CN104911705A - Method for growing ABX3 perovskite single crystals in low-temperature solution - Google Patents

Method for growing ABX3 perovskite single crystals in low-temperature solution Download PDF

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CN104911705A
CN104911705A CN201510254128.5A CN201510254128A CN104911705A CN 104911705 A CN104911705 A CN 104911705A CN 201510254128 A CN201510254128 A CN 201510254128A CN 104911705 A CN104911705 A CN 104911705A
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monocrystalline
single crystal
uhligite
crystal growing
growing liquid
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CN104911705B (en
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刘生忠
刘渝城
杨周
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Shaanxi Normal University
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Shaanxi Normal University
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Abstract

The invention provides a method for growing ABX3 perovskite single crystals in a low-temperature solution. According to the invention, a continuous growing method is adopted, and the ABX3 perovskite single crystals are rapidly grown in the low-temperature solution continuously with multiple periods and different stages. The concentration of the solution is high, and the raw materials required by growing are uniformly dissolved. Growing periods are added, and growing conditions are finely controlled, such that ABX3 perovskite single crystals with large sizes, regular shapes and high quality can be easily obtained. The method has the advantages of simple process, high operability, mild growing conditions, low required temperature, low energy consumption, low equipment requirement, low cost, high success rate, fast single crystal growth speed, fewer defects, good stability, large single crystal size (>10mm)*(>10mm)*(>10mm), and the like. Therefore, basic mechanism theoretical researches on perovskite materials and related optoelectronic devices (including solar cell, photodetector, LED and laser) are promoted.

Description

ABX is grown in cryogenic fluid 3the method of uhligite monocrystalline
[technical field]
The invention belongs to area of solar cell, be specifically related to grow ABX in a kind of cryogenic fluid 3the method of uhligite monocrystalline.
[background technology]
Along with the fast development of economic globalization, the demand of countries in the world to the energy increases year by year, the traditional fossil energy approach exhaustions gradually such as coal, oil, Sweet natural gas, and also brings a series of ecological environment problem while using traditional energy.Therefore, change current energy structure, find the clean energy supply of renewable, economy, environmental protection, as sun power, Hydrogen Energy, wind energy, tidal energy etc., become the research topic that countries in the world are paid close attention to.Sun power is clean energy the abundantest in the world, and its total amount being radiated earth surface every year far exceedes hundred times of the total margin of fossil energy on the earth.Making full use of sun power, is one of important method meeting energy demand growing in global range.
Be a kind of effective method of electric energy by solar energy converting be the solar cell of preparation based on photovoltaic effect.The novel solar cell of research and development low-cost high-efficiency is the technical foundation realizing solar energy power generating wide popularization and application.A kind of CH based on perovskite structure 3nH 3pbX 3the solar cell of (X represents haloid element) material causes the very big concern of photovoltaic research field in recent years.Through the development of short 6 years, up to the present, the highest authentication efficiency of uhligite solar cell reaches 20.1%.
At present, attention is more the performance, the raising aspect such as cell photoelectric efficiency of conversion and stability test that are placed on synthetic method or the material how improving film by people.It develops the raising speed making the research of Related Mechanism not catch up with efficiency fast, still lacks and is familiar with the deep layer of uhligite solar cell microphysics mechanism.We need more to pay close attention to the essential property of perovskite material and battery operated principle, and this not only contributes to the performance improving perovskite typed solar cell further, also can provide thinking for people find simpler or more effective new texture.Therefore, large size, regular shape, high-quality ABX is grown 3uhligite monocrystalline is in order to being very urgent and necessary to the fundamental research of perovskite material.
Up to the present, about ABX 3the growth of uhligite monocrystalline and the also few of research report.At the beginning of 2015, Science reports two sections in succession about CH 3nH 3pbX 3uhligite monocrystalline to the microphysics characteristic research of uhligite solar cell (
(1)Q.F.Dong,Y.Fang,；Y.Shao,P.Mulligan,J.Qiu,L.Cao,J.S.Huang,Science 2015,347,967-970.
(2)D.Shi,V.Adinolfi,R.Comin,M.Yuan,E.Alarousu,A.Buin,Y.Chen,S.Hoogland,A.Rothenberger,K.v；Y.Losovyj,X.Zhang,P.A.Dowben,O.F.Mohammed,E.H.Sargent,O.M.Bakr,Science 2015,347,519-522.)。But the technique that in document, growing single-crystal uses is comparatively complicated, loaded down with trivial details, and actually operating gets up to have certain difficulty; And growth conditions is relatively harsh, poor controllability; The most important thing is that the monocrystalline size that the method reported in document grows is less, about 10mm.
[summary of the invention]
The object of the present invention is to provide in a kind of cryogenic fluid and grow ABX 3the method of uhligite monocrystalline, has the advantages such as experimental implementation is simple, success ratio is high, gained monocrystalline size is large.
For achieving the above object, in cryogenic fluid of the present invention, grow ABX 3the method of uhligite monocrystalline is as follows:
ABX 3uhligite monocrystalline, wherein A is CH 3nH 3 +, H 2n-CH=NH 2 +, (CH 3) 4n +, C 7h 7 +, Cs +or C 3h 11sN 3 2+, B is Pb, Ge or Sn; X is Cl, Br or I, gets the metallic compound providing plumbous source, Xi Yuan or germanium source, halides and can dissolve the solvent of this metallic compound; Halides and solvent are mixed with solution, after being added by metallic compound, are made into single crystal growing liquid, adopt the growth of the method for growth continuously to obtain ABX 3uhligite monocrystalline.
Further, take halides during preparation single crystal growing liquid and dissolve by stirring solvent in a reservoir, then sealed vessel is placed on magnetic stirring apparatus, heats more than continuously stirring, concussion or supersound process 12h, obtain single crystal growing liquid at DEG C temperature of room temperature ~ 90.
Further, take halides during preparation single crystal growing liquid and dissolve by stirring solvent in a reservoir, then sealed vessel is placed on magnetic stirring apparatus, heats more than continuously stirring, concussion or supersound process 12h at 20 ~ 80 DEG C of temperature, obtains single crystal growing liquid.
Further, take halides during preparation single crystal growing liquid and dissolve by stirring solvent in a reservoir, then sealed vessel is placed on magnetic stirring apparatus, heats more than continuously stirring, concussion or supersound process 12h at 40 ~ 70 DEG C of temperature, obtains single crystal growing liquid.
Further, first grow the crystal grain that size is less, seed crystal is transferred in fresh single crystal growing liquid afterwards and grow; After growth for some time, fresher single crystal growing liquid is put in the crystal grain of growing up taking-up; Often changing once fresh single crystal growing liquid to the growth time changing single crystal growing liquid is next time a growth cycle, and continuous multiple growth cycle is until obtain the monocrystalline needed and so forth.
Further, described single crystal growing temperature is 50-200 DEG C, and each growth cycle time is more than 24h.
Further, described single crystal growing temperature is 70 ~ 120 DEG C, and each growth cycle time is more than 24h.
Further, during single crystal growing, provide required temperature by heat blowing loft drier, oil bath or water-bath, growth system is heated evenly, controlled the evaporation rate of solvent by the seal degree adjusting container, to control the speed of single crystal growing.
Further, described solvent is the one in hydroiodic acid HI, gamma-butyrolactone (GBA), DMF (DMF), dimethyl sulfoxide (DMSO) (DMSO), METHYLPYRROLIDONE (NMP).
Further, the metallic compound in plumbous source is provided to be lead chloride (PbCl described in 2), lead bromide (PbBr 2), lead iodide (PbI 2) or plumbic acetate (Pb (CH 3cOO) 2xH 2o); The metallic compound of the described Xi Yuan of providing is tin protochloride (SnCl 2), tin tetrachloride (SnCl 4), tin protobromide (SnBr 2) or Tin tetraiodide (SnI 2); The described metallic compound in germanium source that provides is germanium chloride (GeCl 2), bromination germanium (GeBr 2) or iodate germanium (GeI 2).
