CN104372412B - Methylamine lead halide phosphate compounds large-size crystals growing method and device - Google Patents
Methylamine lead halide phosphate compounds large-size crystals growing method and device Download PDFInfo
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- CN104372412B CN104372412B CN201410579570.0A CN201410579570A CN104372412B CN 104372412 B CN104372412 B CN 104372412B CN 201410579570 A CN201410579570 A CN 201410579570A CN 104372412 B CN104372412 B CN 104372412B
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- 239000013078 crystal Substances 0.000 title claims abstract description 110
- -1 Methylamine lead halide phosphate compounds Chemical class 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 24
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005352 clarification Methods 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- 229910052740 iodine Inorganic materials 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 230000026030 halogenation Effects 0.000 claims description 8
- 238000005658 halogenation reaction Methods 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- LFETXMWECUPHJA-UHFFFAOYSA-N methanamine;hydrate Chemical compound O.NC LFETXMWECUPHJA-UHFFFAOYSA-N 0.000 claims description 6
- 230000008033 biological extinction Effects 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 43
- 125000005843 halogen group Chemical group 0.000 abstract description 15
- 239000007864 aqueous solution Substances 0.000 abstract description 4
- 238000001816 cooling Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000001704 evaporation Methods 0.000 abstract description 2
- 230000031700 light absorption Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 230000005622 photoelectricity Effects 0.000 abstract 1
- 238000010583 slow cooling Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 10
- 239000002178 crystalline material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000031709 bromination Effects 0.000 description 3
- 238000005893 bromination reaction Methods 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- IVUHDTWRNCXVCD-UHFFFAOYSA-N methylazanium;iodate Chemical compound [NH3+]C.[O-]I(=O)=O IVUHDTWRNCXVCD-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- LGZXYFMMLRYXLK-UHFFFAOYSA-N mercury(2+);sulfide Chemical compound [S-2].[Hg+2] LGZXYFMMLRYXLK-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000002892 organic cations Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- 241000883990 Flabellum Species 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- VLSWWRJVKAPDDQ-UHFFFAOYSA-N [Pb].[Br].CN Chemical compound [Pb].[Br].CN VLSWWRJVKAPDDQ-UHFFFAOYSA-N 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/54—Organic compounds
-
- 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
- C30B7/08—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by cooling of the solution
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The present invention relates to a kind of methylamine lead halide phosphate compounds large-size crystals growing method and device.Described growing method is bottom seed crystal aqueous solution cooling method, according to stoichiometric proportion by raw material CH3NH2、Pb(CH3COOH)2·3H2O is added sequentially in HX (X is halogen) solution, is precipitated, is stirred continuously, heating so that it is be completely dissolved, and obtains the solution of clarification, is cooled to solution saturation point, enters down seed crystal, and slow cooling carries out crystal growth, growth cycle about month.The present invention also provides for the grower of large-size crystals.The CH of preparation3NH3PbX3Crystal has fine light absorption range, not deliquescence in ultraviolet-visible district, has good stability；Can be applicable to the field such as solar cell, photoelectricity；This method higher temperatures solution evaporation method is easier to obtain large-size high-quality crystal, and raw material is easy to get, low cost.
Description
Technical field
The present invention relates to crystal growth and the application of Organic-inorganic composite semiconductor crystalline material, particularly to methylamine halogen
Change growing method and the device of plumbite compound large-size crystals, belong to crystalline material technical field.
Background technology
Main group metal metal halide phosphate compounds, it is emphasized that lead halide hydrochlorate is as a class novel semi-conductor
Material, has special photoconduction, ionic conduction, conductance, photo-electroluminescence and phase transition performance, owing to having many excellent property
Can, scene effect transistor, light emitting diode and area of solar cell have potential using value, are that the current world is each
The focus of state's research.
