI3With the prelude on the solar cell, having pulled open perovskite material research so that organo-mineral complexing perovskite material
Material obtains in-depth study development.Organo-mineral complexing perovskite material, especially organo-mineral complexing lead-based perovskite material
Material shows special photoelectricity and phase transition performance as a class novel semiconductor material.Based on its plurality of advantages, in solar-electricity
The fields such as pond, photodetector, LED have potential application value, are the emphasis of current countries in the world research.But, on
The majority of such material report is thin-film material, for example, CN105098080A discloses a kind of manufacture organic-inorganic perovskite crystalline substance
The method of body thin film, including organic inorganic calcium titanium ore film is formed on flexible substrates, then made annealing treatment so that the crystalline substance
The average grain size of body thin film increases, and can obtain the crystal grain of more [220] crystal orientation, therefore extends its carrier lifetime, subtracts
Few crystal boundary is combined, so as to improve the photoelectric transformation efficiency of organic-inorganic perovskite solar cell.But, thin-film material stability
There are more defects in generally below monocrystal material, and film polycrystalline, be unfavorable for the research application of material intrinsic performance.
At present, there is the report of a small number of organo-mineral complexing perovskite crystal growths, such as CN104911705A provides a kind of
ABX is grown in cryogenic fluid3(A is CH3NH3 +、H2N-CH=NH2 +、(CH3)4N+、C7H7 +、Cs+Or C3H11SN3 2+, B be Pb, Ge or
Sn；X is Cl, Br or I) method of perovskite monocrystalline, by halides and the solvent of the metallic compound can be dissolved it is hybridly prepared into
Solution, is made into crystal growth liquid, using the continuous multicycle stage by stage low after lead source, Xi Yuan or ge source metallic compound are added
Fast-growth ABX in warm solution3Perovskite monocrystalline, solution concentration used is big, and dissolution of raw material is uniform needed for growth, increases growth week
Phase and the precise controlling to growth conditions, obtain large-sized ABX3Perovskite monocrystalline, so as to promote to perovskite material and phase
Close the basic mechanism theoretical research of photoelectric device (including solar cell, photo-detector, LED and laser etc.).The method step
It is cumbersome, need the multicycle to be grown stage by stage, it is unfavorable for the controllable growth of high-quality monocrystalline.Compared to organo-mineral complexing calcium titanium
For the abundant achievement in research of ore deposit monocrystal thin films, the research of organo-mineral complexing perovskite crystal material is relatively weak, especially
Controllable growth for organo-mineral complexing perovskite monocrystal material and what specially treated was optimized is carried out to gained monocrystalline
The method of converting of monocrystalline, at home and abroad there is not been reported so far.
The content of the invention
In view of the shortcomings of the prior art, present invention offer is a kind of induces organo-mineral complexing perovskite monocrystal material
Optimization processing obtains the method for converting of the broader organo-mineral complexing perovskite monocrystalline of optical absorption ranges.Particularly, based on first
The organo-mineral complexing perovskite monocrystalline induced conversion method of amine atmosphere.After being induced by the method, organo-mineral complexing calcium
Titanium ore monocrystalline had both retained original monocrystalline, and its intrinsic property can be improved again, expanded optical absorption ranges, improved it in solar energy
The aspect application performance such as battery, photodetector, expands range of application.
The present invention also provides the monocrystalline induced conversion device for approach described above.
Term explanation：
Organo-mineral complexing perovskite, with LMX3Or L2MX4General molecular formula, wherein, L is C2H6NH2、C4H9NH3、
C6H13NH3、C8H17NH3、CN3H4Or CH3NH3；M is Pb, Ge or Sn；X is Cl, Br or I.Wherein, C2H6NH2Abbreviation DA, C4H9NH3
Abbreviation BA, C6H13NH3Abbreviation HA, C8H17NH3Abbreviation OA, CN3H4Abbreviation GA, CH3NH3Abbreviation MA.
