WO2023039716A1 - 一种钙钛矿与分子筛的复合材料及其制备方法和应用 - Google Patents

一种钙钛矿与分子筛的复合材料及其制备方法和应用 Download PDF

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WO2023039716A1
WO2023039716A1 PCT/CN2021/118214 CN2021118214W WO2023039716A1 WO 2023039716 A1 WO2023039716 A1 WO 2023039716A1 CN 2021118214 W CN2021118214 W CN 2021118214W WO 2023039716 A1 WO2023039716 A1 WO 2023039716A1
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molecular sieve
cesium
lead
perovskite
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French (fr)
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喻学锋
史桐雨
黄浩
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深圳先进技术研究院
中国科学院深圳理工大学(筹)
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
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    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/55—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing beryllium, magnesium, alkali metals or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/59—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • 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
    • 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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    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

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  • the invention belongs to the field of inorganic luminescent materials, specifically a composite material of perovskite and molecular sieve and a preparation method thereof
  • Inorganic perovskite (CsPbX 3 ) is a kind of optoelectronic material with excellent performance. It has the advantages of narrow half-peak width of fluorescence spectrum, high quantum efficiency, and broadband adjustable emission wavelength. It has been widely used in photovoltaics such as solar cells and light-emitting diodes in recent years. devices and has received more and more attention.
  • the stability of perovskite materials is poor, and they are extremely sensitive to external environments such as organic solvents, humidity, air, and thermal ultraviolet light.
  • the preparation process of perovskite materials is relatively complicated and difficult to produce in large-scale industrial production, which limits calcium The development of titanium ore materials.
  • the protective layer can isolate CsPbX 3 from water and oxygen, and can also prevent ion migration and fusion between particles.
  • Commonly used shell materials include inorganic oxides (SiO 2 , Al 2 O 3 , TiO 2 , etc.), mesoporous materials (MOF , molecular sieve, etc.), organic polymer materials (polyethylenediene, epoxy resin, polymethyl methacrylate, etc.), inorganic salts (NaNO 3 , NH 4 Br).
  • Molecular sieves are a large class of inorganic porous materials that form a three-dimensional network structure through the combination of shared oxygen atoms. Because of their high porosity, large specific surface area, easy adsorption and ion exchange, they can be used as excellent carriers for luminescent materials.
  • Chinese invention CN106701070B discloses a blue-yellow-orange perovskite quantum dot and molecular sieve composite luminescent material and its preparation method and application.
  • the molecular sieve is mixed with cesium halide for ion exchange to obtain a Cs-exchanged molecular sieve, and then octadecene, Oleylamine, oleic acid, and lead halide are used as raw materials to prepare the multi-halogen lead halide solution.
  • Octadecene is added to the Cs-exchanged molecular sieve, and after heating and stirring for a period of time under nitrogen atmosphere, the multi-halogen lead halide solution is added.
  • Sieve, after washing and drying the composite luminescent material of perovskite quantum dots and molecular sieves is obtained, and its fluorescence lifetime and stability are significantly increased.
  • Chinese invention CN107384387B discloses a manganese-doped CsPbBr 3 perovskite quantum dot and molecular sieve composite luminescent material and its preparation method and application.
  • Y-type molecular sieve as the carrier of quantum dots
  • the environmental stability is significantly increased.
  • the preparation methods of the above-mentioned patents are all liquid-phase synthesis methods, and the process is relatively cumbersome. It needs to be operated under N2 atmosphere, and organic ligands need to be added, and post-processing is required to obtain corresponding powder materials, which is not conducive to large-scale application and stability. sexual enhancement.
  • the purpose of the present invention is to introduce a porous material such as molecular sieve as a substrate, realize the preparation and compounding of perovskite through a one-step method, and realize a kind of molecular sieve etching and perovskite confinement
  • the unique process and structure of growth and simultaneous coating are used to solve the problems of poor stability and uneven size of perovskite in humidity and atmospheric environment.
  • Another object of the present invention is to provide a method for preparing composite phosphors that is simple to operate, requires low equipment, and can be produced in large quantities. This method avoids the use of organic solvents, and is easy to operate and has good repeatability, which provides a new idea for the application of large-scale industrial optoelectronic devices.
  • the present invention provides the following technical solutions:
  • One aspect of the present invention provides the preparation method of the composite material of perovskite and molecular sieve, and described preparation method comprises the following steps:
  • Step 1 adding lead source and cesium source into the reaction vessel
  • the lead source, the cesium source and the first halogen source are added to the reaction vessel;
  • Step 2 uniformly dispersing the molecular sieve in the reaction vessel
  • Step 3 putting the crucible into a muffle furnace, performing high-temperature treatment, and the reaction temperature is above 500°C until the reaction is complete;
  • Step 4 after cooling to room temperature, the composite material of perovskite and molecular sieve can be obtained.
  • the preparation method of the composite material of perovskite and molecular sieve also includes step 5, annealing the composite material of perovskite and molecular sieve and the second halogen source to obtain A composite material of perovskite and molecular sieve substituted by halogen in the halogen source; the melting point of the second halogen source is not higher than 350°C.
  • halogen in the composite material of perovskite and molecular sieve obtained in step 4 is not exactly the same as the halogen in the halogen source in step 5.
  • the temperature of the annealing treatment is 150-350°C, for example, 200°C, 250°C, 300°C.
  • the melting point of the second halogen source is 0-350°C, for example, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C °C, 100°C, 150°C, 200°C, 250°C, 300°C.
  • Another aspect of the present invention provides a composite material of perovskite and molecular sieve, and the composite material of perovskite and molecular sieve is prepared by the above-mentioned method of the present invention.
  • the present invention provides a composite material of perovskite and molecular sieve, which has a unique structure of molecular sieve etching, perovskite confined growth and molecular sieve coating perovskite.
  • Halogen ion exchange can be further carried out under certain conditions.
  • the lead source, cesium source and halogen source described in step one are not dissolved, and do not contain any solvent.
  • the amount of perovskite loaded on the molecular sieve can be adjusted according to the etching degree, and the loaded perovskite accounts for 0.1-30% of the total weight, preferably 1-20%, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18% , 19%, 20%, 25%, 30%.
  • the lead source is one or more of halogen-containing lead salts, lead carbonate, lead nitrate, lead sulfate, lead acetate and organic lead salts, and the halogen-containing lead salts are selected from lead chloride, lead bromide or lead iodide.