Lead halide hydrochlorate great majority belong to perovskite structure, and its chemical formula is APbX3(A is alkali metal or organic cation,
X is halogen), structure exists PbX6Octahedron, the real structure of its compound is by different metal cation and PbX6Octahedra
Connection together decides on.The range of choice of organic cation is relatively big, and the structure of organic-inorganic composition can be produced by component change
Impact, structure change will necessarily affect the change of intramolecule bonding state, band structure etc., thus thermally-stabilised to material
Property, optical property and electric property etc. produce impact.
2009, Japan Tong Yin Yokohama university Miyasaka etc., during research sensitization solar cell, used first
There is the organic metal halide CH of perovskite structure3NH3PbBr3And CH3NH3PbI3As sensitizer, pull open perovskite too
The prelude of positive electricity pond research, so that this compounds obtains in-depth study in area of solar cell.Such material relevant
Report be mostly thin-film material, but for CH3NH3PbX3The report of (X is halogen) crystalline material is little, up to now, domestic
The outer report all tested less than the physical property in terms of the growth and crystalline anisotropy of this compounds large-size crystals.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of methylamine lead halide hydrochlorate (CH3NH3PbX3) large-size crystals
Growing method and grower.
Methylamine lead halide hydrochlorate of the present invention is a kind of organic metal halide, and formula is CH3NH3PbX3, X is halogen
Element, selected from Cl, Br or I.
Methylamine lead halide hydrochlorate large-size crystals of the present invention, refers to the monocrystal of length >=5mm.
Technical scheme is as follows:
A kind of methylamine lead halide hydrochlorate (CH3NH3PbX3) growing method of large-size crystals, comprise the following steps that
(1) halogenation methylamine (CH3NH3X) prepare
In ice-water bath, methylamine water solution is joined in halogen acids and react, after having reacted, revolved by Rotary Evaporators
Steam, obtain halogenation methylamine precipitation, add absolute ether recrystallization, vacuum drying, obtain halogenation methylamine (CH3NH3X) crystal.
(2)CH3NH3PbX3The preparation of compound and crystal growth
According to stoichiometric proportion precise Pb (CH3COOH)2·3H2O, joins in HX solution, stirring, is clarified
Solution；The CH prepared according to stoichiometric proportion precise step (1)3NH3X, joins in the solution of above-mentioned clarification, stirs
Mix, produce CH3NH3PbX3The precipitation of compound；Heat up, make precipitation be completely dissolved, then be cooled to solution saturation point；Enter down
Seed crystal, makes seed crystal be positioned at the bottom of solution, rotates seed crystal, control rate of temperature fall 0.5-2 DEG C/day, carry out crystal growth；
Halogen in above-mentioned halogen acids, halogenation methylamine, methylamine lead halide hydrochlorate is Cl, Br or I, i.e. X=Cl, Br or I.
According to currently preferred, in step (1), methylamine: the mol ratio of halogen acids is 1～1.5:1.
According to currently preferred, in step (1), the mass percentage concentration of methylamine water solution is 20～30wt%, adds
React 3-6 hour in halogen acids.Halogen acid solution concentration is 30-45wt%.
According to currently preferred, in step (2), the mass percentage concentration of described HX solution is 30-45wt%.
According to currently preferred, crystal growth cycles 25-35 days.
According to currently preferred, in step (2), described rate of temperature fall is 1 DEG C/day, crystal growth cycles 29～31 days.
Under when entering seed crystal the temperature of solution at 65-70 DEG C.Described seed crystal is CH3NH3PbX3Single grain, seed size one
As be (1～2) × (1～2) × (1～2) mm3。
The rotating speed rotating seed crystal is 30-80r/min.
According to currently preferred, in step (2), seed crystal is fixed on seed crystal plate and is fixed on rotation by seed rod
On agitator.Preferably, in step (2), described seed crystal is positioned at the bottom of solution and refers to that seed crystal bottom is positioned at solution 1/2 height
At lower 5-10cm.
The method using the present invention can obtain length a size of (5～30) × (5～20) × (5～15) mm3's
CH3NH3PbX3Large size single crystal.
The reaction equation of the present invention is as follows:
CH3NH2+HX→CH3NH3X；
In formula, X is halogen, selected from Cl, Br or I.