Technical scheme is as follows：
First, the organo-mineral complexing perovskite monocrystalline induced conversion method based on methylamine atmosphere
A kind of organo-mineral complexing perovskite monocrystalline induced conversion method based on methylamine atmosphere, the organo-mineral complexing
Perovskite, with LMX3Or L2MX4General molecular formula, wherein, L is organic group, L=C2H6NH2、C4H9NH3、C6H13NH3、
C8H17NH3、CN3H4Or CH3NH3, M is Pb, Ge or Sn；X is Cl, Br or I；It is as follows including step：
The organo-mineral complexing perovskite monocrystalline is placed under methylamine atmosphere, treatment 3- is induced at a temperature of 40-150 DEG C
36h。
After being induced more than, the organic group in methylamine molecular moiety substitution monocrystalline, the monocrystalline after gained transformation is a kind of
Complete monocrystalline, had both retained original crystal structure, and have broader optical absorption ranges in ultraviolet-visible light area.
After the organo-mineral complexing perovskite monocrystalline is through methylamine induced conversion, be fully retained it is original monocrystalline, but its
Optical absorption ranges are greatly expanded, and photoelectric properties are greatly improved.After induction, the organic group in former monocrystalline is by methylamine molecular moiety
Substitution, forms the organic cation mono crystalline substance of mixing, makes the reduction of monocrystalline band gap.According to currently preferred, the organo-mineral complexing
Perovskite monocrystalline is organo-mineral complexing bustamentite based perovskite monocrystalline, general molecular formula LPbI3Or L2PbI4, L=C2H6NH2、
C4H9NH3、C6H13NH3、C8H17NH3、CN3H4Or CH3NH3。
It is further preferred that the organo-mineral complexing bustamentite based perovskite monocrystalline is selected from：C2H6NH2PbI3、(C4H9NH3)2PbI4、(C6H13NH3)2PbI4、(C8H17NH3)2PbI4Or CN3H4PbI3。
Wherein, with the C of embodiment 12H6NH2PbI3With (the C of embodiment 34H9NH3)2PbI4As a example by, induced through methylamine atmosphere
Afterwards, C2H6NH2PbI3、(C4H9NH3)2PbI4Part C in monocrystalline2H6NH2(abbreviation DA), C4H9NH3(abbreviation BA) ion is by methylamine
Ionic compartmentation, is changed into mixed single crystal MA respectively0.1DA0.9PbI3、(MA0.66BA0.34)2PbI4.After single crystal transition, retain original
Crystal structure, but such mixed single crystal has CH3NH3PbI3(abbreviation MAPbI3) property, show as semiconductor band gap reduction,
Optical absorption ranges are greatly expanded, and photoelectric properties are greatly improved.For example,
a.C2H6NH2PbI3Its optical absorption ranges of crystal are in 200-500nm scope hypersorptions；After methylamine gas induction
Single crystal transition is MA0.1DA0.9PbI3, its optical absorption ranges expands to 800nm.
b.(C4H9NH3)2PbI4Its optical absorption ranges of crystal are in 200-530nm scope hypersorptions.Methylamine gas induce it
Single crystal transition is (MA0.66BA0.34)2PbI4Its optical absorption ranges expands to 800nm afterwards.
It is described to induce treatment temperature for 100-120 DEG C according to currently preferred.
According to currently preferred, described methylamine atmosphere sent out with the methylamine water solution that mass fraction is 20~40wt%
The raw and methylamine gas through being dried to obtain.
According to the present invention, described crystal induction time needs the size according to the organo-mineral complexing perovskite monocrystalline
Size and inducing temperature determine；When 50-100 DEG C of temperature, induction time is about 8-36h, when temperature is 100-150 DEG C, lures
Lead time about 3-8h.It is preferred that inducing temperature is 100-120 DEG C.
Abductive approach of the invention has universality, it is adaptable to various broad-band gap perovskite crystal materials, such as
C2H6NH2PbI3、(C4H9NH3)2PbI4、(C6H13NH3)2PbI4、(C8H17NH3)2PbI4Or CN3H4PbI3Deng.
The method of the present invention can be used for the induced conversion of the film that organo-mineral complexing perovskite monocrystalline is made, will be described
Film is placed in induced conversion under methylamine atmosphere, and the photo absorption property of the film is increased substantially after induction.
