CN106634987A - Metal halide perovskite quantum dot CsSnX3 and preparation method thereof - Google Patents
Metal halide perovskite quantum dot CsSnX3 and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a metal halide perovskite quantum dot CsSnX3. The method comprises the following steps of providing CsX, a first main solvent and a first cosolvent; after mixing, performing first heating stirring; preparing a Cs precursor; providing SnX2, a second main solvent and a second cosolvent; after mixing, performing second heating stirring; preparing an Sn precursor; heating the Sn precursor; after the temperature rises to 100 to 200 DEG C, adding the Cs precursor; performing stirring treatment; performing constant-temperature reaction for 10 to 20 min; preparing and obtaining the metal halide perovskite quantum dot CsSnX3, wherein in the CsX and the SnX2, the X is at least one of Cl, Br and I; the first cosolvent is diethyl allyl phosphate or N, N-dimethylformamide; the second cosolvent is diethyl allyl phosphate or N, N-dimethylformamide.
Description
Technical field
The invention belongs to quantum dot synthesis technical field, more particularly to a kind of metal halide perovskite quantum dot CsSnX3
And preparation method thereof.
Background technology
Traditional photovoltaic material governs always the development of photovoltaic industry and strengthens because cost is high, energy transformation ratio is low
Greatly.Recent study finds that organic-inorganic metal halide perovskite material has phototranstormation efficiency height, luminescent spectrum width, sky
The advantages of cave-electronics recombination energy is little, carrier mobility speed is big, in photovoltaic industry, LED, optical communication and biologic medical field tool
Have broad application prospects.Compared with organic-inorganic metal halide perovskite material, full-inorganic metal halide perovskite material
Material is presented more excellent optically and electrically stability, with more wide application prospect.
Quanta point material is due to its exciting light spectrum width, emission spectrum is narrow, emission wavelength is adjustable, luminous efficiency is high etc., and optics is special
Point, it is considered to be the novel optoelectronic materials of great potential.Research discovery, based on metal halide perovskite quanta point material too
Up to 20%, this is that other materials cannot match in excellence or beauty to the phototranstormation efficiency of positive energy battery.But, metal halide perovskite quantum
Generally existing heavy metal lead in point material, the preparation technology very complicated of material, high energy consumption cause material to have bio-toxicity,
Cost is high, so as to constrain the development and application of the material.Replaced after the lead in material using nontoxic metal component, material
Defect concentration increases, and the aerial stability and device performance for causing material declines.Therefore, explore new method and prepare environment
The high unleaded metal halide perovskite quanta point material of friendly, cheap, luminous efficiency is current study hotspot.
For the above, patent CN105647530A provides the synthesis side of inorganic metal hal ide perovskite quanta point material
Method, but Jing repetition tests and its accompanying drawing it is seen that, this method is relatively low for the degree of control of quantum dot particle size, it is difficult to
Obtain the high-quality quantum dot of uniform particle diameter.
The content of the invention
It is an object of the invention to provide a kind of metal halide perovskite quantum dot CsSnX3Preparation method, it is intended to solve
The preparation method quantum point grain diameter size of certainly existing inorganic metal hal ide perovskite quanta point material is difficult to control to, and causes to obtain
Quantum point defect density it is high, affect the problem of its performance.
The present invention is achieved in that a kind of metal halide perovskite quantum dot CsSnX3Preparation method, including with
Lower step：
CsX, the first main solvent and the first cosolvent are provided, the first heating stirring is carried out after mixing, prepare Cs presomas；
SnX is provided2, the second main solvent and the second cosolvent, the second heating stirring is carried out after mixing, prepare Sn presomas；
After the Sn presomas are heated into 100-200 DEG C, the Cs presomas are added, stir process, constant temperature is anti-
10-20min is answered, metal halide perovskite quantum dot CsSnX is prepared3；
Wherein, described CsX, SnX2In, X is at least one in Cl, Br, I, and first cosolvent is phosphoric acid pi-allyl
Diethylester or DMF, second cosolvent is phosphoric acid pi-allyl diethylester or DMF.
