CN114836209B - Halide perovskite nanocrystalline, composite material thereof, preparation method and application - Google Patents

Halide perovskite nanocrystalline, composite material thereof, preparation method and application Download PDF

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CN114836209B
CN114836209B CN202110137493.3A CN202110137493A CN114836209B CN 114836209 B CN114836209 B CN 114836209B CN 202110137493 A CN202110137493 A CN 202110137493A CN 114836209 B CN114836209 B CN 114836209B
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halide perovskite
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CN114836209A (en
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郑伟
委娇娇
陈学元
黄萍
宫仲亮
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Fujian Institute of Research on the Structure of Matter of CAS
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Abstract

The invention discloses a halide perovskite nanocrystalline, a composite material thereof, a preparation method and application, and the preparation method does not need to use expensive PbX 2 And the like, while the halide ions are provided by the photosensitive agent halogenated hydrocarbon. The halide perovskite nanocrystalline prepared by the method has good stability and high fluorescence quantum yield (30-80%), and can realize the light emission in the full visible spectrum (400-700 nm). The halide perovskite nanocomposite prepared by the method has good dispersibility and uniform morphology and dimension. Meanwhile, the preparation method can synthesize a target product within 1-60 min, and can control the phase, morphology, size and luminous performance of the halide perovskite nanocrystalline and the nanocomposite thereof by changing the conditions of the type, the proportion, the illumination wavelength, the time and the like of the halogenated alkane. The preparation method has the advantages of simple process, short time consumption, low cost and easy amplification and synthesis, and is suitable for preparing the halide perovskite nano film.

Description

Halide perovskite nanocrystalline, composite material thereof, preparation method and application
Technical Field
The invention belongs to the technical field of nanometer synthesis, and particularly relates to a halide perovskite nanocrystalline, a composite material thereof, a preparation method and application.
Background
Perovskite is a compound which is mixed with perovskite titanate (CaTiO 3 ) Structurally similar materials, having the same formula ABX 3 A represents an organic cation or monovalent Cs + B represents a divalent metal ion, and X represents a halogen ion. Perovskite materials were found in uraer mountain by the german mineralogist gustvo Rose and in 1839 by russiaThe schlemma l.a. Perovski determines the structure and, in order to commemorate this scientist, uses his name to name such mineral materials. The halide perovskite nanocrystalline has excellent optical properties such as large absorption cross section, narrow half-peak width, high fluorescence quantum yield, tunable emission wavelength and the like, and is widely applied to the fields of solar cells, light-emitting diodes, photoelectric detection and the like.
At present, the methods for preparing halide perovskite nanocrystalline mainly comprise a high-temperature hot injection method, a room-temperature supersaturation recrystallization method, an ultrasonic auxiliary synthesis method, a microwave auxiliary synthesis method, a solvothermal method and the like. The halide perovskite nanocrystalline with different morphologies and sizes can be obtained by the method. Compared with the halide perovskite nanocrystalline phase, the halide perovskite nanocomposite combines the advantages of the halide perovskite nanocrystalline phase and other functional materials, so that the halide perovskite nanocomposite can be applied to the fields of nano catalysis, biosensing, nano photonics and the like. The synthesis of monodisperse, uniform morphology halide perovskite nanocomposites presents a significant challenge due to the ionic crystal and efficient halogen ion exchange properties of the halide perovskite materials. Therefore, development of a simple method for preparing halide perovskite nanocrystals and nanocomposite materials thereof with uniform morphology and size and good dispersibility is urgently needed.
Disclosure of Invention
In order to improve the technical problems, the invention provides a preparation method of halide perovskite nanocrystalline, which comprises the following steps:
the halide perovskite nanocrystalline is prepared from raw materials of an A source, a B source and an X source by a light control method.
According to an embodiment of the present invention, the a source is selected from at least one of a compound containing an a group selected from one, two or more of lithium, sodium, potassium, rubidium and cesium, a compound containing an a group selected from a methylamino group and/or a formamidino group, and an elemental a.
According to an embodiment of the present invention, the B source is selected from at least one of a compound containing a B element selected from one, two or more of a lead (Pb) element, a tin (Sn) element, a cadmium (Cd) element, a manganese (Mn) element, a zinc (Zn) element, a nickel (Ni) element, a calcium (Ca) element, a strontium (Sr) element, a barium (Ba) element, a germanium element, a magnesium element, a calcium element, a copper element, a bismuth element, a silver element, a europium element, an antimony element, and an indium element, and a B element.
According to an embodiment of the present invention, the compound containing an element a includes a compound containing an element a but not containing an element B, and a compound containing both an element a and an element B.
According to an embodiment of the present invention, the compound containing the B element includes a compound containing the B element but not containing the a element, and a compound containing both the a element and the B element.
Preferably, the compound containing the element a but not containing the element B may be at least one of carbonate, acetate, oleate, stearate, oxide, hydroxide, nitrate, sulfate, oxalate, borate, vanadate, tungstate, molybdate and chromate containing the element a but not containing the element B. More preferably at least one of acetate and carbonate containing element a but not element B.
Preferably, the compound containing a group is selected from a compound containing a methylamino group and/or a compound containing a formamidino group.
Preferably, the elemental element a is selected from at least one of lithium, sodium, potassium, rubidium, and cesium.
Preferably, the compound containing the B element but not containing the a element may be at least one of acetate, carbonate, oleate, stearate, oxide, hydroxide, acid salt, sulfate, oxalate, borate, vanadate, tungstate, molybdate and chromate containing the B element but not containing the a element. More preferably at least one of acetate and oxalate containing element B but not element a.
Preferably, the elemental B is at least one element selected from the group consisting of lead, tin, cadmium, zinc, germanium, manganese, nickel, magnesium, calcium, copper, bismuth, silver, europium, antimony, and indium.
According to an embodiment of the inventionThe A source and the B source may be compounds containing both an element A and an element B. For example, the compound containing both the A element and the B element is selected from Cs 2 PbO 2 ，Ru 2 PbO 2 ，Cs 2 Sn 2 O 3 ，Ru 2 SnO 2 ，Ru 2 Sn 2 O 3 ，CsCdF 3 Or RuCdF 3 At least one of them.
According to an embodiment of the invention, the X source is a halogenated hydrocarbon containing an element X, which represents a halogen. For example, the X source is selected from one, two or more of halogenated hydrocarbons containing chlorine, bromine or iodine elements. Illustratively, the X source may be selected from one, two or more of methyl chloride, methylene chloride, chloroform, carbon tetrachloride, ethyl chloride, 1, 2-dichloroethane, dibromomethane, bromoisopropyl, iodoisopropyl, and diiodomethane.
According to an embodiment of the invention, the molar ratio of the element A or group A in the source A to the element B in the source B is (0.001-2): 1, preferably (0.5-2): 1; exemplary are 0.01:1, 0.1:1, 0.5:1, 1:1. By regulating the molar ratio of the element A or the group A to the element B, the halide perovskite nanocrystalline with different sizes, shapes and luminous performances can be obtained within the molar ratio range.
Preferably, the element a or the group a in the a source is present in the reaction system in ionic form. Preferably, the element B in the B source is present in the reaction system in ionic form. For example, the a ion may be at least one of lithium ion, sodium ion, potassium ion, rubidium ion, monomethylamino ion, formamidino ion, and cesium ion; for example, the B ion may be at least one of lead ion, tin ion, cadmium ion, zinc ion, germanium ion, manganese ion, nickel ion, magnesium ion, calcium ion, copper ion, bismuth ion, silver ion, europium ion, antimony ion, and indium ion.