Further, described halides is for containing organic or inorganic ionic radius being organic or inorganic halides in one, comprise chloromethane amine (CH 3nH 3cl), chloromethane amidine (H 2n-CH=NH 2cl), tetramethylamine chloride ((CH 3) 4nCl), chlorine Zhuo (C 7h 7cl), chloro 2-isothiourea (C 3h 11sN 3cl 2), bromine methylamine (CH 3nH 3br), bromine carbonamidine (H 2n-CH=NH 2br), bromination tetramethylammonium ((CH 3) 4n Br), bromine Zhuo (C 7h 7br), bromo 2-isothiourea (C 3h 11sN 3br 2), iodine methylamine (CH 3nH 3i), iodine carbonamidine (H 2n-CH=NH 2i), iodate tetramethylammonium ((CH 3) 4n I), iodine Zhuo (C 7h 7i), iodo 2-isothiourea (C 3h 11sN 3i 2) and inorganic CsI.
Further, in described single crystal growing liquid, the metal ion of metallic compound and the ion mol ratio of halides are 1:(0.5 ~ 10).
Further, in described single crystal growing liquid, the metal ion of metallic compound and the ion mol ratio of halides are 1:(0.8 ~ 5).
Further, in described single crystal growing liquid, the metal ion of metallic compound and the ion mol ratio of halides are 1:(1 ~ 3).
Further, the concentration of described single crystal growing liquid is 0.05-5.0mol/L.
The present invention grows ABX fast in cryogenic fluid 3uhligite monocrystalline, compared with prior art, has the following advantages:
The present invention adopts the method for growth continuously, and the continuous multicycle grows ABX fast stage by stage in cryogenic fluid 3uhligite monocrystalline, strength of solution used is large, and growth desired raw material is uniformly dissolved, and increases growth cycle and the precise controlling to growth conditions, is easy to obtain the ABX that size is large, regular shape, quality are high 3uhligite monocrystalline.Method technique is simple, workable; Growth conditions is gentle, temperature required low, energy-conservation; Equipment requirements is low, cost is low; Success ratio is high, growing single-crystal speed is fast; The advantages such as defect is few, good stability, large (>10mm) × (>10mm) × (>10mm) of gained monocrystalline size.Thus promote the basic mechanism theoretical investigation to perovskite material and relative photo electrical part (comprising solar cell, photo-detector, LED and laser apparatus etc.).
[accompanying drawing explanation]
Fig. 1 is single crystal growing simple process figure.
Fig. 2 is the monocrystalline picture that part grown for 1 ~ 4 cycle in the solution respectively.
[embodiment]
Below by embodiment, the present invention is further illustrated, but the present invention is not limited to following examples.
ABX provided by the invention 3uhligite method for monocrystal growth, A is CH 3nH 3 +, H 2n-CH=NH 2 +, (CH 3) 4n +, C 7h 7 +, Cs +or C 3h 11sN 3 2+; B is Pb, Ge or Sn; X be Cl, Br or, concrete grammar comprises following steps:
1) take synthetic halo organic-inorganic thing as above, add in the tall form beaker of 100mL, put into a magnetic stir bar;
2) in step 1 beaker, related solvents is added;
3) beaker is placed in room temperature ~ 90 DEG C on magnetic agitation well heater to stir, in this process, halo organic-inorganic thing dissolves rapidly;
4) weighing metallic compound as above is added in the solution that step 3 obtains;
5) with preservative film, beaker is sealed, continue to be placed in room temperature ~ 90 DEG C on magnetic force heating stirrer and stir more than 12h, obtain clarification, transparent single crystal growing liquid; The concentration of single crystal growing liquid is 0.05 ~ 5.0mol/L.
6) the single crystal growing liquid prepared is transferred in crystallizing dish;
7), after being sealed by crystallizing dish in step 6 with preservative film, in heat blowing loft drier, 50 ~ 200 DEG C of heating more than 24h, obtain more tiny uhligite monocrystalline (seed crystal) bottom crystallizing dish;
8) every uhligite monocrystalline (seed crystal) is transferred in new crystallizing dish respectively;
9) in the crystallizing dish of step 8, add the single crystal growing liquid prepared; Concentration is 0.05 ~ 5.0mol/L;
10) after crystallizing dish in step 9 being sealed with preservative film, in heat blowing loft drier after 50 ~ 200 DEG C of heating 48h, the ABX bottom crystallizing dish 3uhligite monocrystalline size obviously increases;
11) the old single crystal growing liquid in the crystallizing dish of step 10 is inclined to, rejoin the single crystal growing liquid (concentration is 0.05 ~ 5.0mol/L) prepared;
12) after crystallizing dish in step 11 being sealed with preservative film, in heat blowing loft drier after 50-200 DEG C of heating 48h, the ABX bottom crystallizing dish 3uhligite monocrystalline size increases further;
13) in like manner, repeating step 11 and 12 like this, through 4 ~ 5 all after dates, the ABX that size reaches (>10mm) × (>10mm) × (>10mm) just can be obtained 3uhligite monocrystalline;
14) ABX will grown 3uhligite monocrystalline takes out from the single crystal growing liquid crystallizing dish, with cleanings such as anhydrous diethyl ether, toluene, chlorobenzene, Virahol, methylamine solutions;
15) complete ABX is cleaned 3uhligite monocrystalline is 60 DEG C of dry 24h in vacuum drying oven;
16) ABX 3the dry final vacuum packaging of uhligite monocrystalline, uses in order to test.
Further, the tall form beaker used in experiment and crystallizing dish are simple glass material.
Further, the preservative film used in step 5 is common plastics preservative film, without special processing.
Further, in the present invention, the concentration of single crystal growing liquid is the concentration of the metal ion in solution metal compound, and the metal ion in metallic compound and halo organic-inorganic thing Ionic Radius are the mol ratio of ion be 1:0.5 ~ 1:10.
Further, the Heating temperature in step 7 is 50 ~ 200 DEG C, is preferably 100 ~ 120 DEG C.
Embodiment 1
1, monocrystalline (seed crystal) growth media is prepared
Take the iodine methylamine (CH that 0.159g has synthesized 3nH 3i), join in the tall form beaker of 100mL, put into a magnetic stir bar, measure 20mL gamma-butyrolactone (GBA) and add, 20 DEG C of stirring heating on magnetic agitation well heater.Treat iodine methylamine (CH 3nH 3i) after all dissolving, then 0.461g lead iodide (PbI is taken 2) add, continue at 20 DEG C of more than stirring heating 12h on magnetic agitation well heater, obtain single crystal growing liquid (concentration: 0.05M, the metal ion of metallic compound and the ion mol ratio of halides: 1:1).
2, single crystal growing liquid is prepared
Take the iodine methylamine (CH that 3.91g has synthesized 3nH 3i), join in the tall form beaker of 100mL, put into a magnetic stir bar, measure 20mL gamma-butyrolactone (GBA) and add, 20 DEG C of stirring heating on magnetic agitation well heater.Treat iodine methylamine (CH 3nH 3i) after all dissolving, then 11.34g lead iodide (PbI is taken 2) add, continue at 20 DEG C of more than stirring heating 12h on magnetic agitation well heater, obtain single crystal growing liquid (concentration: 1.23M, the metal ion of metallic compound and the ion mol ratio of halides: 1:1), above-mentioned halides also can use C 7h 7i, (CH 3) 4n I or H 2n-CH=NH 2i substitutes.
3, small size monocrystalline (seed crystal) is grown
The monocrystalline prepared (seed crystal) growth media is transferred in the crystallizing dish of clean dried, after three layers of preservative film sealing, in heat blowing loft drier after 50 DEG C of heating 24h, bottom crystallizing dish, obtains small size CH 3nH 3pbI 3uhligite monocrystalline, as shown in Figure 2.