And, a kind of metal halide perovskite quantum dot CsSnX3, the metal halide perovskite quantum dot CsSnX3
For quantum dot prepared by said method.
The metal halide perovskite quantum dot CsSnX that the present invention is provided3Preparation method, first using the first cosolvent system
Standby Cs cation presomas, then Cs cations and Sn presoma heating responses containing the second cosolvent are obtained into metal halide
Perovskite quantum dot CsSnX3。
First, Cs presomas are prepared as the first cosolvent using phosphoric acid pi-allyl diethylester or DMF
When, the phosphoric acid pi-allyl diethylester or DMF participate in Cs1+Coordination, make the free Cs in system1+It is dense
Degree keeps stable, contributes to forming stable organic complex ion, in the step of follow-up synthesis quantum dot, advantageously reduces
The surface energy of nucleation quantum dot, and then be conducive to the formation of monodispersity quantum dot, finally give uniform particle diameter, stable metal
Halide perovskite quantum dot CsSnX3.Meanwhile, the Sn presomas containing the second cosolvent have preferably phase with Cs presomas
Capacitive so that solution is well mixed in course of reaction, further helps in and obtains uniform particle diameter, stable metal halide calcium titanium
Ore deposit quantum dot CsSnX3。
Secondly, the present invention can synthesize different-shape such as monocline by changing halogen species, reaction temperature, stand
Side, the inorganic metal hal ide perovskite quantum dot of orthogonal three kinds of crystallographic systems；By changing halogen species, ratio or reaction time,
To adjust CsSnX3Emission wavelength of the perovskite quantum dot in Visible-to-Near InfaRed region.
Again, the method that the present invention is provided, can adopt the Cs sources or Sn sources of different halogenic ingredients, be directly synthesized containing one
The CsSnX of kind or various halogens3(X=Cl, Br, I) perovskite quantum dot.
Additionally, the metal halide perovskite quantum dot CsSnX that the present invention is provided3Preparation method, method is simple and easy to control,
Low cost, easily realizes industrialization production.
The metal halide perovskite quantum dot CsSnX that the present invention is provided3, not only without heavy metal lead, and with property
Can stable, size uniformity, good dispersion, the advantage that crystal formation is controllable, luminous efficiency is high, it is aobvious in LED advantageous as environment-friendly materials
Show and be used widely with photovoltaic art.
Specific embodiment
In order that the technical problem to be solved in the present invention, technical scheme and beneficial effect become more apparent, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only to explain
The present invention, is not intended to limit the present invention.
Embodiments provide a kind of metal halide perovskite quantum dot CsSnX3Preparation method, it is including following
Step：
S01., CsX, the first main solvent and the first cosolvent are provided, the first heating stirring is carried out after mixing, prepare Cs forerunner
Body；
S02., SnX is provided2, the second main solvent and the second cosolvent, the second heating stirring is carried out after mixing, prepare Sn forerunner
Body；
S03. after the Sn presomas being heated into 100-200 DEG C, the Cs presomas are added, stir process is permanent
Temperature reaction 10-20min, prepares metal halide perovskite quantum dot CsSnX3；
Wherein, described CsX, SnX2In, X is at least one in Cl, Br, I, and first cosolvent is phosphoric acid pi-allyl
Diethylester or DMF, second cosolvent is phosphoric acid pi-allyl diethylester or DMF.
Specifically, in above-mentioned steps S01, first main solvent is the organic solvent that can effectively dissolve the CsX.It is excellent
Choosing, first main solvent is the one kind in tri octyl phosphine, tributylphosphine, trioctylphosphine amine, ethylenediamine, oleyl amine.Preferred
One main solvent, on the one hand, can well dissolve CsX；On the other hand, above-mentioned main solvent is in metal halide perovskite quantum dot
CsSnX3Growth course in simultaneously as surfactant, be coated on quantum dot surface, suppress product to reunite, contribute to being formed
Evengranular quantum dot.
