CN107338044A - The technique that a kind of reversal temperature method prepares perovskite structure luminescent material - Google Patents
The technique that a kind of reversal temperature method prepares perovskite structure luminescent material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000002243 precursor Substances 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 8
- 150000004820 halides Chemical class 0.000 claims abstract description 7
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 7
- 150000005309 metal halides Chemical class 0.000 claims abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 5
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 5
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 229910052718 tin Inorganic materials 0.000 claims abstract description 5
- 238000001556 precipitation Methods 0.000 claims abstract description 4
- 238000011049 filling Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- 229910052745 lead Inorganic materials 0.000 claims abstract description 3
- -1 halogen acids Chemical class 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 claims description 8
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L tin(ii) bromide Chemical compound Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 claims description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229960002358 iodine Drugs 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 230000031709 bromination Effects 0.000 claims description 4
- 238000005893 bromination reaction Methods 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- JTDNNCYXCFHBGG-UHFFFAOYSA-L tin(ii) iodide Chemical compound I[Sn]I JTDNNCYXCFHBGG-UHFFFAOYSA-L 0.000 claims description 4
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 3
- RAJISUUPOAJLEQ-UHFFFAOYSA-N chloromethanamine Chemical compound NCCl RAJISUUPOAJLEQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 3
- 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 compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- QEZYDNSACGFLIC-UHFFFAOYSA-N CN.[I] Chemical compound CN.[I] QEZYDNSACGFLIC-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- GBMPPHPJKKUMPS-UHFFFAOYSA-N [Br].CN Chemical compound [Br].CN GBMPPHPJKKUMPS-UHFFFAOYSA-N 0.000 claims description 2
- IMWLFWNAICWHIL-UHFFFAOYSA-L [Ge+2].I(=O)(=O)[O-].I(=O)(=O)[O-] Chemical compound [Ge+2].I(=O)(=O)[O-].I(=O)(=O)[O-] IMWLFWNAICWHIL-UHFFFAOYSA-L 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 235000014121 butter Nutrition 0.000 claims description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 2
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 claims description 2
- RYTLGWCJESCDMY-UHFFFAOYSA-N carbamimidoyl chloride Chemical compound NC(Cl)=N RYTLGWCJESCDMY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229910001502 inorganic halide Inorganic materials 0.000 claims description 2
- 229910001410 inorganic ion Inorganic materials 0.000 claims description 2
- 125000002346 iodo group Chemical group I* 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 229940108184 stannous iodide Drugs 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 claims description 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 2
- ZRVXFJFFJZFRLQ-UHFFFAOYSA-M tetramethylazanium;iodate Chemical compound [O-]I(=O)=O.C[N+](C)(C)C ZRVXFJFFJZFRLQ-UHFFFAOYSA-M 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims 1
- 235000021419 vinegar Nutrition 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 description 13
- 239000000523 sample Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- 229940058401 polytetrafluoroethylene Drugs 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 6
- 150000001649 bromium compounds Chemical class 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 238000005374 membrane filtration Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 229910052792 caesium Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000006193 liquid solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000009461 vacuum packaging Methods 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- RQQRAHKHDFPBMC-UHFFFAOYSA-L lead(ii) iodide Chemical compound I[Pb]I RQQRAHKHDFPBMC-UHFFFAOYSA-L 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- 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
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/006—Compounds containing, besides lead, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/006—Compounds containing, besides zinc, two ore more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C211/03—Monoamines
- C07C211/04—Mono-, di- or tri-methylamine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C211/03—Monoamines
- C07C211/05—Mono-, di- or tri-ethylamine
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- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/34—Three-dimensional structures perovskite-type (ABO3)
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention discloses the technique that a kind of reversal temperature method prepares perovskite structure luminescent material, comprise the following steps：Step 1：A halides and the thing of metal halide containing B will be contained or oxide is dissolved in solvent M, obtain precursor solution after resulting solution filtering, the A is CH3NH3 +、Cs+、H2N‑CH=NH2 +、(CH3)4N+、C7H7 +、C3H11SN3 2+In one or more mixing, one or more mixing in B Pb, Ge, Sn, X is that one or more in halogen Cl, Br, I mix；Step 2：The container for filling precursor solution is put into 50 200 DEG C of oil bath constant temperature 0.5 5 hours, container bottom can separate out ABX3；Step 3：By the ABX of precipitation3Cleaned with solvent N, and sealed up for safekeeping after being dried in vacuo 0.5 48 hours at 20 200 DEG C.By the above-mentioned means, reversal temperature method of the present invention prepares the technique of perovskite structure luminescent material, there is gained perovskite structure luminescent material ABX3Purity is high, luminous efficiency is high, with short production cycle, device therefor requires the advantages that simple.