  • the cesium source is one or more of halogen-containing cesium salts, cesium carbonate, cesium nitrate, cesium sulfate, cesium acetate and organic cesium salts, and the halogen-containing cesium salts are selected from cesium chloride, cesium bromide Cesium or cesium iodide.
  • the first halogen source is one or more of ammonium halide and organic halide. Described ammonium halide is selected from ammonium chloride, ammonium bromide or ammonium iodide; Organic halide is selected from tetrabutylammonium bromide, tetrabutylammonium chloride, tetraethylammonium chloride, benzyltriethyl Ammonium Chloride, Trioctylmethylammonium Chloride, Lauryltrimethylammonium Chloride, Octyltrimethylammonium Bromide, Decyltrimethylammonium Bromide.
  • the molar ratio of the cesium source and the lead source is 4:1-1:4, preferably 1.2:1-1:1.2, for example 1:1.
  • the molar amounts of the cesium source, the lead source and the first halogen source are more than three times the molar amount of cesium in the cesium source or the molar amount of lead in the lead source.
  • the cesium source and the lead source are placed in a manner selected from mixed placement, stacked up and down or separated and placed at both ends of the reaction vessel. Further preferably, the cesium source and the lead source are placed at both ends of the reaction vessel and do not contact each other. .
  • the weight ratio of the molecular sieve to the total mass of the lead source and the cesium source, or the total mass of the lead source, the cesium source and the first halogen source is 1:0.1 to 1:4, for example 1:0.3, 1 :0.5, 1:0.7, 1:1, 1:5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4.
  • the arrangement of the molecular sieve with the lead source, the cesium source and the first halogen source is to place them in a mixed manner, stack up and down or separate them at both ends of the reaction vessel, preferably the molecular sieve is placed at the lead source, the cesium source and the first halogen source. a halogen source above.
  • the molecular sieve is a zeolite molecular sieve, preferably selected from silica-alumina molecular sieves and titanium-silicon molecular sieves, aluminum phosphate molecular sieves, and aluminum silicate molecular sieves formed after replacement and compounding.
  • the heating rate is 0.5°C/min-20°C/min, such as 1°C, 2°C, 3°C, 4°C, 5°C, 10°C, 15°C, 20°C.
  • the reaction temperature is 500°C-1000°C
  • the holding time is 1-24h; for example, the reaction temperature is 600°C, 700°C, 800°C, 900°C, and the holding time is 2h, 3h, 4h, 5h, 6h , 7h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h.
  • the cooling rate is 1-10°C/min to cool down to room temperature, such as 2°C, 3°C, 4°C, 5°C, 6°C, 7°C, 8°C, 9°C.
  • the second halogen source is preferably an organic halogen source, and the organic halide is selected from tetrabutylammonium bromide, tetrabutylammonium chloride, tetraethylammonium chloride, benzyltriethyl chloride Ammonium Chloride, Trioctylmethylammonium Chloride, Dodecyltrimethylammonium Chloride, Octyltrimethylammonium Bromide, Decyltrimethylammonium Bromide.
  • Another aspect of the present invention provides the application of the composite material described in the present invention as electroluminescence, photoluminescence, and white LED luminescent materials.
  • the present invention unexpectedly finds that at relatively high temperature, thermal movement of molecules in the reaction system forms convection, and lead source, cesium source and halogen source will form cesium halide and lead halide vapor to be adsorbed in the molecular sieve pores.
  • Lead bromide will first react with molecular sieves, and form an intermediate product Si-PbX structure by reacting with Si-OH. Adsorption of titanium ore raw materials, while causing the collapse of the pores will form the encapsulation.
  • the free X - and the intermediate product react with cesium halide to form perovskite, thereby realizing the efficient compounding of perovskite nanocrystals and molecular sieves.
  • molecular sieve As the carrier of perovskite, molecular sieve has a unique pore structure. Due to the presence of etching, even if the molecular sieve structure collapses, there are still certain pores that can perform ion exchange reactions, which is convenient for other ions to enter the pores of the molecular sieve and synthesize related compounds.
  • the pores of the molecular sieve are etched and enlarged, and a large amount of perovskite raw materials are fixed, which can limit the growth size of perovskite nanocrystals, and block the interaction of nanocrystals at high temperatures, reducing the The concentration quenching caused by the agglomeration between the luminescent centers improves the stability of the perovskite in the channel.
  • the present invention has the following remarkable features:
  • the etching of molecular sieve channels has realized a large amount of adsorption and fixation of perovskite raw materials, increased the loading capacity of perovskite, and achieved the efficient compound effect of synchronous coating and confined growth, with good water resistance
  • the oxygen effect improves the environmental stability and thermal stability of the perovskite composite
  • the composite material can also undergo halogen ion exchange under certain conditions, which can expand its spectral range.
  • the composite material exhibits narrow-band emission in the range of 360-700nm, adjustable band gap, narrow half-peak width of about 20nm, and high luminous intensity, which can be applied to lighting fields such as electroluminescence and photoluminescence;
  • the composite material adopts a high-temperature solid-phase synthesis method, which avoids the use of organic solvents, does not need to introduce organic ligands, and is simple to operate, has good repeatability, low equipment requirements, and can be produced in large quantities, which is conducive to industrial applications;
  • the perovskite and molecular sieve composite material prepared by the present invention has a good application prospect in the fields of lighting display, especially white light LED.
  • the composite material prepared by the present invention has a higher loading capacity.
  • the composite material is prepared by dissolving lead bromide and cesium bromide in water.
  • lead bromide is a slightly soluble raw material, the loading capacity of molecular sieves is limited.
  • lead bromide is easily hydrolyzed to form a basic salt, lead bromide and cesium bromide dissolve together, so the structure of perovskite plus crystal water is formed during the drying process, so it needs to increase the annealing process to dehydrate the crystal water .
  • Fig. 1 is a white light picture of the composite material prepared in Example 1 of the present invention.
  • Fig. 2 is a scanning electron microscope image of the composite material prepared in Example 2 of the present invention.
  • Fig. 3 is an X-ray diffraction pattern of the composite material prepared in Example 2 of the present invention.
  • Fig. 4 is a luminescent spectrum diagram of the composite material prepared in Example 7 of the present invention.
  • Fig. 5 is the white light LED spectrum (a) and the spectrum (b) under different currents prepared by preparing green light and red light composite materials combined with blue light chips in Examples 1 and 14 of the present invention.
