CN104911705B - ABX is grown in cryogenic fluid3The method of perovskite monocrystalline - Google Patents
ABX is grown in cryogenic fluid3The method of perovskite monocrystalline Download PDFInfo
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Abstract
The present invention, which is provided in a kind of cryogenic fluid, grows ABX3The method of perovskite monocrystalline, using the method continuously grown, the fast-growth ABX in cryogenic fluid stage by stage of continuous multicycle3Perovskite monocrystalline, solution concentration used is big, and dissolution of raw material needed for growing is uniform, increases growth cycle and the precise controlling to growth conditions, it is easy to obtain the high ABX of big size, regular shape, quality3Perovskite monocrystalline, method and process is simple, strong operability；Growth conditions is mild, and required temperature is low, energy conservation；Equipment requirement is low, at low cost；Success rate is high, growth monocrystalline speed is fast；The advantages that defect is few, stability is good, gained single crystal size (> 10mm) × (> 10mm) × (> 10mm) greatly.To promote the basic mechanism theoretical research to perovskite material and related photoelectric device (including solar cell, optical detector, LED and laser etc.).
Description
[technical field]
The invention belongs to area of solar cell, and in particular to grow ABX in a kind of cryogenic fluid3The side of perovskite monocrystalline
Method.
[background technique]
With the fast development of economic globalization, countries in the world increase the demand of the energy year by year, coal, petroleum, natural
The traditional fossil energies such as gas gradually use up totally, and are asked using a series of ecological environment is also brought while traditional energy
Topic.Therefore, change current energy resource structure, renewable, economic, environmentally protective clean energy resource supply is found, such as solar energy, hydrogen
Energy, wind energy, tide energy etc. have become the research topic that countries in the world are paid close attention to.Solar energy is the most abundant clear in the world
The clean energy is radiated the total amount of earth surface every year far more than hundred times of the total storage level of fossil energy on the earth.It makes full use of
Solar energy is to meet one of the important method of energy demand growing in global range.
A kind of effective method for converting the solar into electric energy is to prepare the sun electricity based on photovoltaic effect
Pond.The novel solar cell for researching and developing low-cost high-efficiency is the technical foundation for realizing solar energy power generating wide popularization and application.
A kind of CH based on perovskite structure3NH3PbX3The solar cell of (X represents halogen) material causes light in recent years
Lie prostrate the very big concern of research field.By short development in 6 years, up to the present, the highest of perovskite solar cell authenticates effect
Rate has had reached 20.1%.
Currently, attention is more placed on the performance of the synthetic method or material that how to improve film, mentioned by people
High cell photoelectric transfer efficiency and stability test etc..Quickly development catches up with the research of Related Mechanism not for it
The raising rate of efficiency still lacks and recognizes the deep layer of perovskite solar cell microphysics mechanism.We need more to close
The fundamental property and battery working principle for infusing perovskite material, are not only does this facilitate and further increase Ca-Ti ore type solar cell
Performance can also find simpler or more effective new construction for people and provide thinking.Therefore, grow large scale, regular shape,
The ABX of high quality3Perovskite monocrystalline is very urgent and necessary to the basic research to perovskite material.
Up to the present, about ABX3It is that the growth and research of perovskite monocrystalline are reported and few.At the beginning of 2015,
Science reports two about CH in succession3NH3PbX3Perovskite monocrystalline grinds the microphysics characteristic of perovskite solar cell
Study carefully (
(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.).However, being grown used in monocrystalline in document
The process is more complicated, cumbersome, and practical operation is got up with certain difficulty；And growth conditions is relatively harsh, poor controllability；It is most heavy
What is wanted is that the single crystal size that method reported in the literature is grown is smaller, about 10mm.
[summary of the invention]
The purpose of the present invention is to provide grow ABX in a kind of cryogenic fluid3The method of perovskite monocrystalline has experiment behaviour
Make the advantages that simple, success rate is high, gained single crystal size is big.
In order to achieve the above objectives, ABX is grown in cryogenic fluid of the present invention3The method of perovskite monocrystalline is as follows:
ABX3Perovskite monocrystalline, wherein A is CH3NH3 +、H2N-CH=NH2 +、(CH3)4N+、C7H7 +、Cs+Or C3H11SN3 2+, B
For Pb, Ge or Sn；X is Cl, Br or I, takes and provides the metallic compound in lead source, tin source or ge source, halides and can dissolve the gold
Belong to the solvent of compound；Halides and solvent are hybridly prepared into solution, crystal growth liquid is made into after metallic compound is added,
It grows to obtain ABX using the method continuously grown3Perovskite monocrystalline.
Further, it weighs halides when preparing crystal growth liquid to be dissolved with stirring solvent in a reservoir, then sealing container
It is placed on magnetic stirring apparatus, heating continuously stirs, shakes or be ultrasonically treated 12h or more at a temperature of room temperature~90 DEG C, obtains
Crystal growth liquid.
Further, it weighs halides when preparing crystal growth liquid to be dissolved with stirring solvent in a reservoir, then sealing container
It is placed on magnetic stirring apparatus, heating continuously stirs, shakes or be ultrasonically treated 12h or more at a temperature of 20~80 DEG C, obtains list
Crystals growth liquid.
Further, it weighs halides when preparing crystal growth liquid to be dissolved with stirring solvent in a reservoir, then sealing container
It is placed on magnetic stirring apparatus, heating continuously stirs, shakes or be ultrasonically treated 12h or more at a temperature of 40~70 DEG C, obtains list
Crystals growth liquid.
Further, the lesser crystal grain of size is first grown, seed crystal is transferred in fresh crystal growth liquid grows later；
After growing a period of time, then the crystal grain grown up is taken out and is put into fresh crystal growth liquid；Often change primary fresh crystal growth
Liquid is a growth cycle to the growth time for changing crystal growth liquid next time, and and so on continuous multiple growth cycles are until obtaining
To the monocrystalline of needs.
Further, the single crystal growth temperature be 50-200 DEG C, each growth cycle time be for 24 hours more than.
Further, the single crystal growth temperature be 70~120 DEG C, each growth cycle time be for 24 hours more than.
Further, the temperature needed for being provided when crystal growth by heat blowing drying box, oil bath or water-bath, makes growth system
It is heated evenly, the evaporation rate of solvent is controlled by adjusting the seal degree of container, to control the speed of crystal growth.
Further, the solvent is hydroiodic acid, gamma-butyrolacton (GBA), n,N-Dimethylformamide (DMF), dimethyl Asia
One of sulfone (DMSO), n-methyl-2-pyrrolidone (NMP).
Further, the metallic compound for providing lead source is lead chloride (PbCl2), lead bromide (PbBr2), lead iodide
(PbI2) or lead acetate (Pb (CH3COO)2·xH2O)；The metallic compound for providing tin source is stannous chloride (SnCl2), four
Stannic chloride (SnCl4), stannous bromide (SnBr2) or stannic iodide (SnI2)；The metallic compound for providing ge source is germanium chloride
(GeCl2), bromination germanium (GeBr2) or iodate germanium (GeI2)。
Further, the halides are to be containing organic or inorganic ionic radiusOrganic or inorganic halides
One of, including chloromethane amine (CH3NH3Cl), chloromethane amidine (H2N-CH=NH2Cl), tetramethylamine chloride ((CH3)4NCl), chlorine is tall and erect
(C7H7Cl), chloro 2- isothiourea (C3H11SN3Cl2), bromine methylamine (CH3NH3Br), bromine carbonamidine (H2N-CH=NH2Br), bromination
Tetramethylammonium ((CH3)4N Br), bromine Zhuo (C7H7Br), bromo 2- isothiourea (C3H11SN3Br2), iodine methylamine (CH3NH3I), iodine first
Amidine (H2N-CH=NH2I), iodate tetramethylammonium ((CH3)4N I), iodine Zhuo (C7H7I), iodo 2- isothiourea (C3H11SN3I2) and
Inorganic CsI.