4, growing large-size monocrystalline
By the small size CH of growth in step 3 3nH 3pbI 3uhligite monocrystalline is transferred in the crystallizing dish of clean dried respectively, adds the single crystal growing liquid prepared, after three layers of preservative film sealing, in heat blowing loft drier after 50 DEG C of heating 48h, and the CH bottom crystallizing dish 3nH 3pbI 3uhligite monocrystalline obviously increases, as shown in Figure 2.
5, fresh single crystal growing liquid is renewed
Single crystal growing liquid old in step 4 crystallizing dish is inclined to, adds the fresh single crystal growing liquid prepared, after three layers of preservative film sealing, in heat blowing loft drier after 50 DEG C of heating 48h, the CH bottom crystallizing dish 3nH 3pbI 3uhligite monocrystalline size increases further.So repeat this step repeatedly after, just can obtain the CH that size reaches (>10mm) × (>10mm) × (>10mm) 3nH 3pbI 3uhligite monocrystalline, as shown in Figure 2.
6, CH 3nH 3pbI 3the cleaning of uhligite monocrystalline, drying and collect
With the CH that anhydrous diethyl ether cleaning growth is complete 3nH 3pbI 3uhligite monocrystalline, in vacuum drying oven after 60 DEG C of dry 24h, vacuum packaging.
Embodiment 2
1, monocrystalline (seed crystal) growth media is prepared
Take the iodine methylamine (CH that 0.318g has synthesized 3nH 3i), join in the tall form beaker of 100mL, put into a magnetic stir bar, measure 20mL gamma-butyrolactone (GBA) and add, 40 DEG C of stirring heating on magnetic agitation well heater.Treat iodine methylamine (CH 3nH 3i) after all dissolving, then 0.461g lead iodide (PbI is taken 2) add, continue at 40 DEG C of more than stirring heating 12h on magnetic agitation well heater, obtain single crystal growing liquid (concentration: 0.05M, the metal ion of metallic compound and the ion mol ratio of halides: 1:2).
2, single crystal growing liquid is prepared
Take the iodine methylamine (CH that 7.82g has synthesized 3nH 3i), join in the tall form beaker of 100mL, put into a magnetic stir bar, measure 20mL gamma-butyrolactone (GBA) and add, 40 DEG C of stirring heating on magnetic agitation well heater.Treat iodine methylamine (CH 3nH 3i) after all dissolving, then 11.34g lead iodide (PbI is taken 2) add, continue at 40 DEG C of more than stirring heating 12h on magnetic agitation well heater, obtain single crystal growing liquid (concentration: 1.23M, the metal ion of metallic compound and the ion mol ratio of halides: 1:2).
3, small size monocrystalline (seed crystal) is grown
The monocrystalline prepared (seed crystal) growth media is transferred in the crystallizing dish of clean dried, after three layers of preservative film sealing, in heat blowing loft drier after 70 DEG C of heating 24h, bottom crystallizing dish, obtains small size CH 3nH 3pbI 3uhligite monocrystalline.
4, growing large-size monocrystalline
By the small size CH of growth in step 3 3nH 3pbI 3uhligite monocrystalline is transferred in the crystallizing dish of clean dried respectively, adds the single crystal growing liquid prepared, after three layers of preservative film sealing, in heat blowing loft drier after 70 DEG C of heating 48h, and the CH bottom crystallizing dish 3nH 3pbI 3uhligite monocrystalline obviously increases.
5, fresh single crystal growing liquid is renewed
Single crystal growing liquid old in step 4 crystallizing dish is inclined to, adds the fresh single crystal growing liquid prepared, after three layers of preservative film sealing, in heat blowing loft drier after 70 DEG C of heating 48h, the CH bottom crystallizing dish 3nH 3pbI 3uhligite monocrystalline size increases further.So repeat this step repeatedly after, just can obtain the CH that size reaches (>10mm) × (>10mm) × (>10mm) 3nH 3pbI 3uhligite monocrystalline.
6, CH 3nH 3pbI 3the cleaning of uhligite monocrystalline, drying and collect
With the CH that anhydrous diethyl ether cleaning growth is complete 3nH 3pbI 3uhligite monocrystalline, in vacuum drying oven after 60 DEG C of dry 24h, vacuum packaging.
Embodiment 3
1, monocrystalline (seed crystal) growth media is prepared
Take the bromine methylamine (CH that 0.112g has synthesized 3nH 3br), join in the tall form beaker of 100mL, put into a magnetic stir bar, measure 20mL DMF (DMF) and add, 70 DEG C of stirring heating on magnetic agitation well heater.Treat bromine methylamine (CH 3nH 3br) after all dissolving, then 0.367g lead bromide (PbBr is taken 2) add, continue at 70 DEG C of more than stirring heating 12h on magnetic agitation well heater, obtain single crystal growing liquid (concentration: 0.05M, the metal ion of metallic compound and the ion mol ratio of halides: 1:1).
2, single crystal growing liquid is prepared
Take the bromine methylamine (CH that 1.12g has synthesized 3nH 3br), join in the tall form beaker of 100mL, put into a magnetic stir bar, measure 20mL DMF (DMF) and add, 70 DEG C of stirring heating on magnetic agitation well heater.Treat bromine methylamine (CH 3nH 3br) after all dissolving, then 3.67g lead bromide (PbBr is taken 2) add, continue at 70 DEG C of more than stirring heating 12h on magnetic agitation well heater, obtain single crystal growing liquid (concentration: 0.5M, the metal ion of metallic compound and the ion mol ratio of halides: 1:1), single crystal growing liquid concentration unit is M (mol/L).
3, small size monocrystalline (seed crystal) is grown
The monocrystalline prepared (seed crystal) growth media is transferred in the crystallizing dish of clean dried, after three layers of preservative film sealing, in heat blowing loft drier after 100 DEG C of heating 24h, bottom crystallizing dish, obtains small size CH 3nH 3pbBr 3uhligite monocrystalline.
4, growing large-size monocrystalline
By the small size CH of growth in step 3 3nH 3pbBr 3uhligite monocrystalline is transferred in the crystallizing dish of clean dried respectively, adds the single crystal growing liquid prepared, after three layers of preservative film sealing, in heat blowing loft drier after 100 DEG C of heating 48h, and the CH bottom crystallizing dish 3nH 3pbBr 3uhligite monocrystalline obviously increases.
5, fresh single crystal growing liquid is renewed
Single crystal growing liquid old in step 4 crystallizing dish is inclined to, adds the fresh single crystal growing liquid prepared, after three layers of preservative film sealing, in heat blowing loft drier after 100 DEG C of heating 48h, the CH bottom crystallizing dish 3nH 3pbBr 3uhligite monocrystalline size increases further.So repeat this step repeatedly after, just can obtain the CH that size reaches (>10mm) × (>10mm) × (>10mm) 3nH 3pbBr 3uhligite monocrystalline.
6, CH 3nH 3pbBr 3the cleaning of uhligite monocrystalline, drying and collect
With the CH that anhydrous diethyl ether cleaning growth is complete 3nH 3pbBr 3uhligite monocrystalline, in vacuum drying oven after 60 DEG C of dry 24h, vacuum packaging.
Embodiment 4
1, monocrystalline (seed crystal) growth media is prepared
Take the chloromethane amine (CH that 0.68g has synthesized 3nH 3cl), join in the tall form beaker of 100mL, put into a magnetic stir bar, measure 20mL DMF (DMF) and add, 45 DEG C of stirring heating on magnetic agitation well heater.Treat chloromethane amine (CH 3nH 3cl) after all dissolving, then 2.78g lead chloride (PbCl is taken 2) add, continue at 45 DEG C of more than stirring heating 12h on magnetic agitation well heater, obtain single crystal growing liquid (concentration: 0.5M, the metal ion of metallic compound and the ion mol ratio of halides: 1:1).