Description
Technical field
The present invention relates to luminescent material preparing technical field, and perovskite structure is prepared more particularly to a kind of reversal temperature method
Luminescent material ABX3Technique.
Background technology
Luminescent material from beginning plays vital effect so far during human social development, except for daily photograph
Bright outer, it is also widely used for the high-tech areas such as communication, optical computer, probe biomolecule, Aero-Space.In recent years one
Kind perovskite structure AnBX2+nMaterial（Particularly organic-inorganic hybrid material CH3NH3PbX3）Just trigger one in semiconductor applications
Revolution, this makes the series material of great interest.Research finds, the series perovskite structural material have excellent optics and
Electrical properties, most common perovskite material are methylamine lead iodides（CH3NH3PbI3）, it is direct band-gap semicondictor, and band gap is about
For 1.5eV.Light activated exciton bind energy only has 0.03eV, illustrates that most of exciton can be separated into free load quickly at room temperature
Stream.Electronics and hole show the effective mass of very little and very high mobility（Electronics：7.5cm2V-1s-1, hole：
12.5cm2V-1s-1）, recombination time was hundreds of nanoseconds, and this causes the carrier diffusion distance grown very much（100-1000nm）.Exactly this
A little properties make the serial hydridization perovskite material have very potential value, especially make perovskite structural material ABX3Glimmering
Light lamp, solar cell, solid state laser, light emitting diode（LED）, photodetector and hydrogen manufacturing etc. have wide answer
Use prospect.
The perovskite structure ABX reported at present3Preparation method be concentrated mainly on and prepare perovskite polycrystal film, for
The light-absorption layer of solar cell, to luminescent powder ABX3Method prepared by material is less.For monocrystalline ABX3Material, its preparation side
Method is based on lowering temperature crystallization, but this method is harsh to temperature control requirement first, and temperature change can not only influence the molten of solute
Xie Du, or even undergo phase transition, while the crystal mass eventually formed can be also influenceed, secondly crystal growth rate is very slow, system
The standby cycle is grown, and can not obtain the crystal of bulk, while its required equipment is complex is not easy to realize have larger room for improvement.
The content of the invention
The present invention solves the technical problem of provide a kind of reversal temperature method to prepare perovskite structure luminescent material
Technique, simplify equipment requirement, shorten the production cycle, lifting perovskite structure luminescent material ABX3Purity and luminous efficiency.
In order to solve the above technical problems, one aspect of the present invention is：A kind of reversal temperature method is provided to prepare
The technique of perovskite structure luminescent material, comprises the following steps：
Step 1：A halides and the thing of metal halide containing B will be contained or oxide is dissolved in solvent M, obtained after resulting solution filtering
Precursor solution, the A are CH3NH3 +、Cs+、H2N-CH=NH2 +、(CH3)4N+、C7H7 +、C3H11SN3 2+In one or more mix
Close, one or more mixing in B Pb, Ge, Sn, X is one or more mixing in halogen Cl, Br, I, described molten
Agent M is to ABX3There are the single solvent or mixed solvent of larger solubility；
Step 2：The container for filling precursor solution is put into 50-200 DEG C of oil bath constant temperature 0.5-5 hours, container bottom
Separate out ABX3；
Step 3：By the ABX of precipitation3Cleaned with solvent N, and sealed up for safekeeping after being dried in vacuo 0.5-48 hours at 20-200 DEG C,
The solvent N is to ABX3Insoluble or slightly soluble, it can be dissolved each other with solvent M, there is certain volatile single solvent or mixed solvent.