First cosolvent is the important substance that the embodiment of the present invention affects quantum dot uniform particle diameter.Specifically, exist
During preparing Cs presomas, the first cosolvent is added with, and first cosolvent is phosphoric acid pi-allyl diethylester or N,
Dinethylformamide.The first cosolvent phosphoric acid pi-allyl diethylester or N,N-dimethylformamide participate in Cs1+Coordination,
The free Cs in system can be made1+Concentration keeps stable, contributes to forming stable organic complex ion, so as to subsequently synthesize
In the step of quantum dot, the surface energy of nucleation quantum dot is advantageously reduced, contribute to preparing evengranular metal halide calcium
Titanium ore quantum dot CsSnX3.First cosolvent is more preferably phosphoric acid pi-allyl diethylester, the phosphoric acid pi-allyl diethylester
It is more beneficial for metal halide perovskite quantum dot CsSnX3Control synthesis, so as to obtain particle diameter with stable quantum dot.
It is further preferred that the consumption of the CsX, the first main solvent and the first cosolvent is 1g:2-20mL:20-
200mL, so as under the premise of ensureing that CsX is deliquescent, preferably regulate and control the synthesis of quantum dot, obtains uniform particle diameter metal halide
Thing perovskite quantum dot CsSnX3.If first main solvent is very few, the solute effect of the CsX is bad, and then affects it
Coordinate；If first cosolvent is very few, metal cation Cs1+Complexing effect it is bad, in course of reaction, free metal sun from
Sub- change in concentration is big, and the quantum point grain diameter that obtains, structure are uneven；If first cosolvent is excessive, free metal sun from
Sub- Cs1+Concentration is low, and reaction rate is little, is easy to get to big particle diameter product.
In the embodiment of the present invention, by the CsX, the first main solvent and the first cosolvent mixed processing, can be will be described
CsX, the first main solvent and the first cosolvent are directly mixed to get mixed system.In order to improve the utilization rate of the CsX, while
To the preferable mixed system of dissolved state, preferably first by CsX, the first main solvent mixed dissolution after, add described first molten altogether
Agent.
Above-mentioned mixed system is carried out the first heating stirring and prepares Cs presomas by the embodiment of the present invention, it is preferred that described the
The heating-up temperature of one heating stirring is 100-150 DEG C, and stir speed (S.S.) is 800-1200rpm.The preferred heating-up temperature and stirring
Speed, contributes to phosphoric acid pi-allyl diethylester or DMF participates in Cs1+Preferably it is coordinated, forms stable organic
Complex ion, in the step of follow-up synthesis quantum dot, advantageously reduces the surface energy of nucleation quantum dot, and then is conducive to list
The formation of dispersed quantum dot, finally gives uniform particle diameter, stable metal halide perovskite quantum dot CsSnX3。
In above-mentioned steps S02, second main solvent is can effectively to dissolve the SnX2Organic solvent.Preferably,
First main solvent is the one kind in tri octyl phosphine, tributylphosphine, trioctylphosphine amine, ethylenediamine, oleyl amine.Preferred first master is molten
Agent, on the one hand, can well dissolve SnX2；On the other hand, above-mentioned main solvent is in metal halide perovskite quantum dot CsSnX3
Growth course in simultaneously as surfactant, be coated on quantum dot surface, suppress product to reunite, contribute to forming particle equal
Even quantum dot.
Second main solvent can be with identical with first main solvent, it is also possible to different.