2, single crystal growing liquid is prepared
Take the chloromethane amine (CH that 1.66g has synthesized 3nH 3cl), join in the tall form beaker of 100mL, put into a magnetic stir bar, measure 20mL DMF and add, 45 DEG C of stirring heating on magnetic agitation well heater.Treat chloromethane amine (CH3NH 3cl) after all dissolving, then 6.84g lead chloride (PbCl is taken 2) add, continue at 45 DEG C of more than stirring heating 12h on magnetic agitation well heater, obtain single crystal growing liquid (concentration: 1.23M, the metal ion of metallic compound and the ion mol ratio of halides: 1:1), the metallic compound in above plumbous source also can use plumbic acetate (Pb (CH 3cOO) 2xH 2o) substitute.
3, small size monocrystalline (seed crystal) is grown
The monocrystalline prepared (seed crystal) growth media is transferred in the crystallizing dish of clean dried, after three layers of preservative film sealing, in heat blowing loft drier after 100 DEG C of heating 24h, bottom crystallizing dish, obtains small size CH 3nH 3pbCl 3uhligite monocrystalline.
4, growing large-size monocrystalline
By the small size CH of growth in step 3 3nH 3pbCl 3uhligite monocrystalline is transferred in the crystallizing dish of clean dried respectively, adds the single crystal growing liquid prepared, after three layers of preservative film sealing, in heat blowing loft drier after 100 DEG C of heating 48h, and the CH bottom crystallizing dish 3nH 3pbCl 3uhligite monocrystalline obviously increases.
5, fresh single crystal growing liquid is renewed
Single crystal growing liquid old in step 4 crystallizing dish is inclined to, adds the fresh single crystal growing liquid prepared, after three layers of preservative film sealing, in heat blowing loft drier after 100 DEG C of heating 48h, the CH bottom crystallizing dish 3nH 3pbCl 3uhligite monocrystalline size increases further.So repeat this step repeatedly after, just can obtain the CH that size reaches (>10mm) × (>10mm) × (>10mm) 3nH 3pbCl 3uhligite monocrystalline.
6, CH 3nH 3pbCl 3the cleaning of uhligite monocrystalline, drying and collect
With the CH that anhydrous diethyl ether cleaning growth is complete 3nH 3pbCl 3uhligite monocrystalline, in vacuum drying oven after 60 DEG C of dry 24h, vacuum packaging.
Embodiment 5
1, monocrystalline (seed crystal) growth media is prepared
Take the iodine methylamine (CH that 1.59g has synthesized 3nH 3i), join in the tall form beaker of 100mL, put into a magnetic stir bar, measure 20mL gamma-butyrolactone (GBA) and add, 80 DEG C of stirring heating on magnetic agitation well heater.Treat iodine methylamine (CH 3nH 3i) after all dissolving, then 4.61g lead iodide (PbI is taken 2) add, continue at 80 DEG C of more than stirring heating 12h on magnetic agitation well heater, obtain single crystal growing liquid (concentration: 0.5M, the metal ion of metallic compound and the ion mol ratio of halides: 1:1).
2, single crystal growing liquid is prepared
Take the iodine methylamine (CH that 3.91g has synthesized 3nH 3i), join in the tall form beaker of 100mL, put into a magnetic stir bar, measure 20mL gamma-butyrolactone (GBA) and add, 80 DEG C of stirring heating on magnetic agitation well heater.Treat iodine methylamine (CH 3nH 3i) after all dissolving, then 11.34g lead iodide (PbI is taken 2) add, continue at 80 DEG C of more than stirring heating 12h on magnetic agitation well heater, obtain single crystal growing liquid (concentration: 1.23M, the metal ion of metallic compound and the ion mol ratio of halides: 1:1).
3, small size monocrystalline (seed crystal) is grown
The monocrystalline prepared (seed crystal) growth media is transferred in the crystallizing dish of clean dried, after three layers of preservative film sealing, in heat blowing loft drier after 120 DEG C of heating 24h, bottom crystallizing dish, obtains small size CH 3nH 3pbI 3uhligite monocrystalline.
4, growing large-size monocrystalline
By the small size CH of growth in step 3 3nH 3pbI 3uhligite monocrystalline is transferred in the crystallizing dish of clean dried respectively, adds the single crystal growing liquid prepared, after three layers of preservative film sealing, in heat blowing loft drier after 120 DEG C of heating 48h, and the CH bottom crystallizing dish 3nH 3pbI 3uhligite monocrystalline obviously increases.
5, fresh single crystal growing liquid is renewed
Single crystal growing liquid old in step 4 crystallizing dish is inclined to, adds the fresh single crystal growing liquid prepared, after three layers of preservative film sealing, in heat blowing loft drier after 120 DEG C of heating 48h, the CH bottom crystallizing dish 3nH 3pbI 3uhligite monocrystalline size increases further.So repeat this step repeatedly after, just can obtain the CH that size reaches (>10mm) × (>10mm) × (>10mm) 3nH 3pbI 3uhligite monocrystalline.
6, CH 3nH 3pbI 3the cleaning of uhligite monocrystalline, drying and collect
With the CH that anhydrous diethyl ether cleaning growth is complete 3nH 3pbI 3uhligite monocrystalline, in vacuum drying oven after 60 DEG C of dry 24h, vacuum packaging.
Embodiment 6
1, monocrystalline (seed crystal) growth media is prepared
Take the iodine methylamine (CH that 4.77g has synthesized 3nH 3i), join in the tall form beaker of 100mL, put into a magnetic stir bar, measure 20mL gamma-butyrolactone (GBA) and add, 90 DEG C of stirring heating on magnetic agitation well heater.Treat iodine methylamine (CH 3nH 3i) after all dissolving, then 4.61g lead iodide (PbI is taken 2) add, continue at 90 DEG C of more than stirring heating 12h on magnetic agitation well heater, obtain single crystal growing liquid (concentration: 0.5M, the metal ion of metallic compound and the ion mol ratio of halides: 1:3).
2, single crystal growing liquid is prepared
Take the iodine methylamine (CH that 11.73g has synthesized 3nH 3i), join in the tall form beaker of 100mL, put into a magnetic stir bar, measure 20mL gamma-butyrolactone (GBA) and add, 90 DEG C of stirring heating on magnetic agitation well heater.Treat iodine methylamine (CH 3nH 3i) after all dissolving, then 11.34g lead iodide (PbI is taken 2) add, continue at 90 DEG C of more than stirring heating 12h on magnetic agitation well heater, obtain single crystal growing liquid (concentration: 1.23M, the metal ion of metallic compound and the ion mol ratio of halides: 1:3).
3, small size monocrystalline (seed crystal) is grown
The monocrystalline prepared (seed crystal) growth media is transferred in the crystallizing dish of clean dried, after three layers of preservative film sealing, in heat blowing loft drier after 150 DEG C of heating 24h, bottom crystallizing dish, obtains small size CH 3nH 3pbI 3uhligite monocrystalline.
4, growing large-size monocrystalline
By the small size CH of growth in step 3 3nH 3pbI 3uhligite monocrystalline is transferred in the crystallizing dish of clean dried respectively, adds the single crystal growing liquid prepared, after three layers of preservative film sealing, in heat blowing loft drier after 150 DEG C of heating 48h, and the CH bottom crystallizing dish 3nH 3pbI 3uhligite monocrystalline obviously increases.
5, fresh single crystal growing liquid is renewed
Single crystal growing liquid old in step 4 crystallizing dish is inclined to, adds the fresh single crystal growing liquid prepared, after three layers of preservative film sealing, in heat blowing loft drier after 150 DEG C of heating 48h, the CH bottom crystallizing dish 3nH 3pbI 3uhligite monocrystalline size increases further.So repeat this step repeatedly after, just can obtain the CH that size reaches (>10mm) × (>10mm) × (>10mm) 3nH 3pbI 3uhligite monocrystalline.
