CN112794362A - Inorganic perovskite material, preparation method thereof and LED device - Google Patents
Inorganic perovskite material, preparation method thereof and LED device Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000002904 solvent Substances 0.000 claims abstract description 27
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 26
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 19
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 18
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- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000460 chlorine Substances 0.000 claims abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- -1 cesium halide Chemical class 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical group Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 10
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical group [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 9
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001622 bismuth compounds Chemical class 0.000 claims description 4
- 150000001805 chlorine compounds Chemical class 0.000 claims description 4
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical group C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- 239000001119 stannous chloride Substances 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 2
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 2
- ATZQZZAXOPPAAQ-UHFFFAOYSA-M caesium formate Chemical compound [Cs+].[O-]C=O ATZQZZAXOPPAAQ-UHFFFAOYSA-M 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- KOPBYBDAPCDYFK-UHFFFAOYSA-N caesium oxide Chemical compound [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001942 caesium oxide Inorganic materials 0.000 claims description 2
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 claims description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 2
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000003495 polar organic solvent Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- PNYYBUOBTVHFDN-UHFFFAOYSA-N sodium bismuthate Chemical compound [Na+].[O-][Bi](=O)=O PNYYBUOBTVHFDN-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 7
- 239000011247 coating layer Substances 0.000 claims 2
- 150000001621 bismuth Chemical class 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 22
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- 238000001514 detection method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- ORFSSYGWXNGVFB-UHFFFAOYSA-N sodium 4-amino-6-[[4-[4-[(8-amino-1-hydroxy-5,7-disulfonaphthalen-2-yl)diazenyl]-3-methoxyphenyl]-2-methoxyphenyl]diazenyl]-5-hydroxynaphthalene-1,3-disulfonic acid Chemical compound COC1=C(C=CC(=C1)C2=CC(=C(C=C2)N=NC3=C(C4=C(C=C3)C(=CC(=C4N)S(=O)(=O)O)S(=O)(=O)O)O)OC)N=NC5=C(C6=C(C=C5)C(=CC(=C6N)S(=O)(=O)O)S(=O)(=O)O)O.[Na+] ORFSSYGWXNGVFB-UHFFFAOYSA-N 0.000 description 4
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 4
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- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 231100000956 nontoxicity Toxicity 0.000 description 2
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
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- 238000001878 scanning electron micrograph Methods 0.000 description 2
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- 238000003860 storage Methods 0.000 description 2
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L tin(ii) bromide Chemical compound Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 description 2
- JTDNNCYXCFHBGG-UHFFFAOYSA-L tin(ii) iodide Chemical compound I[Sn]I JTDNNCYXCFHBGG-UHFFFAOYSA-L 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241000083879 Polyommatus icarus Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940073609 bismuth oxychloride Drugs 0.000 description 1
- TXKAQZRUJUNDHI-UHFFFAOYSA-K bismuth tribromide Chemical compound Br[Bi](Br)Br TXKAQZRUJUNDHI-UHFFFAOYSA-K 0.000 description 1
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 1
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
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- 230000001681 protective effect Effects 0.000 description 1
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- 239000004065 semiconductor Substances 0.000 description 1
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- 229940108184 stannous iodide Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- KOECRLKKXSXCPB-UHFFFAOYSA-K triiodobismuthane Chemical compound I[Bi](I)I KOECRLKKXSXCPB-UHFFFAOYSA-K 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
- C01G29/006—Compounds containing, besides bismuth, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- C09K11/74—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing arsenic, antimony or bismuth
- C09K11/7428—Halogenides
- C09K11/7435—Halogenides with alkali or alkaline earth metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/01—Particle morphology depicted by an image
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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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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Abstract
The invention discloses an inorganic perovskite material, a preparation method thereof and an LED device, wherein the preparation method comprises the following steps: s1, dissolving a tin source and a bismuth source in a first solvent to obtain a first solution; dissolving a cesium source in a second solvent to obtain a second solution; the tin source is a stannous compound; and the cesium source, the tin source and the bismuth source are chlorine sources, and/or the first solvent and the second solvent are chlorine sources; and S2, mixing the first solution and the second solution, stirring and heating for reaction, then carrying out solid-liquid separation, washing and drying. The preparation raw materials of the invention have low cost, safety and innocuity, the synthesis operation is simple, the crystal can be obtained by heating reaction, the equipment requirement is low, the reaction condition requirement is loose, the product has good crystallinity and uniform particles, the fluorescence yield is high, the obtained inorganic perovskite material has no organic group, the light stability and the thermal stability are strong, and the invention has the potential application value of preparing blue light fluorescent powder with high fluorescence yield, and further can be applied to preparing LED devices.