According to an embodiment of the present invention, mixing is performed in the order of addition of the A source, the B source, and the X source. For example, under inert atmosphere, the source A and the source B are firstly dissolved in the surfactant, or the source A and the source B are firstly dissolved in the solvent containing the surfactant to obtain mixed solution; the mixed solution was then added to the X source.
According to an embodiment of the present invention, the surfactant is selected from at least one of oleic acid, oleylamine, tri-n-octylphosphine oxide, stearic acid, sodium dodecylbenzenesulfonate, cetyltrimethylammonium bromide, polyacrylic acid, lauric acid, citric acid, ethylenediamine tetraacetic acid and sodium ethylenediamine tetraacetate. Preferably at least one of oleic acid, oleylamine and tri-n-octylphosphine. More preferably, the surfactant is selected from one or two of oleic acid and oleylamine.
Preferably, when the surfactant is selected from two of oleic acid and oleylamine, the molar ratio of oleic acid to oleylamine is 1 (0.1-20), more preferably 1 (0.25-10), still more preferably 1 (0.5-5); exemplary are 1:0.1, 1:0.25, 1:0.5, 1:1, 1:5, 1:8, 1:10, 1:20.
According to an embodiment of the present invention, the solvent is selected from at least one of octadecene, trioctylamine, butyl stearate, tripentylene, tetrapentylene, cyclohexane, n-hexane and toluene. Preferably one or both of octadecene and trioctylamine. More preferably octadecene.
According to an embodiment of the present invention, the molar ratio of the solvent to the surfactant is 1 (0.001-50); preferably 1 (0.1-20). Exemplary are 1:0.1, 1:1, 1:2, 1:5, 1:10, 1:15. The surfactant and the solvent with the molar ratio are more favorable for dissolving the source A and the source B, so that higher perovskite nanocrystalline yield can be obtained on the premise of low solvent consumption.
According to an embodiment of the invention, the ratio of the molar amount of surfactant to the total molar amount of A ions and B ions is 1 (1-100), preferably 1 (5-50); exemplary are 1:1, 1:5, 1:10, 1:20, 1:30, 1:40, 1:60, 1:80, 1:100.
The halide perovskite nanocrystalline with different sizes, shapes and luminous performances can be obtained by regulating the molar ratio of the total amount of the ions A and the ions B to the surfactant; wherein the surfactant can slow down the diffusion of the A ions and the B ions in the reaction system; under other conditions, the larger the ratio of the molar ratio of the surfactant to the total molar amount of a ions and B ions, the slower the nucleation and growth rate of the halide perovskite nanocrystals, the smaller the size of the resulting product, and the blue shift in the emission spectrum.
According to an embodiment of the present invention, the volume ratio of the mixed solution (mixed solution of a source and B source) to the X source (halogenated hydrocarbon) is 1: (1-8000), preferably 1 (2-5000), more preferably 1 (5-1000), and exemplary are 1:1, 1:2, 1:5, 1:10, 1:50, 1:80, 1:100, 1:500, 1:800, 1:1000, 1:5000, 1:8000.
Preferably, halide perovskite nanocrystals of different compositions and luminescent properties can be obtained by varying the type and/or the ratio of haloalkanes; for example, by varying the ratio of Cl, br or I in the X source, the composition of the resulting halide perovskite nanocrystals can be derived from CsPbCl 3 ，CsPbBr 3 To CsPbI 3 Evolving, the corresponding band gap and emission spectrum can be regulated and controlled within the range of 400-750nm, so as to prepare the halide perovskite nanocrystalline products with different performance requirements.
According to an embodiment of the invention, the inert atmosphere is nitrogen and/or argon.
According to an embodiment of the invention, the temperature of the dissolution is 80-250 ℃, preferably 120-200 ℃. Exemplary are 80 ℃, 100 ℃, 120 ℃, 150 ℃, 180 ℃, 200 ℃, 220 ℃, 250 ℃.
According to an embodiment of the invention, the dissolution time is between 5min and 72h, preferably between 10 and 120min. Exemplary are 5min, 10min, 30min, 60min, 90min, 120min, 4h, 6h, 8h, 12h, 24h, 48h, 60h, 72h.
According to an embodiment of the invention, the light control method has an illumination wavelength in the range of 100-1000nm, preferably 250-700nm; exemplary are 100nm, 250nm, 365nm, 500nm, 700nm, 800nm, 900nm, 1000nm. By regulating the illumination wavelength range, the halide perovskite nanocrystalline with different sizes, shapes and luminous performances can be obtained.
According to an embodiment of the present invention, the photoreaction time of the photocontrol is greater than 0 seconds and not more than 12 hours, preferably 1s to 6 hours, and more preferably 2s to 1 hour; exemplary are 1s, 2s, 10s, 30s, 60s, 10min, 30min, 60min, 2h, 3h, 4h, 5h, 6h. By regulating the illumination reaction time, halide perovskite nanocrystals with different sizes, shapes and luminous performances can be obtained.
According to an embodiment of the present invention, the preparation method further includes a process of performing solid-liquid separation on the reaction system to obtain a solid product (precipitate) after the reaction is completed. For example, the solid-liquid separation may employ means known in the art, such as centrifugation.
According to an embodiment of the present invention, the preparation method further includes washing the solid product obtained by the solid-liquid separation to remove the surfactant remaining on the surface of the solid product.
Preferably, the washing solvent is an organic solvent. For example, the washing solvent may be at least one of acetone, acetonitrile, n-butanol, isopropanol, t-butanol, diethyl ether, methyl ethyl ketone, octane, cyclohexane, and toluene. Acetone and/or cyclohexane are preferred. As another example, the washing may be a filtration washing or a centrifugal washing.
According to one embodiment of the invention, the preparation method further comprises drying the washed solid product to obtain perovskite nanocrystalline solid powder. For example, the drying temperature is 30-100deg.C, preferably 50-80deg.C, and exemplified by 30deg.C, 40deg.C, 50deg.C, 60deg.C, 70deg.C, 80deg.C, 90deg.C, 100deg.C.
According to another embodiment of the present invention, the preparation method further comprises dispersing the washed product in a nonpolar organic solvent to obtain a perovskite nanocrystalline solution. For example, the nonpolar organic solvent is selected from one, two or more of n-hexane, cyclohexane and toluene; cyclohexane and/or toluene are preferred.
According to an embodiment of the present invention, the method for preparing halide perovskite nanocrystals includes the steps of:
(1) In inert atmosphere, dissolving a source A and a source B in a surfactant or a solvent containing the surfactant to obtain a mixed solution;
(2) Adding the mixed solution obtained in the step (1) into halogenated hydrocarbon, and reacting under illumination to obtain a precipitate;
(3) Centrifuging and washing the precipitate obtained in the step (2), and dispersing the washed solid product in a nonpolar solvent to obtain a halide perovskite nanocrystalline solution; or drying the washed product to obtain the halide perovskite nanocrystalline solid.