The method using the present invention, obtained methylamine lead halide hydrochlorate crystal is preferably:
a.CH3NH3PbBr3Crystal, size 6 × 4 × 2mm3；Extinction is had, in 200-580nm scope in ultraviolet-visible light district
Fully absorb.
Or
b.CH3NH3PbI3Crystal, size 10 × 10 × 8mm3；Extinction is had, at 250-800nm model in ultraviolet-visible light district
Enclose and fully absorb.
The CH that the present invention prepares3NH3PbX3The XRD that powder X-ray RD of (X is halogen) calculates with mono-crystalline structures theory is consistent
, it was demonstrated that CH3NH3PbX3(X is halogen) is pure phase, such as the XRD spectra of Fig. 3 and Fig. 7.
The CH that the present invention prepares3NH3PbX3(X is halogen) monocrystalline, exposes a few days not deliquescence in atmosphere, and decomposition temperature is equal
At about 300 DEG C, the stability having had, such as the thermogravimetric analysis figure of Fig. 5 and Fig. 9.
In order to be cheaper to obtain high-quality CH3NH3PbX3Large-size crystals, the present invention also provides for a kind of CH3NH3PbX3Brilliant
Bulk-growth special purpose device.Technical scheme is as follows:
The grower (structure is as shown in Figure 1) of a kind of methylamine lead halide hydrochlorate large-size crystals, including tank, at water
Being vertically installed with the seed rod that electric rotating machine drives in the middle part of groove, seed rod lower end connects seed crystal rest stand, described seed crystal rest stand
The cage structure being made up of the vertical struts of the most parallel disk and connection two disks, lower disc is seed crystal plate；At tank
The side of interior seed rod is sequentially provided with heater and temperature sensor from inside to outside, and opposite side is sequentially provided with stirring from inside to outside
Device and thermometer.
Preferably, described electric rotating machine 2 is directly fixing with Stirring device 13 to be connected, and seed rod 1 is fixed on Stirring
On device 13.
CH of the present invention3NH3PbX3The grower of large-size crystals, efficiently solves this compounds and uses existing skill
The problem that art vaporization at high temperature solwution method can not get large-size high-quality crystal.Compared with conventional solution falling temperature method device, the present invention
Seed rod is structurally improved.The seed rod that conventional solution falling temperature method device uses is to connect seed crystal with flabellum
Plate, is usually the bottom that seed crystal is fixed on seed rod, and solution mass transfer is uneven, it is easy to occur stray crystal bottom solution；And
Use the cage structure seed crystal rest stand of the present invention, seed crystal is fixed on seed rod rest stand, seed crystal solution fall bottom employing
Warm therapy carries out crystal growth, it is easier to obtain the crystal of large-size high-quality, it is to avoid the phenomenon of stray crystal occur.Present invention success
Prepare large scale methylamine lead halide hydrochlorate (CH3NH3PbX3) monocrystalline, it is critical only that material purity, rate of temperature fall, seed crystal
Selection and the observing and controlling of solution saturation point temperature, and use cage structure seed crystal rest stand so that solution mass transfer evenly,
Stray crystal is avoided to be formed well.The present invention uses bottom seed crystal aqueous solution cooling method, and higher temperatures solution evaporation method is easier to obtain greatly
Size high quality crystal, and raw material is easy to get, with low cost, operating condition is easily achieved.
CH prepared by the present invention3NH3PbX3(X is halogen Cl, Br, I) crystal is as semiconductor crystalline material, in ultraviolet-can
Jian Guang district has fine light absorption range (as shown in Figure 4 and Figure 6), can apply to photoconduction and optical detection field.Particular use
As follows:
CH3NH3PbX3(X is halogen Cl, Br, I) crystal is as the application of solar cell；
CH3NH3PbX3(X is halogen Cl, Br, I) crystal is as the application of electrooptical material；
CH3NH3PbX3(X is halogen Cl, Br, I) crystal is as the application of ferroelectric material；
CH3NH3PbX3(X is halogen Cl, Br, I) crystal is as the application of LED material；
CH3NH3PbX3(X is halogen Cl, Br, I) crystal is as the application of field-effect transistor materials；
CH3NH3PbX3(X is halogen Cl, Br, I) crystal is as the application of thermoelectric material.