  • Fig. 6 shows the water stability (a), 80°C-80% humidity environmental aging stability (b) and ultraviolet radiation stability (c) of blue light, green light and red light composite materials in the examples of the present invention.
  • Fig. 7 shows the thermal stability of blue light (a), green light (b) and red light (c) composite materials in the examples of the present invention.
  • Fig. 8 is the characterization of the reaction mechanism in the present invention, that is, Si 2p (a) and O 1s (b) orbital binding energy in the binding energy spectrum when bromine and lead exist at the same time have a large shift towards the low binding energy direction, illustrating the new structure generation.
  • Embodiment 1 The preparation of the composite material of perovskite and molecular sieve
  • Step 1 take by weighing 1.47g (4mmol) lead bromide and 0.851g (4mmol) cesium bromide respectively and join in the alumina crucible;
  • Step 2 covering the raw material with 2g of molecular sieve as a substrate;
  • Step 3 put the alumina crucible with the raw materials into the muffle furnace, heat for 100 minutes to 650°C, and keep the temperature for 5 hours;
  • Step 4 after cooling to room temperature at 5°C/min, the composite material of perovskite and molecular sieve can be obtained.
  • the output of the composite luminescent material prepared in this example is relatively high, and the loading capacity of perovskite is about 20%. Structure of domain growth and simultaneous cladding.
  • Embodiment 2 The preparation of the composite material of perovskite and molecular sieve
  • Step 1 take by weighing 1.764g (4.8mmol) lead bromide and 0.851g (4mmol) cesium bromide respectively, join in the alumina crucible;
  • Step 2 covering the molecular sieve of 2.25g on the raw material as the substrate;
  • Step 3 put the alumina crucible with raw materials into the muffle furnace, heat up to 650°C at a heating rate of 75min, and keep the temperature for 24h;
  • Step 4 after cooling to room temperature at 3°C/min, the composite material of perovskite and molecular sieve can be obtained.
  • a green phosphor with high quality and yield can also be obtained.
  • the perovskite loading is about 18%.
  • the scanning electron microscope image is shown in Figure 2, and the XRD result of the perovskite composite powder is shown in Figure 3. .
  • Embodiment 3 preparation of the composite material of perovskite and molecular sieve
  • Step 1 take by weighing 5.86g (16mmol) lead bromide and 0.851g (4mmol) cesium bromide respectively, join in the aluminum oxide crucible;
  • Step 2 covering the molecular sieve of 10g on the raw material as the base material;
  • Step 3 put the alumina crucible with raw materials into the muffle furnace, heat up to 650°C at a heating rate of 100min, and keep it warm for 1h;
  • Step 4 after cooling to room temperature at 10°C/min, the composite material of perovskite and molecular sieve can be obtained.
  • the feed of lead bromide is more, and the output of the overall composite phosphor is slightly lower.
  • Step 1 take by weighing 1.47g (4mmol) lead bromide and 0.6734g (4mmol) cesium chloride respectively, join in the alumina crucible;
  • Step 2 covering the raw material with 2g of molecular sieve as a substrate;
  • Step 3 put the alumina crucible with raw materials into the muffle furnace, heat for 75 minutes to 670°C, and keep the temperature for 5 hours;
  • Step 4 after cooling to room temperature at 8°C/min, the composite material of perovskite and molecular sieve can be obtained.
  • blue fluorescent powder can be synthesized, and the output is relatively high.
  • Embodiment 5 The preparation of the composite material of perovskite and molecular sieve
  • Step 1 respectively weigh 1.112g (4mmol) lead chloride and 0.6734g (4mmol) cesium chloride, 0.053g (1mmol) ammonium chloride, join in the alumina crucible;
  • Step 2 covering the raw material with 2g of molecular sieve as a substrate;
  • Step 3 put the alumina crucible with raw materials into the muffle furnace, heat for 75 minutes to 670°C, and keep the temperature for 5 hours;
  • Step 4 after cooling to room temperature at 2°C/min, the composite material of perovskite and molecular sieve can be obtained.
  • purple fluorescent powder can be synthesized with high yield.
  • Embodiment 6 The preparation of the composite material of perovskite and molecular sieve
  • Step 1 take by weighing 1.47g (4mmol) lead bromide and 0.851g (4mmol) cesium bromide respectively, join in the aluminum oxide crucible;
  • Step 2 covering the molecular sieve of 5g on the raw material as the base material;
  • Step 3 put the alumina crucible with the raw materials into the muffle furnace, heat for 100 minutes to 500°C, and keep the temperature for 5 hours;
  • Step 4 after cooling to room temperature at 1°C/min, the composite material of perovskite and molecular sieve can be obtained.
  • a green fluorescent powder can be synthesized, but some molecular sieves are not reacted, and the perovskite loading is about 3%.
  • Step 1 take by weighing 1.764g (4.8mmol) lead bromide and 0.851g (4mmol) cesium bromide respectively, join in the alumina crucible;
  • Step 2 covering the molecular sieve of 2.5g on the raw material as the substrate;
  • Step 3 put the alumina crucible with raw materials into the muffle furnace, heat for 30 minutes to 650°C, and keep the temperature for 5 hours;
  • Step 4 after cooling to room temperature at 5°C/min, the composite material of perovskite and molecular sieve can be obtained.
  • a green fluorescent powder can be synthesized.
  • the perovskite loading is about 15%.
  • the fluorescence emission spectrum is shown in Figure 4.
  • the half-maximum width of the visible material is very narrow, only about 20nm, and the size is uniform.
  • Step 1 respectively weigh 1.764g (4.8mmol) lead bromide and 0.851g (4mmol) cesium bromide, 0.098g (1mmol) ammonium bromide, join in the alumina crucible;
  • Step 2 covering the molecular sieve of 2.5g on the raw material as the substrate;
  • Step 3 put the alumina crucible with raw materials into the muffle furnace, heat for 1300min to 670°C, and keep it warm for 5h;
  • Step 4 after cooling to room temperature at 5°C/min, the composite material of perovskite and molecular sieve can be obtained.
  • green fluorescent powder can be synthesized, but there is agglomeration at the bottom, and the yield is reduced.