The invention also provides a halide perovskite nanocrystalline prepared by the preparation method, wherein the halide perovskite nanocrystalline takes a chemical formula as ABX 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein:
a represents one, two or more of methylamine cation, formamidine cation, lithium ion, sodium ion, potassium ion, rubidium (Rb) ion and cesium (Cs) ion; preferably Cs ions and/or Rb ions; more preferably Cs ions;
b represents one, two or more of lead (Pb) ion, tin (Sn) ion, cadmium (Cd) ion, manganese (Mn) ion, zinc (Zn) ion, nickel (Ni) ion, calcium (Ca) ion, strontium (Sr) ion, barium (Ba) ion, germanium ion, magnesium ion, calcium ion, copper ion, bismuth ion, silver ion, europium ion, antimony ion and indium ion; preferably one, two or more of Pb ion, sn ion, cd ion, mn ion, ni ion, zn ion, ca ion, sr ion, and Ba ion; more preferably Pb ions;
X represents a halogen ion, for example, one, two or more of F ion, cl ion, br ion and I ion; preferably represents one or two of Cl ion, br ion and I ion; more preferably two; for example, represents Cl ions and Br ions, br ions and I ions.
According to an embodiment of the invention, the halide perovskite nanocrystals are halide perovskite quantum dots or halide perovskite nanowires.
According to an embodiment of the invention, the halide perovskite quantum dots have a particle size of 5-30nm, preferably 6-15nm.
According to an embodiment of the invention, the halide perovskite nanowire has a one-dimensional size of 1 to 500nm; preferably 2-400nm.
In accordance with an embodiment of the present invention,the halide perovskite nanocrystalline may be CsPbX 3 、CH 3 NH 3 PbX 3 、FAPbX 3 、APbX 3 、CsBX 3 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, X represents at least one of Cl, br, I; preferably two, for example, X represents Cl and Br, or Br and I.
Preferably, the halide perovskite nanocrystalline is CsPbX 3 . More preferably CsPb (Cl) x /Br y ) And CsPb (Br) x /I y ) At least one of (a) and (b), wherein: x+y=3, 0.ltoreq.x.ltoreq.3, 0.ltoreq.y.ltoreq.3, and x and y are not both 0. Illustratively, x=0, 1, 1.5, 2, 3; y=0, 1, 1.5, 2, 3.
For example, the halide perovskite nanocrystalline CsPbX 3 Can be CsPbCl 3 、CsPbCl 1 Br 2 、CsPbBr 3 、CsPbBr 2 I 1 、CsPbCl 1.5 Br 1.5 、CsPbCl 2 Br 1 、CsPbBr 1.5 I 1.5 、CsPbBr 1 I 2 。
Preferably, the halide perovskite nanocrystals are CH 3 NH 3 PbX 3 . More preferably CH 3 NH 3 Pb(Cl x /Br y ) And CsPb (Br) x /I y ) At least one of (a) and (b), wherein: x+y=3, 0.ltoreq.x.ltoreq.3, 0.ltoreq.y.ltoreq.3, and x and y are not both 0. Illustratively, x=0, 1, 1.5, 2, 3; y=0, 1, 1.5, 2, 3.
Preferably, the halide perovskite nanocrystalline is FAPbX 3 More preferably FAPb (Cl) x /Br y ) And FAPb (Br) x /I y ) At least one of (a) and (b), wherein: x+y=3, 0.ltoreq.x.ltoreq.3, 0.ltoreq.y.ltoreq.3, and x and y are not both 0. Illustratively, x=0, 1, 1.5, 2, 3; y=0, 1, 1.5, 2, 3.
Preferably, the halide perovskite nanocrystals are APbX 3 More preferably (Cs) x /Ru y )PbX 3 Wherein: x+y=1, 0.ltoreq.x.ltoreq.1, 0.ltoreq.y.ltoreq.1, and x and y are not simultaneously 0. Illustratively, x=0, 0.5, 1; y=0, 0.5, 1.
PreferablyThe ABX is 3 Is CsBX 3 More preferably Cs (Pb) x /Mn y )X 3 Wherein: x+y=1, 0.ltoreq.x.ltoreq.1, 0.ltoreq.y.ltoreq.1, and x and y are not simultaneously 0. Illustratively, x=0, 0.5, 1; y=0, 0.5, 1.
The invention also provides application of the perovskite nanocrystalline in the fields of solar cells, light-emitting diodes, photoelectric detection and the like.
The invention also provides a composite material, which comprises the halide perovskite nanocrystalline.
According to an embodiment of the invention, the composite material comprises a matrix and the halide perovskite nanocrystals. For example, the halide perovskite nanocrystals may be located within the matrix and/or at the surface of the matrix. For example, cations in the halide perovskite nanocrystals may be incorporated into the pores of the matrix by capillary adsorption and/or bound to the matrix surface by chemical bonding.
Preferably, the composite material comprises a matrix and halide perovskite nanocrystals grown in the matrix. The term "growth" as used herein refers to limited domain growth of halide perovskite nanocrystals in a substrate.
Preferably, the matrix is selected from mesoporous silica (mSiO) 2 ) One, two or more of mesoporous titanium dioxide, mesoporous aluminum oxide, microcrystalline glass, zinc sulfide, graphene, zeolite and metal organic framework materials. More preferably, the matrix is selected from one, two or more of mesoporous silica, alumina and metal organic framework materials. Mesoporous silica is further preferred.
According to an embodiment of the present invention, the halide perovskite nanocrystals account for 1% or more and less than 100% by mass of the composite material, preferably from 2 to 90%, more preferably from 5 to 80%; exemplary are 5%, 10%, 20%, 30%, 40%, 50%.
According to an embodiment of the invention, the composite material is a composite nanomaterial. Preferably, the composite has at least one dimension in the range of 1-1000nm, preferably in the range of 2-500 nm.
According to an embodiment of the present invention, the composite nanomaterial may be CsPbX 3 @mSiO 2 、CH 3 NH 3 PbX 3 @mSiO 2 、FAPbX 3 @mSiO 2 、APbX 3 @mSiO 2 、CsBX 3 @mSiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, X represents at least one of Cl, br, I; preferably two, for example, cl, br or Br, I.
Preferably, the composite nanomaterial is CsPbX 3 @mSiO 2 More preferably CsPb (Cl) x /Br y )@mSiO 2 And CsPb (Br) x /I y )@mSiO 2 Wherein x+y=3, 0.ltoreq.x.ltoreq.3, 0.ltoreq.y.ltoreq.3, and x and y are not simultaneously 0. Illustratively, x=0, 1, 1.5, 2, 3; y=0, 1, 1.5, 2, 3.
Preferably, the composite nanomaterial is CH 3 NH 3 PbX 3 @mSiO 2 . More preferably CH 3 NH 3 Pb(Cl x /Br y )@mSiO 2 And CsPb (Br) x /I y )@mSiO 2 At least one of (a) and (b), wherein: x+y=3, 0.ltoreq.x.ltoreq.3, 0.ltoreq.y.ltoreq.3, and x and y are not both 0. Illustratively, x=0, 1, 1.5, 2, 3; y=0, 1, 1.5, 2, 3.
Preferably, the composite nanomaterial is selected from FAPbX 3 @mSiO 2 More preferably FAPb (Cl) x /Br y )@mSiO 2 And FAPb (Br) x /I y )@mSiO 2 At least one of (a) and (b), wherein: x+y=3, 0.ltoreq.x.ltoreq.3, 0.ltoreq.y.ltoreq.3, and x and y are not both 0. Illustratively, x=0, 1, 1.5, 2, 3; y=0, 1, 1.5, 2, 3.