Accompanying drawing explanation
Fig. 1 is CH of the present invention3NH3PbX3Crystal growing apparatus schematic diagram, 1. seed rod, 2. electric rotating machine, 3. heater,
4. temperature sensor, 5. leaf paddle stirrer, 6. thermometer, 7. tank, 8. seed crystal, 9, caged seed crystal rest stand, 10, upper disk,
11, lower disc, 12, pole, 13, Stirring device.
Large scale CH of Fig. 2 present invention growth3NH3PbBr3Crystallogram；Fig. 3 is CH3NH3PbBr3XRD spectra；
Fig. 4 is CH3NH3PbBr3Uv-visible absorption spectra；Fig. 5 is CH3NH3PbBr3Thermogravimetric analysis figure；
Large scale CH of Fig. 6 present invention growth3NH3PbI3Crystal picture；Fig. 7 CH3NH3PbI3XRD spectra；
Fig. 8 is CH3NH3PbI3Ultraviolet-visible absorption spectroscopy；Fig. 9 is CH3NH3PbI3Thermogravimetric analysis figure.
Detailed description of the invention
Below by embodiment, the present invention is further illustrated, but the present invention is not limited to following example.
Embodiment 1, crystal growing apparatus
The grower of a kind of methylamine lead halide hydrochlorate large-size crystals, structure is as it is shown in figure 1, hang down in the middle part of tank 7
Directly be provided with electric rotating machine 2 drive seed rod 1, seed rod 1 lower end connect seed crystal rest stand 9, described seed crystal rest stand be by
The cage structure of vertical struts 12 composition of upper and lower parallel disk 10,11 and connection two disks, lower disc 11 is seed crystal plate；
In tank 7, the side of seed rod 1 is sequentially provided with heater 3 and temperature sensor 4 from inside to outside, and opposite side depends on from inside to outside
Secondary it is provided with leaf paddle stirrer 5 and thermometer 6.Electric rotating machine 2 is directly fixing with Stirring device 13 to be connected, and seed rod 1 is fixed on
On Stirring device 13.Solution is heated and passes through temperature sensor 4 by heater 3 and connects temperature control by this device, and thermometer 6 is seen
Examine mensuration solution temperature.Owing to tank is relatively large, leaf paddle stirrer 5 is set and makes solution concentration, homogeneous temperature, solution mass transfer
Well, beneficially temperature keeps constant.
Embodiment 2, large scale CH3NH3PbBr3Crystal growth
A. bromination methylamine (CH3NH3Br) synthetically prepared: by CH in ice-water bath3NH2The aqueous solution joins in HBr solution,
React 3.5 hours；CH3NH2: HBr=1.5:1 mol ratio.The mass percentage concentration of methylamine water solution is 30wt%, HBr solution
Mass percentage concentration is 40wt%.
Steam through vacuum rotary evaporator rotation, obtain the bromination methylamine of white.The bromination methylamine that will obtain add anhydrous
Ether, recrystallizes 3 times, obtains the CH of white3NH3Br.The white CH that will obtain3NH3Br, being placed in vacuum drying chamber, to be dried 2 little
Time, obtain colourless CH3NH3Br crystal.
B. in the Water Tank with Temp.-controlled of 300cm × 30cm, according to stoichiometric proportion precise Pb (CH3COOH)2·3H2O adds
Enter to 40wt%HBr solution, obtain colourless transparent solution.