  • Step 1 take by weighing 1.764g (4.8mmol) lead bromide and 0.851g (4mmol) cesium bromide respectively, join in the alumina crucible;
  • Step 2 covering the molecular sieve of 2.5g on the raw material as the substrate;
  • Step 3 put the alumina crucible with raw materials into the muffle furnace, heat for 300 minutes to 1000°C, and keep it warm for 5 hours;
  • Step 4 after cooling to room temperature at 5°C/min, the composite material of perovskite and molecular sieve can be obtained.
  • a green phosphor can be synthesized, and the perovskite load is excessively agglomerated.
  • Step 1 take by weighing 1.47g (4mmol) lead bromide and 0.851g (4mmol) cesium bromide respectively and join in the alumina crucible;
  • Step 2 covering the molecular sieve of 10g on the raw material as the base material;
  • Step 3 put the alumina crucible with the raw material into the muffle furnace, heat it for 100 minutes to 650°C, and keep it warm for 15 hours;
  • Step 4 after cooling to room temperature at 5°C/min, the composite material of perovskite and molecular sieve can be obtained.
  • a green fluorescent powder can be synthesized, but some molecular sieves are not reacted, and the perovskite loading is about 1%.
  • Step 1 take by weighing 1.47g (4mmol) lead bromide and 0.851g (4mmol) cesium bromide respectively and join in the alumina crucible;
  • Step 2 covering the raw material with 1g of molecular sieve as a substrate;
  • Step 3 put the alumina crucible with the raw material into the muffle furnace, heat it for 100 minutes to 650°C, and keep it warm for 10 hours;
  • Step 4 after cooling to room temperature at 5°C/min, the composite material of perovskite and molecular sieve can be obtained.
  • a green fluorescent powder can be synthesized, but due to the small amount of molecular sieve added, the perovskite is loaded too much and agglomerates.
  • Step 1 respectively weigh 1.068g (4mmol) lead carbonate, 0.851g cesium bromide (4mmol), 0.79g (8mmol) ammonium bromide and join in the alumina crucible;
  • Step 2 covering the raw material with 2g of molecular sieve as a substrate;
  • Step 3 put the alumina crucible with the raw materials into the muffle furnace, heat for 100 minutes to 650°C, and keep the temperature for 5 hours;
  • Step 4 after cooling to room temperature at 5°C/min, the composite material of perovskite and molecular sieve can be obtained.
  • This example can synthesize green fluorescent powder.
  • Step 1 respectively weigh 1.5g (4.6mmol) lead acetate, 0.8g (4.2mmol) cesium acetate, 3.2g (9.9mmol) tetrabutylammonium bromide and join in the alumina crucible;
  • Step 2 covering the raw material with 2g of molecular sieve as a substrate;
  • Step 3 put the alumina crucible with the raw materials into the muffle furnace, heat for 100 minutes to 650°C, and keep the temperature for 5 hours;
  • Step 4 after cooling to room temperature at 5°C/min, the composite material of perovskite and molecular sieve can be obtained.