Description
Technical Field
The invention relates to the technical field of photoelectric materials, in particular to an inorganic perovskite material, a preparation method thereof and an LED device.
Background
In the existing perovskite materials, two-dimensional hybrid organic-inorganic perovskites (2D-HOIPs) are typical, and the most common synthesis method is a solution cooling method, which specifically comprises the steps of dissolving reaction raw materials in a same solution according to a certain proportion, heating to a certain temperature to completely dissolve the reaction raw materials, and then cooling and crystallizing; when the temperature is reduced, the solubility of the 2D-HOIPs is reduced and the 2D-HOIPs are separated out from the solution, and in order to control the crystallization speed to obtain crystals with good crystallinity, a constant cooling rate needs to be kept, so that the key of crystal acquisition depends on a controlled cooling program, and the synthesis method has high requirements on equipment. In addition, the 2D-HOIPs contain organic groups, so that the material has poor light stability and is easy to decompose under illumination; furthermore, the organic group in the perovskite causes poor conductivity of the perovskite, and current is difficult to inject, so that deep blue light is difficult to obtain, and the efficiency and the brightness of the device are influenced. It is reported that 2D-HOIPs can be applied to the preparation of electroluminescent devices, but in the application process, it is necessary to dissolve it in an organic solvent first, and then prepare a luminescent film by spin coating or evaporation, so the application is complicated, and its solubility is generally poor, crystallization is too fast, and then an uneven discrete film can be formed, and it is difficult to satisfy the emission of pure blue light.
In addition, most of the existing common blue light powder is mixed with Eu2+As the activated central ion, the high temperature solid phase method is a common synthesis method, but the method has high reaction temperature and large energy consumption, and the heterogeneous phase such as Eu is easy to appear in the reaction at high temperature2+The impurities are oxidized to cause impurity phases, and the quality of the product is further influenced. In addition, the synthesis conditions are harsh, the equipment requirements are high, and if raw materials which are easy to oxidize are involved, the reaction needs to be carried out under a protective atmosphere. For example, Eu is added2+The raw materials are generally Eu, which is relatively easy to store, when being introduced into the fluorescent powder3+Oxide Eu of2O3Therefore, the reaction is carried out in a reducing gas H2Under the protection of (1), but the construction of a reduction system is not easy due to Eu introduced into the phosphor2+The content is small, and the system is only very largeWith a very small amount of oxidizing agent (e.g., water and oxygen), it is possible to reduce the amount of Eu originally contained2+The oxidation will cause the product to fail, and therefore, the reaction conditions are very severe.
Cesium tin chloride (Cs)2SnCl6) The double perovskite structure is an inorganic non-metallic material and is also a direct band gap semiconductor material. Into which Bi is doped3+Produced Cs2SnCl6:Bi3+Under the condition of external excitation of light, electricity and the like, the fluorescent light can emit fluorescence in a visible light wave band, has high luminous efficiency and has potential value in a white light LED. Cesium tin chloride can be synthesized by a hydrothermal method, and CsSnCl is easily formed in air due to the divalent Sn of the raw material of the product3The product crystallinity and fluorescence yield and phase purity are seriously affected by the impurity phase. Therefore, a perovskite material preparation method which is simple in synthesis process, low in equipment requirement, good in product crystallinity and high in fluorescence yield is urgently needed.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides an inorganic perovskite material, a preparation method thereof and an LED device.
In a first aspect of the present invention, there is provided a method for preparing an inorganic perovskite material, comprising the steps of:
s1, dissolving a tin source and a bismuth source in a first solvent to obtain a first solution; dissolving a cesium source in a second solvent to obtain a second solvent; the tin source is a stannous compound;
additionally, the cesium source, the tin source, and the bismuth source are chlorides, and/or the first solvent and the second solvent are chlorine sources;
s2, mixing the first solution and the second solution, stirring and heating to react to generate Cs2SnCl6:Bi3+Precipitating, then carrying out solid-liquid separation, washing and drying.