During Sn presomas are prepared, the second cosolvent is added with, and second cosolvent is phosphoric acid pi-allyl
Diethylester or N,N-dimethylformamide.The addition of second cosolvent, before the Sn presomas and the Cs can be caused
Drive body it is preferably compatible, so as to improve subsequent reactions system in presoma solubility property, obtain uniform reaction system.It is described
Second cosolvent is more preferably phosphoric acid pi-allyl diethylester, and the phosphoric acid pi-allyl diethylester is more beneficial for metal halide calcium titanium
Ore deposit quantum dot CsSnX3Control synthesis, so as to obtain particle diameter with stable quantum dot.Second is total to described in the embodiment of the present invention
Solvent can be identical with first cosolvent, it is also possible to different.Preferably, first cosolvent, the second cosolvent are identical.
More preferably described first cosolvent, the second cosolvent are phosphoric acid pi-allyl diethylester, so as to advantageously promote the Sn before
Drive the compatibility between body and the Cs presomas.
It is further preferred that the SnX2, the second main solvent and the second cosolvent amount ratio be 1g:2-20mL:20-
200mL, so as to ensure SnX2Under the premise of deliquescent, preferably regulate and control the synthesis of quantum dot, obtain uniform particle diameter metal halogen
Compound perovskite quantum dot CsSnX3.If second main solvent is very few, it is unfavorable for SnX2Dissolving；If second cosolvent
It is very few, then the second cosolvent and Sn2+Interact uncertain, Sn presomas are bad with the compatibility of the Cs presomas；If institute
State the second cosolvent excessive, ion concentration is little, nucleation is slow and few, and particle size is bigger than normal.
In the embodiment of the present invention, by the SnX2, the second main solvent and the second cosolvent mixed processing, can be will be described
SnX2, the second main solvent and the second cosolvent be directly mixed to get mixed system.In order to improve the SnX2Utilization rate, while
The preferable mixed system of dissolved state is obtained, preferably first by SnX2, after the second main solvent mixed dissolution, add described second and be total to
Solvent.
Above-mentioned mixed system is carried out the second heating stirring and prepares Sn presomas by the embodiment of the present invention, it is preferred that described the
The heating-up temperature of two heating stirrings is 100-150 DEG C, and stir speed (S.S.) is 800-1200rpm.The preferred heating-up temperature and stirring
Speed, contributes to forming uniform and stable Sn presomas.
In above-mentioned steps S03, in order to avoid a large amount of volatilizations of cosolvent destroy the stability of reaction system, before the Sn
Drive after body is heated to 100-200 DEG C and add the Cs presomas.Wherein, if reaction temperature is too low, reaction nucleation is slower,
And nuclear volume is fewer, the particle size for obtaining is bigger than normal；If reaction temperature is too high, cosolvent volatilizees rapidly, can destroy reaction
The stability of system.It is furthermore preferred that preparing metal halide perovskite quantum dot CsSnX3The step of in, by the Sn presomas
After being heated to 170-180 DEG C, the Cs presomas are added.
Preferably, metal halide perovskite quantum dot CsSnX is prepared3The step of in, the Sn presomas and the Cs
The mol ratio of presoma is 1:3-3:1.The mol ratio for stating Sn presomas and the Cs presomas is too high or too low, is all unfavorable for obtaining
Obtain the quantum dot product of uniform particle diameter.It is furthermore preferred that the mol ratio of the Sn presomas and the Cs presomas is 1:1.