  • This example can synthesize green fluorescent powder.
  • the method of the present invention can adopt a one-step method to prepare perovskite-loaded molecular sieve composite materials, and different lead sources, different cesium sources, and different ratios can be used to prepare composite materials. And by adjusting the halogen species in the lead source, composite materials with different colors can also be obtained. By adjusting the ratio of each component and the reaction temperature and time, a composite material with more perovskite loading and more complete reaction can be obtained. In addition, more colorful perovskite composites can be formed by further ion exchange.
  • Fig. 8 has shown the binding energy spectrogram of material of the present invention, illustrates the reaction mechanism characterization in the invention, namely Si 2p (a) and O 1s (b) track binding energy to low binding energy in binding energy spectrum when bromine and lead exist simultaneously A large shift in orientation indicates the generation of a new structure.
  • the method of the present invention completely avoids the use of organic solvents and does not need to introduce organic ligands. There is no need to add liquid solvents such as water, and the preparation is realized under the condition of all solid phases, so the whole preparation process has only one step, the reaction method and equipment used are very simple, and the reaction time is very short. More importantly, during the preparation process of the present invention, the pores of the molecular sieve are further etched to form a coating structure, which improves the stability of the perovskite loaded thereon.

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  • Luminescent Compositions (AREA)

Abstract

本发明涉及一种钙钛矿与分子筛复合材料及其制备方法和应用，具体涉及一种利用高温固相反应制备全无机钙钛矿与分子筛复合材料。所述制备方法包括以下步骤：步骤一，将铅源、铯源，以及任选的第一卤素源，加入到反应容器中；步骤二，将分子筛均匀分散在反应容器中；步骤三，将坩埚放入马弗炉中，进行高温处理，反应温度为500℃以上至反应完全；步骤四，冷却至室温后即可获得钙钛矿与分子筛的复合材料。该方法能够充分利用分子筛网络结构、高稳定性和超高的孔隙率，在保留钙钛矿原有优良的发光性能的前提下，大幅提高钙钛矿的环境稳定性和热稳定性，而且方法简单，设备要求低，无需额外的有机配体，可大批量生产。

Description

一种钙钛矿与分子筛的复合材料及其制备方法和应用 技术领域：
本发明属于无机发光材料领域，具体为一种钙钛矿与分子筛的复合材料及其制备方法
背景技术
无机钙钛矿(CsPbX 3)是一种性能优良的光电材料，具有荧光光谱半峰宽窄，量子效率高，宽带可调发射波长等优点，近年来已经被广泛应用到太阳能电池、发光二极管等光电器件中并受到人们越来越多的关注。但钙钛矿材料稳定性较差，对有机溶剂、湿度、空气、热紫外等外部环境极为敏感，并且目前钙钛矿材料的制备工艺相对比较复杂且很难大规模工业化生产制备，限制了钙钛矿材料的发展。
目前为止，已经开发出各种提升CsPbX 3的方法来解决钙钛矿稳定性的问题，包括进行表面钝化、掺杂以及采用无机或有机保护层进行包覆，其中，包覆被认为是最有效、直接的方法。保护层可以将CsPbX 3与水、氧隔离，也可以防止离子迁移和粒子间的聚变，常用的壳材包括无机氧化物(SiO 2，Al 2O 3，TiO 2等)，介孔材料(MOF、分子筛等)、有机高分子材料(聚乙二烯、环氧树脂、聚甲基丙烯酸甲酯等)、无机盐(NaNO 3，NH 4Br)。然而这些保护层只能减缓CsPbX 3被外界环境因素降解的速度，不能完全保护CsPbX 3，如孔结构暴露在外不能完全隔离钙钛矿和水氧，而无机氧化物在较低的退火温度下不够致密，对外部的水和氧有较高的渗透率，但较高的温度会损伤剥离有机配体导致团聚进而荧光淬灭。