Preferably, the composite nanomaterial is selected from APbX 3 @mSiO 2 More preferably (Cs) x /Ru y )PbX 3 @mSiO 2 Wherein: x+y=1, 0.ltoreq.x.ltoreq.1, 0.ltoreq.y.ltoreq.1, and x and y are not simultaneously 0. Illustratively, x=0, 0.5, 1; y=0, 0.5, 1.
Preferably, the composite nanomaterial is selected from CsBX 3 @mSiO 2 More preferably Cs (Pb) x /Mn y )X 3 @mSiO 2 Wherein: x+y=1, 0.ltoreq.x.ltoreq.1, 0.ltoreq.y.ltoreq.1, and x and y are not simultaneously 0. Illustratively, x=0, 0.5, 1; y=0, 0.5, 1.
The invention also provides a preparation method of the composite material, which comprises the preparation method of the halide perovskite nanocrystalline.
According to an embodiment of the invention, the preparation process is carried out in the presence of a matrix. Preferably, the mixing is performed in the order of addition of the source A, the source B, the matrix and the source X. For example, under an inert atmosphere, firstly dissolving a source A and a source B in a surfactant and/or a solvent containing the surfactant to obtain a mixed solution; and mixing the mixed solution with a matrix, and separating solid matters in the liquid from an X source (halogenated hydrocarbon) to perform light-operated reaction.
Preferably, the step of stirring the mixed solution to promote the adsorption of the a ions and the B ions in the matrix is further included after the mixed solution is mixed with the matrix. For example, the stirring time is 1 to 24 hours, and exemplified are 1 hour, 4 hours, 8 hours, 12 hours, 24 hours, preferably 24 hours.
According to an embodiment of the invention, the mass ratio of the matrix to the halogenated hydrocarbon is 1 (10) 3 -10 7 ) Preferably 1 (10) 4 -10 6 ) Exemplary is 1:10 3 、1:10 4 、1:10 5 、1:10 6 、1:10 7 。
According to the embodiment of the invention, the preparation method further comprises the process of carrying out solid-liquid separation on the reaction system to obtain a solid after the stirring reaction is finished. For example, the solid-liquid separation may employ means known in the art, such as centrifugation.
According to the embodiment of the invention, the preparation method further comprises the step of washing the solid matters obtained by the solid-liquid separation to remove the A ions and the B ions remained on the surface of the matrix. For example, the washing solvent is an organic solvent, and may be at least one of acetone, acetonitrile, n-butanol, isopropanol, t-butanol, diethyl ether, methyl ethyl ketone, octane, cyclohexane, and toluene, for example. Acetone and/or cyclohexane are preferred. As another example, the washing may be a filtration washing or a centrifugal washing.
According to an embodiment of the present invention, the method for preparing the composite material comprises the steps of:
(1) In inert atmosphere, dissolving a source A and a source B in a surfactant or a solvent containing the surfactant to obtain a mixed solution;
(2) Mixing the mixed solution obtained in the step (1) with a matrix, and stirring to enable the A ions and the B ions to be adsorbed on the matrix (including adsorbing on the surface and/or inside the matrix);
(3) Centrifuging and washing the solid obtained in the step (2), dispersing the product in halogenated hydrocarbon, and reacting under illumination to obtain a precipitate, thereby preparing the composite material;
(4) Centrifuging and washing the precipitate obtained in the step (3), and dispersing the product in a nonpolar solvent to obtain the composite material solution; alternatively, the washed product is dried to obtain the composite solid (e.g., solid powder).
The invention also provides application of the composite material in the fields of nano catalysis, biological sensing, nano photonics and the like.
The invention has the beneficial effects that:
(1) The preparation method of the halide perovskite nanocrystalline and the nanocomposite thereof is simple and easy to operate, and does not need to use expensive PbX 2 Raw materials are prepared; while the halide ions are provided by the photosensitive agent halocarbon. The halide perovskite nanocrystalline prepared by the method has the advantages of monodispersity, good stability and high fluorescence quantum yield. The halide perovskite nanocomposite prepared by the method has good dispersibility and uniform morphology and dimension. Meanwhile, the preparation method can synthesize a target product within 1-60 min, and can control the phase, morphology, size and luminous performance of the halide perovskite nanocrystalline and the nanocomposite thereof by changing the conditions of the type, the proportion, the illumination wavelength, the time and the like of the halogenated alkane. The preparation method disclosed by the invention is simple in process, short in time consumption, low in cost, easy to amplify and synthesize and suitable for preparing the halide perovskite nano film.
(2) The halide perovskite nanocrystalline has the advantages of less solvent consumption and lower raw material unit price in the preparation process (such as lead acetate and the like with low price are used for replacing PbX with high price) 2 Raw materials), halogen ions are provided by the photosensitive reagent halohydrocarbon, the requirement on the environment in the preparation process is not high, and a glove box is not needed, so that the whole operation process is simple, and the cost of raw materials and instruments is greatly reduced.
(3) The halide perovskite nanocrystalline has good stability, high fluorescence quantum yield (30% -80%), can realize the luminescence in the full visible spectrum (400-700 nm), and has the advantages of simple process, short time consumption, low cost and easy amplification synthesis.
(4) The halide perovskite nanocomposite disclosed by the invention has the advantages of good dispersibility, uniform size and simple preparation method and process.
(5) The light-emitting wavelength of the halide perovskite nanocrystalline in the halide perovskite nanocomposite of the present invention ranges from 400 to 1500nm, preferably from 450 to 700nm.
Drawings
FIG. 1 is CsPbCl in examples 1-5 3 、CsPbCl 1 Br 2 、CsPbBr 3 ，CsPbBr 2 I 1 ，CsPbI 3 X-ray powder diffraction pattern of perovskite nanocrystals.
FIGS. 2A 1-a4, b1-b4, c1-c4 correspond to a) CsPbCl in examples 1, 3, 5, respectively 3 ，b)CsPbBr 3 ，c)CsPbI 3 And (3) representing results of perovskite nanocrystalline, wherein a1, b1 and c1 are high-resolution transmission electron microscope images, a2, b2 and c2 are selected-area electron diffraction images, a3, b3 and c3 are particle size statistical distribution diagrams, and a4, b4 and c4 are EDS (energy dispersion) energy spectrograms.
FIG. 3 shows CsPbCl in examples 1, 3 and 5 3 ，CsPbBr 3 ，CsPbI 3 A luminescence photograph (a) of a cyclohexane solution of perovskite nanocrystals (the concentration of the perovskite nanocrystals was 1 mg/mL) under sunlight and a luminescence photograph (b) under 365nm ultraviolet lamp irradiation.
FIG. 4 is CsPbCl in examples 1-5 3 ，CsPbCl 1 Br 2 ，CsPbBr 3 ，CsPbBr 2 I 1 And CsPbI 3 An absorption spectrum and a fluorescence emission spectrum (excitation wavelength: 365 nm) of the perovskite nanocrystal, wherein a dotted line represents an absorption spectrum curve and a solid line represents an emission spectrum curve.
FIG. 5 is CsPbCl in examples 1-5 3 ，CsPbCl 1 Br 2 ，CsPbBr 3 ，CsPbBr 2 I 1 And CsPbI 3 Fluorescence decay curve of perovskite nanocrystals.
FIG. 6 is CsPbBr in example 7 3 Transmission electron microscopy pictures of perovskite nanowires.