Further, the ion molar ratio of the metal ion of metallic compound and halides is 1 in the crystal growth liquid:
(0.5~10).
Further, the ion molar ratio of the metal ion of metallic compound and halides is 1 in the crystal growth liquid:
(0.8~5).
Further, the ion molar ratio of the metal ion of metallic compound and halides is 1:(1 in the crystal growth liquid
~3).
Further, the concentration of the crystal growth liquid is 0.05-5.0mol/L.
Present invention fast-growth ABX in cryogenic fluid3Perovskite monocrystalline has the advantage that compared with prior art
The present invention is using the method that continuously grows, the fast-growth ABX in cryogenic fluid stage by stage of continuous multicycle3Calcium titanium
Mine monocrystalline, solution concentration used is big, and dissolution of raw material needed for growing is uniform, increases growth cycle and the fine control to growth conditions
System, it is easy to obtain the high ABX of big size, regular shape, quality3Perovskite monocrystalline.Method and process is simple, strong operability；
Growth conditions is mild, and required temperature is low, energy conservation；Equipment requirement is low, at low cost；Success rate is high, growth monocrystalline speed is fast；Defect
Less, the advantages that stability is good, gained single crystal size (> 10mm) × (> 10mm) × (> 10mm) greatly.To promote to perovskite material
The basic mechanism theoretical research of material and related photoelectric device (including solar cell, optical detector, LED and laser etc.).
[Detailed description of the invention]
Fig. 1 is crystal growth simple process figure.
Fig. 2 is the monocrystalline picture that part grown for 1~4 period respectively in the solution.
[specific embodiment]
Below by embodiment, the present invention is further illustrated, but the present invention is not limited to following embodiments.
ABX provided by the invention3Perovskite method for monocrystal growth, A CH3NH3 +、H2N-CH=NH2 +、(CH3)4N+、 C7H7 +、Cs+Or C3H11SN3 2+；B is Pb, Ge or Sn；X is Cl, Br or, specific method comprises the steps of:
1) synthetic halogenated organic-inorganic object as described above is weighed, is added in the beaker in tall form of 100mL, is put into one
Magnetic stir bar；
2) related solvents are added into step 1 beaker；
3) it places the beaker room temperature~90 DEG C on magnetic agitation heater to stir, halogenated organic-inorganic object is rapid during this
Dissolution；
4) metallic compound as described above is weighed to be added in the solution that step 3 obtains；
5) beaker is sealed with preservative film, continues to be placed in room temperature~90 DEG C in magnetic heating stirrer and stir 12h or more, obtains
To clarification, transparent crystal growth liquid；The concentration of crystal growth liquid is 0.05~5.0mol/L.
6) prepared crystal growth liquid is transferred in crystallising dish；
7) with preservative film by step 6 crystallising dish sealing after, in heat blowing drying box 50~200 DEG C heating for 24 hours with
On, more tiny perovskite monocrystalline (seed crystal) is obtained in crystallising dish bottom；
8) every perovskite monocrystalline (seed crystal) is transferred to respectively in new crystallising dish；
9) prepared crystal growth liquid is added into the crystallising dish of step 8；Concentration is 0.05~5.0mol/L；
10) with preservative film by step 9 crystallising dish sealing after, in heat blowing drying box 50~200 DEG C of heating 48h with
Afterwards, the ABX of crystallising dish bottom3Perovskite single crystal size significantly increases；
11) the old crystal growth liquid in the crystallising dish of step 10 is poured out, rejoins prepared crystal growth liquid
(concentration is 0.05~5.0mol/L)；
12) with preservative film by step 11 crystallising dish sealing after, in heat blowing drying box 50-200 DEG C of heating 48h with
Afterwards, the ABX of crystallising dish bottom3Perovskite single crystal size further increases；
13) step 11 and 12 similarly, is so repeated, after 4~5 periods, size can be obtained up to (> 10mm)
× (> 10mm) × (> 10mm) ABX3Perovskite monocrystalline；
14) ABX that will have been grown3Perovskite monocrystalline takes out from the crystal growth liquid in crystallising dish, with anhydrous ether, first
The cleaning such as benzene, chlorobenzene, isopropanol, methylamine solution；
15) ABX finished is cleaned360 DEG C of dryings are for 24 hours in a vacuum drying oven for perovskite monocrystalline；
16)ABX3It is vacuum-packed after perovskite monocrystalline is dry, in case test uses.
Further, beaker in tall form and crystallising dish used in experiment are simple glass material.
Further, preservative film used in step 5 is common plastics preservative film, not specially treated.
Further, the present invention in crystal growth liquid concentration be solution metal compound in metal ion concentration,
Metal ion in metallic compound is with halogenated organic-inorganic object Ionic RadiusIon molar ratio be 1:
0.5~1:10.
Further, the heating temperature in step 7 is 50~200 DEG C, preferably 100~120 DEG C.
Embodiment 1
1, monocrystalline (seed crystal) growth-promoting media is prepared
Weigh the iodine methylamine (CH that 0.159g has been synthesized3NH3I), it is added in the beaker in tall form of 100mL, is put into a magnetic force
Stirrer measures 20mL gamma-butyrolacton (GBA) and is added, in 20 DEG C of agitating and heatings on magnetic agitation heater.To iodine methylamine
(CH3NH3I) all after dissolution, then 0.461g lead iodide (PbI is weighed2) be added, it continues on magnetic agitation heater and stirs for 20 DEG C
Heating 12h or more is mixed, obtaining crystal growth liquid, (concentration: 0.05M, the metal ion of metallic compound and the ion of halides rub
That ratio: 1:1).
2, crystal growth liquid is prepared
Weigh the iodine methylamine (CH that 3.91g has been synthesized3NH3I), it is added in the beaker in tall form of 100mL, is put into a magnetic force
Stirrer measures 20mL gamma-butyrolacton (GBA) and is added, in 20 DEG C of agitating and heatings on magnetic agitation heater.To iodine methylamine
(CH3NH3I) all after dissolution, then 11.34g lead iodide (PbI is weighed2) be added, it continues on magnetic agitation heater and stirs for 20 DEG C
Heating 12h or more is mixed, obtaining crystal growth liquid, (concentration: 1.23M, the metal ion of metallic compound and the ion of halides rub
That ratio: 1:1), C also can be used in above-mentioned halides7H7I、(CH3)4N I or H2N-CH=NH2I substitution.
3, small size monocrystalline (seed crystal) is grown
Prepared monocrystalline (seed crystal) growth-promoting media is transferred in the crystallising dish of clean dried, is sealed with three layers of preservative film
Afterwards, small size CH is obtained in crystallising dish bottom after 50 DEG C of heating for 24 hours in heat blowing drying box3NH3PbI3Perovskite list
Crystalline substance, as shown in Figure 2.
4, growing large-size monocrystalline
The small size CH that will be grown in step 33NH3PbI3Perovskite monocrystalline is transferred to respectively in the crystallising dish of clean dried,
Prepared crystal growth liquid is added, after being sealed with three layers of preservative film, in heat blowing drying box after 50 DEG C of heating 48h,
The CH of crystallising dish bottom3NH3PbI3Perovskite monocrystalline significantly increases, as shown in Figure 2.
5, renew fresh crystal growth liquid
Crystal growth liquid old in step 4 crystallising dish is poured out, prepared fresh crystal growth liquid is added, is protected with three layers
After fresh film sealing, in heat blowing drying box after 50 DEG C of heating 48h, the CH of crystallising dish bottom3NH3PbI3Perovskite monocrystalline
Size further increases.So repeat this step it is multiple after, size can be obtained up to (> 10mm) × (> 10mm) × (> 10mm)
CH3NH3PbI3Perovskite monocrystalline, as shown in Figure 2.