The preparation method of the inorganic perovskite material provided by the embodiment of the invention has at least the following beneficial effects: the preparation method adopts liquid phase synthesis, wherein Bi is introduced3+Ion, Bi3+At all timesBi which can maintain stability even when completely exposed to air or water at room temperature3+Introduction of ions, capable of being in situ with Cs2SnCl6The defect energy level is introduced to the energy level of the blue light, so that the electron transition is easier, and the intense 456nm blue light is caused; meanwhile, a protective layer of basic bismuth oxychloride BiOCl (non-toxic) can be covered on the surface of the material, so that the material is protected from the influence of external environment such as water and oxygen, and the stability of the material is improved. The preparation method has the advantages of low raw material cost, safety, no toxicity, simple synthesis operation, capability of obtaining crystals through heating reaction, low equipment requirement, loose reaction condition requirement, good product crystallinity, uniform particles, high fluorescence yield, no organic groups in the obtained inorganic perovskite material, strong light stability and thermal stability, potential application value of preparing blue-light fluorescent powder with high fluorescence yield, capability of being applied to preparing LED devices and high display color saturation.
According to some embodiments of the invention, in step S1, the molar ratio of the cesium source, the tin source, and the bismuth source is 2:1: 6.
According to some embodiments of the invention, the first solvent and the second solvent are hydrochloric acid; the cesium source is selected from inorganic cesium compounds and/or organic cesium compounds; the tin source is selected from inorganic stannous compound and/or organic stannous compound; the bismuth source is selected from an inorganic bismuth compound and/or an organic bismuth compound.
According to some embodiments of the invention, the cesium source is selected from at least one of cesium halides (such as cesium chloride, cesium iodide and cesium bromide), cesium oxide, cesium hydroxide, cesium formate; the tin source is at least one selected from stannous oxalate, stannous acetate, stannous halide (such as stannous chloride, stannous iodide and stannous bromide), and stannous oxide; the bismuth source is at least one selected from bismuth oxide, bismuth halide (such as bismuth chloride, bismuth iodide and bismuth bromide), bismuth sulfate, bismuth nitrate and sodium bismuthate.
According to some embodiments of the invention, the hydrochloric acid is concentrated hydrochloric acid with a mass fraction of more than 20%.
According to some embodiments of the invention, the first solvent and the second solvent are polar organic solvents and the cesium source, the tin source and the bismuth source are chlorides.
According to some embodiments of the invention, the first solvent and the second solvent are selected from at least one of N, N-dimethylformamide, dimethyl sulfoxide, ethanol; the cesium source is selected from cesium chloride, the tin source is selected from stannous chloride, and the bismuth source is selected from bismuth chloride.
According to some embodiments of the invention, in the step S2, the reaction temperature of the stirring and heating reaction is 60 to 120 ℃.
In addition, to facilitate dissolution of the tin source, bismuth source, and cesium source, dissolving the tin source, bismuth source in the first solvent and dissolving the cesium source in the second solvent can be accelerated by heating.
In a second aspect of the present invention, there is provided an inorganic perovskite material, which is prepared by any one of the methods for preparing an inorganic perovskite material provided in the first aspect of the present invention; having a chemical formula of Cs2SnCl6:Bi3+。
In a third aspect of the invention, an LED device is provided, which includes an LED chip and a coating applied on the surface of the LED chip, wherein the coating is prepared by mixing raw materials including any one of the inorganic perovskite materials provided by the second aspect of the invention and a binder and coating the raw materials on the surface of the LED chip.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is a reaction system employed in the preparation of an inorganic perovskite material of example 1;
FIG. 2 is an SEM image of an inorganic perovskite material of example 1;
FIG. 3 is an SEM image of an inorganic perovskite material of comparative example 1;
FIG. 4 is a PL diagram for the inorganic perovskite material of example 1;
FIG. 5 is a PL diagram for the inorganic perovskite materials of example 1 and comparative example 1;
FIG. 6 is a plot of PL relative intensity versus inorganic perovskite material of example 1 and comparative example 2;
FIG. 7 is a plot of PL relative intensity versus inorganic perovskite material of example 1 and comparative example 3;
FIG. 8 is a PL profile before and after exposure of the inorganic perovskite material of example 1 to light;
FIG. 9 is an XRD pattern of the inorganic perovskite material of example 1 before and after being placed under illumination;
FIG. 10 is an XRD pattern of the inorganic perovskite material of comparative example 1;
FIG. 11 is a PL profile of the inorganic perovskite material of example 1 after storage at different temperatures;
FIG. 12 shows the inorganic perovskite Material Cs of example 12SnCl6:Bi3+The blue light CIE coordinate diagram of (a).