Further, also include the product to obtaining be passivated successively, clean, dried process, obtain metal halide
Perovskite quantum dot CsSnX3。
Metal halide perovskite quantum dot CsSnX provided in an embodiment of the present invention3Preparation method, it is first common using first
Solvent prepares Cs cation presomas, then Cs cations and Sn presoma heating responses containing the second cosolvent are obtained into metal
Halide perovskite quantum dot CsSnX3。
First, Cs presomas are prepared as the first cosolvent using phosphoric acid pi-allyl diethylester or DMF
When, the phosphoric acid pi-allyl diethylester or DMF participate in Cs1+Coordination, make the free Cs in system1+It is dense
Degree keeps stable, contributes to forming stable organic complex ion, in the step of follow-up synthesis quantum dot, advantageously reduces
The surface energy of nucleation quantum dot, and then be conducive to the formation of monodispersity quantum dot, finally give uniform particle diameter, stable metal
Halide perovskite quantum dot CsSnX3.Meanwhile, the Sn presomas containing the second cosolvent have preferably phase with Cs presomas
Capacitive so that solution is well mixed in course of reaction, further helps in and obtains uniform particle diameter, stable metal halide calcium titanium
Ore deposit quantum dot CsSnX3。
Secondly, the embodiment of the present invention can synthesize different-shape such as list by changing halogen species, reaction temperature
Tiltedly, cube, the inorganic metal hal ide perovskite quantum dot of orthogonal three kinds of crystallographic systems；By changing halogen species, ratio or reaction
Time adjusts CsSnX3Emission wavelength of the perovskite quantum dot in Visible-to-Near InfaRed region.
Again, the method that the present invention is provided, can adopt the Cs sources or Sn sources of different halogenic ingredients, be directly synthesized containing one
The CsSnX of kind or various halogens3(X=Cl, Br, I) perovskite quantum dot.
Additionally, metal halide perovskite quantum dot CsSnX provided in an embodiment of the present invention3Preparation method, method letter
Single easily-controllable, low cost, easily realizes industrialization production.
And, the embodiment of the present invention additionally provides a kind of metal halide perovskite quantum dot CsSnX3, the metal halogen
Compound perovskite quantum dot CsSnX3For quantum dot prepared by said method.
Metal halide perovskite quantum dot CsSnX provided in an embodiment of the present invention3, not only without heavy metal lead, and
Have the advantages that stable performance, size uniformity, good dispersion, crystal formation be controllable, luminous efficiency is high, exist advantageous as environment-friendly materials
LED shows and photovoltaic art is used widely.
Illustrate with reference to specific embodiment.
Embodiment 1
A kind of metal halide perovskite quantum dot CsSnCl3Preparation method, comprise the following steps：
It is prepared by S11.Cs presomas
0.285g cesium chlorides (CsCl), 5mL oleyl amines are added in 100mL three-neck flasks, under an ar atmosphere agitating heating is simultaneously
Dissolving；8mL phosphoric acid pi-allyls diethylester is added into three-neck flask, is stirred and 120 DEG C of formation Cs precursor liquids of constant temperature.
It is prepared by S12.Sn presomas
By 0.361g stannous chloride (SnCl2), 5mL oleyl amines add in 100mL three-neck flasks, agitating heating under an ar atmosphere
And dissolve；18mL phosphoric acid pi-allyls diethylester is added in 100mL three-neck flasks, is stirred and 120 DEG C of constant temperature is formed before Sn
Drive liquid.
S13.CsSnCl3The synthesis of perovskite quantum dot, purifying
Treat that Sn precursor solution temperature rises to 180 DEG C, adjust stir speed (S.S.) to 1800rpm and be rapidly injected Cs forerunner
Liquid.After reacting 2mins at 170 DEG C, rapidly reactant liquor water-bath is cooled into 50 DEG C.Then, reactant liquor is poured into centrifuge tube,
N-hexane and methyl alcohol are added, and be centrifuged under 5000rpm and is precipitated, be scattered in precipitating in toluene again, and repeated washing
Purifying 2 times.Quantum dot toluene dispersion liquid after purification is placed in vacuum drying oven and is fully dried, obtain final CsSnCl3Calcium
Titanium ore quantum dot.
The CsSnCl that the embodiment of the present invention 1 is prepared3Belong to monoclinic system perovskite amount under perovskite quantum dot room temperature
Sub-, emission wavelength is in 420 ± 2nm.
Embodiment 2
A kind of metal halide perovskite quantum dot CsSnCl3Preparation method, comprise the following steps：
It is prepared by S21.Cs presomas
0.285g cesium chlorides (CsCl), 4.5mL tri octyl phosphines are added in 100mL three-neck flasks, is stirred under an ar atmosphere
Heat and dissolve；18ML DMFs are added into three-neck flask, is stirred and 120 DEG C of formation Cs forerunners of constant temperature
Liquid.