FIG. 7 is CsPbCl in example 6 3 :Mn 2+ Characterization results of perovskite nanocrystals: a) a transmission electron microscope picture, b) a high-resolution transmission electron microscope picture, c) a selected area electron diffraction pattern, d) an X-ray powder diffraction pattern, e) a fluorescence emission spectrum, and the excitation wavelength is 365nm.
FIG. 8 is CsPbBr in example 8 3 @mSiO 2 Characterization results of perovskite nanocomposite: a) Transmission electron microscope pictures, b) high resolution transmission electron microscope pictures, c-h) EDX element distribution map, i) fluorescence emission spectrum, j) CsPbBr 3 @mSiO 2 Fluorescence decay curve of perovskite nanocomposite.
FIG. 9 is CsPbBr obtained in example 8 3 @mSiO 2 X-ray powder diffraction pattern of perovskite nanocomposite.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Instrument and apparatus:
the product of the embodiment of the invention is characterized by powder diffraction, the model of the instrument is MiniFlex2, the manufacturer is Rigaku, and the radiation wavelength of a copper target is lambda= 0.154187nm.
The product of the embodiment of the invention is provided with a JEM-2010 type instrument used for carrying out X-ray energy spectrum analysis, and a JEOL manufacturer.
The product of the embodiment of the invention uses the TECNAI G as the model of the instrument for transmission electron microscope detection 2 F20, manufacturer is FEI.
The product of the embodiment of the invention is characterized by ultraviolet-visible absorption spectrum, wherein the model of the instrument is Lambda365, and the manufacturer is Perkin-Elmer.
The product of the embodiment of the invention uses the FLS980 as the model of the instrument for fluorescence emission spectrum and fluorescence lifetime characterization, the Edinburgh as the manufacturer, and the xenon lamp and the 390nm LD pulse laser as the excitation light source.
Example 1 CsPbCl 3 Preparation of perovskite nanocrystals
(1) 1.6mmol of lead acetate and 1.6mmol of cesium acetate are weighed, then 4mL of oleic acid, 4mL of oleylamine and 12mL of octadecene are added, nitrogen is introduced for protection, the temperature is raised to 120 ℃ and the temperature is kept for 10min, a transparent solution is formed, and then the transparent solution is cooled to room temperature;
(2) Adding 60 mu L of the mixed solution obtained in the step (1) into 5mL of carbon tetrachloride, and irradiating for 60min by utilizing a 365nm LED lamp;
(3) Centrifuging the precipitate obtained in step (2), washing with 5mL of cyclohexane for 1 time, and dispersing the washed precipitate in 3mL of cyclohexane to obtain CsPbCl 3 Perovskite nanocrystalline solution.
CsPbCl prepared in this example 3 The X-ray powder diffraction pattern (figure 1) of the perovskite nanocrystalline shows that the nanocrystalline has good crystallinity, and the diffraction peak position and the relative intensity of the nanocrystalline and the cubic phase CsPbCl 3 The PDF standard card (JCPDS No. 75-0411) is consistent, belonging to the cubic system.
CsPbCl prepared in this example 3 The transmission electron microscope and the particle size distribution diagram of the perovskite nanocrystalline are shown as a1 and a3 in fig. 2, respectively, and the results in the figures show that: the nano-crystal is crystallized well, and the grain diameter is about 9.2nm; the selected area electron diffraction picture (a 2 in figure 2) further shows that the nanocrystal has good crystallization; the EDS spectrum (a 4 in fig. 2) shows that Cs, pb, and Cl elements are present in the perovskite nanocrystals obtained in this example.
CsPbCl obtained in this example 3 A photograph of a cyclohexane solution of perovskite nanocrystals (concentration of perovskite nanocrystals 1 mg/mL) under sunlight is shown as 1) in FIG. 3, where the results indicate that the solution is milky white and exhibits intense violet emission under 365nm UV light (1) in FIG. 3).
CsPbCl obtained in this example 3 The absorption spectrum of perovskite nanocrystals (fig. 4) shows that the nanocrystals have strong absorption in the ultraviolet region, with absorption edges of about 410nm; and the fluorescence emission spectrum (figure 4) under 365nm ultraviolet light excitation shows that the nanocrystal has strong luminescence at 410nm and the half-peak width is about 12nm.
CsPbCl obtained in this example 3 The fluorescence decay curve of the perovskite nanocrystals (fig. 5) shows that the effective fluorescence lifetime of the nanocrystals is about 2.6ns; the fluorescence quantum yield test result shows that the absolute fluorescence quantum yield of the nanocrystalline is about 57.6%.
Example 2 CsPbCl 1 Br 2 Preparation of perovskite nanocrystals
(1) 1.6mmol of lead acetate and 1.6mmol of cesium acetate are weighed, then 4mL of oleic acid, 4mL of oleylamine and 12mL of octadecene are added, nitrogen is introduced for protection, the temperature is raised to 120 ℃ and the temperature is kept for 10min, a transparent solution is formed, and then the transparent solution is cooled to room temperature;
(2) Adding 60 mu L of the mixed solution obtained in the step (1) into a mixed solution containing 3mL of dibromomethane and 2mL of carbon tetrachloride, and irradiating for 60min by utilizing a 365nm LED lamp;
(3) Centrifuging the precipitate obtained in step (2), washing with 5mL of cyclohexane for 1 time, and dispersing the washed precipitate in 3mL of cyclohexane to obtain CsPbCl 1 Br 2 Perovskite nanocrystalline solution.
CsPbCl prepared in this example 1 Br 2 The X-ray powder diffraction pattern (figure 1) of the perovskite nanocrystalline shows that the nanocrystalline has good crystallinity, and the diffraction peak position and the relative intensity of the nanocrystalline and the cubic phase CsPbCl 3 And CsPbBr 3 The PDF standard cards (JCPDS No.75-0411 and 75-0412) are basically consistent and are between the two, belonging to the cubic system.
C prepared in this examplesPbCl 1 Br 2 The absorption spectrum of perovskite nanocrystals (fig. 4) shows that the nanocrystals have strong absorption in the uv and violet regions, with absorption edges of about 477nm; and the fluorescence emission spectrum (figure 4) under 365nm ultraviolet light excitation shows that the nanocrystal has strong luminescence at 485nm and the half-peak width is about 17nm.
CsPbCl prepared in this example 1 Br 2 The fluorescence decay curve of the perovskite nanocrystals (fig. 5) shows that the effective fluorescence lifetime of the nanocrystals is about 12.2ns; the fluorescence quantum yield test result shows that the absolute fluorescence quantum yield of the nanocrystalline is about 38%.
Example 3 CsPbBr 3 Preparation of perovskite nanocrystals
(1) 1.6mmol of lead acetate and 1.6mmol of cesium acetate are weighed, then 4mL of oleic acid, 4mL of oleylamine and 12mL of octadecene are added, nitrogen is introduced for protection, the temperature is raised to 120 ℃ and the temperature is kept for 10min, a transparent solution is formed, and then the transparent solution is cooled to room temperature;
(2) Adding 60 mu L of the mixed solution obtained in the step (1) into 5mL of dibromomethane, and irradiating for 18min by using a 365nm LED lamp;
(3) Centrifuging the precipitate obtained in the step (2), washing with 5mL of cyclohexane for 1 time, and dispersing the washed precipitate in 3mL of cyclohexane to obtain CsPbBr 3 Perovskite nanocrystalline solution.