Reference numerals: 11-double-mouth glass flask, 12-oil bath kettle, 13-condenser, 14-rubber tube, 15-funnel and 16-tail gas treatment container.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
An inorganic perovskite material is prepared and synthesized in a reaction system shown in figure 1 by a liquid phase method, and the preparation method comprises the following steps:
s1, weighing 0.6734g of cesium chloride, 0.4010g of stannous oxalate and 0.0189g of bismuth chloride, putting the stannous oxalate and the bismuth chloride into a double-mouth glass flask 11, then injecting 5mL of concentrated hydrochloric acid into the double-mouth glass flask, and putting a rotary stirring magneton into the double-mouth glass flask; mixing cesium chloride and 11ml of concentrated hydrochloric acid in a small bottle, and heating the small bottle to 80 ℃ for about 30min by using a water bath to obtain a cesium chloride-concentrated hydrochloric acid mixed solution;
s2, putting the double-mouth glass flask 11 into an oil bath 12 with a heat collection type constant-temperature heating magnetic stirrer, wherein the upper opening of the double-mouth glass flask 11 is connected with a condenser 13, the side opening of the double-mouth glass flask is connected with a funnel 15 through a rubber tube 14, and the opening of the funnel 15 is contacted with the surface of a potassium hydroxide aqueous solution contained in a tail gas treatment container 16 so as to be used for discharging concentrated hydrochloric acid volatilized in the double-mouth glass flask 11, carbon dioxide and formic acid generated by reaction into the potassium hydroxide aqueous solution contained in the tail gas treatment container, so that accidents caused by over-high pressure of the flask are prevented; then starting a heat collection type constant temperature heating magnetic stirrer to stir the material in the double-mouth glass flask 11;
and S3, starting the condenser 13, raising the temperature of the oil bath pot 12 to 80 ℃, wherein the heating rate is 5.7 ℃/min, opening the side opening when the sample is heated to 80 ℃, and pouring the cesium chloride-concentrated hydrochloric acid mixed solution into a reaction glass bottle. Closing the side opening, and then preserving heat for 3 hours to carry out reaction;
s4, after the reaction is finished, closing the heat collection type heating magnetic stirrer and the oil bath pot 12, taking the double-opening glass bottle 11 out of the oil bath pot 12, and quickly taking down the condenser pipe 13 and the funnel 14 to prevent air from entering; cooling the temperature of the double-mouth glass flask 11 to room temperature, then pouring the solid-liquid phase product in the double-mouth glass flask 11 into a glass beaker, covering the mouth of the glass beaker with tinfoil paper, standing for 8 hours, pouring out a clear liquid after layering, cleaning the product particles with absolute ethyl alcohol, standing for 4 hours, repeating the operation for 3-4 times until the pH of the supernatant absolute ethyl alcohol liquid is neutral, and finishing cleaning;
s5, covering the mouth of the beaker filled with the cleaned solid product by using tin foil paper, then putting the beaker into a vacuum drying box, and drying the beaker for 6 hours at 70 ℃ in a vacuum environment; and then putting the product into an agate mortar, grinding the product into powder, putting the powder into a small glass bottle, sealing, drying and storing.