6、CH3NH3PbI3Cleaning, drying and the collection of perovskite monocrystalline
The CH that growth finishes is cleaned with anhydrous ether3NH3PbI3Perovskite monocrystalline, 60 DEG C of dryings are for 24 hours in a vacuum drying oven
Afterwards, it is vacuum-packed.
Embodiment 2
1, monocrystalline (seed crystal) growth-promoting media is prepared
Weigh the iodine methylamine (CH that 0.318g has been synthesized3NH3I), it is added in the beaker in tall form of 100mL, is put into a magnetic force
Stirrer measures 20mL gamma-butyrolacton (GBA) and is added, in 40 DEG C of agitating and heatings on magnetic agitation heater.To iodine methylamine
(CH3NH3I) all after dissolution, then 0.461g lead iodide (PbI is weighed2) be added, it continues on magnetic agitation heater and stirs for 40 DEG C
Heating 12h or more is mixed, obtaining crystal growth liquid, (concentration: 0.05M, the metal ion of metallic compound and the ion of halides rub
That ratio: 1:2).
2, crystal growth liquid is prepared
Weigh the iodine methylamine (CH that 7.82g has been synthesized3NH3I), it is added in the beaker in tall form of 100mL, is put into a magnetic force
Stirrer measures 20mL gamma-butyrolacton (GBA) and is added, in 40 DEG C of agitating and heatings on magnetic agitation heater.To iodine methylamine
(CH3NH3I) all after dissolution, then 11.34g lead iodide (PbI is weighed2) be added, it continues on magnetic agitation heater and stirs for 40 DEG C
Heating 12h or more is mixed, obtaining crystal growth liquid, (concentration: 1.23M, the metal ion of metallic compound and the ion of halides rub
That ratio: 1:2).
3, small size monocrystalline (seed crystal) is grown
Prepared monocrystalline (seed crystal) growth-promoting media is transferred in the crystallising dish of clean dried, is sealed with three layers of preservative film
Afterwards, small size CH is obtained in crystallising dish bottom after 70 DEG C of heating for 24 hours in heat blowing drying box3NH3PbI3Perovskite list
It is brilliant.
4, growing large-size monocrystalline
The small size CH that will be grown in step 33NH3PbI3Perovskite monocrystalline is transferred to respectively in the crystallising dish of clean dried,
Prepared crystal growth liquid is added, after being sealed with three layers of preservative film, in heat blowing drying box after 70 DEG C of heating 48h,
The CH of crystallising dish bottom3NH3PbI3Perovskite monocrystalline significantly increases.
5, renew fresh crystal growth liquid
Crystal growth liquid old in step 4 crystallising dish is poured out, prepared fresh crystal growth liquid is added, is protected with three layers
After fresh film sealing, in heat blowing drying box after 70 DEG C of heating 48h, the CH of crystallising dish bottom3NH3PbI3Perovskite monocrystalline
Size further increases.So repeat this step it is multiple after, size can be obtained up to (> 10mm) × (> 10mm) × (> 10mm)
CH3NH3PbI3Perovskite monocrystalline.
6、CH3NH3PbI3Cleaning, drying and the collection of perovskite monocrystalline
The CH that growth finishes is cleaned with anhydrous ether3NH3PbI3Perovskite monocrystalline, 60 DEG C of dryings are for 24 hours in a vacuum drying oven
Afterwards, it is vacuum-packed.
Embodiment 3
1, monocrystalline (seed crystal) growth-promoting media is prepared
Weigh the bromine methylamine (CH that 0.112g has been synthesized3NH3Br), it is added in the beaker in tall form of 100mL, is put into a magnetic
Power stirrer measures 20mL n,N-Dimethylformamide (DMF) and is added, in 70 DEG C of agitating and heatings on magnetic agitation heater.To
Bromine methylamine (CH3NH3Br) all after dissolution, then 0.367g lead bromide (PbBr is weighed2) be added, continue at magnetic agitation heater
Upper 70 DEG C of agitating and heating 12h or more obtain crystal growth liquid (concentration: 0.05M, the metal ion and halides of metallic compound
Ion molar ratio: 1:1).
2, crystal growth liquid is prepared
Weigh the bromine methylamine (CH that 1.12g has been synthesized3NH3Br), it is added in the beaker in tall form of 100mL, is put into a magnetic force
Stirrer measures 20mL n,N-Dimethylformamide (DMF) and is added, in 70 DEG C of agitating and heatings on magnetic agitation heater.To bromine
Methylamine (CH3NH3Br) all after dissolution, then 3.67g lead bromide (PbBr is weighed2) be added, it continues at 70 on magnetic agitation heater
DEG C agitating and heating 12h or more, obtains crystal growth liquid (concentration: 0.5M, the metal ion of metallic compound and the ion of halides
Molar ratio: 1:1), crystal growth liquid concentration unit is M (mol/L).
3, small size monocrystalline (seed crystal) is grown
Prepared monocrystalline (seed crystal) growth-promoting media is transferred in the crystallising dish of clean dried, is sealed with three layers of preservative film
Afterwards, small size CH is obtained in crystallising dish bottom after 100 DEG C of heating for 24 hours in heat blowing drying box3NH3PbBr3Perovskite
Monocrystalline.
4, growing large-size monocrystalline
The small size CH that will be grown in step 33NH3PbBr3Perovskite monocrystalline is transferred to the crystallising dish of clean dried respectively
In, prepared crystal growth liquid is added, after being sealed with three layers of preservative film, in heat blowing drying box 100 DEG C of heating 48h with
Afterwards, the CH of crystallising dish bottom3NH3PbBr3Perovskite monocrystalline significantly increases.
5, renew fresh crystal growth liquid
Crystal growth liquid old in step 4 crystallising dish is poured out, prepared fresh crystal growth liquid is added, is protected with three layers
After fresh film sealing, in heat blowing drying box after 100 DEG C of heating 48h, the CH of crystallising dish bottom3NH3PbBr3Perovskite list
Brilliant size further increases.So repeat this step it is multiple after, size can be obtained up to (> 10mm) × (> 10mm) × (> 10mm)
CH3NH3PbBr3Perovskite monocrystalline.
6、CH3NH3PbBr3Cleaning, drying and the collection of perovskite monocrystalline
The CH that growth finishes is cleaned with anhydrous ether3NH3PbBr3Perovskite monocrystalline, in a vacuum drying oven 60 DEG C of dryings
After for 24 hours, vacuum packaging.
Embodiment 4
1, monocrystalline (seed crystal) growth-promoting media is prepared
Weigh the chloromethane amine (CH that 0.68g has been synthesized3NH3Cl), it is added in the beaker in tall form of 100mL, is put into a magnetic force
Stirrer measures 20mL n,N-Dimethylformamide (DMF) and is added, in 45 DEG C of agitating and heatings on magnetic agitation heater.To chlorine
Methylamine (CH3NH3Cl) all after dissolution, then 2.78g lead chloride (PbCl is weighed2) be added, it continues at 45 on magnetic agitation heater
DEG C agitating and heating 12h or more, obtains crystal growth liquid (concentration: 0.5M, the metal ion of metallic compound and the ion of halides
Molar ratio: 1:1).
2, crystal growth liquid is prepared
Weigh the chloromethane amine (CH that 1.66g has been synthesized3NH3Cl), it is added in the beaker in tall form of 100mL, is put into a magnetic force
Stirrer measures 20mL n,N-Dimethylformamide and is added, in 45 DEG C of agitating and heatings on magnetic agitation heater.To chloromethane amine
(CH3NH3Cl) all after dissolution, then 6.84g lead chloride (PbCl is weighed2) be added, it continues on magnetic agitation heater and stirs for 45 DEG C
Heating 12h or more is mixed, obtaining crystal growth liquid, (concentration: 1.23M, the metal ion of metallic compound and the ion of halides rub
That ratio: 1:1), the metallic compound in the above lead source can also use lead acetate (Pb (CH3COO)2·xH2O it) substitutes.