2nd, the present invention also provides a kind of bustamentite methylamine (MAPbI for superficial degradation3) crystalline material repair method
A kind of bustamentite methylamine (MAPbI of superficial degradation3) crystalline material restorative procedure, by the bustamentite methylamine of superficial degradation
Crystal, is placed under methylamine atmosphere, and treatment 3-36h is induced at a temperature of 40-150 DEG C.After bustamentite methylamine plane of crystal is by degrading
Yellow gradually becomes black.It is preferred that at 100-120 DEG C, inducing 5-7h.
The method is used for the devices such as the solar cell that reparation is degraded.
3rd, organo-mineral complexing perovskite monocrystalline of the present invention can be prepared by prior art.It is currently preferred
Preparation method, with LPbI3Or L2PbI4As a example by, step is as follows：
A kind of preparation method of organo-mineral complexing perovskite monocrystalline, according to LPbI3Or L2PbI4(L=C2H6NH2、
C4H9NH3、C6H13NH3、C8H17NH3Or CN3H4) stoichiometric proportion weigh halogeno-amine or amine salt, PbO, be dissolved in hydroiodic acid (HI)
In solution, being warming up to 70-100 DEG C makes to be completely dissolved to form transparent settled solution, and after being down to saturation point, slow cooling is to there is monocrystalline
Separate out.
Preferably, the halogeno-amine is iodate dimethylamine, iodate butylamine, iodate hexylamine, iodate octylame or iodate guanidine.Wherein
Above-mentioned halogeno-amine also can use corresponding amine salt to substitute, for example：Dimethylamine hydrochloride, guanidine hydrochloride.
Preferably, the hydroiodic acid liquid quality fraction is 30-45wt%.
4th, the special purpose device of the organo-mineral complexing perovskite monocrystalline induced conversion method based on methylamine atmosphere
A kind of device for the inventive method, including：
- methylamine gas generator, for containing methylamine water solution,
- breather pipe, for connecting methylamine gas generator and methylamine atmosphere crystal processor,
- temperature control heating platform, for placing and heats methylamine gas generator, methylamine atmosphere crystal processor,
- gas-drying apparatus, is installed on breather pipe stage casing, for drying methylamine gas,
- organo-mineral complexing perovskite monocrystalline is placed in methylamine atmosphere crystal processor.
According to currently preferred, it is provided with gas output tube on methylamine atmosphere crystal processor top and is passed through gas recovery dress
Put, the methylamine gas for reclaiming effusion.Preferably, methylamine gas absorbent is contained with gas concentration unit, it is such as acid molten
Liquid, makes it be neutralized with methylamine.
According to the present invention, the organo-mineral complexing perovskite monocrystalline through the monocrystalline after methylamine induced conversion application, base
In after induction crystal optics absorption region increase, optical band gap is substantially reduced, photoelectric properties are improved, for photodetector,
The fields such as solar cell, field-effect transistor materials.
Especially, C2H6NH2PbI3、(C4H9NH3)2PbI4、(C6H13NH3)2PbI4Or (C8H17NH3)2PbI4Deng monocrystalline through this
After inventive method induction, the application for solar cell, the application as photodetector；Or as field-effect transistor
The application of material.
Technical characterstic of the invention and excellent results：
1st, using the method for the present invention, organo-mineral complexing perovskite broad-band gap monocrystalline is induced, in Induction Process
In, the organic radical moiety in monocrystalline is replaced by methylamine molecule, forms the organic cation mono crystalline substance of mixing, makes the reduction of monocrystalline band gap,
Optical absorption ranges expand, so as to improve its optical property.With the expansion of optical absorption ranges, the photoelectric properties of crystal are therewith
Change.
2nd, using the obtained C of method of the present invention induction2H6NH2PbI3Deng crystal, its photoelectric properties is increased substantially, and is such as schemed
Shown in 8.
3rd, the crystal for degrading can be repaired using this method, methylamine gas molecule can supplement having due to crystal degraded missing
Machine molecular radical.The method of the present invention can also induce the devices such as the solar cell that reparation degrades.