Example 2
An inorganic perovskite material, which comprises the following steps:
s1, weighing 0.6734g of cesium chloride, 0.4514mg of stannous chloride dihydrate and 0.0189g of bismuth chloride, putting the stannous chloride dihydrate and the bismuth chloride into a reaction glass bottle, and then injecting 5mL of ethanol into the reaction glass bottle to obtain a first mixture; mixing cesium chloride and 11ml of ethanol in a small vial, and heating the small vial to 60 ℃ for about 30mins using a water bath to obtain a second mixture;
s2, raising the temperature of the first mixture obtained in the step S1 to 80 ℃ under the stirring state, wherein the temperature raising rate is 8 ℃/min, and when the temperature of the sample is raised to 80 ℃, the side opening is opened, and the second mixture is poured into a reaction glass bottle. Closing the side opening, and then carrying out heat preservation reaction for 3 hours;
s3, cooling the material to room temperature after the reaction is finished, standing for layering to obtain a solid product, washing product particles with absolute ethyl alcohol, standing for 4 hours, then washing the product particles with absolute ethyl alcohol, standing for 4 hours, repeating the steps for 3-4 times until the pH value of the supernatant absolute ethyl alcohol liquid is neutral, and finishing washing; then placing the mixture in a vacuum drying oven, and drying the mixture for 6 hours at 70 ℃ in a vacuum environment; and putting the product into an agate mortar, grinding the product into powder, putting the powder into a small glass bottle, sealing, drying and storing.
Comparative example 1
The preparation method of the inorganic perovskite material is different from that of the inorganic perovskite material in the embodiment 1 in that: in this comparative example, a hydrothermal reactor was used in place of the conventional two-neck glass flask, and the operation was otherwise the same as in example 1. The specific mode is as follows:
s1, weighing 0.6734g of cesium chloride, 0.4010g of stannous oxalate and 0.0189g of bismuth chloride, putting the stannous oxalate and the bismuth chloride into a polytetrafluoroethylene lining of a hydrothermal kettle, then injecting 5mL of concentrated hydrochloric acid into the lining, and putting a rotary stirring magneton into the lining; mixing cesium chloride and 11ml of concentrated hydrochloric acid in a small bottle, and heating the small bottle to 80 ℃ for about 30min by using a water bath to obtain a cesium chloride-concentrated hydrochloric acid mixed solution;
s2, putting the polytetrafluoroethylene lining into a matched steel sleeve (body), putting the steel sleeve into an oil bath pan with a heat collection type constant temperature heating magnetic stirrer, starting the heat collection type constant temperature heating magnetic stirrer to stir materials in the polytetrafluoroethylene lining, and covering an opening on the lining with a matched cover of the polytetrafluoroethylene lining;
and S3, raising the temperature of the oil bath to 80 ℃, wherein the heating rate is 5.7 ℃/min, when the temperature of the sample is raised to 80 ℃, the cover on the polytetrafluoroethylene inner liner is opened, and the cesium chloride-concentrated hydrochloric acid mixed solution is poured into the inner liner. Closing the cover, tightly covering the whole lining cover with a steel sleeve cover, and then preserving heat for 3 hours to carry out reaction;
s4, after the reaction is finished, closing the heat collection type heating magnetic stirrer and the oil bath pot, taking the hydrothermal reaction kettle out of the oil bath pot, cooling the temperature of the hydrothermal reaction kettle to room temperature, taking out the polytetrafluoroethylene lining, pouring a solid-liquid phase product in the hydrothermal reaction kettle into a glass beaker, covering the mouth of the glass beaker with tin foil paper, standing for 8 hours, pouring out a clear liquid after layering, washing the product particles with absolute ethyl alcohol, standing for 4 hours, repeating the steps for 3-4 times until the pH of the supernatant absolute ethyl alcohol liquid is neutral, and finishing the washing;
s5, covering the mouth of the beaker filled with the cleaned solid product by using tin foil paper, then putting the beaker into a vacuum drying box, and drying the beaker for 6 hours at 70 ℃ in a vacuum environment; and then putting the product into an agate mortar, grinding the product into powder, putting the powder into a small glass bottle, sealing, drying and storing.
Comparative example 2
The preparation method of the inorganic perovskite material is different from that of the inorganic perovskite material in the embodiment 1 in that: in this comparative example, tin tetrachloride was used instead of stannous oxalate, and the other operations were the same as in example 1.
Comparative example 3
The preparation method of the inorganic perovskite material is different from that of the inorganic perovskite material in the embodiment 1 in that: in this comparative example, bismuth chloride was not added, and the other operations were the same as in example 1.