3, small size monocrystalline (seed crystal) is grown
Prepared monocrystalline (seed crystal) growth-promoting media is transferred in the crystallising dish of clean dried, is sealed with three layers of preservative film
Afterwards, small size CH is obtained in crystallising dish bottom after 100 DEG C of heating for 24 hours in heat blowing drying box3NH3PbCl3Perovskite
Monocrystalline.
4, growing large-size monocrystalline
The small size CH that will be grown in step 33NH3PbCl3Perovskite monocrystalline is transferred to the crystallising dish of clean dried respectively
In, prepared crystal growth liquid is added, after being sealed with three layers of preservative film, in heat blowing drying box 100 DEG C of heating 48h with
Afterwards, the CH of crystallising dish bottom3NH3PbCl3Perovskite monocrystalline significantly increases.
5, renew fresh crystal growth liquid
Crystal growth liquid old in step 4 crystallising dish is poured out, prepared fresh crystal growth liquid is added, is protected with three layers
After fresh film sealing, in heat blowing drying box after 100 DEG C of heating 48h, the CH of crystallising dish bottom3NH3PbCl3Perovskite list
Brilliant size further increases.So repeat this step it is multiple after, size can be obtained up to (> 10mm) × (> 10mm) × (> 10mm)
CH3NH3PbCl3Perovskite monocrystalline.
6、CH3NH3PbCl3Cleaning, drying and the collection of perovskite monocrystalline
The CH that growth finishes is cleaned with anhydrous ether3NH3PbCl3Perovskite monocrystalline, in a vacuum drying oven 60 DEG C of dryings
After for 24 hours, vacuum packaging.
Embodiment 5
1, monocrystalline (seed crystal) growth-promoting media is prepared
Weigh the iodine methylamine (CH that 1.59g has been synthesized3NH3I), it is added in the beaker in tall form of 100mL, is put into a magnetic force
Stirrer measures 20mL gamma-butyrolacton (GBA) and is added, in 80 DEG C of agitating and heatings on magnetic agitation heater.To iodine methylamine
(CH3NH3I) all after dissolution, then 4.61g lead iodide (PbI is weighed2) be added, continue at 80 DEG C of stirrings on magnetic agitation heater
12h or more is heated, crystal growth liquid (concentration: 0.5M, the metal ion of metallic compound and the ion mole of halides is obtained
Than: 1:1).
2, crystal growth liquid is prepared
Weigh the iodine methylamine (CH that 3.91g has been synthesized3NH3I), it is added in the beaker in tall form of 100mL, is put into a magnetic force
Stirrer measures 20mL gamma-butyrolacton (GBA) and is added, in 80 DEG C of agitating and heatings on magnetic agitation heater.To iodine methylamine
(CH3NH3I) all after dissolution, then 11.34g lead iodide (PbI is weighed2) be added, it continues on magnetic agitation heater and stirs for 80 DEG C
Heating 12h or more is mixed, obtaining crystal growth liquid, (concentration: 1.23M, the metal ion of metallic compound and the ion of halides rub
That ratio: 1:1).
3, small size monocrystalline (seed crystal) is grown
Prepared monocrystalline (seed crystal) growth-promoting media is transferred in the crystallising dish of clean dried, is sealed with three layers of preservative film
Afterwards, small size CH is obtained in crystallising dish bottom after 120 DEG C of heating for 24 hours in heat blowing drying box3NH3PbI3Perovskite list
It is brilliant.
4, growing large-size monocrystalline
The small size CH that will be grown in step 33NH3PbI3Perovskite monocrystalline is transferred to respectively in the crystallising dish of clean dried,
Prepared crystal growth liquid is added, after being sealed with three layers of preservative film, in heat blowing drying box after 120 DEG C of heating 48h,
The CH of crystallising dish bottom3NH3PbI3Perovskite monocrystalline significantly increases.
5, renew fresh crystal growth liquid
Crystal growth liquid old in step 4 crystallising dish is poured out, prepared fresh crystal growth liquid is added, is protected with three layers
After fresh film sealing, in heat blowing drying box after 120 DEG C of heating 48h, the CH of crystallising dish bottom3NH3PbI3Perovskite monocrystalline
Size further increases.So repeat this step it is multiple after, size can be obtained up to (> 10mm) × (> 10mm) × (> 10mm)
CH3NH3PbI3Perovskite monocrystalline.
6、CH3NH3PbI3Cleaning, drying and the collection of perovskite monocrystalline
The CH that growth finishes is cleaned with anhydrous ether3NH3PbI3Perovskite monocrystalline, 60 DEG C of dryings are for 24 hours in a vacuum drying oven
Afterwards, it is vacuum-packed.
Embodiment 6
1, monocrystalline (seed crystal) growth-promoting media is prepared
Weigh the iodine methylamine (CH that 4.77g has been synthesized3NH3I), it is added in the beaker in tall form of 100mL, is put into a magnetic force
Stirrer measures 20mL gamma-butyrolacton (GBA) and is added, in 90 DEG C of agitating and heatings on magnetic agitation heater.To iodine methylamine
(CH3NH3I) all after dissolution, then 4.61g lead iodide (PbI is weighed2) be added, continue at 90 DEG C of stirrings on magnetic agitation heater
12h or more is heated, crystal growth liquid (concentration: 0.5M, the metal ion of metallic compound and the ion mole of halides is obtained
Than: 1:3).
2, crystal growth liquid is prepared
Weigh the iodine methylamine (CH that 11.73g has been synthesized3NH3I), it is added in the beaker in tall form of 100mL, is put into a magnetic force
Stirrer measures 20mL gamma-butyrolacton (GBA) and is added, in 90 DEG C of agitating and heatings on magnetic agitation heater.To iodine methylamine
(CH3NH3I) all after dissolution, then 11.34g lead iodide (PbI is weighed2) be added, it continues on magnetic agitation heater and stirs for 90 DEG C
Heating 12h or more is mixed, obtaining crystal growth liquid, (concentration: 1.23M, the metal ion of metallic compound and the ion of halides rub
That ratio: 1:3).
3, small size monocrystalline (seed crystal) is grown
Prepared monocrystalline (seed crystal) growth-promoting media is transferred in the crystallising dish of clean dried, is sealed with three layers of preservative film
Afterwards, small size CH is obtained in crystallising dish bottom after 150 DEG C of heating for 24 hours in heat blowing drying box3NH3PbI3Perovskite list
It is brilliant.
4, growing large-size monocrystalline
The small size CH that will be grown in step 33NH3PbI3Perovskite monocrystalline is transferred to respectively in the crystallising dish of clean dried,
Prepared crystal growth liquid is added, after being sealed with three layers of preservative film, in heat blowing drying box after 150 DEG C of heating 48h,
The CH of crystallising dish bottom3NH3PbI3Perovskite monocrystalline significantly increases.
5, renew fresh crystal growth liquid
Crystal growth liquid old in step 4 crystallising dish is poured out, prepared fresh crystal growth liquid is added, is protected with three layers
After fresh film sealing, in heat blowing drying box after 150 DEG C of heating 48h, the CH of crystallising dish bottom3NH3PbI3Perovskite monocrystalline
Size further increases.So repeat this step it is multiple after, size can be obtained up to (> 10mm) × (> 10mm) × (> 10mm)
CH3NH3PbI3Perovskite monocrystalline.
6、CH3NH3PbI3Cleaning, drying and the collection of perovskite monocrystalline
The CH that growth finishes is cleaned with anhydrous ether3NH3PbI3Perovskite monocrystalline, 60 DEG C of dryings are for 24 hours in a vacuum drying oven
Afterwards, it is vacuum-packed.
