CN114517088A - Halide perovskite nano material and preparation method thereof - Google Patents
Halide perovskite nano material and preparation method thereof Download PDFInfo
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- CN114517088A CN114517088A CN202111641210.5A CN202111641210A CN114517088A CN 114517088 A CN114517088 A CN 114517088A CN 202111641210 A CN202111641210 A CN 202111641210A CN 114517088 A CN114517088 A CN 114517088A
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 45
- 150000004820 halides Chemical class 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 20
- 238000002844 melting Methods 0.000 claims abstract description 18
- 230000008018 melting Effects 0.000 claims abstract description 18
- -1 cesium halide Chemical class 0.000 claims abstract description 14
- 239000002159 nanocrystal Substances 0.000 claims abstract description 14
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 13
- 239000013335 mesoporous material Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000013110 organic ligand Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 238000002955 isolation Methods 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 32
- 238000001816 cooling Methods 0.000 claims description 23
- 239000000377 silicon dioxide Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 239000012298 atmosphere Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- 239000007790 solid phase Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 230000004888 barrier function Effects 0.000 claims 1
- 235000010265 sodium sulphite Nutrition 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 description 21
- 239000000843 powder Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000005424 photoluminescence Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000002096 quantum dot Substances 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 7
- 238000000295 emission spectrum Methods 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 5
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001748 luminescence spectrum Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052924 anglesite Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 1
- HOPSCVCBEOCPJZ-UHFFFAOYSA-N carboxymethyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC(O)=O HOPSCVCBEOCPJZ-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/664—Halogenides
- C09K11/665—Halogenides with alkali or alkaline earth metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a halide perovskite nano material and a preparation method thereof, wherein the preparation method comprises the following steps: melting and crystallizing a mixture of a perovskite precursor and a mesoporous material, removing perovskite nanocrystals on the surface of the material, and then forming an isolation layer on the surface of the material by using an inorganic substance; wherein, the perovskite precursor is cesium halide and lead halide; the melting temperature is 450-650 ℃. The preparation method of the halide perovskite nano material has the advantages of simple operation, low cost, high product generation rate and high synthesis speed, and can be used without adding an organic solvent and an organic ligand; the halide perovskite nano material has the advantages of high luminous intensity, narrow half-peak width, high luminous color purity, good environmental tolerance and capability of covering the whole visible light region by luminous wavelength.
Description
Technical Field
The invention relates to a halide perovskite nano material and a preparation method thereof.
Background
Halide perovskite materials have the characteristics of tunable luminescence spectrum in a visible light region, high carrier migration rate, high fluorescence quantum yield, narrow half-height width of the luminescence spectrum and the like, and are widely applied to photoelectric devices such as solar cells, lasers, light emitting diodes and the like. However, the halide perovskite material has poor environmental stability, and is degraded to different degrees in light, heat and air, so that the practical application of the halide perovskite material is severely limited.
At present, common methods for improving the stability of halide perovskite materials include ion doping, organic ligand modification, inorganic surface modification and the like.
The ion doping method is simple, not only can the stability be properly improved, but also the photoelectric characteristics of the perovskite quantum dot can be adjusted, such as adjusting the band gap of the perovskite quantum dot; but has the defect of limited stability improvement and can not meet the requirements of practical application systems.
The organic ligand method can utilize the ligand to carry out surface passivation on the perovskite quantum dots, the ligand can separate the quantum dots from each other without agglomeration, and the stability is greatly improved; but the defects are that the acting force of the ligand and the crystal is too weak, the falling can occur, meanwhile, the organic matter can pollute the environment, the cost is higher, the stability improvement aspect is still limited, and the requirements of the practical application system can not be met.
The method for modifying the surface of the inorganic substance has the characteristics of stability of most inorganic substances, mechanical strength and high heat resistance, and greatly improves the stability; but the defect is the influence of inorganic substances and solvents in a composite system, the crystallization process of the perovskite quantum dots in the inorganic system is very complicated, and therefore, the modification of the interface of the inorganic substances and the perovskite is very important. Wrapping perovskite nano-materials in silicon dioxide is a common effective method for modifying the surface of inorganic substances. For example, chinese patent document CN107557004A discloses a method for stabilizing perovskite quantum dots, which is to embed a lead halide precursor for preparing perovskite quantum dots into the pore diameter of mesoporous silica by using the principle of physical adsorption, add a cesium oleate precursor, and perform stirring and ultrasound to prepare mesoporous silica/perovskite quantum dots that are stable in air. However, the method utilizes mesoporous pore channel liquid phase physical adsorption, and cannot achieve enough concentration difference to help diffusion through low temperature (<200 ℃) diffusion and in-situ crystallization growth, so that the synthesis rate is slow; in addition, their pore structure is still open to the outside, and an organic ligand needs to be further added for blocking moisture and oxygen, thereby improving the stability thereof, but this causes an increase in cost, and the stability thereof is far from meeting the requirement of long-term use in a high humidity environment.