6, CH 3nH 3pbI 3the cleaning of uhligite monocrystalline, drying and collect
With the CH that anhydrous diethyl ether cleaning growth is complete 3nH 3pbI 3uhligite monocrystalline, in vacuum drying oven after 60 DEG C of dry 24h, vacuum packaging.
Embodiment 7
1, monocrystalline (seed crystal) growth media is prepared
Take the bromine methylamine (CH that 1.12g has synthesized 3nH 3br), join in the tall form beaker of 100mL, put into a magnetic stir bar, measure 20mL DMF (DMF) and add, 90 DEG C of stirring heating on magnetic agitation well heater.Treat bromine methylamine (CH 3nH 3br) after all dissolving, then 3.67g lead bromide (PbBr is taken 2) add, continue at 90 DEG C of more than stirring heating 12h on magnetic agitation well heater, obtain single crystal growing liquid (concentration: 0.5M, the metal ion of metallic compound and the ion mol ratio of halides: 1:1).
2, single crystal growing liquid is prepared
Take the bromine methylamine (CH that 2.24g has synthesized 3nH 3br), join in the tall form beaker of 100mL, put into a magnetic stir bar, measure 20mL DMF (DMF) and add, 90 DEG C of stirring heating on magnetic agitation well heater.Treat bromine methylamine (CH 3nH 3br) after all dissolving, then 7.34g lead bromide (PbBr is taken 2) add, continue at 90 DEG C of more than stirring heating 12h on magnetic agitation well heater, obtain single crystal growing liquid (concentration: 1M, the metal ion of metallic compound and the ion mol ratio of halides: 1:1).
3, small size monocrystalline (seed crystal) is grown
The monocrystalline prepared (seed crystal) growth media is transferred in the crystallizing dish of clean dried, after three layers of preservative film sealing, in heat blowing loft drier after 150 DEG C of heating 24h, bottom crystallizing dish, obtains small size CH 3nH 3pbBr 3uhligite monocrystalline.
4, growing large-size monocrystalline
By the small size CH of growth in step 3 3nH 3pbBr 3uhligite monocrystalline is transferred in the crystallizing dish of clean dried respectively, adds the single crystal growing liquid prepared, after three layers of preservative film sealing, in heat blowing loft drier after 150 DEG C of heating 48h, and the CH bottom crystallizing dish 3nH 3pbBr 3uhligite monocrystalline obviously increases.
5, fresh single crystal growing liquid is renewed
Single crystal growing liquid old in step 4 crystallizing dish is inclined to, adds the fresh single crystal growing liquid prepared, after three layers of preservative film sealing, in heat blowing loft drier after 150 DEG C of heating 48h, the CH bottom crystallizing dish 3nH 3pbBr 3uhligite monocrystalline size increases further.So repeat this step repeatedly after, just can obtain the CH that size reaches (>10mm) × (>10mm) × (>10mm) 3nH 3pbBr 3uhligite monocrystalline.
6, CH 3nH 3pbBr 3the cleaning of uhligite monocrystalline, drying and collect
With the CH that anhydrous diethyl ether cleaning growth is complete 3nH 3pbBr 3uhligite monocrystalline, in vacuum drying oven after 60 DEG C of dry 24h, vacuum packaging.
Embodiment 8
1, monocrystalline (seed crystal) growth media is prepared
Take the iodine methylamine (CH3NH that 1.59g has synthesized 3i), join in the tall form beaker of 100mL, put into a magnetic stir bar, measure 20mL gamma-butyrolactone (GBA) and add, 20 DEG C of stirring heating on magnetic agitation well heater.Treat iodine methylamine (CH 3nH 3i) after all dissolving, then 4.61g lead iodide (PbI is taken 2) add, continue at 20 DEG C of more than stirring heating 12h on magnetic agitation well heater, obtain single crystal growing liquid (concentration: 0.5M, the metal ion of metallic compound and the ion mol ratio of halides: 1:1).
2, single crystal growing liquid is prepared
Take the iodine methylamine (CH that 3.91g has synthesized 3nH 3i), join in the tall form beaker of 100mL, put into a magnetic stir bar, measure 20mL gamma-butyrolactone (GBA) and add, 20 DEG C of stirring heating on magnetic agitation well heater.Treat iodine methylamine (CH 3nH 3i) after all dissolving, then 11.34g lead iodide (PbI is taken 2) add, continue at 20 DEG C of more than stirring heating 12h on magnetic agitation well heater, obtain single crystal growing liquid (concentration: 1.23M, the metal ion of metallic compound and the ion mol ratio of halides: 1:1).
3, small size monocrystalline (seed crystal) is grown
The monocrystalline prepared (seed crystal) growth media is transferred in the crystallizing dish of clean dried, after three layers of preservative film sealing, in heat blowing loft drier after 200 DEG C of heating 24h, bottom crystallizing dish, obtains small size CH 3nH 3pbI 3uhligite monocrystalline.
4, growing large-size monocrystalline
By the small size CH of growth in step 3 3nH 3pbI 3uhligite monocrystalline is transferred in the crystallizing dish of clean dried respectively, adds the single crystal growing liquid prepared, after three layers of preservative film sealing, in heat blowing loft drier after 200 DEG C of heating 48h, and the CH bottom crystallizing dish 3nH 3pbI 3uhligite monocrystalline obviously increases.
5, fresh single crystal growing liquid is renewed
Single crystal growing liquid old in step 4 crystallizing dish is inclined to, adds the fresh single crystal growing liquid prepared, after three layers of preservative film sealing, in heat blowing loft drier after 200 DEG C of heating 48h, the CH bottom crystallizing dish 3nH 3pbI 3uhligite monocrystalline size increases further.So repeat this step repeatedly after, just can obtain the CH that size reaches (>10mm) × (>10mm) × (>10mm) 3nH 3pbI 3uhligite monocrystalline.
6, CH 3nH 3pbI 3the cleaning of uhligite monocrystalline, drying and collect
With the CH that anhydrous diethyl ether cleaning growth is complete 3nH 3pbI 3uhligite monocrystalline, in vacuum drying oven after 60 DEG C of dry 24h, vacuum packaging.
Embodiment 9
1, monocrystalline (seed crystal) growth media is prepared
Take the iodine methylamine (CH that 3.18g has synthesized 3nH 3i), join in the tall form beaker of 100mL, put into a magnetic stir bar, measure 20mL DMF (DMF) and add, 40 DEG C of stirring heating on magnetic agitation well heater.Treat iodine methylamine (CH 3nH 3i) after all dissolving, then 4.61g lead iodide (PbI is taken 2) add, continue at 40 DEG C of more than stirring heating 12h on magnetic agitation well heater, obtain single crystal growing liquid (concentration: 0.5M, the metal ion of metallic compound and the ion mol ratio of halides: 1:2).
2, single crystal growing liquid is prepared
Take the iodine methylamine (CH that 7.82g has synthesized 3nH 3i), join in the tall form beaker of 100mL, put into a magnetic stir bar, measure 20mL DMF (DMF) and add, 40 DEG C of stirring heating on magnetic agitation well heater.Treat iodine methylamine (CH 3nH 3i) after all dissolving, then 11.34g lead iodide (PbI is taken 2) add, continue at 40 DEG C of more than stirring heating 12h on magnetic agitation well heater, obtain single crystal growing liquid (concentration: 1.23M, the metal ion of metallic compound and the ion mol ratio of halides: 1:2).
3, small size monocrystalline (seed crystal) is grown
The monocrystalline prepared (seed crystal) growth media is transferred in the crystallizing dish of clean dried, after three layers of preservative film sealing, in heat blowing loft drier after 70 DEG C of heating 24h, bottom crystallizing dish, obtains small size CH 3nH 3pbI 3uhligite monocrystalline.