Embodiment 7
1, monocrystalline (seed crystal) growth-promoting media is prepared
Weigh the bromine methylamine (CH that 1.12g has been synthesized3NH3Br), it is added in the beaker in tall form of 100mL, is put into a magnetic force
Stirrer measures 20mL n,N-Dimethylformamide (DMF) and is added, in 90 DEG C of agitating and heatings on magnetic agitation heater.To bromine
Methylamine (CH3NH3Br) all after dissolution, then 3.67g lead bromide (PbBr is weighed2) be added, it continues at 90 on magnetic agitation heater
DEG C agitating and heating 12h or more, obtains crystal growth liquid (concentration: 0.5M, the metal ion of metallic compound and the ion of halides
Molar ratio: 1:1).
2, crystal growth liquid is prepared
Weigh the bromine methylamine (CH that 2.24g has been synthesized3NH3Br), it is added in the beaker in tall form of 100mL, is put into a magnetic force
Stirrer measures 20mL n,N-Dimethylformamide (DMF) and is added, in 90 DEG C of agitating and heatings on magnetic agitation heater.To bromine
Methylamine (CH3NH3Br) all after dissolution, then 7.34g lead bromide (PbBr is weighed2) be added, it continues at 90 on magnetic agitation heater
DEG C agitating and heating 12h or more, obtaining crystal growth liquid, (concentration: 1M, the metal ion of metallic compound and the ion of halides rub
That ratio: 1:1).
3, small size monocrystalline (seed crystal) is grown
Prepared monocrystalline (seed crystal) growth-promoting media is transferred in the crystallising dish of clean dried, is sealed with three layers of preservative film
Afterwards, small size CH is obtained in crystallising dish bottom after 150 DEG C of heating for 24 hours in heat blowing drying box3NH3PbBr3Perovskite
Monocrystalline.
4, growing large-size monocrystalline
The small size CH that will be grown in step 33NH3PbBr3Perovskite monocrystalline is transferred to the crystallising dish of clean dried respectively
In, prepared crystal growth liquid is added, after being sealed with three layers of preservative film, in heat blowing drying box 150 DEG C of heating 48h with
Afterwards, the CH of crystallising dish bottom3NH3PbBr3Perovskite monocrystalline significantly increases.
5, renew fresh crystal growth liquid
Crystal growth liquid old in step 4 crystallising dish is poured out, prepared fresh crystal growth liquid is added, is protected with three layers
After fresh film sealing, in heat blowing drying box after 150 DEG C of heating 48h, the CH of crystallising dish bottom3NH3PbBr3Perovskite list
Brilliant size further increases.So repeat this step it is multiple after, size can be obtained up to (> 10mm) × (> 10mm) × (> 10mm)
CH3NH3PbBr3Perovskite monocrystalline.
6、CH3NH3PbBr3Cleaning, drying and the collection of perovskite monocrystalline
The CH that growth finishes is cleaned with anhydrous ether3NH3PbBr3Perovskite monocrystalline, in a vacuum drying oven 60 DEG C of dryings
After for 24 hours, vacuum packaging.
Embodiment 8
1, monocrystalline (seed crystal) growth-promoting media is prepared
Weigh the iodine methylamine (CH3NH that 1.59g has been synthesized3I), it is added in the beaker in tall form of 100mL, is put into a magnetic force
Stirrer measures 20mL gamma-butyrolacton (GBA) and is added, in 20 DEG C of agitating and heatings on magnetic agitation heater.To iodine methylamine
(CH3NH3I) all after dissolution, then 4.61g lead iodide (PbI is weighed2) be added, continue at 20 DEG C of stirrings on magnetic agitation heater
12h or more is heated, crystal growth liquid (concentration: 0.5M, the metal ion of metallic compound and the ion mole of halides is obtained
Than: 1:1).
2, crystal growth liquid is prepared
Weigh the iodine methylamine (CH that 3.91g has been synthesized3NH3I), it is added in the beaker in tall form of 100mL, is put into a magnetic force
Stirrer measures 20mL gamma-butyrolacton (GBA) and is added, in 20 DEG C of agitating and heatings on magnetic agitation heater.To iodine methylamine
(CH3NH3I) all after dissolution, then 11.34g lead iodide (PbI is weighed2) be added, it continues on magnetic agitation heater and stirs for 20 DEG C
Heating 12h or more is mixed, obtaining crystal growth liquid, (concentration: 1.23M, the metal ion of metallic compound and the ion of halides rub
That ratio: 1:1).
3, small size monocrystalline (seed crystal) is grown
Prepared monocrystalline (seed crystal) growth-promoting media is transferred in the crystallising dish of clean dried, is sealed with three layers of preservative film
Afterwards, small size CH is obtained in crystallising dish bottom after 200 DEG C of heating for 24 hours in heat blowing drying box3NH3PbI3Perovskite list
It is brilliant.
4, growing large-size monocrystalline
The small size CH that will be grown in step 33NH3PbI3Perovskite monocrystalline is transferred to respectively in the crystallising dish of clean dried,
Prepared crystal growth liquid is added, after being sealed with three layers of preservative film, in heat blowing drying box after 200 DEG C of heating 48h,
The CH of crystallising dish bottom3NH3PbI3Perovskite monocrystalline significantly increases.
5, renew fresh crystal growth liquid
Crystal growth liquid old in step 4 crystallising dish is poured out, prepared fresh crystal growth liquid is added, is protected with three layers
After fresh film sealing, in heat blowing drying box after 200 DEG C of heating 48h, the CH of crystallising dish bottom3NH3PbI3Perovskite monocrystalline
Size further increases.So repeat this step it is multiple after, size can be obtained up to (> 10mm) × (> 10mm) × (> 10mm)
CH3NH3PbI3Perovskite monocrystalline.
6、CH3NH3PbI3Cleaning, drying and the collection of perovskite monocrystalline
The CH that growth finishes is cleaned with anhydrous ether3NH3PbI3Perovskite monocrystalline, 60 DEG C of dryings are for 24 hours in a vacuum drying oven
Afterwards, it is vacuum-packed.
Embodiment 9
1, monocrystalline (seed crystal) growth-promoting media is prepared
Weigh the iodine methylamine (CH that 3.18g has been synthesized3NH3I), it is added in the beaker in tall form of 100mL, is put into a magnetic force
Stirrer measures 20mL n,N-Dimethylformamide (DMF) and is added, in 40 DEG C of agitating and heatings on magnetic agitation heater.To iodine
Methylamine (CH3NH3I) all after dissolution, then 4.61g lead iodide (PbI is weighed2) be added, 40 DEG C are continued on magnetic agitation heater
Agitating and heating 12h or more, obtaining crystal growth liquid, (concentration: 0.5M, the metal ion of metallic compound and the ion of halides rub
That ratio: 1:2).
2, crystal growth liquid is prepared
Weigh the iodine methylamine (CH that 7.82g has been synthesized3NH3I), it is added in the beaker in tall form of 100mL, is put into a magnetic force
Stirrer measures 20mL n,N-Dimethylformamide (DMF) and is added, in 40 DEG C of agitating and heatings on magnetic agitation heater.To iodine
Methylamine (CH3NH3I) all after dissolution, then 11.34g lead iodide (PbI is weighed2) be added, it continues at 40 on magnetic agitation heater
DEG C agitating and heating 12h or more, obtain crystal growth liquid (concentration: 1.23M, the metal ion of metallic compound and halides from
Sub- molar ratio: 1:2).
3, small size monocrystalline (seed crystal) is grown
Prepared monocrystalline (seed crystal) growth-promoting media is transferred in the crystallising dish of clean dried, is sealed with three layers of preservative film
Afterwards, small size CH is obtained in crystallising dish bottom after 70 DEG C of heating for 24 hours in heat blowing drying box3NH3PbI3Perovskite list
It is brilliant.