In a preferred embodiment of the present invention, the solvent M includes but is not limited to water, halogen acids, DMSO, N-
N-methyl-2-2-pyrrolidone N, gamma-butyrolacton and DMF.
In a preferred embodiment of the present invention, the solvent N includes but is not limited to dichloromethane, isopropanol, toluene, right
Dimethylbenzene, ethanol and ether.
In a preferred embodiment of the present invention, the ABX3Typical material chemical molecular formula include but is not limited to
CH3NH3PbBr3、CH3NH3PbCl3、CH3NH3PbI3、(CH3NH3)0.5Cs0.5PbBr3、CsPbBr3、CsPbI3、CsPbBrCl2、
CsPbIBr2、CsSnBr3、CsGeBr3、CsPb0.5Sn0.5Br3、(CH3NH3)0.5Cs0.5PbIBr2、(CH3NH3)0.5Cs0.5Pb0.5Sn0.5IBr2。
In a preferred embodiment of the present invention, the halides containing A be containing ionic radius be 1.5-2.5 it is organic
Or one or more mixing in the organic or inorganic halides of inorganic ions, including cesium chloride, cesium bromide, cesium iodide, chloromethane
Amine, chloromethane amidine, tetramethylamine chloride, chlorine Zhuo, chloro 2- isothioureas, bromine methylamine, bromine carbonamidine, bromination tetramethylammonium, bromine Zhuo, bromo
2- isothioureas, iodine methylamine, iodine carbonamidine, iodate tetramethylammonium, iodine Zhuo and iodo 2- isothioureas.
In a preferred embodiment of the present invention, the thing of metal halide containing B or oxide are one in following compound
Kind or a variety of mixing：Lead chloride, lead bromide, lead iodide, lead acetate, stannous chloride, butter of tin, stannous bromide, stannous iodide,
Stannous oxide, tin oxide, germanium chloride, bromination germanium, iodate germanium.
In a preferred embodiment of the present invention, halides containing A and the thing of metal halide containing B or oxygen in the precursor solution
The mol ratio of compound is 1：0.2~2.
In a preferred embodiment of the present invention, the concentration of the precursor solution is 0.01-5.0mol/L.
The beneficial effects of the invention are as follows：A kind of reversal temperature method that the present invention points out prepares perovskite structure luminescent material
Technique, there are following advantages：
（1）The zero dimension perovskite luminescent material ABX prepared3, for purity more than 99%, luminous efficiency is high；
（2）Working condition is gentle, and required temperature is low, and equipment requirement is simple, even can in the production process of some kinds of perovskite-likes
Under the room temperature condition without any electrical equipment, the energy is saved；
（3）Short preparation period, ABX3Precipitation only needs 0.5-5 hours；
（4）Simple, workable, the repeatable height of the method for the invention technique, there is wide application in actual production
Prospect.
Brief description of the drawings
Technical scheme in order to illustrate the embodiments of the present invention more clearly, make required in being described below to embodiment
Accompanying drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the present invention, for
For those of ordinary skill in the art, on the premise of not paying creative work, it can also be obtained according to these accompanying drawings other
Accompanying drawing, wherein：
Fig. 1 is the flow for the preferred embodiment of technique one that a kind of reversal temperature method of the present invention prepares perovskite structure luminescent material
Figure；
Fig. 2 is that the technique for preparing perovskite structure luminescent material using a kind of reversal temperature method of the present invention is prepared
CH3NH3PbBr3The XRD of powder；
Fig. 3 is that the technique for preparing perovskite structure luminescent material using a kind of reversal temperature method of the present invention is prepared
CH3NH3PbBr3The XRD of monocrystalline；
Fig. 4 is that the technique for preparing perovskite structure luminescent material using a kind of reversal temperature method of the present invention is prepared
CH3NH3PbCl3The XRD of powder；
Fig. 5 is that the technique for preparing perovskite structure luminescent material using a kind of reversal temperature method of the present invention is prepared
CH3NH3PbCl3The XRD of monocrystalline.