C. the CH prepared according to stoichiometric proportion precise step a3NH3Br, adds it to the achromaticity and clarification of step b
In solution, produce Chinese red precipitate C H3NH3PbBr3Compound (also referred to as methylamine bromine lead), heats up, makes precipitation be completely dissolved, obtain
The solution of achromaticity and clarification, is down to solution saturation point, enters down seed crystal, and seed crystal is 1 × 1 × 1mm3Natural-surface rule
CH3NH3PbX3Single grain, with 1 DEG C/day rate of temperature fall cooling growth, growth cycle one month, obtains Chinese red transparent
CH3NH3PbBr3Crystal, crystalline size: 6 × 4 × 2mm3, crystallogram is as shown in Figure 2.The method obtains powder X-ray RD of crystal
Completely the same with the XRD that mono-crystalline structures theory calculates, it was demonstrated that to be CH3NH3PbBr3Crystal, as shown in Figure 3.
Monocrystalline embodiment 1 obtained, grind into powder is made solid-ultraviolet spectra, is inhaled completely in 200-580nm scope
Receive, CH simultaneously3NH3PbBr3Absorption of crystal cut-off limit is 580nm, shows that this compound band gap is about 2.14eV, as shown in Figure 4.
Embodiment 3, large scale CH3NH3PbI3Crystal growth
A. iodate methylamine (CH3NH3I) synthesis
By CH in ice-water bath3NH2The aqueous solution joins in HI solution, CH3NH2: HI=1.2:1 mol ratio, reaction 4 is little
Time.The mass percentage concentration of methylamine water solution be the mass percentage concentration of 30wt%, HI solution be 40wt%.
Steam through vacuum rotary evaporator rotation, obtain the iodate methylamine of white.The iodate methylamine that will obtain add anhydrous
Ether, recrystallizes 3 times, obtains the CH of white3NH3I.The white CH that will obtain3NH3I, is placed in vacuum drying chamber and is dried a few hours,
Finally give colourless CH3NH3I crystal.
B. in Water Tank with Temp.-controlled (300cm × 30cm), according to stoichiometric proportion precise Pb (CH3COOH)2·3H2O adds
Enter in 45wt%HI solution, obtain yellow transparent solution.
C. the CH prepared according to stoichiometric proportion precise step a3NH3I, the yellow clarification adding it to step b is molten
In liquid, produce black precipitate CH3NH3PbI3Compound (also referred to as methylamine bustamentite), is warming up to precipitation and is completely dissolved, obtain yellow clear
Clear solution, is down to solution saturation point, enters down seed crystal, and seed crystal is 2 × 2 × 2mm3The CH of natural-surface rule3NH3PbX3Single
Jingjing grain, with 1 DEG C/day rate of temperature fall cooling growth, growth cycle about month, obtains bright black CH3NH3PbI3Crystal (chi
Very little: 10 × 10 × 8mm3), crystallogram is as shown in Figure 6.
It is consistent that the method obtains the XRD that crystal powder XRD calculates with mono-crystalline structures theory, it was demonstrated that be CH3NH3PbI3
Crystal, as shown in Figure 7.
Single crystal grain embodiment 2 obtained, grind into powder is made solid-ultraviolet spectra, is inhaled completely in 250-800nm scope
Receive, cover whole ultraviolet-visible light, simultaneously CH3NH3PbI3Absorption of crystal cut-off limit is 836nm.Show this compound band gap about
For 1.48eV, as shown in Figure 8.
Claims (9)
1. a growing method for methylamine lead halide hydrochlorate large-size crystals, comprises the following steps that
(1) prepared by halogenation methylamine
In ice-water bath, methylamine water solution is joined in halogen acids and reacts, after having reacted, steamed by Rotary Evaporators rotation,
Obtain halogenation methylamine precipitation, add absolute ether recrystallization, vacuum drying, obtain halogenation methylamine crystal；
(2) CH3NH3PbX3The preparation of compound and crystal growth
According to stoichiometric proportion precise Pb (CH3COOH)2·3H2O, joins in HX solution, stirring, obtains the molten of clarification
Liquid；The CH prepared according to stoichiometric proportion precise step (1)3NH3X, joins in the solution of above-mentioned clarification, stirring, produces
Raw CH3NH3PbX3The precipitation of compound；Heat up, make precipitation be completely dissolved, then be cooled to solution saturation point；Enter seed crystal down,
Make seed crystal be positioned at the bottom of solution, rotate seed crystal, control rate of temperature fall 0.5-2 DEG C/day, carry out crystal growth；
Halogen in above-mentioned halogen acids, halogenation methylamine, methylamine lead halide hydrochlorate is Cl, Br or I, i.e. X=Cl, Br or I.