It is prepared by S22.Sn presomas
By 0.361g stannous chloride (SnCl2), 4.5mL tri octyl phosphines add 100mL three-neck flasks in, stir under an ar atmosphere
Mix and heat and dissolve；18ML DMFs are added in 100mL three-neck flasks, is stirred and 120 DEG C of shapes of constant temperature
Into Sn precursor liquids.
S23.CsSnCl3The synthesis of perovskite quantum dot, purifying
Treat that Sn precursor solution temperature rises to 180 DEG C, adjust stir speed (S.S.) to 1800rpm and be rapidly injected Cs forerunner
Liquid.After reacting 2mins at 170 DEG C, rapidly reactant liquor water-bath is cooled into 50 DEG C.Then, reactant liquor is poured into centrifuge tube,
Ethyl acetate and n-butanol are added, and be centrifuged under 5000rpm and is precipitated, precipitation is scattered in toluene again, and repeatedly
Cleaning purifying 2 times.Quantum dot toluene dispersion liquid after purification is placed in vacuum drying oven and is fully dried, obtain final
CsSnCl3Perovskite quantum dot.
The CsSnCl that the embodiment of the present invention 2 is prepared3Belong to monoclinic system perovskite amount under perovskite quantum dot room temperature
Sub-, emission wavelength is in 420 ± 5nm.
Embodiment 3
A kind of metal halide perovskite quantum dot CsSnBr3Preparation method, comprise the following steps：
It is prepared by S31.Cs presomas
0.320g cesium bromides (CsBr), 5mL oleyl amines are added in 100mL three-neck flasks, under an ar atmosphere agitating heating is simultaneously
Dissolving.8mL phosphoric acid pi-allyls diethylester is added in 100mL three-neck flasks, is stirred and 120 DEG C of formation Cs forerunners of constant temperature
Liquid.
It is prepared by S32.Sn presomas
By 0.417g stannous bromide (SnBr2), 7mL oleyl amines add in 100mL three-neck flasks, agitating heating under an ar atmosphere
And dissolve.12mL phosphoric acid pi-allyls diethylester is added in 100mL three-neck flasks, is stirred and 120 DEG C of constant temperature is formed before Sn
Drive liquid.
S33.CsSnBr3The synthesis of perovskite quantum dot, purifying
Treat that Sn precursor solution temperature rises to 170 DEG C, adjust stir speed (S.S.) to 1800rpm and be rapidly injected Cs forerunner
Liquid.After reacting 5mins at 170 DEG C, rapidly reactant liquor water-bath is cooled into 50 DEG C.Then, reactant liquor is poured into centrifuge tube,
N-hexane and methyl alcohol are added, and be centrifuged under 5000rpm and is precipitated, be scattered in precipitating in toluene again, and repeated washing
Purifying 2 times.Quantum dot toluene dispersion liquid after purification is placed in vacuum drying oven and is fully dried, obtain final CsSnBr3Calcium
Titanium ore quantum dot.
The CsSnBr that the embodiment of the present invention 3 is prepared3Belong to cubic system perovskite quantum dot, emission wavelength under room temperature
In 702 ± 2nm.
Embodiment 4
A kind of metal halide perovskite quantum dot CsSnClBr2Preparation method, comprise the following steps：
It is prepared by S41.Cs presomas
0.320g cesium chlorides (CsCl), 4.5mL tri octyl phosphines are added in 100mL three-neck flasks, is stirred under an ar atmosphere
Heat and dissolve.18mL DMFs are added in 100mL three-neck flasks, is stirred and 120 DEG C of formation of constant temperature
Cs precursor liquids.