4, growing large-size monocrystalline
The small size CH that will be grown in step 33NH3PbI3Perovskite monocrystalline is transferred to respectively in the crystallising dish of clean dried,
Prepared crystal growth liquid is added, after being sealed with three layers of preservative film, in heat blowing drying box after 70 DEG C of heating 48h,
The CH of crystallising dish bottom3NH3PbI3Perovskite monocrystalline significantly increases.
5, renew fresh crystal growth liquid
Crystal growth liquid old in step 4 crystallising dish is poured out, prepared fresh crystal growth liquid is added, is protected with three layers
After fresh film sealing, in heat blowing drying box after 70 DEG C of heating 48h, the CH of crystallising dish bottom3NH3PbI3Perovskite monocrystalline
Size further increases.So repeat this step it is multiple after, size can be obtained up to (> 10mm) × (> 10mm) × (> 10mm)
CH3NH3PbI3Perovskite monocrystalline.
6、CH3NH3PbI3Cleaning, drying and the collection of perovskite monocrystalline
The CH that growth finishes is cleaned with anhydrous ether3NH3PbI3Perovskite monocrystalline, 60 DEG C of dryings are for 24 hours in a vacuum drying oven
Afterwards, it is vacuum-packed.
Embodiment 10
1, monocrystalline (seed crystal) growth-promoting media is prepared
Weigh the chloromethane amine (CH that 0.68g has been synthesized3NH3Cl), it is added in the beaker in tall form of 100mL, is put into a magnetic force
Stirrer measures 20mL dimethyl sulfoxide (DMSO) and is added, in 70 DEG C of agitating and heatings on magnetic agitation heater.To chloromethane amine
(CH3NH3Cl) all after dissolution, then 2.78g lead chloride (PbCl is weighed2) be added, it continues on magnetic agitation heater and stirs for 70 DEG C
Heating 12h or more is mixed, crystal growth liquid (concentration: 0.5M, the metal ion of metallic compound and the ion mole of halides is obtained
Than: 1:1).
2, crystal growth liquid is prepared
Weigh the chloromethane amine (CH that 0.68g has been synthesized3NH3Cl), it is added in the beaker in tall form of 100mL, is put into a magnetic force
Stirrer measures 20mL dimethyl sulfoxide (DMSO) and is added, in 70 DEG C of agitating and heatings on magnetic agitation heater.To chloromethane amine
(CH3NH3Cl) all after dissolution, then 2.78g lead chloride (PbCl is weighed2) be added, it continues on magnetic agitation heater and stirs for 70 DEG C
Heating 12h or more is mixed, crystal growth liquid (concentration: 0.5M, the metal ion of metallic compound and the ion mole of halides is obtained
Than: 1:1).
3, small size monocrystalline (seed crystal) is grown
Prepared monocrystalline (seed crystal) growth-promoting media is transferred in the crystallising dish of clean dried, is sealed with three layers of preservative film
Afterwards, small size CH is obtained in crystallising dish bottom after 100 DEG C of heating for 24 hours in heat blowing drying box3NH3PbCl3Perovskite
Monocrystalline.
4, growing large-size monocrystalline
The small size CH that will be grown in step 33NH3PbCl3Perovskite monocrystalline is transferred to the crystallising dish of clean dried respectively
In, prepared crystal growth liquid is added, after being sealed with three layers of preservative film, in heat blowing drying box 100 DEG C of heating 48h with
Afterwards, the CH of crystallising dish bottom3NH3PbCl3Perovskite monocrystalline significantly increases.
5, renew fresh crystal growth liquid
Crystal growth liquid old in step 4 crystallising dish is poured out, prepared fresh crystal growth liquid is added, is protected with three layers
After fresh film sealing, in heat blowing drying box after 100 DEG C of heating 48h, the CH of crystallising dish bottom3NH3PbCl3Perovskite list
Brilliant size further increases.So repeat this step it is multiple after, size can be obtained up to (> 10mm) × (> 10mm) × (> 10mm)
CH3NH3PbCl3Perovskite monocrystalline.
6、CH3NH3PbCl3Cleaning, drying and the collection of perovskite monocrystalline
The CH that growth finishes is cleaned with anhydrous ether3NH3PbCl3Perovskite monocrystalline, in a vacuum drying oven 60 DEG C of dryings
After for 24 hours, vacuum packaging.
Embodiment 11
1, monocrystalline (seed crystal) growth-promoting media is prepared
Weigh the iodine methylamine (CH that 0.745g has been synthesized3NH3I), it is added in the beaker in tall form of 100mL, is put into a magnetic force
Stirrer measures 20mL gamma-butyrolacton (GBA) and is added, in 45 DEG C of agitating and heatings on magnetic agitation heater.To iodine methylamine
(CH3NH3I) all after dissolution, then 4.61g lead iodide (PbI is weighed2) be added, continue at 45 DEG C of stirrings on magnetic agitation heater
12h or more is heated, crystal growth liquid (concentration: 0.5M, the metal ion of metallic compound and the ion mole of halides is obtained
Than: 1:0.5).
2, crystal growth liquid is prepared
Weigh the iodine methylamine (CH that 4.77g has been synthesized3NH3I), it is added in the beaker in tall form of 100mL, is put into a magnetic force
Stirrer measures 20mL gamma-butyrolacton (GBA) and is added, in 45 DEG C of agitating and heatings on magnetic agitation heater.To iodine methylamine
(CH3NH3I) all after dissolution, then 27.66g lead iodide (PbI is weighed2) be added, it continues on magnetic agitation heater and stirs for 45 DEG C
Heating 12h or more is mixed, crystal growth liquid (concentration: 3M, the metal ion of metallic compound and the ion mole of halides is obtained
Than: 1:0.5).
3, small size monocrystalline (seed crystal) is grown
Prepared monocrystalline (seed crystal) growth-promoting media is transferred in the crystallising dish of clean dried, is sealed with three layers of preservative film
Afterwards, small size CH is obtained in crystallising dish bottom after 110 DEG C of heating for 24 hours in heat blowing drying box3NH3PbI3Perovskite list
It is brilliant.
4, growing large-size monocrystalline
The small size CH that will be grown in step 33NH3PbI3Perovskite monocrystalline is transferred to respectively in the crystallising dish of clean dried,
Prepared crystal growth liquid is added, after being sealed with three layers of preservative film, in heat blowing drying box after 110 DEG C of heating 48h,
The CH of crystallising dish bottom3NH3PbI3Perovskite monocrystalline significantly increases.
5, renew fresh crystal growth liquid
Crystal growth liquid old in step 4 crystallising dish is poured out, prepared fresh crystal growth liquid is added, is protected with three layers
After fresh film sealing, in heat blowing drying box after 110 DEG C of heating 48h, the CH of crystallising dish bottom3NH3PbI3Perovskite monocrystalline
Size further increases.So repeat this step it is multiple after, size can be obtained up to (> 10mm) × (> 10mm) × (> 10mm)
CH3NH3PbI3Perovskite monocrystalline.
6、CH3NH3PbI3Cleaning, drying and the collection of perovskite monocrystalline
The CH that growth finishes is cleaned with anhydrous ether3NH3PbI3Perovskite monocrystalline, 60 DEG C of dryings are for 24 hours in a vacuum drying oven
Afterwards, it is vacuum-packed.
Embodiment 12
1, monocrystalline (seed crystal) growth-promoting media is prepared
Weigh the iodine methylamine (CH that 0.745g has been synthesized3NH3I), it is added in the beaker in tall form of 100mL, is put into a magnetic force
Stirrer measures 20mL n,N-Dimethylformamide (DMF) and is added, in 45 DEG C of agitating and heatings on magnetic agitation heater.To iodine
Methylamine (CH3NH3I) all after dissolution, then 4.61g lead iodide (PbI is weighed2) be added, 45 DEG C are continued on magnetic agitation heater
Agitating and heating 12h or more, obtaining crystal growth liquid, (concentration: 0.5M, the metal ion of metallic compound and the ion of halides rub
That ratio: 1:0.5).