The results of observing the inorganic perovskite materials prepared in example 1 and comparative example 1 by Scanning Electron Microscopy (SEM) are shown in fig. 2 and 3, respectively, and SEM detection is performed at nearly the same magnification, so that the particle size and crystallization of the sample can be detected at the same magnification. From fig. 2 and 3, the inorganic perovskite material of example 1 has good crystallinity and uniform particles, as compared with comparative example 1. Photoluminescence spectra (PL) of the inorganic perovskite materials prepared in example 1 and comparative examples 1 to 3 were respectively detected, and the results are shown in FIGS. 4 to 7. As can be seen from FIG. 4, the peak position of the inorganic perovskite material of example 1 is 456 nm; the 456nm emission peak position is fixed, the peak position of the excitation spectrum is detected to be 362nm, namely, under the 362nm excitation light source, the 456nm blue light can be obtained through photoluminescence. As can be seen from fig. 5, the inorganic perovskite material prepared by the liquid phase method in example 1 has a stronger luminous intensity than the inorganic perovskite material prepared by the hydrothermal method in comparative example 1. As can be seen from FIGS. 2 and 3, the larger particle size of the example and the stronger crystallinity than those of the crystal of comparative example 1 and the larger number of the smaller particles of the crystal of comparative example 1 indicate that the crystallinity of the product obtained by the reaction in the hydrothermal reactor is inferior to that obtained in the double-neck glass flask, which affects the luminous intensity of the product.
As can be seen from fig. 6, in comparative example 2, the Sn source was replaced by tin tetrachloride, and the emission intensity of the target product was not as high as that of the product obtained in example 1 using tin (ii) as the reaction material. As can be seen from FIG. 7, Bi was doped in example 13+Cs of (A)2SnCl6The luminous intensity of the material is far higher than that of the material of comparative example 3 which is not doped with Bi3+Cs of (A)2SnCl6The luminous intensity of the material.
In addition, the inorganic perovskite material prepared in example 1 was left to stand under light for 15 days, and the results of photoluminescence spectrum detection were performed on the inorganic perovskite material before and after the left to stand under light, respectively, as shown in fig. 8, and the results of photoluminescence spectrum detection were performed on the inorganic perovskite material before and after the left to stand under light in example 1 and the inorganic perovskite material prepared in comparative example 1, respectively, using an X-ray diffractometer (XRD), as shown in fig. 9 and 10. As can be seen from fig. 8 and 9, the inorganic perovskite material obtained in example 1 has high photostability. As is clear from fig. 9 and 10, XRD of the inorganic perovskite material of comparative example 1 is a pure phase, which is not different from XRD of the inorganic perovskite material of example 1, and it is demonstrated that the pure phase can be synthesized by the raw material addition method according to this synthesis scheme when the reaction vessel is replaced (double-neck glass flask, hydrothermal reaction vessel). The inorganic perovskite material prepared in example 1 was stored at different temperatures for 1 day, and then the inorganic perovskite material was subjected to photoluminescence spectrum detection, and the obtained results are shown in fig. 11. As can be seen from fig. 11, the inorganic perovskite material of example 1 has high thermal stability, and the emission peak position thereof is not changed after storage under different temperature conditions, and the emission intensity thereof is not significantly different, and no PL shift occurs.
FIG. 12 shows the inorganic perovskite material Cs obtained in example 12SnCl6:Bi3+The black point M is a powder CIE coordinate calculated according to the PL data of the powder, and it can be seen that the black point M is close to the edge of the color coordinate, and actually, the closer the point is to the edge of the color coordinate, the purer the light of the powder is. The calculated color coordinates (x, y) ═ 0.1400,0.0850, x + y 0.2250<0.3, and judging whether the powder body is pure blue light or not is carried out by judging whether the color coordinate of the powder body is pure blue light or not<0.3, color coordinates of the powder<0.3, indicating that the blue light of the powder is pure blue light. The purer the light of the powder, the larger the color gamut which can be covered by the powder, the higher the color saturation applied to display, the closer the displayed light is to the light which is true to an object, the closer the display is to the reality, and the more distortion of the color caused by the light-emitting material is avoided. Further, the application of the inorganic perovskite material to the preparation of an LED device shows that the display color saturation is high. Meanwhile, the monochromatic light purity is calculated to be about 91.6% according to the following formula:
xi, yi CIE coordinates of the sample.
xd, yd: the CIE value of the emission peak position of the sample, the emission peak position of the sample is 456nm, (xd, yd) is about (0.1459, 0.0452).
x, y: the CIE coordinates of the standard white light are (0.3333 ).