It is prepared by S42.Sn presomas
By 0.417g stannous bromide (SnBr2), 4.5mL tri octyl phosphines add 100mL three-neck flasks in, stir under an ar atmosphere
Mix and heat and dissolve.18mL DMFs are added in 100mL three-neck flasks, is stirred and 120 DEG C of shapes of constant temperature
Into Sn precursor liquids.
S43.CsSnClBr2The synthesis of perovskite quantum dot, purifying
Treat that Sn precursor solution temperature rises to 170 DEG C, adjust stir speed (S.S.) to 1800rpm and be rapidly injected Cs forerunner
Liquid.After reacting 5mins at 170 DEG C, rapidly reactant liquor water-bath is cooled into 50 DEG C.Then, reactant liquor is poured into centrifuge tube,
Ethyl acetate and n-butanol are added, and be centrifuged under 5000rpm and is precipitated, precipitation is scattered in toluene again, and repeatedly
Cleaning purifying 2 times.Quantum dot toluene dispersion liquid after purification is placed in vacuum drying oven and is fully dried, obtain final
CsSnClBr2Perovskite quantum dot.
The CsSnClBr that the embodiment of the present invention 4 is prepared2Belong to cubic system perovskite quantum dot under room temperature, light ripple
Length is in 702 ± 2nm.
Embodiment 5
A kind of metal halide perovskite quantum dot CsSnI3Preparation method, comprise the following steps：
It is prepared by S51.Cs presomas
0.390g cesium iodides (CsI), 5mL oleyl amines are added in 100mL three-neck flasks, under an ar atmosphere agitating heating and molten
Solution.8mL phosphoric acid pi-allyls diethylester is added in 100mL three-neck flasks, is stirred and 120 DEG C of formation Cs precursor liquids of constant temperature.
It is prepared by S52.Sn presomas
By 0.558g stannous iodide (SnI2), 5mL oleyl amines add in 100mL three-neck flasks, agitating heating under an ar atmosphere
And dissolve.18mL phosphoric acid pi-allyls diethylester is added in 100mL three-neck flasks, is stirred and 120 DEG C of constant temperature is formed before Sn
Drive liquid.
S53.CsSnI3The synthesis of perovskite quantum dot, purifying
Treat that Sn precursor solution temperature rises to 170 DEG C, adjust stir speed (S.S.) to 1800rpm and be rapidly injected Cs forerunner
Liquid.After reacting 5mins at 170 DEG C, rapidly reactant liquor water-bath is cooled into 50 DEG C.Then, reactant liquor is poured into centrifuge tube,
N-hexane and methyl alcohol are added, and be centrifuged under 5000rpm and is precipitated, be scattered in precipitating in toluene again, and repeated washing
Purifying 2 times.Quantum dot toluene dispersion liquid after purification is placed in vacuum drying oven and is fully dried, obtain final CsSnI3 calcium titaniums
Ore deposit quantum dot.
The CsSnI that the embodiment of the present invention 5 is prepared3Belong to rhombic system perovskite quantum dot, emission wavelength under room temperature
In 950 ± 2nm.
Embodiment 6
A kind of preparation method of metal halide perovskite quantum dot CsSnClBrI, comprises the following steps：
It is prepared by S61.Cs presomas
0.285g cesium chlorides (CsCl), 5mL oleyl amines are added in 100mL three-neck flasks, under an ar atmosphere agitating heating is simultaneously
Dissolving；8mL phosphoric acid pi-allyls diethylester is added into three-neck flask, is stirred and 120 DEG C of formation Cs precursor liquids of constant temperature.
It is prepared by S62.Sn presomas
By 0.208g stannous bromide (SnBr2), 0.279g stannous iodide (SnI2), 4.5mL tri octyl phosphines add 100mL tri-
In neck flask, agitating heating and dissolve under an ar atmosphere.18mL DMFs are added in 100mL three-neck flasks,
Stir and 120 DEG C of formation Sn precursor liquids of constant temperature.