2, crystal growth liquid is prepared
Weigh the iodine methylamine (CH that 7.95g has been synthesized3NH3I), it is added in the beaker in tall form of 100mL, is put into a magnetic force
Stirrer measures 20mL n,N-Dimethylformamide (DMF) and is added, in 45 DEG C of agitating and heatings on magnetic agitation heater.To iodine
Methylamine (CH3NH3I) all after dissolution, then 46.11g lead iodide (PbI is weighed2) be added, it continues at 45 on magnetic agitation heater
DEG C agitating and heating 12h or more, obtaining crystal growth liquid, (concentration: 5M, the metal ion of metallic compound and the ion of halides rub
That ratio: 1:0.5).
3, small size monocrystalline (seed crystal) is grown
Prepared monocrystalline (seed crystal) growth-promoting media is transferred in the crystallising dish of clean dried, is sealed with three layers of preservative film
Afterwards, small size CH is obtained in crystallising dish bottom after 120 DEG C of heating for 24 hours in heat blowing drying box3NH3PbI3Perovskite list
It is brilliant.
4, growing large-size monocrystalline
The small size CH that will be grown in step 33NH3PbI3Perovskite monocrystalline is transferred to respectively in the crystallising dish of clean dried,
Prepared crystal growth liquid is added, after being sealed with three layers of preservative film, in heat blowing drying box after 120 DEG C of heating 48h,
The CH of crystallising dish bottom3NH3PbI3Perovskite monocrystalline significantly increases.
5, renew fresh crystal growth liquid
Crystal growth liquid old in step 4 crystallising dish is poured out, prepared fresh crystal growth liquid is added, is protected with three layers
After fresh film sealing, in heat blowing drying box after 120 DEG C of heating 48h, the CH of crystallising dish bottom3NH3PbI3Perovskite monocrystalline
Size further increases.So repeat this step it is multiple after, size can be obtained up to (> 10mm) × (> 10mm) × (> 10mm)
CH3NH3PbI3Perovskite monocrystalline.
6、CH3NH3PbI3Cleaning, drying and the collection of perovskite monocrystalline
The CH that growth finishes is cleaned with anhydrous ether3NH3PbI3Perovskite monocrystalline, 60 DEG C of dryings are for 24 hours in a vacuum drying oven
Afterwards, it is vacuum-packed.
Embodiment 13
1, monocrystalline (seed crystal) growth-promoting media is prepared
Weigh the bromine methylamine (CH that 0.896g has been synthesized3NH3Br), it is added in the beaker in tall form of 100mL, is put into a magnetic
Power stirrer measures 20mL n,N-Dimethylformamide (DMF) and is added, in 70 DEG C of agitating and heatings on magnetic agitation heater.To
Bromine methylamine (CH3NH3Br) all after dissolution, then 3.67g lead bromide (PbBr is weighed2) be added, it continues on magnetic agitation heater
70 DEG C of agitating and heating 12h or more, obtain crystal growth liquid (concentration: 0.5M, the metal ion of metallic compound and halides from
Sub- molar ratio: 1:0.8).
2, crystal growth liquid is prepared
Weigh the bromine methylamine (CH that 5.37g has been synthesized3NH3Br), it is added in the beaker in tall form of 100mL, is put into a magnetic force
Stirrer measures 20mL n,N-Dimethylformamide (DMF) and is added, in 70 DEG C of agitating and heatings on magnetic agitation heater.To bromine
Methylamine (CH3NH3Br) all after dissolution, then 22.03g lead bromide (PbBr is weighed2) be added, it continues on magnetic agitation heater
70 DEG C of agitating and heating 12h or more obtain crystal growth liquid (concentration: 3M, the metal ion of metallic compound and the ion of halides
Molar ratio: 1:0.8).
3, small size monocrystalline (seed crystal) is grown
Prepared monocrystalline (seed crystal) growth-promoting media is transferred in the crystallising dish of clean dried, is sealed with three layers of preservative film
Afterwards, small size is obtained in crystallising dish bottom after 100 DEG C of heating for 24 hours in heat blowing drying box, oil bath or water-bath
CH3NH3PbBr3Perovskite monocrystalline.
4, growing large-size monocrystalline
The small size CH that will be grown in step 33NH3PbBr3Perovskite monocrystalline is transferred to the crystallising dish of clean dried respectively
In, prepared crystal growth liquid is added, after being sealed with three layers of preservative film, in heat blowing drying box 100 DEG C of heating 48h with
Afterwards, the CH of crystallising dish bottom3NH3PbBr3Perovskite monocrystalline significantly increases.
5, renew fresh crystal growth liquid
Crystal growth liquid old in step 4 crystallising dish is poured out, prepared fresh crystal growth liquid is added, is protected with three layers
After fresh film sealing, in heat blowing drying box after 100 DEG C of heating 48h, the CH of crystallising dish bottom3NH3PbBr3Perovskite list
Brilliant size further increases.So repeat this step it is multiple after, size can be obtained up to (> 10mm) × (> 10mm) × (> 10mm)
CH3NH3PbBr3Perovskite monocrystalline.
6、CH3NH3PbBr3Cleaning, drying and the collection of perovskite monocrystalline
The CH that growth finishes is cleaned with anhydrous ether3NH3PbBr3Perovskite monocrystalline, in a vacuum drying oven 60 DEG C of dryings
After for 24 hours, vacuum packaging.
Embodiment 14
1, monocrystalline (seed crystal) growth-promoting media is prepared
Weigh the chloromethane amine (CH that 3.376g has been synthesized3NH3Cl), it is added in the beaker in tall form of 100mL, is put into a magnetic
Power stirrer measures 20mL dimethyl sulfoxide (DMSO) and is added, in 60 DEG C of agitating and heatings on magnetic agitation heater.To chloromethane amine
(CH3NH3Cl) all after dissolution, then 2.78g lead chloride (PbCl is weighed2) be added, it continues on magnetic agitation heater and stirs for 60 DEG C
Heating 12h or more is mixed, crystal growth liquid (concentration: 0.5M, the metal ion of metallic compound and the ion mole of halides is obtained
Than: 1:5).
2, crystal growth liquid is prepared
Weigh the chloromethane amine (CH that 6.75g has been synthesized3NH3Cl), it is added in the beaker in tall form of 100mL, is put into a magnetic force
Stirrer measures 20mL dimethyl sulfoxide (DMSO) and is added, in 60 DEG C of agitating and heatings on magnetic agitation heater.To chloromethane amine
(CH3NH3Cl) all after dissolution, then 5.56g lead chloride (PbCl is weighed2) be added, 60 DEG C are continued on magnetic agitation heater
Agitating and heating 12h or more obtains crystal growth liquid (concentration: 1M, the metal ion of metallic compound and the ion mole of halides
Than: 1:5).
3, small size monocrystalline (seed crystal) is grown
Prepared monocrystalline (seed crystal) growth-promoting media is transferred in the crystallising dish of clean dried, is sealed with three layers of preservative film
Afterwards, small size CH is obtained in crystallising dish bottom after 100 DEG C of heating for 24 hours in heat blowing drying box3NH3PbCl3Perovskite
Monocrystalline.
4, growing large-size monocrystalline
The small size CH that will be grown in step 33NH3PbCl3Perovskite monocrystalline is transferred to the crystallising dish of clean dried respectively
In, prepared crystal growth liquid is added, after being sealed with three layers of preservative film, in heat blowing drying box 100 DEG C of heating 48h with
Afterwards, the CH of crystallising dish bottom3NH3PbCl3Perovskite monocrystalline significantly increases.