4th, C prepared by present invention induction2H6NH2PbI3、(C4H9NH3)2PbI4Deng crystal as semiconductor crystalline material,
Ultraviolet-visible light area has fine light absorption range (as shown in fig 6 and fig 13), can apply to light guide and optical detection field.
5th, method of the present invention realizes transformation from monocrystalline to monocrystalline and with universality, and this method equipment is simple,
Cheap, material prepares efficient.
Brief description of the drawings
Fig. 1 is methylamine induction single crystal transition device of the invention, 1. methylamine gas generator (splendid attire methylamine water solution), 2.
Temperature control heating platform, 3. gas-drying apparatus, 4. breather pipe, 5, methylamine atmosphere crystal processor, 6. organo-mineral complexing perovskite list
Crystalline substance, 7. gas output tube, 8, methylamine gas retracting device, 9, methylamine gas absorbing liquid.
Fig. 2 is the DAPbI before the induction of the methylamine gas of embodiment 13Crystallogram；
Fig. 3 is the MA after the induction of the methylamine gas of embodiment 10.1DA0.9PbI3Crystallogram；
Fig. 4 is the DAPbI before and after the induction of the methylamine gas of embodiment 13、MA0.1DA0.9PbI3XRD spectra；Abscissa is 2 θ,
Unit：Degree (°)；Ordinate is intensity, arbitrary unit.
Fig. 5 is the DAPbI before the induction of the methylamine gas of embodiment 13Uv-visible absorption spectra and PL absorption spectrums；It is horizontal
Coordinate is absorbing wavelength (nm)；Left ordinate scale is to absorb (O.D.), and right ordinate scale is PL intensity, arbitrary unit.
Fig. 6 is the MA after the induction of the methylamine gas of embodiment 10.1DA0.9PbI3Uv-visible absorption spectra and PL absorb light
Spectrum；Abscissa is absorbing wavelength (nm)；Left ordinate scale is to absorb (O.D.), and right ordinate scale is PL intensity, arbitrary unit.
Fig. 7 is the DAPbI before the induction of the methylamine gas of embodiment 13Photoelectric properties figure；Abscissa is time, unit second；It is vertical
Coordinate is electric current, unit μ A.
Fig. 8 is the MA after the induction of the methylamine gas of embodiment 10.1DA0.9PbI3Photoelectric properties figure；Abscissa is the time, single
Bps；Ordinate is electric current, unit μ A.Fig. 9 is the BA before the induction of the methylamine gas of embodiment 32PbI4Crystallogram.
Figure 10 is (MA after the induction of the methylamine gas of embodiment 30.66BA0.34)2PbI4Crystallogram.
Figure 11 is the BA before and after the induction of the methylamine gas of embodiment 32PbI4(MA0.66BA0.34)2PbI4XRD spectra；Horizontal seat
Mark is 2 θ, unit：Degree (°)；Ordinate is intensity, arbitrary unit.
Figure 12 is the BA before the induction of the methylamine gas of embodiment 32PbI4Uv-visible absorption spectra and PL absorption spectrums；It is horizontal
Coordinate is absorbing wavelength (nm)；Left ordinate scale is to absorb (O.D.), and right ordinate scale is PL intensity, arbitrary unit.
Figure 13 is (MA after the induction of the methylamine gas of embodiment 30.66BA0.34)2PbI4Uv-visible absorption spectra and PL
Absorption spectrum；Abscissa is absorbing wavelength (nm)；Left ordinate scale is to absorb (O.D.), and right ordinate scale is PL intensity, arbitrarily
Unit.
Figure 14 is embodiment 4 to the monocrystalline before and after the induced conversion of several organo-mineral complexing bustamentite based perovskite monocrystalline
Photo；A upper row is the monocrystalline before transformation, and next row is the monocrystalline after transformation, by being successively from left to right：(C4H9NH3)2PbI4、
(C6H13NH3)2PbI4、C2H6NH2PbI3、(C8H17NH3)2PbI4And CN3H3PbI3。
Figure 15 is the methylamine gas of embodiment 5 to various sizes of MAPbI after degraded3Carry out the photograph that different time induction is repaired
Piece；Upper row is successively small size MAPbI3Photo of the crystal in induction time 0,0.5h, 3h, 7h, lower row is successively large scale
MAPbI3Photo of the crystal in induction time 0,0.5h, 3h, 7h.