Disclosure of Invention
The invention aims to overcome the defects of low perovskite quantum dot generation rate, low stability and poor environmental tolerance in the prior art and provides a halide perovskite nano material and a preparation method thereof. The invention takes the mesoporous material as a template, synthesizes the halide perovskite nano material by adopting a solid-phase high-temperature melting method, does not need to add an organic solvent and an organic ligand, forms a stable inorganic substance at the orifice of the pore for isolating the external environment by adding a saturated salt solution, and the synthesized fluorescent perovskite product has high luminous intensity, narrow half-peak width, high luminous color purity, luminous wavelength capable of covering the whole visible light region, high stability in a water phase and good environmental tolerance.
The invention solves the technical problems through the following technical scheme.
The invention provides a preparation method of a halide perovskite nano material, which comprises the following steps:
melting and crystallizing a mixture of a perovskite precursor and a mesoporous material, removing perovskite nanocrystals on the surface of the material, and then forming an isolation layer on the surface of the material by using an inorganic substance;
wherein the perovskite precursor is cesium halide and lead halide; the melting temperature is 450-650 ℃.
In the present invention, the cesium halide may be one or more cesium halide compounds.
In the present invention, the lead halide may be one or more lead halide compounds.
In the present invention, the halogen in the cesium halide or the lead halide is a halogen atom, preferably Cl, Br or I.
In the present invention, the molar ratio of the cesium halide, the lead halide and the mesoporous material may be 1: 1: (1-20), preferably 1: 1: (6-10).
In the present invention, the mesoporous material may be a mesoporous material conventional in the art, and is preferably mesoporous silica. The pore diameter of the mesoporous material is preferably 2-50 nm. The mesoporous silica is preferably available from Sienna Rexi Biotechnology, Inc. under the trade designation R-JK100 nm.
In the present invention, the perovskite precursor is generally present in the form of a solid powder. The perovskite precursor is preferably subjected to a milling treatment, the milled powder preferably having a size of 0.1-0.4 mm. The lead halide is preferably lead bromide, preferably available from Macklin under the designation L871769-5g at a concentration of 99.9%. The cesium halide is preferably cesium bromide, preferably from Macklin, having a commercial designation C804175-10g, at a concentration of 99.5%.
In the invention, the mixture of the perovskite precursor and the mesoporous material can be obtained by a solid-phase mixing method, and the solid-phase mixing process generally comprises grinding.
In the present invention, the operation and conditions of the melting may be conventional in the art, and are generally carried out under an inert atmosphere which does not participate in the reaction. The inert atmosphere may be a nitrogen atmosphere or an inert gas atmosphere formed by an inert gas. The inert gas atmosphere may be an argon atmosphere or a neon atmosphere.
In the present invention, the heating rate before reaching the melting temperature is preferably 1 to 5 ℃/min, for example, 1 ℃/min and 3 ℃/min.
In the present invention, the melting temperature is preferably 500 to 600 ℃, for example, 550 ℃ and 570 ℃.
In the present invention, the melting time is preferably 10 to 150min, such as 100min and 120 min.
In the present invention, the crystallization can be performed by cooling crystallization, and the cooling crystallization can be performed by a method conventional in the art. In the cooling crystallization process, the cooling rate is preferably 5 to 15 ℃/min, for example 10 ℃/min.
In the present invention, the method for removing the perovskite nanocrystals on the surface of the material may be a method conventional in the art, and preferably includes the steps of heating, holding, and cooling.
Wherein the temperature rise is preferably performed in an air atmosphere.
The rate of temperature rise is preferably 1 to 5 deg.C/min, for example 1 deg.C/min.
The temperature is preferably raised to 450 to 600 ℃, for example 550 ℃.
Wherein, the time of the heat preservation is preferably 60-300 min, such as 240 min.