4, growing large-size monocrystalline
By the small size CH of growth in step 3 3nH 3pbI 3uhligite monocrystalline is transferred in the crystallizing dish of clean dried respectively, adds the single crystal growing liquid prepared, after three layers of preservative film sealing, in heat blowing loft drier after 70 DEG C of heating 48h, and the CH bottom crystallizing dish 3nH 3pbI 3uhligite monocrystalline obviously increases.
5, fresh single crystal growing liquid is renewed
Single crystal growing liquid old in step 4 crystallizing dish is inclined to, adds the fresh single crystal growing liquid prepared, after three layers of preservative film sealing, in heat blowing loft drier after 70 DEG C of heating 48h, the CH bottom crystallizing dish 3nH 3pbI 3uhligite monocrystalline size increases further.So repeat this step repeatedly after, just can obtain the CH that size reaches (>10mm) × (>10mm) × (>10mm) 3nH 3pbI 3uhligite monocrystalline.
6, CH 3nH 3pbI 3the cleaning of uhligite monocrystalline, drying and collect
With the CH that anhydrous diethyl ether cleaning growth is complete 3nH 3pbI 3uhligite monocrystalline, in vacuum drying oven after 60 DEG C of dry 24h, vacuum packaging.
Embodiment 10
1, monocrystalline (seed crystal) growth media is prepared
Take the chloromethane amine (CH that 0.68g has synthesized 3nH 3cl), join in the tall form beaker of 100mL, put into a magnetic stir bar, measure 20mL dimethyl sulfoxide (DMSO) (DMSO) and add, 70 DEG C of stirring heating on magnetic agitation well heater.Treat chloromethane amine (CH 3nH 3cl) after all dissolving, then 2.78g lead chloride (PbCl is taken 2) add, continue at 70 DEG C of more than stirring heating 12h on magnetic agitation well heater, obtain single crystal growing liquid (concentration: 0.5M, the metal ion of metallic compound and the ion mol ratio of halides: 1:1).
2, single crystal growing liquid is prepared
Take the chloromethane amine (CH that 0.68g has synthesized 3nH 3cl), join in the tall form beaker of 100mL, put into a magnetic stir bar, measure 20mL dimethyl sulfoxide (DMSO) (DMSO) and add, 70 DEG C of stirring heating on magnetic agitation well heater.Treat chloromethane amine (CH 3nH 3cl) after all dissolving, then 2.78g lead chloride (PbCl is taken 2) add, continue at 70 DEG C of more than stirring heating 12h on magnetic agitation well heater, obtain single crystal growing liquid (concentration: 0.5M, the metal ion of metallic compound and the ion mol ratio of halides: 1:1).
3, small size monocrystalline (seed crystal) is grown
The monocrystalline prepared (seed crystal) growth media is transferred in the crystallizing dish of clean dried, after three layers of preservative film sealing, in heat blowing loft drier after 100 DEG C of heating 24h, bottom crystallizing dish, obtains small size CH 3nH 3pbCl 3uhligite monocrystalline.
4, growing large-size monocrystalline
By the small size CH of growth in step 3 3nH 3pbCl 3uhligite monocrystalline is transferred in the crystallizing dish of clean dried respectively, adds the single crystal growing liquid prepared, after three layers of preservative film sealing, in heat blowing loft drier after 100 DEG C of heating 48h, and the CH bottom crystallizing dish 3nH 3pbCl 3uhligite monocrystalline obviously increases.
5, fresh single crystal growing liquid is renewed
Single crystal growing liquid old in step 4 crystallizing dish is inclined to, adds the fresh single crystal growing liquid prepared, after three layers of preservative film sealing, in heat blowing loft drier after 100 DEG C of heating 48h, the CH bottom crystallizing dish 3nH 3pbCl 3uhligite monocrystalline size increases further.So repeat this step repeatedly after, just can obtain the CH that size reaches (>10mm) × (>10mm) × (>10mm) 3nH 3pbCl 3uhligite monocrystalline.
6, CH 3nH 3pbCl 3the cleaning of uhligite monocrystalline, drying and collect
With the CH that anhydrous diethyl ether cleaning growth is complete 3nH 3pbCl 3uhligite monocrystalline, in vacuum drying oven after 60 DEG C of dry 24h, vacuum packaging.
Embodiment 11
1, monocrystalline (seed crystal) growth media is prepared
Take the iodine methylamine (CH that 0.745g has synthesized 3nH 3i), join in the tall form beaker of 100mL, put into a magnetic stir bar, measure 20mL gamma-butyrolactone (GBA) and add, 45 DEG C of stirring heating on magnetic agitation well heater.Treat iodine methylamine (CH 3nH 3i) after all dissolving, then 4.61g lead iodide (PbI is taken 2) add, continue at 45 DEG C of more than stirring heating 12h on magnetic agitation well heater, obtain single crystal growing liquid (concentration: 0.5M, the metal ion of metallic compound and the ion mol ratio of halides: 1:0.5).
2, single crystal growing liquid is prepared
Take the iodine methylamine (CH that 4.77g has synthesized 3nH 3i), join in the tall form beaker of 100mL, put into a magnetic stir bar, measure 20mL gamma-butyrolactone (GBA) and add, 45 DEG C of stirring heating on magnetic agitation well heater.Treat iodine methylamine (CH 3nH 3i) after all dissolving, then 27.66g lead iodide (PbI is taken 2) add, continue at 45 DEG C of more than stirring heating 12h on magnetic agitation well heater, obtain single crystal growing liquid (concentration: 3M, the metal ion of metallic compound and the ion mol ratio of halides: 1:0.5).
3, small size monocrystalline (seed crystal) is grown
The monocrystalline prepared (seed crystal) growth media is transferred in the crystallizing dish of clean dried, after three layers of preservative film sealing, in heat blowing loft drier after 110 DEG C of heating 24h, bottom crystallizing dish, obtains small size CH 3nH 3pbI 3uhligite monocrystalline.
4, growing large-size monocrystalline
By the small size CH of growth in step 3 3nH 3pbI 3uhligite monocrystalline is transferred in the crystallizing dish of clean dried respectively, adds the single crystal growing liquid prepared, after three layers of preservative film sealing, in heat blowing loft drier after 110 DEG C of heating 48h, and the CH bottom crystallizing dish 3nH 3pbI 3uhligite monocrystalline obviously increases.
5, fresh single crystal growing liquid is renewed
Single crystal growing liquid old in step 4 crystallizing dish is inclined to, adds the fresh single crystal growing liquid prepared, after three layers of preservative film sealing, in heat blowing loft drier after 110 DEG C of heating 48h, the CH bottom crystallizing dish 3nH 3pbI 3uhligite monocrystalline size increases further.So repeat this step repeatedly after, just can obtain the CH that size reaches (>10mm) × (>10mm) × (>10mm) 3nH 3pbI 3uhligite monocrystalline.
6, CH 3nH 3pbI 3the cleaning of uhligite monocrystalline, drying and collect
With the CH that anhydrous diethyl ether cleaning growth is complete 3nH 3pbI 3uhligite monocrystalline, in vacuum drying oven after 60 DEG C of dry 24h, vacuum packaging.
Embodiment 12
1, monocrystalline (seed crystal) growth media is prepared
Take the iodine methylamine (CH that 0.745g has synthesized 3nH 3i), join in the tall form beaker of 100mL, put into a magnetic stir bar, measure 20mL DMF (DMF) and add, 45 DEG C of stirring heating on magnetic agitation well heater.Treat iodine methylamine (CH 3nH 3i) after all dissolving, then 4.61g lead iodide (PbI is taken 2) add, continue at 45 DEG C of more than stirring heating 12h on magnetic agitation well heater, obtain single crystal growing liquid (concentration: 0.5M, the metal ion of metallic compound and the ion mol ratio of halides: 1:0.5).