The synthesis of S63.CsSnClBrI perovskites quantum dot, purifying
Treat that Sn precursor solution temperature rises to 170 DEG C, adjust stir speed (S.S.) to 1800rpm and be rapidly injected Cs forerunner
Liquid.After reacting 5mins at 170 DEG C, rapidly reactant liquor water-bath is cooled into 50 DEG C.Then, reactant liquor is poured into centrifuge tube,
Ethyl acetate and n-butanol are added, and be centrifuged under 5000rpm and is precipitated, precipitation is scattered in toluene again, and repeatedly
Cleaning purifying 2 times.Quantum dot toluene dispersion liquid after purification is placed in vacuum drying oven and is fully dried, obtain final
CsSnClBrI perovskite quantum dots.
Presently preferred embodiments of the present invention is the foregoing is only, not to limit the present invention, all essences in the present invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.
Claims (8)
1. a kind of metal halide perovskite quantum dot CsSnX3Preparation method, comprise the following steps：
CsX, the first main solvent and the first cosolvent are provided, the first heating stirring is carried out after mixing, prepare Cs presomas；
SnX is provided2, the second main solvent and the second cosolvent, the second heating stirring is carried out after mixing, prepare Sn presomas；
After the Sn presomas are heated into 100-200 DEG C, the Cs presomas, stir process, isothermal reaction 10- are added
20min, prepares metal halide perovskite quantum dot CsSnX3；
Wherein, described CsX, SnX2In, X is at least one in Cl, Br, I, and first cosolvent is phosphoric acid pi-allyl diethyl
Ester or DMF, second cosolvent is phosphoric acid pi-allyl diethylester or DMF.
2. metal halide perovskite quantum dot CsSnX as claimed in claim 13Preparation method, it is characterised in that it is described
First cosolvent is phosphoric acid pi-allyl diethylester；Second cosolvent is phosphoric acid pi-allyl diethylester.
3. metal halide perovskite quantum dot CsSnX as claimed in claim 13Preparation method, it is characterised in that it is described
The amount ratio of CsX, the first main solvent and the first cosolvent is 1g:2-20mL:20-200mL；And/or
The SnX2, the second main solvent and the second cosolvent amount ratio be 1g:2-20mL:20-200mL.
4. the metal halide perovskite quantum dot CsSnX as described in claim 1-3 is arbitrary3Preparation method, its feature exists
In the heating-up temperature of first heating stirring is 100-150 DEG C, and stir speed (S.S.) is 800-1200rpm；And/or
The heating-up temperature of second heating stirring is 100-150 DEG C, and stir speed (S.S.) is 800-1200rpm.
5. the metal halide perovskite quantum dot CsSnX as described in claim 1-3 is arbitrary3Preparation method, its feature exists
In first main solvent is the one kind in tri octyl phosphine, tributylphosphine, trioctylphosphine amine, ethylenediamine, oleyl amine；And/or
Second main solvent is the one kind in tri octyl phosphine, tributylphosphine, trioctylphosphine amine, ethylenediamine, oleyl amine.
6. the metal halide perovskite quantum dot CsSnX as described in claim 1-3 is arbitrary3Preparation method, its feature exists
In preparing metal halide perovskite quantum dot CsSnX3The step of in, the Sn presomas and the Cs presomas mole
Than for 1:3-3:1.
7. the preparation method of the metal halide perovskite quantum dot CsSnX3 as described in claim 1-3 is arbitrary, its feature exists
In preparing metal halide perovskite quantum dot CsSnX3The step of in, the Sn presomas are heated into 170-180 DEG C
Afterwards, the Cs presomas are added.
8. a kind of metal halide perovskite quantum dot CsSnX3, it is characterised in that the metal halide perovskite quantum dot
CsSnX3For quantum dot prepared by the arbitrary methods described of claim 1-7.
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| CN107697946A (en) * | 2017-11-03 | 2018-02-16 | 深圳大学 | A kind of preparation method of full-inorganic perovskite quantum dot |
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