Wherein the cooling rate is preferably 5-15 deg.C/min, such as 10 deg.C/min.
In the present invention, the removal of the perovskite nanocrystals from the surface of the material can be performed in a conventional apparatus in the art, typically a muffle furnace.
In the present invention, the forming of the isolation layer by using the inorganic substance generally means that the inorganic substance is used to form the isolation layer on the periphery of the material with the surface perovskite nanocrystal removed, so as to isolate external moisture and oxygen.
In the present invention, the inorganic substance is preferably a saturated inorganic salt solution. The saturation refers to a solution that can not dissolve a certain solute in a certain amount of solvent at a certain temperature, namely, a solution that has reached the solubility of the solute.
Wherein, the saturated inorganic salt solution can be one or more of saturated sodium sulfate solution, saturated sodium carbonate solution and saturated sodium sulfite solution, and is preferably saturated sodium sulfate solution.
The method for forming the insulating layer using an inorganic substance preferably includes the steps of: and mixing the material with the surface perovskite nanocrystal removed and the inorganic substance for reaction.
Wherein, the mass ratio of the material with the surface perovskite nanocrystalline removed and the inorganic matter is preferably 1: (50-200), for example, 1: 100.
wherein, when the saturated inorganic salt solution is sulfuric acidIn the case of sodium solution, the following chemical reactions take place during the mixing reaction: pb2++SO4 2-→PbSO4。
Wherein, the mixing reaction can be carried out at room temperature, and is generally realized by stirring.
The mixing reaction time is preferably 0.5 to 12 hours, for example, 10 hours.
Wherein, the operation of filtration, water washing and precipitation is preferably included after the mixing reaction.
The filtration is a filtration method conventional in the art, and preferably can be performed by centrifugation.
The water washing is a washing method conventional in the art. The washing with water means that two types of substances having different solubilities are simultaneously dissolved in water in one type and not in the other type, and then the aqueous layer is removed by a liquid separation method.
The precipitation is a washing method conventional in the art. The precipitation is a unit operation for separating the target product or main impurities in the solution in an amorphous solid phase.
According to the preparation method of the halide perovskite nano material, an organic solvent and/or an organic ligand are/is not required to be added. The organic solvent and/or organic ligand may be an organic substance, such as n-hexane and/or toluene, which is conventionally used in the art for isolating external moisture and oxygen when preparing perovskite nanomaterials.
In the invention, the diameter range of the halide perovskite nano material can be 200-500 nm, such as 300 nm.
In the invention, the average particle size of the mesopores of the halide perovskite nano material can be 10-20 nm, for example 10 nm.
The invention provides a halide perovskite nano material which is prepared by the preparation method.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
1. the preparation method of the halide perovskite nano material has the advantages of simple operation, low cost, high product generation rate and high synthesis speed, and can be used without adding an organic solvent and an organic ligand.
2. The method can prepare halide perovskite nano materials with different components, the materials have high luminous intensity, narrow half-peak width and high luminous color purity, the luminous wavelength can cover the whole visible light region, the outstanding environmental tolerance is shown, the high water resistance and high temperature resistance stability are realized, the requirements of practical application can be met, and the method has wide application prospects in the fields of wide color gamut LED display, laser, nonlinear optics and the like.
Drawings
FIG. 1 shows CsPbBr of example 13Scanning transmission electron microscope high angle annular dark field image (HAADF-SEM) and energy dispersive spectroscopy (EDS mapping) of/MS nanomaterials.
FIG. 2 shows CsPbBr of example 13Scanning Electron Microscope (SEM) image of/MS nano material.
FIG. 3 shows CsPbBr of example 13Transmission Electron Microscopy (TEM) image of/MS nanomaterial.
FIG. 4 shows CsPbBr of example 13Absorption spectrum and emission spectrum of/MS nano material.
FIG. 5 is CsPbCl of example 23Absorption spectrum and emission spectrum of/MS nano material.
FIG. 6 is CsPbBr of comparative example 13Absorption spectrum and emission spectrum of/MS nano material.
FIG. 7 shows CsPbBr of example 13Graph of emitted light versus intensity over time at 200 ℃ environment for/MS nanomaterials.
FIG. 8 shows CsPbBr of example 13A curve diagram of relative intensity of emitted light of the MS nano material under water phase immersion at normal temperature along with time change.