分子筛是一大类无机多孔材料，通过共有的氧原子结合而形成三维网状结构，因其高孔隙率、超大比表面积、易于吸附和离子交换等特点，可作为发光材料的优良载体。中国发明CN106701070B公开了一种蓝黄橙光钙钛矿量子点与分子筛复合发光材料及其制备方法与应用，首先将分子筛与卤化铯混合进行离子交换得到Cs交换的分子筛，再以十八烯、油胺、油酸、卤化铅为原料制备多卤素卤化铅溶液的制备，在Cs交换的分子筛中加入十八烯，并在氮气氛围下加热搅拌一段之间后，再加入多卤素卤化铅溶液子筛，经过洗涤干燥后得到钙钛矿量子点与分子筛复合发光材料，其荧光寿命以及稳定性得到明显增加。类似地，中国发明CN107384387B公开了一种锰掺杂CsPbBr 3钙钛矿量子点与分子筛复合发光材料及其制备方法与应用，通过引入Y型分子筛作为量子点存在的载体，环境稳定性得到明显增加。但上述专利的制备方法均为液相合成方法，过程较为繁琐，需要在N 2氛围下操作，且需加入有机配体，还需进行后处理得到相应粉体材料，不利于大规模应用和稳定性的提升。
发明内容
发明目的：鉴于现有技术存在的问题，本发明的目的是引入分子筛这种多孔材料作为基材，通过一步法实现钙钛矿的制备和复合，实现一种分子筛刻蚀、钙钛矿限域生长和同步包覆的独特过程和结构，用以解决钙钛矿在湿度及大气环境下稳定性差、尺寸不够均匀的问题。本发明的另一目的是提供一种操作简单、设备要求低、可大批量进行生产的复合荧光粉的制备方法。该方法避免了使用有机溶剂，并且操作简单，可重复性好，为之后大规模产业化光电子器件的应用提供了新的思路。
为实现上述目的，本发明提供如下技术方案：
本发明一个方面提供了钙钛矿与分子筛的复合材料的制备方法，所述制备方法包括以下步骤：
步骤一，将铅源、铯源，加入到反应容器中，
或者，将铅源、铯源和第一卤素源，加入到反应容器中；
步骤二，将分子筛均匀分散在反应容器中；
步骤三，将坩埚放入马弗炉中，进行高温处理，反应温度为500℃以上至反应完全；
步骤四，冷却至室温后即可获得钙钛矿与分子筛的复合材料。
在本发明的一些具体的技术方案中，所述钙钛矿与分子筛的复合材料的制备方法还包括步骤五，将所得的钙钛矿与分子筛的复合材料与第二卤素源进行退火处理，得到以卤素源中卤素进行取代的钙钛矿与分子筛的取代的复合材料；所述第二卤素源的熔点为不高于350℃。
其中步骤四得到的钙钛矿与分子筛的复合材料中的卤素与步骤五中的卤素源中的卤素种类不完全相同。
在本发明的一些技术方案中，退火处理的温度为150-350℃，例如，200℃、250℃、300℃。
在本发明的一些技术方案中，所述第二卤素源的熔点为0-350℃，例如，10℃、20℃、30℃、40℃、50℃、60℃、70℃、80℃、90℃、100℃、150℃、200℃、250℃、300℃。
本发明另一个方面提供了一种钙钛矿与分子筛的复合材料，所述钙钛矿与分子筛的复合材料通过本发明上述方法制备而成。
本发明在一个方面提供了一种钙钛矿与分子筛的复合材料，具有分子筛刻蚀、钙钛矿限域生长和分子筛包覆钙钛矿的独特结构。一定条件下可进一步进行卤素离子交换。
在本发明的技术方案中，在步骤一种所述的铅源、铯源和卤素源不进行溶解，且不包含任何溶剂。
在本发明的技术方案中，在步骤一到步骤四中，不使用任何溶剂或溶液。
所述的钙钛矿与分子筛的复合材料，分子筛负载钙钛矿量可根据刻蚀程度进行调控，负载钙钛矿占总重量比0.1～30％，优选为1-20％，例如1％、2％、3％、4％、5％、6％、7％、8％、9％、10％、11％、12％、13％、14％、15％、16％、17％、18％、19％、20％、25％、30％。
所述的铅源为含卤素的铅盐、碳酸铅、硝酸铅、硫酸铅、醋酸铅以及有机铅盐中的一种或几种，所述含卤素的铅盐选自氯化铅、溴化铅或碘化铅。
所述的铯源为含卤素的铯盐、碳酸铯、硝酸铯、硫酸铯、醋酸铯以及有机铯盐中的一种或几种，所述含卤素的铯盐选自氯化铯、溴化铯或碘化铯。
第一卤素源为卤化铵以及有机卤化物中的一种或几种。所述的卤化铵选自氯化铵、溴化铵或碘化铵；有机卤化物选自四丁基溴化铵、四丁基氯化铵、四乙基氯化铵、苄基三乙基氯化铵、三辛基甲基氯化铵、十二烷基三甲基氯化铵、八烷基三甲基溴化铵、十烷基三甲基溴化铵。
所述步骤一中，铯源、铅源的摩尔比为4:1-1:4，优选为1.2:1-1:1.2，例如为1:1。
所述步骤一中，铯源、铅源与第一卤素源中卤素的摩尔量为铯源中铯的摩尔量或者铅源中铅的摩尔量的3倍以上。
所述步骤一中，铯源、铅源的放置方式选自混合放置、上下堆叠或分离放置于反应容器两端，进一步优选地，铯源、铅源分置于反应容器两端并不相互接触。
所述步骤二中，分子筛与铅源和铯源的总质量，或者与铅源、铯源和第一卤素源的总质量的重量比为1:0.1～1:4，例如1:0.3、1:0.5、1:0.7、1:1、1:5、1:2、1:2.5、1:3、1:3.5、1:4。
所述步骤二中，分子筛与铅源、铯源和第一卤素源的摆放方式为，混合放置、上下堆叠或分离放置于反应容器两端，优选为分子筛放置于铅源、铯源和第一卤素源上面。
所述分子筛为沸石分子筛，优选选自硅铝分子筛及取代复合后形成的钛硅分子筛、磷酸铝分子筛、硅酸铝分子筛。
所述步骤三中，升温速率为0.5℃/min～20℃/min，例如为1℃、2℃、3℃、4℃、5℃、10℃、15℃、20℃。
所述步骤三中，反应温度为500℃～1000℃，保温时间为1-24h；例如反应温度为 600℃、700℃、800℃、900℃，保温时间为2h、3h、4h、5h、6h、7h、8h、10h、12h、14h、16h、18h、20h、22h、24h。
所述步骤四中，1-10℃/min降温速率使其冷却至室温，例如为2℃、3℃、4℃、5℃、6℃、7℃、8℃、9℃。
所述步骤五中，第二卤素源优选为有机卤素源，所述有机卤化物选自四丁基溴化铵、四丁基氯化铵、四乙基氯化铵、苄基三乙基氯化铵、三辛基甲基氯化铵、十二烷基三甲基氯化铵、八烷基三甲基溴化铵、十烷基三甲基溴化铵。
本发明再一个方面提供了本发明所述的复合材料作为电致发光、光致发光、白光LED发光材料中的应用。
本发明意外发现较高温度下，反应体系内分子热运动形成对流，铅源、铯源和卤素源会形成卤化铯和卤化铅蒸汽吸附到分子筛孔隙中。溴化铅会首先和分子筛发生反应，通过与Si-OH进行反应，形成中间产物Si-PbX结构，在此过程中产生的HX对分子筛微孔(Si-O网络结构)进行刻蚀，增加钙钛矿原料的吸附，同时使得孔道坍塌将形成封装。进一步地，游离的X -、中间产物再与卤化铯反应生成钙钛矿，从而实现钙钛矿纳米晶与分子筛的高效复合。
分子筛作为钙钛矿的载体，具有形状独特的孔道结构，由于刻蚀作用存在，即使分子筛结构垮塌仍存在一定孔隙可以进行离子交换反应，便于其他离子进入分子筛孔道并合成相关化合物。在高温反应过程中，分子筛的孔道被刻蚀增大，且大量固定钙钛矿原料，这可以限制钙钛矿纳米晶的生长尺寸，而且阻断了纳米晶在高温下的相互作用，减少了发光中心之间团聚引起的浓度淬灭，提升了孔道内钙钛矿的稳定性。
有益效果：本发明和现有技术相比，具有以下显著特点：
1、分子筛孔道的刻蚀实现了对钙钛矿原料的大量吸附和固定，提升了钙钛矿的负载量，且达到同步包覆和限域生长的高效复合效果，具有较好的阻水阻氧效果，提升了钙钛矿复合材料的环境稳定和热稳定性；
2、复合材料由于刻蚀微孔道存在，一定条件下还可进行卤素离子交换，可拓展其光谱范围。复合材料在360-700nm范围内呈现为窄带发射，带隙可调，半峰宽窄，约为20nm左右，且发光强度高，可应用于电致发光、光致发光等照明领域；