Figure 16 is the methylamine gas reparation of embodiment 5 degraded MAPbI3Front and rear XRD spectrum；Abscissa is 2 θ, unit：Degree
(°)；Ordinate is intensity, arbitrary unit.
Specific embodiment
Below by embodiment, the present invention is further illustrated, but the present invention is not limited to following examples.
Embodiment 1, methylamine gas induces one-dimensional DAPbI3The transformation of monocrystalline
First, DAPbI3Single crystal preparation
A () is added it in the HI solution of 45wt% according to stoichiometric proportion precise dimethylamine hydrochloride, obtain
Yellow transparent solution.
B () is added in the yellow transparent solution of step (a) according to stoichiometric proportion precise PbO, produce faint yellow
Precipitate, being warming up to precipitation in oil bath pan is completely dissolved, obtain the solution of yellow clarification, after being down to saturation point, slow cooling, from
Hair crystallizes out DAPbI3Yellow single crystal, photo are as shown in Fig. 2 crystalline size is about 1mm.
2nd, methylamine gas induction DAPbI3Monocrystalline
DAPbI prepared by by more than3Monocrystalline is placed under methylamine atmosphere, and treatment 3h-5h is induced at a temperature of 120 DEG C, is obtained
To black MA0.1DA0.9PbI3Monocrystalline, crystallogram is as shown in Figure 3.
The crystal powder XRD that this abductive approach is obtained and pure phase DAPbI3Powder X-ray RD is different, and it is induced in methylamine gas
Afterwards, DA+Ion is by MA+Part replaces, and forms MA0.1DA0.9PbI3Monocrystalline, as shown in Figure 4.
The pure phase DAPbI that embodiment 1 is obtained3Black MA after monocrystalline and methylamine gas induction0.1DA0.9PbI3Monocrystalline
Grind into powder tests its solid-ultraviolet spectra and photoluminescence spectra (PL spectrum).Pure phase DAPbI3Absorption of crystal ends side
After 500nm or so (Fig. 5), methylamine gas induction, MA0.1DA0.9PbI3Monocrystalline absorbs cut-off side and expands to 800nm, its PL
Absorption spectrum also extends to 800nm.Its compound band gap width is reduced to 1.53eV after showing induction, as shown in Figure 6.
Embodiment 1 is obtained into pure phase DAPbI3Monocrystalline is dissolved in DMF, and the spin coating 40s in the case where rotating speed is 2000r/min, obtains
Its film.Film is placed under methylamine atmosphere and is induced.Its photo absorption property is increased substantially after induction, as Figure 7-8.
Embodiment 2, as described in Example 1, except that, methylamine gas induction DAPbI3During monocrystalline, in 100 DEG C of temperature
Lower induction treatment 8-10h, obtains black MA0.1DA0.9PbI3Monocrystalline.
Embodiment 3, methylamine gas induction two dimension BA2PbI4Monocrystalline
First, BA2PbI4The preparation of monocrystalline
(a) iodate butylamine CH3(CH2)3NH3I's is synthetically prepared：
By CH in ice-water bath3(CH2)3NH3Solution is added in HI solution, reacts 3.5h；CH3(CH2)3NH2:HI=
1.5:1 mol ratio.The mass percentage concentration of butylamine solution is 99wt%, and the mass percentage concentration of HI solution is 45wt%.By
Vacuum rotary evaporator is rotated, and obtains the iodate butylamine of white, and is placed on vacuum drying chamber and is dried 2h, obtains drying iodate
Butylamine crystal.
B () is added it in 45wt%HI solution according to stoichiometric proportion precise PbO, obtain yellow transparent molten
Liquid.