FIG. 9 is CsPbBr of comparative example 23/MS nano material soaked in water phase at normal temperatureGraph of the relative intensity of the emitted light as a function of time.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. Experimental procedures without specifying specific conditions in the following examples were selected in accordance with conventional procedures and conditions, or in accordance with commercial instructions.
Laboratory instruments and materials
Fluorescence spectrophotometer: PE LS-55 model
Uv-vis spectrophotometer: lambda950 model
Mesoporous silica: xian Ruixi Biotech Co., Ltd, cat # R-JK100nm
Lead bromide: macklin, cat # L871769-5g, concentration 99.9%
Cesium bromide: macklin, cat # C804175-10g, 99.5% strength
Example 1
CsPbBr3Preparation of/MS composite material
(1) Putting 0.1mmol of lead bromide, 0.1mmol of cesium bromide solid powder and 0.8mmol of mesoporous silica powder into a grinding machine, fully grinding, and carrying out solid mixing to obtain a uniform mixture;
(2) in the argon atmosphere, heating the uniform mixture obtained in the step (1) at 5 ℃/min, melting at 600 ℃ for 120min, cooling at 10 ℃/min, and cooling and crystallizing to form the mesoporous silica/perovskite composite material;
(3) putting the mesoporous silica/perovskite composite material obtained in the step (2) into a muffle furnace, heating at 1 ℃/min in the air atmosphere, preserving the heat at 550 ℃ for 240min, and cooling at 10 ℃/min;
(4) putting the powder obtained in the step (3) into a saturated sodium sulfate solution, wherein the mass ratio of the powder to the saturated sodium sulfate solution is 1: 100, stirring and reacting for 10 hours at room temperature, centrifuging/washing with water, and precipitating to obtain the product.
Example 2
(1) Putting 0.1mmol of lead chloride, 0.1mmol of cesium chloride solid powder and 1.0mmol of mesoporous silica powder into a grinding machine, fully grinding, and carrying out solid mixing to obtain a uniform mixture;
(2) in the argon atmosphere, heating the uniform mixture obtained in the step (1) at 5 ℃/min, melting at 570 ℃ for 100min, cooling at 10 ℃/min, and cooling and crystallizing to form the mesoporous silica/perovskite composite material;
(3) placing the mesoporous silica/perovskite composite material obtained in the step (2) in a muffle furnace, heating at 3 ℃/min under the air atmosphere, preserving the temperature at 550 ℃ for 200min, cooling at 10 ℃/min, and oxidizing perovskite nanocrystals exposed on the surface;
(4) putting the powder obtained in the step (3) into a saturated sodium sulfate solution, wherein the mass ratio of the powder to the saturated sodium sulfate solution is 1: 100, stirring and reacting for 8 hours at room temperature, centrifuging/washing with water, and precipitating to obtain the product.
Comparative example 1
CsPbBr3Preparation of/MS composite material
(1) Putting 0.1mmol of lead bromide, 0.1mmol of cesium bromide solid powder and 0.8mmol of mesoporous silica powder into a grinding machine, fully grinding, and carrying out solid mixing to obtain a uniform mixture;
(2) in the argon atmosphere, heating the uniform mixture obtained in the step (1) at 5 ℃/min, melting at 700 ℃ for 120min, cooling at 10 ℃/min, and cooling and crystallizing to form the mesoporous silica/perovskite composite material;
(3) placing the mesoporous silica/perovskite composite material obtained in the step (2) in a muffle furnace, heating at 1 ℃/min under the air atmosphere, preserving the temperature at 550 ℃ for 240min, cooling at 10 ℃/min, and oxidizing perovskite nanocrystals exposed on the surface;
(4) putting the powder obtained in the step (3) into a saturated sodium sulfate solution, wherein the mass ratio of the powder to the saturated sodium sulfate solution is 1: 100, stirring and reacting for 10 hours at room temperature, centrifuging/washing with water, and precipitating to obtain the product.
Comparative example 2
(1) Putting 0.1mmol of lead bromide, 0.1mmol of cesium bromide solid powder and 0.8mmol of mesoporous silica powder into a grinding machine, fully grinding, and carrying out solid mixing to obtain a uniform mixture;
(2) in the argon atmosphere, heating the uniform mixture obtained in the step (1) at 5 ℃/min, melting at 600 ℃ for 120min, cooling at 10 ℃/min, and cooling and crystallizing to form the mesoporous silica/perovskite composite material;
(3) and (3) placing the mesoporous silica/perovskite composite material obtained in the step (2) in a muffle furnace, heating at 1 ℃/min under the air atmosphere, preserving the heat at 550 ℃ for 240min, and cooling at 10 ℃/min to obtain a product.