3、复合材料采用高温固相合成法，避免了使用有机溶剂，无需引入有机配体，并且操作简单，可重复性好，设备要求低，可大批量进行生产，有利于工业化应用；
4、本发明制备的钙钛矿与分子筛复合材料在照明显示尤其是白光LED等领域具有很 好的应用前景。
5、本发明制备得到的复合材料具有更高的载量，现有技术中用水溶解溴化铅和溴化铯制备复合材料。但是由于溴化铅属于微溶原料，所以分子筛负载量有限。而且由于溴化铅易水解形成碱式盐，溴化铅溴化铯共同溶解，所以在干燥过程中形成的是钙钛矿加结晶水的结构，因此其需要增加退火过程以进行结晶水的脱水。
附图说明
图1是本发明实例1中所制备的复合材料的白光图片。
图2是本发明实例2中所制备的复合材料的扫描电子显微镜图。
图3是本发明实例2中所制备的复合材料的X射线衍射图。
图4是本发明实例7中所制备的复合材料的发光光谱图。
图5是本发明实施例1和14中制备绿光和红光复合材料结合蓝光芯片制备的白光LED光谱(a)及不同电流下的光谱(b)。
图6是本发明实施例中蓝光、绿光、红光复合材料的水稳定性(a)、80℃-80％湿度环境老化稳定性(b)以及紫外辐照稳定性(c)。
图7是本发明实施例中蓝光(a)、绿光(b)、红光(c)复合材料的热稳定性。
图8是本发明中反应机理表征，即溴和铅同时存在时在结合能谱中Si 2p(a)以及O 1s(b)轨道结合能往低结合能方向出现大的偏移，说明新结构的生成。
具体实施方式
下面结合实施例对本发明作进一步的说明，但不应以此限制本发明的保护范围。以下各实施例中，原料均为直接购买。
实施例1 钙钛矿与分子筛的复合材料的制备
包含以下步骤：
步骤一，分别称取1.47g(4mmol)溴化铅和0.851g(4mmol)溴化铯加入到氧化铝坩埚中；
步骤二，在原料上覆盖2g的分子筛作为基材；
步骤三，将装有原料的氧化铝坩埚放入马弗炉中，加热100min升温至650℃，保温5h；
步骤四，以5℃/min冷却至室温后即可获得钙钛矿与分子筛复合材料。
本实施例制备的复合发光材料的产量较高，钙钛矿负载量约为20％，粉末白光图片如图1所示，可观察到钙钛矿被均匀镶嵌在分子筛的孔隙中，形成了限域生长和同步包覆的结构。
实施例2 钙钛矿与分子筛的复合材料的制备
包含以下步骤:
步骤一，分别称取1.764g(4.8mmol)溴化铅和0.851g(4mmol)溴化铯，加入到氧化铝坩埚中；
步骤二，在原料上覆盖2.25g的分子筛作为基材；
步骤三，将装有原料的氧化铝坩埚放入马弗炉中，加热75min的升温速率升温至650℃，保温24h；
步骤四，以3℃/min冷却至室温后即可获得钙钛矿与分子筛复合材料。
本实例也可得到质量和产量均较高的绿色荧光粉，钙钛矿负载量约为18％，其扫描电子显微镜图如图2所示，钙钛矿复合粉体XRD结果如图3所示。
实施例3 钙钛矿与分子筛的复合材料的制备
包含以下步骤:
步骤一，分别称取5.86g(16mmol)溴化铅和0.851g(4mmol)溴化铯，加入到氧化铝坩埚中；
步骤二，在原料上覆盖10g的分子筛作为基材；
步骤三，将装有原料的氧化铝坩埚放入马弗炉中，加热100min的升温速率升温至650℃，保温1h；
步骤四，以10℃/min冷却至室温后即可获得钙钛矿与分子筛复合材料。
本实例溴化铅的投料较多，整体复合荧光粉产量稍低。
实施例4 钙钛矿与分子筛的复合材料的制备
包含以下步骤:
步骤一，分别称取1.47g(4mmol)溴化铅和0.6734g(4mmol)氯化铯，加入到氧化铝坩埚中；
步骤二，在原料上覆盖2g的分子筛作为基材；
步骤三，将装有原料的氧化铝坩埚放入马弗炉中，加热75min升温至670℃，保温5h；
步骤四，以8℃/min冷却至室温后即可获得钙钛矿与分子筛复合材料。
本实例可合成蓝色的荧光粉，产量较高。
实施例5 钙钛矿与分子筛的复合材料的制备
包含以下步骤:
步骤一，分别称取1.112g(4mmol)氯化铅和0.6734g(4mmol)氯化铯，0.053g(1mmol)氯化铵，加入到氧化铝坩埚中；
步骤二，在原料上覆盖2g的分子筛作为基材；
步骤三，将装有原料的氧化铝坩埚放入马弗炉中，加热75min升温至670℃，保温5h；
步骤四，以2℃/min冷却至室温后即可获得钙钛矿与分子筛复合材料。
本实例可合成紫色的荧光粉，产量较高。
实施例6 钙钛矿与分子筛的复合材料的制备
包含以下步骤:
步骤一，分别称取1.47g(4mmol)溴化铅和0.851g(4mmol)溴化铯，加入到氧化铝坩埚中；
步骤二，在原料上覆盖5g的分子筛作为基材；
步骤三，将装有原料的氧化铝坩埚放入马弗炉中，加热100min升温至500℃，保温5h；
步骤四，以1℃/min冷却至室温后即可获得钙钛矿与分子筛复合材料。
本实例可合成绿色的荧光粉，但部分分子筛未被反应，钙钛矿负载量约为3％。
实施例7 钙钛矿与分子筛的复合材料的制备
包含以下步骤:
步骤一，分别称取1.764g(4.8mmol)溴化铅和0.851g(4mmol)溴化铯，加入到氧化铝坩埚中；
步骤二，在原料上覆盖2.5g的分子筛作为基材；
步骤三，将装有原料的氧化铝坩埚放入马弗炉中，加热30min升温至650℃，保温5h；
步骤四，以5℃/min冷却至室温后即可获得钙钛矿与分子筛复合材料。
本实例可合成绿色的荧光粉，钙钛矿负载量约为15％，荧光发射光谱如图4所示，可见材料的半峰宽很窄，仅为20nm左右，尺寸均匀。
实施例8 钙钛矿与分子筛的复合材料的制备
包含以下步骤:
步骤一，分别称取1.764g(4.8mmol)溴化铅和0.851g(4mmol)溴化铯，0.098g(1mmol)溴化铵，加入到氧化铝坩埚中；
步骤二，在原料上覆盖2.5g的分子筛作为基材；
步骤三，将装有原料的氧化铝坩埚放入马弗炉中，加热1300min升温至670℃，保温5h；
步骤四，以5℃/min冷却至室温后即可获得钙钛矿与分子筛复合材料。
本实例可合成绿色的荧光粉，底部有结块，产量降低。
实施例9 钙钛矿与分子筛的复合材料的制备
包含以下步骤:
步骤一，分别称取1.764g(4.8mmol)溴化铅和0.851g(4mmol)溴化铯，加入到氧化铝坩埚中；
步骤二，在原料上覆盖2.5g的分子筛作为基材；
步骤三，将装有原料的氧化铝坩埚放入马弗炉中，加热300min升温至1000℃，保温5h；
步骤四，以5℃/min冷却至室温后即可获得钙钛矿与分子筛复合材料。
本实例可合成绿色的荧光粉，钙钛矿负载过多结块产生。
实施例10 钙钛矿与分子筛的复合材料的制备
包含以下步骤：
步骤一，分别称取1.47g(4mmol)溴化铅和0.851g(4mmol)溴化铯加入到氧化铝坩埚中；
步骤二，在原料上覆盖10g的分子筛作为基材；
步骤三，将装有原料的氧化铝坩埚放入马弗炉中，加热100min升温至650℃，保温15h；
步骤四，以5℃/min冷却至室温后即可获得钙钛矿与分子筛复合材料。
本实例可合成绿色的荧光粉，但部分分子筛未被反应，钙钛矿负载量约为1％。