C () is according to stoichiometric proportion precise CH3(CH2)3NH3I, adds it to the yellow transparent solution of step (b)
In, pale yellow precipitate is produced, being warming up to precipitation in oil bath pan is completely dissolved, and obtains the solution of yellow green clarification, is down to saturation
After point, slow cooling, spontaneous crystallization goes out BA2PbI4Monocrystalline, photo are as shown in figure 9, its size is about 7mm.
2nd, methylamine gas induction two dimension BA2PbI4The transformation of monocrystalline
By prepared BA2PbI4Monocrystalline is placed under methylamine atmosphere, and (or 100 DEG C for the treatment of 3h-5h is induced at a temperature of 120 DEG C
When 8-10h), obtain black (MA0.66DA0.34)2PbI4Monocrystalline, crystallogram is as shown in Figure 10.
(MA after this induced conversion0.66DA0.34)2PbI4The crystal powder XRD of monocrystalline pure phase BAs preceding with induction2PbI4Powder
XRD is different, after methylamine gas induction, BA+Ion is by MA+Part replaces, and forms (MA0.66DA0.34)2PbI4Monocrystalline, such as schemes
Shown in 11.
The pure phase BA that embodiment 3 is obtained2PbI4Black (MA after monocrystalline and methylamine gas induction0.66DA0.34)2PbI4
Monocrystalline grind into powder tests its solid-ultraviolet spectra and photoluminescence spectra (PL spectrum).Pure phase BA2PbI4Absorption of crystal cuts
Only side is in 530nm or so (Figure 12), after methylamine gas are induced, (MA0.66DA0.34)2PbI4Monocrystalline absorbs cut-off side and expands to
800nm.Its compound band gap width is reduced to 1.55eV after showing induction, as shown in figure 13.
Embodiment 4, universality is tested
The method in embodiment 1 and 2 is utilized respectively, (C is prepared4H9NH3)2PbI4、(C6H13NH3)2PbI4、C2H6NH2PbI3、
(C8H17NH3)2PbI4And CN3H4PbI3Deng organo-mineral complexing perovskite monocrystal material, and the induction treatment at a temperature of 120 DEG C
3h-5h, (C4H9NH3)2PbI4、(C6H13NH3)2PbI4、C2H6NH2PbI3、(C8H17NH3)2PbI4And CN3H4PbI3Etc. pure phase crystal
Blackening, shows that its optical absorption ranges expands, and band gap narrows, as shown in figure 14.
Experiment shows that this method is that a kind of methylamine gas of universality induce organo-mineral complexing perovskite monocrystalline to monocrystalline
The method of transformation.
Bustamentite methylamine (the MAPbI of embodiment 5, superficial degradation3) crystalline material reparation
By the bustamentite methylamine MAPbI of two sizes of size of superficial degradation3Crystal, at 100-120 DEG C, is placed in methylamine gas
In atmosphere induce, after 0.5h, surface is to change, by degrading after yellow gradually become black, with the extension of induction time
There is not dissolved state in (3h, 7h), plane of crystal, and as shown in figure 15, the transformation of crystal color shows the reparation on its surface.Figure
In 15, a upper row is small size (being about 2.5mm) MAPbI3Photo of the crystal in induction time 0,0.5h, 3h, 7h, next row
It is large scale (being about 15mm) MAPbI3Photo of the crystal in induction time 0,0.5h, 3h, 7h.
The bustamentite methylamine crystal powder XRD (such as Figure 16 (a) upper curves) of degraded shows that its peak position is different from MAPbI completely3
XRD standard diagrams (such as Figure 16 (a) lower curves).After carrying out methylamine gas induction and recovering, its XRD peak position (such as Figure 16 (b)
Upper curve) matched completely with standard XRD pattern (such as Figure 16 (b) lower curves), show what methylamine gas were degraded after inducing
MAPbI3It is restored, as shown in figure 16.
Experiment shows the method that methylamine gas of the present invention induce organo-mineral complexing perovskite monocrystalline to single crystal transition, to table
The organo-mineral complexing bustamentite based perovskite crystalline material of face degraded has certain prosthetic.