2. the growing method of crystal as claimed in claim 1, it is characterised in that in step (1), methylamine: the mol ratio of halogen acids
It is 1 ~ 1.5:1.
3. the growing method of crystal as claimed in claim 1, it is characterised in that in step (1), the quality hundred of methylamine water solution
Point concentration is 20 ~ 30 wt%, joins in halogen acids and reacts 3-6 hour.
4. the growing method of crystal as claimed in claim 1, it is characterised in that in step (2), the quality hundred of described HX solution
Point concentration is 30-45 wt%.
5. the growing method of crystal as claimed in claim 1, it is characterised in that crystal growth cycles 25-35 days.
6. the growing method of crystal as claimed in claim 1, it is characterised in that during the running seed crystal, the temperature of solution is at 65-
70 ℃。
7. the growing method of crystal as claimed in claim 1, it is characterised in that the rotating speed of described rotation seed crystal is 30-80 r/
min。
8. the growing method of crystal as claimed in claim 1, it is characterised in that gained methylamine lead halide hydrochlorate large-size crystals
Size be length: (6 ~ 10) × (4 ~ 10) × (2 ~ 8) mm3Monocrystalline.
9. the growing method of crystal as claimed in claim 1, it is characterised in that obtained methylamine lead halide hydrochlorate crystal is:
CH3NH3PbBr3Crystal, size 6 × 4 × 2 mm3；Extinction is had in ultraviolet-visible light district, complete in 200-580 nm scope
Absorbing, heat decomposition temperature is at 300 DEG C；Or
CH3NH3PbI3Crystal, 10 × 10 × 8 mm3；There is extinction in ultraviolet-visible light district, inhale completely in 250-800 nm scope
Receive.
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|---|---|---|---|---|
| KR20180013859A (en) * | 2015-03-24 | 2018-02-07 | 킹 압둘라 유니버시티 오브 사이언스 앤드 테크놀로지 | Methods of preparing organometallic halide structures |
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| CN106065494B (en) * | 2016-06-07 | 2018-09-18 | 中国科学院新疆理化技术研究所 | A kind of synthetic method of morphology controllable hybrid inorganic-organic bismuthino crystal |
| CN106283195B (en) * | 2016-09-07 | 2018-12-07 | 上海大学 | The device and method of continuous growing large-size perovskite monocrystalline |
| TWI630293B (en) | 2017-05-19 | 2018-07-21 | 國立清華大學 | Method for preparing perovskite crystal |
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| CN108034989B (en) * | 2017-12-04 | 2020-09-29 | 山东大学 | Method and device for growing large-size methylamine lead bromide crystal by controllable anti-solvent diffusion method |
| CN109695060B (en) * | 2019-02-14 | 2020-11-20 | 南京航空航天大学 | Dynamic growth device and method for large-size perovskite single crystal |
| CN112410884A (en) * | 2020-11-19 | 2021-02-26 | 吉林大学 | Rare earth doped single crystal perovskite and preparation method thereof and photoelectric detector |
| CN114016120A (en) * | 2021-11-10 | 2022-02-08 | 山东省科学院新材料研究所 | Preparation method and device of thiourea zinc sulfate crystal |
| CN114525577A (en) * | 2022-02-21 | 2022-05-24 | 电子科技大学 | Method for preparing wafer-level perovskite chip in aqueous phase solution, chip and application |
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| CN103541007A (en) * | 2013-11-12 | 2014-01-29 | 青岛大学 | Directional growth method for cone face of KDP (Potassium Dihydrogen Phosphate) crystal |
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| CN103541007A (en) * | 2013-11-12 | 2014-01-29 | 青岛大学 | Directional growth method for cone face of KDP (Potassium Dihydrogen Phosphate) crystal |
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