Effect example 1
CsPbBr prepared in example 1 and comparative example 23/MS composite, and CsPbCl prepared in example 23And carrying out morphology and optical performance tests on the/MS composite material.
FIG. 1 shows CsPbBr prepared in example 13Scanning transmission electron microscope high angle annular dark field image (HAADF-SEM) (FIG. 1a) and energy dispersive spectroscopy (EDSmapping) (FIG. 1 b-FIG. 1f) of/MS composite material from which CsPbBr can be seen3The nanocrystals are distributed inside the MS particles. In FIG. 1a, the upper left corner labeled HAADF represents a high-angle annular dark field, which is an imaging mode of a scanning transmission electron microscope.
FIG. 2 shows CsPbBr prepared in example 13SEM image of/MS nano material, from which CsPbBr can be seen3The diameter of the/MS nano material is about 300 nm.
FIG. 3 is CsPbBr prepared in example 13TEM image of the/MS composite material, from which CsPbBr can be seen3Embedded in the mesoporous silicon dioxide, the average grain diameter of the mesoporous silicon dioxide is about 10 nm.
The samples of example 1, example 2 and comparative example 1 were placed in four-way cuvettes, respectively, the cuvettes were placed in an instrumental cell, and their absorption spectrum and emission spectrum were measured using a fluorescence spectrophotometer and an ultraviolet-visible spectrophotometer, as shown in fig. 4, fig. 5 and fig. 6.
FIG. 4 shows CsPbBr prepared in example 13Absorption spectrum and emission spectrum of/MS nano material, band gap absorption edge is 508nm, fluorescence emission peak position is 518nm, half-peak widthIs 20 nm.
FIG. 5 is CsPbCl prepared in example 23The absorption spectrum and the emission spectrum of the/MS composite material have a band gap absorption edge of 392nm, a fluorescence emission peak position of 404nm and a half-peak width of 16 nm. The data of the graphs in fig. 4 and fig. 7 show that the material has good luminescence performance and narrow half-peak width, which indicates that the sample is relatively pure in crystal phase and relatively uniform in size distribution.
FIG. 6 is CsPbBr prepared in comparative example 13Absorption spectrum and emission spectrum of/MS nano material. The band gap absorption edge of the fluorescent material shows two peaks which are about 436 nm and 508nm, and the fluorescence emission peak also shows two peaks which are 465.5 nm and 506nm respectively. Indicating the appearance of a heterogeneous phase whose luminescent color purity deteriorated.
Effect example 2
CsPbBr prepared in example 1 and comparative example 23The stability of the/MS nano material is measured:
FIG. 7 is CsPbBr prepared in example 13Thermal stability of/MS nanomaterials. Under 150 deg.C, the photoluminescence intensity is 50831, 49820, 48320, 44803 after 0, 2, 4, 6 hours, respectively, and the photoluminescence intensity is maintained above 100, 98, 95, 88% after 2, 4, 6 hours, respectively.
The highest temperature of the material is 200 ℃ and the time of the material is 3 hours, and the photoluminescence intensity of the material is not obviously reduced and is maintained to be more than 80 percent of the original photoluminescence intensity.
FIG. 8 is CsPbBr prepared in example 13The emission intensity of the/MS composite material is stable under the condition of water phase soaking at normal temperature. CsPbBr3The photoluminescence intensity of the/MS composite material is still maintained to be more than 80 percent after the/MS composite material is dispersed and soaked in deionized water for 14 days. CsPbBr3The photoluminescence intensity of the/MS composite material is maintained to be about 100%, 98%, 95%, 94%, 90%, 89% and 86% at 0, 2, 6, 8, 10, 12 and 14 days respectively; the corresponding photoluminescence intensities were 546647, 546453, 535720, 519300, 492003, 486602 and 470203, respectively.
The maximum water resistance time of the material is 2 months, and the photoluminescence intensity of the material is not obviously reduced and still maintains more than 80 percent of the original photoluminescence intensity.
The material can not be deteriorated in the air, the material has no obvious change after being placed for one year, the photoluminescence intensity of the material is not obviously reduced, and the photoluminescence intensity is still maintained to be more than 80 percent of the original photoluminescence intensity.