Claims (10)
1. a kind of organo-mineral complexing perovskite monocrystalline induced conversion method based on methylamine atmosphere, the organo-mineral complexing calcium
Titanium ore monocrystalline, with LMX3Or L2MX4General molecular formula, wherein, L is organic group, L=C2H6NH2、C4H9NH3、C6H13NH3、
C8H17NH3、CN3H4Or CH3NH3, M is Pb, Ge or Sn；X is Cl, Br or I；It is as follows including step：
The organo-mineral complexing perovskite monocrystalline is placed under methylamine atmosphere, treatment 3-36h is induced at a temperature of 40-150 DEG C；
Preferably, treatment 3-8h is induced at 100-120 DEG C.
2. the organo-mineral complexing perovskite monocrystalline induced conversion method of methylamine atmosphere is based on as claimed in claim 1, and it is special
Levy and be, the organo-mineral complexing perovskite monocrystalline is organo-mineral complexing bustamentite based perovskite monocrystalline, general molecular formula is
LPbI3Or L2PbI4, L=C2H6NH2、C4H9NH3、C6H13NH3、C8H17NH3、CN3H4Or CH3NH3。
3. the organo-mineral complexing perovskite monocrystalline induced conversion method of methylamine atmosphere is based on as claimed in claim 1, and it is special
Levy and be, the organo-mineral complexing bustamentite based perovskite monocrystalline is selected from C2H6NH2PbI3、(C4H9NH3)2PbI4、(C6H13NH3)2PbI4、(C8H17NH3)2PbI4Or CN3H4PbI3。
4. the organo-mineral complexing perovskite monocrystalline induced conversion method of methylamine atmosphere is based on as claimed in claim 1, and it is special
Levy and be, described methylamine atmosphere is that occur with the methylamine water solution that mass fraction is 20~40wt% and the first through being dried to obtain
Amine gas.
5. the organo-mineral complexing perovskite monocrystalline induced conversion method of methylamine atmosphere is based on as claimed in claim 2, and it is special
Levy and be, the organo-mineral complexing perovskite monocrystalline is prepared according to the following steps：
According to LPbI3Or L2PbI4Stoichiometric proportion weigh halogeno-amine or amine salt, PbO, be dissolved in hydroiodic acid solution, be warming up to
70-100 DEG C makes to be completely dissolved to form transparent settled solution, and after being down to saturation point, slow cooling is separated out to there is monocrystalline.
6. the organo-mineral complexing perovskite monocrystalline induced conversion method of methylamine atmosphere is based on as claimed in claim 2, and it is special
Levy and be, the halogeno-amine is iodate dimethylamine, iodate butylamine, iodate hexylamine, iodate octylame or iodate guanidine；The amine salt is two
Methylamine hydrochloride, guanidine hydrochloride；Preferably, the hydroiodic acid liquid quality fraction is 30-45wt%.
7. the bustamentite methylamine (MAPbI of a kind of superficial degradation3) crystalline material restorative procedure, the bustamentite methylamine of superficial degradation is brilliant
Body, is placed under methylamine atmosphere, and treatment 3-36h is induced at a temperature of 40-150 DEG C.
8. a kind of device for claim 1-8 any one methods describeds, including：
- methylamine gas generator, for containing methylamine water solution,
- breather pipe, for connecting methylamine gas generator and methylamine atmosphere crystal processor,
- temperature control heating platform, for placing and heats methylamine gas generator, methylamine atmosphere crystal processor,
- gas-drying apparatus, is installed on breather pipe stage casing, for drying methylamine gas,
- organo-mineral complexing perovskite monocrystalline is placed in methylamine atmosphere crystal processor.
9. device as claimed in claim 8, it is characterised in that be provided with gas output tube on methylamine atmosphere crystal processor top
Gas concentration unit is passed through, the methylamine gas for reclaiming effusion.
10. the application of monocrystalline prepared by any one of claim 1-7 methods described, based on the crystal optics absorption region after induction
Increase, optical band gap is substantially reduced, photoelectric properties are improved, for photodetector, solar cell, field effect transistor tubing
Material.
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