2, single crystal growing liquid is prepared
Take the iodine methylamine (CH that 7.95g has synthesized 3nH 3i), join in the tall form beaker of 100mL, put into a magnetic stir bar, measure 20mL DMF (DMF) and add, 45 DEG C of stirring heating on magnetic agitation well heater.Treat iodine methylamine (CH 3nH 3i) after all dissolving, then 46.11g lead iodide (PbI is taken 2) add, continue at 45 DEG C of more than stirring heating 12h on magnetic agitation well heater, obtain single crystal growing liquid (concentration: 5M, the metal ion of metallic compound and the ion mol ratio of halides: 1:0.5).
3, small size monocrystalline (seed crystal) is grown
The monocrystalline prepared (seed crystal) growth media is transferred in the crystallizing dish of clean dried, after three layers of preservative film sealing, in heat blowing loft drier after 120 DEG C of heating 24h, bottom crystallizing dish, obtains small size CH 3nH 3pbI 3uhligite monocrystalline.
4, growing large-size monocrystalline
By the small size CH of growth in step 3 3nH 3pbI 3uhligite monocrystalline is transferred in the crystallizing dish of clean dried respectively, adds the single crystal growing liquid prepared, after three layers of preservative film sealing, in heat blowing loft drier after 120 DEG C of heating 48h, and the CH bottom crystallizing dish 3nH 3pbI 3uhligite monocrystalline obviously increases.
5, fresh single crystal growing liquid is renewed
Single crystal growing liquid old in step 4 crystallizing dish is inclined to, adds the fresh single crystal growing liquid prepared, after three layers of preservative film sealing, in heat blowing loft drier after 120 DEG C of heating 48h, the CH bottom crystallizing dish 3nH 3pbI 3uhligite monocrystalline size increases further.So repeat this step repeatedly after, just can obtain the CH that size reaches (>10mm) × (>10mm) × (>10mm) 3nH 3pbI 3uhligite monocrystalline.
6, CH 3nH 3pbI 3the cleaning of uhligite monocrystalline, drying and collect
With the CH that anhydrous diethyl ether cleaning growth is complete 3nH 3pbI 3uhligite monocrystalline, in vacuum drying oven after 60 DEG C of dry 24h, vacuum packaging.
Embodiment 13
1, monocrystalline (seed crystal) growth media is prepared
Take the bromine methylamine (CH that 0.896g has synthesized 3nH 3br), join in the tall form beaker of 100mL, put into a magnetic stir bar, measure 20mL DMF (DMF) and add, 70 DEG C of stirring heating on magnetic agitation well heater.Treat bromine methylamine (CH 3nH 3br) after all dissolving, then 3.67g lead bromide (PbBr is taken 2) add, continue at 70 DEG C of more than stirring heating 12h on magnetic agitation well heater, obtain single crystal growing liquid (concentration: 0.5M, the metal ion of metallic compound and the ion mol ratio of halides: 1:0.8).
2, single crystal growing liquid is prepared
Take the bromine methylamine (CH that 5.37g has synthesized 3nH 3br), join in the tall form beaker of 100mL, put into a magnetic stir bar, measure 20mL DMF (DMF) and add, 70 DEG C of stirring heating on magnetic agitation well heater.Treat bromine methylamine (CH 3nH 3br) after all dissolving, then 22.03g lead bromide (PbBr is taken 2) add, continue at 70 DEG C of more than stirring heating 12h on magnetic agitation well heater, obtain single crystal growing liquid (concentration: 3M, the metal ion of metallic compound and the ion mol ratio of halides: 1:0.8).
3, small size monocrystalline (seed crystal) is grown
The monocrystalline prepared (seed crystal) growth media is transferred in the crystallizing dish of clean dried, after three layers of preservative film sealing, in heat blowing loft drier, oil bath or water-bath after 100 DEG C of heating 24h, bottom crystallizing dish, obtains small size CH 3nH 3pbBr 3uhligite monocrystalline.
4, growing large-size monocrystalline
By the small size CH of growth in step 3 3nH 3pbBr 3uhligite monocrystalline is transferred in the crystallizing dish of clean dried respectively, adds the single crystal growing liquid prepared, after three layers of preservative film sealing, in heat blowing loft drier after 100 DEG C of heating 48h, and the CH bottom crystallizing dish 3nH 3pbBr 3uhligite monocrystalline obviously increases.
5, fresh single crystal growing liquid is renewed
Single crystal growing liquid old in step 4 crystallizing dish is inclined to, adds the fresh single crystal growing liquid prepared, after three layers of preservative film sealing, in heat blowing loft drier after 100 DEG C of heating 48h, the CH bottom crystallizing dish 3nH 3pbBr 3uhligite monocrystalline size increases further.So repeat this step repeatedly after, just can obtain the CH that size reaches (>10mm) × (>10mm) × (>10mm) 3nH 3pbBr 3uhligite monocrystalline.
6, CH 3nH 3pbBr 3the cleaning of uhligite monocrystalline, drying and collect
With the CH that anhydrous diethyl ether cleaning growth is complete 3nH 3pbBr 3uhligite monocrystalline, in vacuum drying oven after 60 DEG C of dry 24h, vacuum packaging.
Embodiment 14
1, monocrystalline (seed crystal) growth media is prepared
Take the chloromethane amine (CH that 3.376g has synthesized 3nH 3cl), join in the tall form beaker of 100mL, put into a magnetic stir bar, measure 20mL dimethyl sulfoxide (DMSO) (DMSO) and add, 60 DEG C of stirring heating on magnetic agitation well heater.Treat chloromethane amine (CH 3nH 3cl) after all dissolving, then 2.78g lead chloride (PbCl is taken 2) add, continue at 60 DEG C of more than stirring heating 12h on magnetic agitation well heater, obtain single crystal growing liquid (concentration: 0.5M, the metal ion of metallic compound and the ion mol ratio of halides: 1:5).
2, single crystal growing liquid is prepared
Take the chloromethane amine (CH that 6.75g has synthesized 3nH 3cl), join in the tall form beaker of 100mL, put into a magnetic stir bar, measure 20mL dimethyl sulfoxide (DMSO) (DMSO) and add, 60 DEG C of stirring heating on magnetic agitation well heater.Treat chloromethane amine (CH 3nH 3cl) after all dissolving, then 5.56g lead chloride (PbCl is taken 2) add, continue at 60 DEG C of more than stirring heating 12h on magnetic agitation well heater, obtain single crystal growing liquid (concentration: 1M, the metal ion of metallic compound and the ion mol ratio of halides: 1:5).
3, small size monocrystalline (seed crystal) is grown
The monocrystalline prepared (seed crystal) growth media is transferred in the crystallizing dish of clean dried, after three layers of preservative film sealing, in heat blowing loft drier after 100 DEG C of heating 24h, bottom crystallizing dish, obtains small size CH 3nH 3pbCl 3uhligite monocrystalline.
4, growing large-size monocrystalline
By the small size CH of growth in step 3 3nH 3pbCl 3uhligite monocrystalline is transferred in the crystallizing dish of clean dried respectively, adds the single crystal growing liquid prepared, after three layers of preservative film sealing, in heat blowing loft drier after 100 DEG C of heating 48h, and the CH bottom crystallizing dish 3nH 3pbCl 3uhligite monocrystalline obviously increases.
5, fresh single crystal growing liquid is renewed
Single crystal growing liquid old in step 4 crystallizing dish is inclined to, adds the fresh single crystal growing liquid prepared, after three layers of preservative film sealing, in heat blowing loft drier after 100 DEG C of heating 48h, the CH bottom crystallizing dish 3nH 3pbCl 3uhligite monocrystalline size increases further.So repeat this step repeatedly after, just can obtain the CH that size reaches (>10mm) × (>10mm) × (>10mm) 3nH 3pbCl 3uhligite monocrystalline.