FIG. 9 is CsPbBr prepared in comparative example 23The stability change curve of the emitted light intensity of the MS composite material under the condition of water phase soaking at normal temperature. From fig. 9, it can be seen that the photoluminescence intensity of the product was reduced to below 3% after the product was dispersed and soaked in deionized water for 6 days.
Claims (10)
1. A preparation method of halide perovskite nano material is characterized in that a mixture of a perovskite precursor and a mesoporous material is melted and crystallized, perovskite nano crystals on the surface of the material are removed, and then an inorganic substance is used for forming an isolation layer on the surface of the material;
wherein the perovskite precursor is cesium halide and lead halide; the melting temperature is 450-650 ℃.
2. The method of preparing a halide perovskite nanomaterial of claim 1, wherein the cesium halide is one or more cesium halide compounds;
and/or the lead halide is one or more lead halide compounds;
and/or, the halogen atom in the cesium halide or the lead halide is Cl, Br or I;
and/or the molar ratio of the cesium halide, the lead halide and the mesoporous material is 1: 1: (1-20), preferably 1: 1: (6-10);
and/or the mesoporous material is mesoporous silicon dioxide;
and/or the aperture of the mesoporous material is 2-50 nm;
and/or the mixture of the perovskite precursor and the mesoporous material is obtained by a solid-phase mixing method, and the solid-phase mixing process preferably further comprises a grinding operation.
3. The method for preparing a halide perovskite nanomaterial as claimed in claim 1, wherein the melting is carried out under an inert atmosphere that does not participate in the reaction, preferably under a nitrogen atmosphere or an inert gas atmosphere, preferably under an argon atmosphere or a neon atmosphere;
and/or the heating rate before reaching the melting temperature is 1-5 ℃/min, such as 1 ℃/min and 3 ℃/min;
and/or the melting temperature is 500-600 ℃, such as 550 ℃ and 570 ℃;
and/or the melting time is 10-150 min, such as 100min and 120 min;
and/or the crystallization is cooling crystallization, and in the cooling crystallization process, the cooling rate is preferably 5-15 ℃/min, such as 10 ℃/min;
and/or removing the perovskite nanocrystals on the surface of the material in a muffle furnace device.
4. The method for preparing a halide perovskite nanomaterial as claimed in claim 1, wherein the method for removing perovskite nanocrystals from the surface of the material comprises the steps of: heating, preserving heat and cooling.
5. The method for producing a halide perovskite nanomaterial as claimed in claim 4, wherein the temperature rise is performed in an air atmosphere;
and/or the rate of temperature rise is 1-5 ℃/min, such as 1 ℃/min;
and/or the temperature of the heat preservation is 450-600 ℃, such as 550 ℃;
and/or the heat preservation time is 60-300 min, such as 240 min;
and/or the cooling rate is 5-15 ℃/min, such as 10 ℃/min.
6. The method of producing a halide perovskite nanomaterial of claim 1, wherein the inorganic substance is a saturated inorganic salt solution, preferably one or more of a saturated sodium sulfate solution, a saturated sodium carbonate solution, and a sodium sulfite solution, more preferably a saturated sodium sulfate solution.
7. The method of making a halide perovskite nanomaterial of claim 1, wherein the method of forming the barrier layer from an inorganic substance comprises the steps of: and mixing the material with the surface perovskite nanocrystal removed and the inorganic substance for reaction.
8. The method for producing a halide perovskite nanomaterial as claimed in claim 7, wherein the mass ratio of the material from which the surface perovskite nanocrystals have been removed to the inorganic substance is 1: (50-200), for example, 1: 100, respectively;
and/or, the mixing reaction is carried out at room temperature;
and/or the mixing reaction time is 0.5-12 hours, such as 10 hours;
and/or, the operations of filtering, washing and precipitating are also included after the mixing reaction.
9. The method of producing a halide perovskite nanomaterial as claimed in claim 1, wherein no organic solvent and/or organic ligand is added to the method of producing the halide perovskite nanomaterial.
10. The halide perovskite nano material prepared by the preparation method according to any one of claims 1 to 9; the diameter range of the halide perovskite nano material is 200-500 nm, such as 300 nm;
and/or the average particle size range of mesopores of the halide perovskite nano material is 10-20 nm.
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