From the above, the inorganic perovskite material synthesized by the liquid phase method in example 1 has good crystallinity and uniform particles, high fluorescence yield, strong light stability and thermal stability, low cost of the synthetic raw materials, safety, no toxicity, simple synthesis operation, low requirement on equipment, loose requirement on reaction conditions, and suitability for industrial production, and the raw materials are mixed and then are heated for reaction in the synthesis process to obtain crystals. The inorganic perovskite material has potential application value of preparing blue-light fluorescent powder with high fluorescence yield, can be further applied to preparation of LED devices, and is high in display color saturation.
Therefore, the invention also provides an LED device, which comprises an LED chip and a coating coated on the surface of the LED chip, wherein the coating is prepared by mixing the raw materials comprising the inorganic perovskite material and the binder, and coating the raw materials on the surface of the LED chip. The composite material can be prepared by mixing an inorganic perovskite material with a binder and encapsulating the mixture on a chip, and the traditional arrangement of a hole transmission layer and an electron transmission layer is not required to be designed, and the composite material does not need to be firstly formed into a film, so that the structure is simple and the operation is convenient; and other colors of fluorescent powder can be added to prepare corresponding LED devices, for example, yellow fluorescent powder can be added to prepare white LED devices. In addition, organic silica gel can be used as the binder, and the organic silica gel has good temperature tolerance, so that the thermal stability of the device can be ensured.
Claims (10)
1. A preparation method of an inorganic perovskite material is characterized by comprising the following steps:
s1, dissolving a tin source and a bismuth source in a first solvent to obtain a first solution; dissolving a cesium source in a second solvent to obtain a second solution; the tin source is a stannous compound;
additionally, the cesium source, the tin source, and the bismuth source are chlorides, and/or the first solvent and the second solvent are chlorine sources;
s2, mixing the first solution and the second solution, stirring and heating to react to generate Cs2SnCl6:Bi3+Precipitating, then carrying out solid-liquid separation, washing and drying.
2. The method for producing an inorganic perovskite material as claimed in claim 1, wherein in step S1, the molar ratio of the cesium source, the tin source and the bismuth source is 2:1: 6.
3. The method for producing an inorganic perovskite material as claimed in claim 1, wherein the first solvent and the second solvent are hydrochloric acid; the cesium source is selected from inorganic cesium compounds and/or organic cesium compounds; the tin source is selected from inorganic stannous compound and/or organic stannous compound; the bismuth source is selected from an inorganic bismuth compound and/or an organic bismuth compound.
4. The method for producing an inorganic perovskite material as claimed in claim 3, wherein the cesium source is at least one selected from cesium halide, cesium oxide, cesium hydroxide, cesium formate; the tin source is at least one of stannous oxalate, stannous acetate, stannous halide and stannous oxide; the bismuth source is at least one selected from bismuth oxide, halogenated bismuth, bismuth sulfate, bismuth nitrate and sodium bismuthate.
5. The method according to claim 3, wherein the hydrochloric acid is concentrated hydrochloric acid having a mass fraction of more than 20%.
6. The method for producing an inorganic perovskite material as claimed in claim 1, wherein the first solvent and the second solvent are polar organic solvents, and the cesium source, the tin source and the bismuth source are chlorides.
7. The method for producing an inorganic perovskite material as claimed in claim 6, wherein the first solvent and the second solvent are selected from at least one of N, N-dimethylformamide, dimethylsulfoxide and ethanol; the cesium source is selected from cesium chloride, the tin source is selected from stannous chloride, and the bismuth source is selected from bismuth chloride.
8. The method for producing an inorganic perovskite material as claimed in any one of claims 1 to 7, wherein the reaction temperature of the stirring heating reaction in step S2 is 60 to 120 ℃.
9. An inorganic perovskite material, characterized by being produced by the production method for an inorganic perovskite material according to any one of claims 1 to 8.
10. An LED device comprising an LED chip and a coating layer applied on the surface of the LED chip, wherein the coating layer is prepared by mixing the raw materials comprising the inorganic perovskite material according to claim 9 and a binder and coating the raw materials on the surface of the LED chip.
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