CsPbBr prepared in this example 3 The X-ray powder diffraction pattern (figure 1) of the perovskite nanocrystalline shows that the nanocrystalline has good crystallinity, and the diffraction peak position and the relative intensity of the nanocrystalline and the cubic phase CsPbBr 3 The PDF standard card (JCPDS No. 75-0412) is consistent, belonging to the cubic system.
CsPbBr prepared in this example 3 The transmission electron microscope and particle size distribution diagram of the perovskite nanocrystals (shown as b1 and b3 in fig. 2, respectively) show that: csPbBr prepared in this example 3 The perovskite nanocrystalline is well crystallized, and the grain diameter is about 14.8nm; the selected area electron diffraction picture (b 2 in fig. 2) further shows that the nanocrystal has good crystallization; EDS energy spectrum (b 4 in FIG. 2) shows that the nanocrystalline contains Cs, pb and Br elements.
CsPbBr prepared in this example 3 Perovskite nanocrystalsA photograph of the cyclohexane solution (perovskite nanocrystals concentration of 1 mg/mL) under sunlight is shown as 2) in fig. 3 a, which shows that the solution is yellow and exhibits strong green emission under 365nm uv lamp (2) in fig. 3 b).
CsPbBr prepared in this example 3 The absorption spectrum of perovskite nanocrystals (fig. 4) shows that the nanocrystals have strong absorption in the ultraviolet region, with absorption edges of about 503nm; and the fluorescence emission spectrum (figure 4) under 365nm ultraviolet light excitation shows that the nanocrystalline has strong luminescence at 512nm and the half-peak width is about 20nm.
CsPbBr prepared in this example 3 The fluorescence decay curve of the perovskite nanocrystals (fig. 5) shows that the effective fluorescence lifetime of the nanocrystals is about 29.1ns; the fluorescence quantum yield test result shows that the absolute fluorescence quantum yield of the nanocrystalline is about 80.0%.
Example 4 CsPbBr 2 I 1 Preparation of perovskite nanocrystals
(1) 1.6mmol of lead acetate and 1.6mmol of cesium acetate are weighed, then 4mL of oleic acid, 4mL of oleylamine and 12mL of octadecene are added, nitrogen is introduced for protection, the temperature is raised to 120 ℃ and the temperature is kept for 10min, a transparent solution is formed, and then the transparent solution is cooled to room temperature;
(2) Adding 60 mu L of the mixed solution obtained in the step (1) into a mixed solution containing 3mL of dibromomethane and 2mL of iodized isopropyl, and irradiating for 18min by using a 365nm LED lamp;
(3) Centrifuging the precipitate obtained in the step (2), washing with 5mL of cyclohexane for 1 time, and dispersing the washed precipitate in 3mL of cyclohexane to obtain CsPbBr 2 I 1 Perovskite nanocrystalline solution.
CsPbBr prepared in this example 2 I 1 The X-ray powder diffraction pattern (figure 1) of the perovskite nanocrystalline shows that the nanocrystalline has good crystallinity, and the diffraction peak position and the relative intensity of the nanocrystalline and the cubic phase CsPbBr 3 The PDF standard card (JCPDS No. 75-0412) is basically consistent, belonging to the cubic system.
CsPbBr prepared in this example 2 I 1 The absorption spectrum of perovskite nanocrystals (FIG. 4) shows that the nanocrystals have strong absorption in the ultraviolet to yellow region, with about the absorption edge569nm; and the fluorescence emission spectrum (figure 4) under 365nm ultraviolet light excitation shows that the nanocrystalline has strong luminescence at 580nm, and the half-peak width is about 29nm.
CsPbCl prepared in this example 1 Br 2 The fluorescence decay curve of the perovskite nanocrystals (fig. 5) shows that the effective fluorescence lifetime of the nanocrystals is about 61.9ns; the fluorescence quantum yield test result shows that the absolute fluorescence quantum yield of the nanocrystalline is about 33.2%.
Example 5 CsPbI 3 Preparation of perovskite nanocrystals
(1) 1.6mmol of lead acetate and 1.6mmol of cesium acetate are weighed, then 4mL of oleic acid, 4mL of oleylamine and 12mL of octadecene are added, nitrogen is introduced for protection, the temperature is raised to 120 ℃ and the temperature is kept for 10min, a transparent solution is formed, and then the transparent solution is cooled to room temperature;
(2) Adding 60 mu L of the mixed solution obtained in the step (1) into 5mL of iodinated isopropyl, and irradiating for 18min by using a 365nm LED lamp;
(3) Centrifuging the precipitate obtained in step (2), washing with 5mL of cyclohexane for 1 time, and dispersing the washed precipitate in 3mL of cyclohexane to obtain CsPbI 3 Perovskite nanocrystalline solution.
CsPbI prepared in this example 3 The X-ray powder diffraction pattern (figure 1) of the perovskite nanocrystalline shows that the nanocrystalline has good crystallinity, and the diffraction peak position and the relative intensity of the nanocrystalline are between that of a cubic phase CsPbBr 3 (JCPDS No. 75-0412) and quadrature phase CsPbI 3 (JCPLDS No. 74-1970) belongs to the cubic crystal system.
CsPbI prepared in this example 3 The transmission electron microscope and the particle size distribution diagram of the perovskite nanocrystalline are shown as c1 and c 3) in fig. 2, respectively, and the results in the graph show that: the nanocrystalline has good dispersibility and uniform morphology, and the grain diameter is about 11.6nm; the electron diffraction picture (c 2 in figure 2) of the selected area shows that the nanocrystal has good crystallization; EDS spectrum (FIG. 2c 4) shows that CsPbI prepared in this example 3 The perovskite nanocrystalline contains Cs, pb and I elements.
CsPbI prepared in this example 3 A photograph of a cyclohexane solution of perovskite nanocrystals (concentration of perovskite nanocrystals 1 mg/mL) under sunlight is shown as 3) in FIG. 3, aThe results indicated that the solution was brown and exhibited Jiang Shengong light emission under a 365nm uv lamp (3 in fig. 3 b).
CsPbI prepared in this example 3 The absorption spectrum of perovskite nanocrystals (fig. 4) shows that the nanocrystals have strong absorption in the uv and entire visible region, with absorption edges of about 680nm; and the fluorescence emission spectrum (figure 4) under 365nm ultraviolet light excitation shows that the nanocrystal has strong luminescence at 696nm and half-peak width of about 29nm.
CsPbI prepared in this example 3 The fluorescence decay curve of the perovskite nanocrystals (fig. 5) shows that the effective fluorescence lifetime of the nanocrystals is about 86.0ns; the fluorescence quantum yield test result shows that the absolute fluorescence quantum yield of the nanocrystalline is about 36.5%.
Referring to the preparation method, the following nano-crystals are prepared by changing the types and the molar ratio of the halogenated alkane: csPbCl 1.5 Br 1.5 、CsPbCl 2 Br 1 、CsPbBr 1.5 I 1.5 、CsPbBr 1 I 2 。
EXAMPLE 6 CsPbCl 3 :Mn 2+ Preparation of perovskite nanocrystals
(1) 1.6mmol of lead acetate, 1.6mmol of cesium acetate and 1.6mmol of manganese acetate are weighed, then 4mL of oleic acid, 4mL of oleylamine and 12mL of octadecene are added, nitrogen is introduced for protection, the temperature is raised to 120 ℃ and kept for 10min, a transparent solution is formed, and then the solution is cooled to room temperature;
(2) Adding 60 mu L of the mixed solution obtained in the step (1) into 5mL of carbon tetrachloride, and irradiating for 60min by utilizing a 365nm LED lamp;
(3) Centrifuging the precipitate obtained in step (2), washing with 5mL of cyclohexane for 1 time, and dispersing the washed precipitate in 3mL of cyclohexane to obtain CsPbCl 3 :Mn 2+ Perovskite nanocrystalline solution.