6, CH 3nH 3pbCl 3the cleaning of uhligite monocrystalline, drying and collect
With the CH that anhydrous diethyl ether cleaning growth is complete 3nH 3pbCl 3uhligite monocrystalline, in vacuum drying oven after 60 DEG C of dry 24h, vacuum packaging.
Embodiment 15
1, monocrystalline (seed crystal) growth media is prepared
Take the 15.89 iodine methylamine (CH synthesized 3nH 3i), join in the tall form beaker of 100mL, put into a magnetic stir bar, measure 20mL gamma-butyrolactone (GBA) and add, 45 DEG C of stirring heating on magnetic agitation well heater.Treat iodine methylamine (CH 3nH 3i) after all dissolving, then 4.61g lead iodide (PbI is taken 2) add, continue at 45 DEG C of more than stirring heating 12h on magnetic agitation well heater, obtain single crystal growing liquid (concentration: 0.5M, the metal ion of metallic compound and the ion mol ratio of halides: 1:10).
2, single crystal growing liquid is prepared
Take the iodine methylamine (CH that 95.38g has synthesized 3nH 3i), join in the tall form beaker of 100mL, put into a magnetic stir bar, measure 20mL gamma-butyrolactone (GBA) and add, 45 DEG C of stirring heating on magnetic agitation well heater.Treat iodine methylamine (CH 3nH 3i) after all dissolving, then 27.66g lead iodide (PbI is taken 2) add, continue at 45 DEG C of more than stirring heating 12h on magnetic agitation well heater, obtain single crystal growing liquid (concentration: 3M, the metal ion of metallic compound and the ion mol ratio of halides: 1:10).
3, small size monocrystalline (seed crystal) is grown
The monocrystalline prepared (seed crystal) growth media is transferred in the crystallizing dish of clean dried, after three layers of preservative film sealing, in heat blowing loft drier after 120 DEG C of heating 24h, bottom crystallizing dish, obtains small size CH 3nH 3pbI 3uhligite monocrystalline.
4, growing large-size monocrystalline
By the small size CH of growth in step 3 3nH 3pbI 3uhligite monocrystalline is transferred in the crystallizing dish of clean dried respectively, adds the single crystal growing liquid prepared, after three layers of preservative film sealing, in heat blowing loft drier after 120 DEG C of heating 48h, and the CH bottom crystallizing dish 3nH 3pbI 3uhligite monocrystalline obviously increases.
5, fresh single crystal growing liquid is renewed
Single crystal growing liquid old in step 4 crystallizing dish is inclined to, adds the fresh single crystal growing liquid prepared, after three layers of preservative film sealing, in heat blowing loft drier after 120 DEG C of heating 48h, the CH bottom crystallizing dish 3nH 3pbI 3uhligite monocrystalline size increases further.So repeat this step repeatedly after, just can obtain the CH that size reaches (>10mm) × (>10mm) × (>10mm) 3nH 3pbI 3uhligite monocrystalline.
6, CH 3nH 3pbI 3the cleaning of uhligite monocrystalline, drying and collect
With the CH that anhydrous diethyl ether cleaning growth is complete 3nH 3pbI 3uhligite monocrystalline, in vacuum drying oven after 60 DEG C of dry 24h, vacuum packaging.
All the other embodiments see the following form:

Claims (10)

1. grow ABX in cryogenic fluid 3the method of uhligite monocrystalline, wherein A is CH 3nH 3 +, H 2n-CH=NH 2 +, (CH 3) 4n +, C 7h 7 +, Cs +or C 3h 11sN 3 2+, B is Pb, Ge or Sn; X is Cl, Br or I, it is characterized in that: get the metallic compound providing plumbous source, Xi Yuan or germanium source, halides and can dissolve the solvent of this metallic compound; Halides and solvent are mixed with solution, after being added by metallic compound, are made into single crystal growing liquid, adopt the growth of the method for growth continuously to obtain ABX 3uhligite monocrystalline.
2. grow ABX in cryogenic fluid according to claim 1 3the method of uhligite monocrystalline, it is characterized in that: take halides during preparation single crystal growing liquid and dissolve by stirring solvent in a reservoir, then metallic compound is added, sealed vessel is placed on magnetic stirring apparatus, at DEG C temperature of room temperature ~ 90, heat more than continuously stirring, concussion or supersound process 12h, obtain single crystal growing liquid.
3. grow ABX in cryogenic fluid according to claim 1 3the method of uhligite monocrystalline, is characterized in that: first grow the crystal grain that size is less, is transferred to by seed crystal in fresh single crystal growing liquid afterwards and grows; After growth for some time, fresher single crystal growing liquid is put in the crystal grain of growing up taking-up; Often changing once fresh single crystal growing liquid to the growth time changing single crystal growing liquid is next time a growth cycle, and continuous multiple growth cycle is until obtain the monocrystalline needed and so forth.
4. grow ABX in cryogenic fluid according to claim 3 3the method of uhligite monocrystalline, is characterized in that: described single crystal growing temperature is 50-200 DEG C, and each growth cycle time is more than 24h.
5. grow ABX in cryogenic fluid according to claim 3 3the method of uhligite monocrystalline, it is characterized in that: during single crystal growing, provide required temperature by heat blowing loft drier, oil bath or water-bath, growth system is heated evenly, is controlled the evaporation rate of solvent by the seal degree adjusting container, to control the speed of single crystal growing.
6. in the cryogenic fluid according to any one of claim 1-5, grow ABX 3the method of uhligite monocrystalline, it is characterized in that: described solvent is the one in hydroiodic acid HI, gamma-butyrolactone (GBA), DMF (DMF), dimethyl sulfoxide (DMSO) (DMSO), METHYLPYRROLIDONE (NMP).
7. in the cryogenic fluid according to any one of claim 1-5, grow ABX 3the method of uhligite monocrystalline, is characterized in that: described in provide the metallic compound in plumbous source to be lead chloride (PbCl 2), lead bromide (PbBr 2), lead iodide (PbI 2) or plumbic acetate (Pb (CH 3cOO) 2xH 2o); The metallic compound of the described Xi Yuan of providing is tin protochloride (SnCl 2), tin tetrachloride (SnCl 4), tin protobromide (SnBr 2) or tin protoiodide (SnI 2); The described metallic compound in germanium source that provides is germanium chloride (GeCl 2), bromination germanium (GeBr 2) or iodate germanium (GeI 2).
8. in the cryogenic fluid according to any one of claim 1-5, grow ABX 3the method of uhligite monocrystalline, is characterized in that: described halides is for containing organic or inorganic ionic radius being organic or inorganic halides in one, comprise chloromethane amine (CH 3nH 3cl), chloromethane amidine (H 2n-CH=NH 2cl), tetramethylamine chloride ((CH 3) 4n Cl), chlorine Zhuo (C 7h 7cl), chloro 2-isothiourea (C 3h 11sN 3cl 2), bromine methylamine (CH 3nH 3br), bromine carbonamidine (H 2n-CH=NH 2br), bromination tetramethylammonium ((CH 3) 4nBr), bromine Zhuo (C 7h 7br), bromo 2-isothiourea (C 3h 11sN 3br 2), iodine methylamine (CH 3nH 3i), iodine carbonamidine (H 2n-CH=NH 2i), iodate tetramethylammonium ((CH 3) 4n I), iodine Zhuo (C 7h 7i), iodo 2-isothiourea (C 3h 11sN 3i 2) and inorganic CsI.
9. in the cryogenic fluid according to any one of claim 1-5, grow ABX 3the method of uhligite monocrystalline, is characterized in that: in described single crystal growing liquid, the metal ion of metallic compound and the ion mol ratio of halides are 1:(0.5 ~ 10).
10. in the cryogenic fluid according to any one of claim 1-5, grow ABX 3the method of uhligite monocrystalline, is characterized in that: the concentration of described single crystal growing liquid is 0.05-5.0mol/L.
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