实施例11 钙钛矿与分子筛的复合材料的制备
包含以下步骤：
步骤一，分别称取1.47g(4mmol)溴化铅和0.851g(4mmol)溴化铯加入到氧化铝坩埚中；
步骤二，在原料上覆盖1g的分子筛作为基材；
步骤三，将装有原料的氧化铝坩埚放入马弗炉中，加热100min升温至650℃，保温10h；
步骤四，以5℃/min冷却至室温后即可获得钙钛矿与分子筛复合材料。
本实例可合成绿色的荧光粉，但由于分子筛的加入量较少，钙钛矿负载过多结块产生。
实施例12 钙钛矿与分子筛的复合材料的制备
包含以下步骤：
步骤一，分别称取1.068g(4mmol)碳酸铅、0.851g溴化铯(4mmol)、0.79g(8mmol)溴化铵加入到氧化铝坩埚中；
步骤二，在原料上覆盖2g的分子筛作为基材；
步骤三，将装有原料的氧化铝坩埚放入马弗炉中，加热100min升温至650℃，保温5h；
步骤四，以5℃/min冷却至室温后即可获得钙钛矿与分子筛复合材料。
本实例可合成绿色的荧光粉。
实施例13 钙钛矿与分子筛的复合材料的制备
包含以下步骤：
步骤一，分别称取1.5g(4.6mmol)醋酸铅、0.8g(4.2mmol)醋酸铯、3.2g(9.9mmol)四丁基溴化铵加入到氧化铝坩埚中；
步骤二，在原料上覆盖2g的分子筛作为基材；
步骤三，将装有原料的氧化铝坩埚放入马弗炉中，加热100min升温至650℃，保温5h；
步骤四，以5℃/min冷却至室温后即可获得钙钛矿与分子筛复合材料。
本实例可合成绿色的荧光粉。
实施例14 钙钛矿与分子筛的复合材料中卤素种类的取代实验
在坩埚中加入过量四丁基碘化铵与实施例1中的复合材料粉体的混合物，300℃进行退火处理即可完成复合材料中溴的碘取代，从而使得复合材料荧光从绿色变成红色。
在坩埚中加入过量四乙基氯化铵与实施例1中的复合材料粉体的混合物，250℃进行退火处理即可完成复合材料中溴的氯取代，从而使得复合材料荧光从绿色变成蓝紫色。
通过以上实施例可知，通过本发明的方法可以采用一步法制备获得负载钙钛矿的分子筛复合材料，不同的铅源、不同的铯源，不同的配比均可以制备获得复合材料。且通过调 节铅源中的卤素种类，还可以获得不同颜色的复合材料。而通过调节各组分的配比以及反应温度和时间可以获得负载更多钙钛矿，且反应更完全的复合材料。此外，还可以通过进一步离子交换形成更多色彩的钙钛矿复合材料。
实施例15
分别检测实施例1和14中制备绿光和红光复合材料结合蓝光芯片制备的白光LED光谱及不同电流下的光谱，实验结果见图5。
分别检测实施例中蓝光、绿光、红光复合材料的水稳定性、80℃-80％湿度环境老化稳定性以及紫外辐照稳定性，以及蓝光、绿光、红光复合材料的热稳定性。实验结果见图6-7，说明本发明制备得到的材料稳定性高。
图8显示了本发明材料的结合能谱图，说明发明中反应机理表征，即溴和铅同时存在时在结合能谱中Si 2p(a)以及O 1s(b)轨道结合能往低结合能方向出现大的偏移，说明新结构的生成。
本发明的方法完全避免了使用有机溶剂，无需引入有机配体。也不需要加入水等液体溶剂，在全固相的条件下实现了制备，所以整个制备过程只有一步，反应方法和所用的设备非常简单，反应时间很短。更重要的是，本发明制备过程中进一步刻蚀分子筛的孔道，形成了包覆结构，提高了其上负载的钙钛矿的稳定性。
上述实施例为本发明的部分实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

  1. 钙钛矿与分子筛的复合材料的制备方法，其特征在于，所述制备方法包括以下步骤：
    步骤一，将铅源、铯源，加入到反应容器中，
    或者，将铅源、铯源和第一卤素源，加入到反应容器中；
    步骤二，将分子筛均匀分散在反应容器中；
    步骤三，进行高温处理，反应温度为500℃以上至反应完全；
    步骤四，冷却至室温后即可获得钙钛矿与分子筛的复合材料；
    优选地，在步骤一到步骤四中，不使用任何溶剂或溶液；
    优选地，在步骤一种所述的铅源、铯源和卤素源不进行溶解，且不包含任何溶剂。
  2. 根据权利要求1所述的制备方法，其特征在于，所述钙钛矿与分子筛的复合材料的制备方法还包括步骤五，
    步骤五，将所得的钙钛矿与分子筛的复合材料与第二卤素源进行退火处理，得到以卤素源中卤素进行取代的钙钛矿与分子筛的取代的复合材料；所述第二卤素源的熔点为不高于350℃；其中步骤四得到的钙钛矿与分子筛的复合材料中的卤素与步骤五中的卤素源中的卤素种类不完全相同；
    优选地，其中步骤五的退火处理的温度为150-350℃；
    更优选地，第二卤素源为有机卤素源，所述有机卤化物选自四丁基溴化铵、四丁基氯化铵、四乙基氯化铵、苄基三乙基氯化铵、三辛基甲基氯化铵、十二烷基三甲基氯化铵、八烷基三甲基溴化铵、十烷基三甲基溴化铵中的至少一种。
  3. 根据权利要求1所述的制备方法，其特征在于，所述的铅源为含卤素的铅盐、碳酸铅、硝酸铅、硫酸铅、醋酸铅以及有机铅盐中的一种或几种；
    所述的铯源为含卤素的铯盐、碳酸铯、硝酸铯、硫酸铯、醋酸铯以及有机铯盐中的一种或几种；
    第一卤素源为卤化铵以及有机卤化物中的一种或几种；
    优选地，所述含卤素的铅盐选自氯化铅、溴化铅或碘化铅；所述含卤素的铯盐选自氯化铯、溴化铯或碘化铯；所述的卤化铵选自氯化铵、溴化铵或碘化铵；有机卤化物选自四丁基溴化铵、四丁基氯化铵、四乙基氯化铵、苄基三乙基氯化铵、三辛基甲基氯化铵、十 二烷基三甲基氯化铵、八烷基三甲基溴化铵或十烷基三甲基溴化铵。
  4. 根据权利要求1所述的制备方法，其特征在于，所述步骤一中，铯源、铅源的摩尔比为4:1-1:4，优选为1.2:1-1:1.2。
  5. 根据权利要求1所述的制备方法，其特征在于，所述步骤一中，铯源、铅源与第一卤素源中卤素的摩尔量为铯源中铯的摩尔量或者铅源中铅的摩尔量的3倍以上。
  6. 根据权利要求1所述的制备方法，其特征在于，分子筛的质量与铅源和铯源的总质量，或者与铅源、铯源和第一卤素源的总质量的重量比为1:0.1～1:4。
  7. 根据权利要求1所述的制备方法，其特征在于，所述分子筛为沸石分子筛，优选选自硅铝分子筛及取代复合后形成的钛硅分子筛、磷酸铝分子筛、硅酸铝分子筛。
  8. 根据权利要求1所述的制备方法，其特征在于，所述步骤三中，反应温度为500℃～1000℃，升温速率为0.5℃/min～20℃/min，保温时间为1-24h；
    所述步骤四中，1-10℃/min降温速率使其冷却至室温。
  9. 一种钙钛矿与分子筛的复合材料，其特征在于，所述复合材料通过权利要求1-8任一项所述的制备方法获得。
  10. 权利要求1-8任一项所述制备方法获得的复合材料或权利要求9所述的复合材料作为电致发光、光致发光、白光LED发光材料中的应用。
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