CsPbCl prepared in this example 3 :Mn 2+ The transmission electron microscope image (a in fig. 7) of the perovskite nanocrystalline shows that the nanocrystalline has good dispersibility, uniform morphology and a particle size of about 8.0nm; the high resolution transmission electron microscope and the selected electron diffraction pattern (b in fig. 7 and c in fig. 7) further indicate that the nanocrystals have good crystallization.
CsPbCl prepared in this example 3 :Mn 2+ The X-ray powder diffraction pattern (d in FIG. 7) of the perovskite nanocrystals shows that the nanocrystals have good crystallinity with diffraction peak positions and relative intensities and cubic phase CsPbCl 3 (JCPDS No. 75-0411) is basically consistent and belongs to a cubic crystal system; fluorescence emission spectrum at 365nm excitation (e in FIG. 7) shows that the nanocrystals have CsPbCl except at 403nm 3 The emission of nanocrystals, mn was also observed at 612nm 2+ Characteristic emission of (C), thereby indicating Mn 2+ In CsPbCl 3 Efficient doping and sensitized luminescence in nanocrystals.
Example 7 CsPbBr 3 Preparation of perovskite nanowires
(1) 1.6mmol of lead acetate and 1.6mmol of cesium acetate are weighed, then 4mL of oleic acid, 4mL of oleylamine and 12mL of octadecene are added, nitrogen is introduced for protection, the temperature is raised to 120 ℃ and the temperature is kept for 10min, a transparent solution is formed, and then the transparent solution is cooled to room temperature;
(2) Adding 60 mu L of the mixed solution obtained in the step (1) into 5mL of dibromomethane, and irradiating for 3min by using a 365nm LED lamp;
(3) Centrifuging the precipitate obtained in step (2), washing with 5mL of cyclohexane for 1 time, and dispersing the washed precipitate in 5mL of cyclohexane to obtain CsPbBr 3 Perovskite nanowire solutions.
CsPbBr prepared in this example 3 The transmission electron microscope image (figure 6) of the perovskite nanocrystalline shows that the nanowire has good dispersibility and uniform morphology, and the size of the nanowire is about 3 multiplied by 400 nm.
Example 8 CsPbBr 3 @mSiO 2 Preparation of perovskite nanocomposite
(1) 1.6mmol of lead acetate and 1.6mmol of cesium acetate are weighed, then 4mL of oleic acid, 4mL of oleylamine and 12mL of octadecene are added, nitrogen is introduced for protection, the temperature is raised to 120 ℃ and the temperature is kept for 10min, a transparent solution is formed, and then the transparent solution is cooled to room temperature;
(2) Adding 1mL of the mixed solution obtained in the step (1) into 1mL of cyclohexane containing 5mg of mesoporous silica, and stirring for 24h at normal temperature;
(3) Centrifugally separating the precipitate obtained in the step (2), washing for 1 time by using 5mL of cyclohexane, dispersing the precipitate in 5mL of dibromomethane, and irradiating a 365nm LED lamp for 18min;
(4) Centrifuging the precipitate obtained in step (3), washing with 5mL of cyclohexane for 1 time, and dispersing the precipitate in 5mL of cyclohexane to obtain CsPbBr 3 @mSiO 2 Perovskite nanocomposite solution.
CsPbBr prepared in this example 3 @mSiO 2 The transmission electron microscope image (a in fig. 8) of the composite nanocrystal shows that: csPbBr prepared in this example 3 @mSiO 2 The perovskite composite nanocrystalline has good dispersibility, uniform morphology and size of about 300nm; high resolution transmission electron microscopy (b in FIG. 8) further demonstrates CsPbBr in mesoporous silica grown in confinement regions 3 The perovskite nanocrystalline is well crystallized; the X-ray powder diffraction pattern (figure 9) shows that the composite nanocrystalline material has good crystallinity, and the diffraction peak position and the relative intensity and the cubic phase CsPbBr of the composite nanocrystalline material 3 (JCPLDS No. 75-0412) is basically consistent and belongs to a cubic crystal system; EDX element distribution (c-h in FIG. 8) shows CsPbBr prepared in this example 3 @mSiO 2 Si, O, cs, pb and Br elements are uniformly distributed in the perovskite nanocomposite; fluorescence emission spectra under 365nm ultraviolet excitation (i in FIG. 8) indicate CsPbBr in mesoporous silica grown in confinement 3 The perovskite nanocrystalline has strong luminescence at 483 nm; the fluorescence decay curve (j in FIG. 8) shows CsPbBr prepared in this example 3 @mSiO 2 The effective fluorescence lifetime of the composite nanocrystals was about 3.7ns; the fluorescence quantum yield test shows that the absolute fluorescence quantum yield of the nanocrystalline is about 11.4%.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (64)

1. A method for preparing halide perovskite nanocrystalline, which is characterized by comprising the following steps:
(1) In inert atmosphere, dissolving a source A and a source B in a surfactant or a solvent containing the surfactant to obtain a mixed solution;
(2) Adding the mixed solution obtained in the step (1) into halohydrocarbon, reacting under illumination, and preparing a precipitate by a light-operated method;
(3) Centrifuging and washing the precipitate obtained in the step (2), and dispersing the washed solid product in a nonpolar solvent to obtain a halide perovskite nanocrystalline solution; or, drying the washed product to obtain halide perovskite nanocrystalline solid;
the source A is compound cesium acetate containing cesium; the source B is lead acetate containing lead element and/or manganese acetate containing manganese element; the halohydrocarbon is one or more of carbon tetrachloride, dibromomethane and iodinated isopropyl;
the surfactant is selected from two of oleic acid and oleylamine;
the solvent is octadecene;
the halide perovskite nanocrystalline has a chemical formula of Cs (Pb x /Mn y )X 3 Wherein: x+y=1, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1;
x represents at least one of Cl ion, br ion and I ion.
2. The method according to claim 1, wherein the molar ratio of cesium in the source A to lead in the source B is (0.001-2): 1.
3. The method according to claim 2, wherein the molar ratio of cesium in the source A to lead in the source B is (0.5-2): 1.
4. The process according to claim 1, wherein the molar ratio of oleic acid to oleylamine is 1 (0.1-20).
5. The process according to claim 4, wherein the molar ratio of oleic acid to oleylamine is 1 (0.25-10).
6. The process according to claim 5, wherein the molar ratio of oleic acid to oleylamine is 1 (0.5-5).
7. The process according to claim 1, wherein the molar ratio of the solvent to the surfactant is 1 (0.001-50).
8. The process according to claim 7, wherein the molar ratio of the solvent to the surfactant is 1 (0.1-20).
9. The method of claim 1, wherein the ratio of the molar amount of the surfactant to the total molar amount of cesium ions and lead ions is 1 (1-100).
10. The method of claim 9, wherein the ratio of the molar amount of the surfactant to the total molar amount of cesium ions and lead ions is 1 (5-50).
11. The method of claim 1 wherein the volume ratio of the mixed solution of source a and source B to the halogenated hydrocarbon is 1: (1-8000).