5, renew fresh crystal growth liquid
Crystal growth liquid old in step 4 crystallising dish is poured out, prepared fresh crystal growth liquid is added, is protected with three layers
After fresh film sealing, in heat blowing drying box after 100 DEG C of heating 48h, the CH of crystallising dish bottom3NH3PbCl3Perovskite list
Brilliant size further increases.So repeat this step it is multiple after, size can be obtained up to (> 10mm) × (> 10mm) × (> 10mm)
CH3NH3PbCl3Perovskite monocrystalline.
6、CH3NH3PbCl3Cleaning, drying and the collection of perovskite monocrystalline
The CH that growth finishes is cleaned with anhydrous ether3NH3PbCl3Perovskite monocrystalline, in a vacuum drying oven 60 DEG C of dryings
After for 24 hours, vacuum packaging.
Embodiment 15
1, monocrystalline (seed crystal) growth-promoting media is prepared
Weigh the 15.89 iodine methylamine (CH synthesized3NH3I), it is added in the beaker in tall form of 100mL, is put into a magnetic force
Stirrer measures 20mL gamma-butyrolacton (GBA) and is added, in 45 DEG C of agitating and heatings on magnetic agitation heater.To iodine methylamine
(CH3NH3I) all after dissolution, then 4.61g lead iodide (PbI is weighed2) be added, continue at 45 DEG C of stirrings on magnetic agitation heater
12h or more is heated, crystal growth liquid (concentration: 0.5M, the metal ion of metallic compound and the ion mole of halides is obtained
Than: 1:10).
2, crystal growth liquid is prepared
Weigh the iodine methylamine (CH that 95.38g has been synthesized3NH3I), it is added in the beaker in tall form of 100mL, is put into a magnetic force
Stirrer measures 20mL gamma-butyrolacton (GBA) and is added, in 45 DEG C of agitating and heatings on magnetic agitation heater.To iodine methylamine
(CH3NH3I) all after dissolution, then 27.66g lead iodide (PbI is weighed2) be added, it continues on magnetic agitation heater and stirs for 45 DEG C
Heating 12h or more is mixed, crystal growth liquid (concentration: 3M, the metal ion of metallic compound and the ion mole of halides is obtained
Than: 1:10).
3, small size monocrystalline (seed crystal) is grown
Prepared monocrystalline (seed crystal) growth-promoting media is transferred in the crystallising dish of clean dried, is sealed with three layers of preservative film
Afterwards, small size CH is obtained in crystallising dish bottom after 120 DEG C of heating for 24 hours in heat blowing drying box3NH3PbI3Perovskite list
It is brilliant.
4, growing large-size monocrystalline
The small size CH that will be grown in step 33NH3PbI3Perovskite monocrystalline is transferred to respectively in the crystallising dish of clean dried,
Prepared crystal growth liquid is added, after being sealed with three layers of preservative film, in heat blowing drying box after 120 DEG C of heating 48h,
The CH of crystallising dish bottom3NH3PbI3Perovskite monocrystalline significantly increases.
5, renew fresh crystal growth liquid
Crystal growth liquid old in step 4 crystallising dish is poured out, prepared fresh crystal growth liquid is added, is protected with three layers
After fresh film sealing, in heat blowing drying box after 120 DEG C of heating 48h, the CH of crystallising dish bottom3NH3PbI3Perovskite monocrystalline
Size further increases.So repeat this step it is multiple after, size can be obtained up to (> 10mm) × (> 10mm) × (> 10mm)
CH3NH3PbI3Perovskite monocrystalline.
6、CH3NH3PbI3Cleaning, drying and the collection of perovskite monocrystalline
The CH that growth finishes is cleaned with anhydrous ether3NH3PbI3Perovskite monocrystalline, 60 DEG C of dryings are for 24 hours in a vacuum drying oven
Afterwards, it is vacuum-packed.
Remaining embodiment see the table below:
Claims (6)
1. growing ABX in cryogenic fluid3The method of perovskite monocrystalline, wherein A is CH3NH3 +、H2N-CH=NH2 +、(CH3)4N+、
C7H7 +、Cs+Or C3H11SN3 2+, B Pb, Ge or Sn；X is Cl, Br or I, it is characterised in that: takes and provides lead source, tin source or ge source
Metallic compound, halides and the solvent that the metallic compound can be dissolved；Halides and solvent are hybridly prepared into solution, it will
Metallic compound is made into crystal growth liquid after being added, and grows to obtain ABX using the method continuously grown3Perovskite monocrystalline；
Halides are weighed when preparing crystal growth liquid to be dissolved with stirring solvent in a reservoir, metallic compound is then added, and are sealed
Container is placed on magnetic stirring apparatus, and heating continuously stirs, shakes or be ultrasonically treated 12h or more at a temperature of room temperature~90 DEG C,
Obtain crystal growth liquid；
The lesser seed crystal of size is first grown, seed crystal is transferred in fresh crystal growth liquid grows later；When growing one section
Between after, then by the crystal grain grown up taking-up be put into fresh crystal growth liquid；Primary fresh crystal growth liquid is often changed to next time
The growth time for changing crystal growth liquid is a growth cycle, and and so on continuous multiple growth cycles are until the list that is needed
It is brilliant；
The single crystal growth temperature is 50-200 DEG C and is higher than the configuration temperature of crystal growth liquid, and each growth cycle time is
More than for 24 hours；
The solvent is gamma-butyrolacton (GBA), n,N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and N- methyl-
One of 2-Pyrrolidone (NMP).
2. growing ABX in cryogenic fluid according to claim 13The method of perovskite monocrystalline, it is characterised in that: monocrystalline is raw
Temperature needed for being provided when long by heat blowing drying box, oil bath or water-bath, is heated evenly growth system, by adjusting container
Seal degree control the evaporation rate of solvent, to control the speed of crystal growth.
3. growing ABX in cryogenic fluid according to claim 13The method of perovskite monocrystalline, it is characterised in that: described to mention
Metallic compound for lead source is lead chloride (PbCl2), lead bromide (PbBr2), lead iodide (PbI2) or lead acetate (Pb
(CH3COO)2·xH2O)；The metallic compound for providing tin source is stannous chloride (SnCl2), tin tetrachloride (SnCl4), bromination
Stannous (SnBr2) or stannous iodide (SnI2)；The metallic compound for providing ge source is germanium chloride (GeCl2), bromination germanium
(GeBr2) or iodate germanium (GeI2)。
4. growing ABX in cryogenic fluid according to claim 13The method of perovskite monocrystalline, it is characterised in that: the halogen
It is to be containing radius for objectOne of organic or inorganic ion organic or inorganic halides, including chloromethane amine
(CH3NH3Cl), chloromethane amidine (H2N-CH=NH2Cl), tetramethylamine chloride ((CH3)4N Cl), chlorine Zhuo (C7H7Cl), chloro 2- is different
Thiocarbamide (C3H11SN3Cl2), bromine methylamine (CH3NH3Br), bromine carbonamidine (H2N-CH=NH2Br), bromination tetramethylammonium ((CH3)4N Br)、
Bromine Zhuo (C7H7Br), bromo 2- isothiourea (C3H11SN3Br2), iodine methylamine (CH3NH3I), iodine carbonamidine (H2N-CH=NH2I), iodine
Change tetramethylammonium ((CH3)4NI), iodine Zhuo (C7H7I), iodo 2- isothiourea (C3H11SN3I2) and inorganic CsI.
5. growing ABX in cryogenic fluid according to claim 13The method of perovskite monocrystalline, it is characterised in that: the list
Organic cation ion molar ratio in crystals growth liquid in the metal ion and halides of metallic compound is 1:(0.5~10).
6. growing ABX in cryogenic fluid according to claim 13The method of perovskite monocrystalline, it is characterised in that: the list
The concentration of crystals growth liquid is 0.05-5.0mol/L.
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