12. The process according to claim 11, wherein the volume ratio of the mixed solution of source A and source B to the halogenated hydrocarbon is 1 (2-5000).
13. The process according to claim 12, wherein the volume ratio of the mixed solution of source A and source B to the halogenated hydrocarbon is 1 (5-1000).
14. The method of claim 1, wherein the inert atmosphere is nitrogen and/or argon.
15. The method of claim 1, wherein the dissolution temperature is 80-250 ℃.
16. The method of claim 15, wherein the dissolution temperature is 120-200 ℃.
17. The method of claim 1, wherein the dissolution time is from 5 minutes to 72 hours.
18. The method of claim 17, wherein the dissolution time is 10 to 120 minutes.
19. The method of claim 1, wherein the light control has a wavelength of light in the range of 100 nm to 1000nm.
20. The method of claim 19, wherein the light control has a wavelength of light in the range of 250-700nm.
21. The method of claim 1, wherein the light control has a light reaction time of greater than 0 seconds and no more than 12 hours.
22. The method of claim 21, wherein the light control has a light reaction time of 1s to 6 hours.
23. The method of claim 22, wherein the light control has a light reaction time of 2s to 1h.
24. The method of claim 1, wherein the washing solvent is an organic solvent.
25. The method of claim 24, wherein the washing solvent is at least one of acetone, acetonitrile, n-butanol, isopropanol, t-butanol, diethyl ether, methyl ethyl ketone, octane, cyclohexane, and toluene.
26. The method of claim 25, wherein the washing solvent is acetone and/or cyclohexane.
27. The method of claim 1, wherein the washing is performed by filtration or centrifugation.
28. The method of claim 1, wherein the drying temperature is 30-100 ℃.
29. The method of claim 28, wherein the drying temperature is 50-80 ℃.
30. The method of claim 1, wherein the nonpolar solvent is selected from one, two or more of n-hexane, cyclohexane and toluene.
31. The method of claim 30, wherein the nonpolar solvent is cyclohexane and/or toluene.
32. The method of claim 1, wherein X represents two of Cl ion, br ion, and I ion.
33. The method of claim 32, wherein X represents Cl and Br ions or Br and I ions.
34. The method of preparation of claim 1, wherein the halide perovskite nanocrystals are halide perovskite quantum dots or halide perovskite nanowires.
35. The method of claim 34, wherein the halide perovskite quantum dots have a particle size of 5-30nm.
36. The method of claim 35, wherein the halide perovskite quantum dots have a particle size of 6 to 15nm.
37. The method of preparing of claim 34, wherein the halide perovskite nanowires have a one-dimensional size of 1-500nm.
38. The method of preparing of claim 37, wherein the halide perovskite nanowires have a one-dimensional size of 2-400nm.
39. The method of preparing of claim 1, wherein the halide perovskite nanocrystalline CsPbX 3 Is CsPbCl 3 、CsPbCl 1 Br 2 、CsPbBr 3 、CsPbBr 2 I 1 、CsPbCl 1.5 Br 1.5 、CsPbCl 2 Br 1 、CsPbBr 1.5 I 1.5 、CsPbBr 1 I 2 One of them.
40. The method of claim 1, wherein x = 0, 0.5, 1; y=0, 0.5, 1.
41. The preparation method according to claim 1, wherein the prepared halide perovskite nanocrystalline is used in the field of solar cells, light emitting diodes or photoelectric detection.
42. A method of preparing a composite material, the composite material comprising a matrix and halide perovskite nanocrystals;
the preparation method comprises the following steps:
(1) In inert atmosphere, dissolving a source A and a source B in a surfactant or a solvent containing the surfactant to obtain a mixed solution;
(2) Mixing the mixed solution obtained in the step (1) with a matrix, and stirring to enable cesium ions and lead ions to be adsorbed on the matrix;
(3) Centrifuging and washing the solid obtained in the step (2), dispersing the product in halogenated hydrocarbon, and reacting under illumination to obtain a precipitate, thus obtaining the composite nanocrystalline material;
(4) Centrifuging and washing the precipitate obtained in the step (3), and dispersing the product in a nonpolar solvent to obtain the composite material solution; or drying the washed product to obtain the composite material solid; the source A is compound cesium acetate containing cesium; the source B is lead acetate containing lead element and/or manganese acetate containing manganese element; the halohydrocarbon is one or more of carbon tetrachloride, dibromomethane and iodinated isopropyl;
The surfactant is selected from two of oleic acid and oleylamine;
the solvent is octadecene;
the halide perovskite nanocrystalline has a chemical formula of Cs (Pb x /Mn y )X 3 Wherein: x+y=1, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1;
x represents at least one of Cl ion, br ion and I ion.
43. The method of claim 42, wherein the halide perovskite nanocrystals are located within the matrix and/or on the surface of the matrix.
44. The method of claim 43, wherein the composite material comprises a matrix and halide perovskite nanocrystals grown within the matrix.
45. The method of claim 42, wherein the matrix is selected from the group consisting of mesoporous silica mSiO 2 One, two or more of mesoporous titanium dioxide, mesoporous aluminum oxide, microcrystalline glass, zinc sulfide, graphene, zeolite and metal organic framework materials.
46. The method of claim 45, wherein the matrix is selected from one, two or more of mesoporous silica, aluminum oxide, and a metal organic framework material.
47. The method of claim 46, wherein the matrix is mesoporous silica.
48. The method of claim 42, wherein the halide perovskite nanocrystals comprise 1% or more and less than 100% by mass of the composite material.
49. The method of claim 42, wherein the composite material is a composite nanomaterial.
50. The method of claim 49, wherein the composite material has at least one dimension in the range of 1-1000 nm.
51. The method of claim 50, wherein the composite material has at least one dimension in the range of 2-500 nm.
52. The method of claim 45, wherein the composite nanomaterial is Cs (Pb x /Mn y )X 3 @mSiO 2 ；x+y＝1，0≤x≤1，0≤y≤1；
X represents at least one of Cl ion, br ion and I ion.
53. The method of claim 52, wherein X represents two of Cl ion, br ion and I ion.
54. The method of claim 53, wherein X represents Cl ion and Br ion, or both Br ion and I ion.
55The method of claim 52, wherein the composite nanomaterial is CsPbX 3 @mSiO 2 。
56. The method of claim 55, wherein the composite nanomaterial is CsPb (Cl x’ /Br y’ )@mSiO 2 Or CsPb (Br) x’ /I y’ )@mSiO 2 Wherein x '+y' =3, 0.ltoreq.x '. Ltoreq.3, 0.ltoreq.y'. Ltoreq.3.
57. The method of claim 56, wherein x' =0, 1, 1.5, 2, 3; y' =0, 1, 1.5, 2, 3.
58. The method of claim 52, wherein x = 0, 0.5, 1; y=0, 0.5, 1.
59. The method of claim 42, wherein the stirring is for a period of 1 to 24 hours.
60. The method of claim 42, wherein the washing solvent is an organic solvent.
61. The method of claim 60, wherein the washing solvent is at least one of acetone, acetonitrile, n-butanol, isopropanol, t-butanol, diethyl ether, methyl ethyl ketone, octane, cyclohexane, and toluene.
62. The process of claim 61 wherein the washing solvent is acetone and/or cyclohexane.
63. The method of claim 42, wherein the washing is performed by filtration or centrifugation.
64. The method of claim 42, wherein the composite material is used in the fields of nano catalysis, biosensing or nanophotonics.
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