Embodiment
The technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that described implementation
Example is only the part of the embodiment of the present invention, rather than whole embodiments.It is common based on the embodiment in the present invention, this area
All other embodiment that technical staff is obtained under the premise of creative work is not made, belong to the model that the present invention protects
Enclose.
Fig. 1 ~ Fig. 5 is referred to, the embodiment of the present invention includes：
Embodiment 1
CH3NH3PbBr3The preparation method of material：
1st, precursor solution is configured
Weigh 0.7833g bromine methylamines（CH3NH3Br）, 2.569g lead bromides（PbBr2）In being put into the 50ml beakers of stirrer,
Add 10ml DMFs（DMF）, sealed with PM-996 and poly tetrafluoroethylene duplicature, use magnetic stirring apparatus
It is stirred at room temperature more than 12 hours, can be dissolved with ultrasonic assistant, with 22 μm of PTFE membrane filtration solution of diameter, before obtains
Drive liquid solution.
2nd, prepared by material
Take precursor solution in step 1 in 4 10ml sample bottles, every bottle of each 2.5ml, the sample bottle of precursor solution will to be filled
It is put into 80 DEG C of oil bath constant temperature 3 hours, container bottom can separate out 0.5 ~ 10mm CH3NH3PbBr3。
3、CH3NH3PbBr3Material is cleaned, dries and collected
CH is cleaned with absolute ether3NH3PbBr3Material, in vacuum drying chamber after 60 DEG C of dryings 24 hours, it is vacuum-packed.
Embodiment 2
CH3NH3PbCl3The preparation method of material：
1st, precursor solution is configured
Weigh 0.4722g chloromethane amine（CH3NH3Cl）, 1.9467g lead chlorides（PbCl2）In the 50ml beakers P for being put into stirrer
In, add 10ml DMSOs（DMSO）, sealed with PM-996 and poly tetrafluoroethylene duplicature, with magnetic stirring apparatus in room
The lower stirring of temperature more than 12 hours, can be dissolved, solution uses the PTFE membrane filtrations of 22 μm of diameter after fully dissolving with ultrasonic assistant
Solution, obtain precursor solution.
2nd, prepared by material
Take precursor solution in step 1 in 4 10ml sample bottles, every bottle of each 2.5ml, the sample bottle of precursor solution will to be filled
It is put into 90 DEG C of oil bath constant temperature 3 hours, container bottom can separate out 0.5 ~ 10mm CH3NH3PbCl3。
3、CH3NH3PbCl3Material is cleaned, dries and collected
CH is cleaned with absolute ether3NH3PbCl3Material, 60 DEG C of dryings 24 hours in vacuum drying chamber, is carried out after thoroughly drying
Vacuum packaging.
Embodiment 3
CH3NH3PbIBr2The preparation method of material：
1st, precursor solution is configured
Weigh 0.6885g iodine methylamines（CH3NH3I）, 1.997g lead iodides（PbI2）In being put into the 50ml beakers of stirrer,
Add 3ml gamma-butyrolactons（GBL）Sealed with PM-996 and poly tetrafluoroethylene duplicature, with magnetic stirring apparatus in room temperature
Lower stirring more than 12 hours, can be dissolved with ultrasonic assistant.
Weigh 0.5222 bromine methylamine（CH3NH3Br）, 1.1726g lead bromides（PbBr2）Burnt in the 50ml for being put into stirrer
In cup, 7ml DMFs are added（DMF）, sealed with PM-996 and poly tetrafluoroethylene duplicature, stirred with magnetic force
Mix device to be stirred at room temperature more than 12 hours, can be dissolved with ultrasonic assistant.
After above-mentioned two parts of solution fully dissolves, it is mixed in the one 50ml beaker for being put into stirrer, uses magnetic
Power agitator dissolves 30min at room temperature, and solution uses the PTFE membrane filtration solution of 22 μm of diameter, obtains forerunner after fully dissolving
Liquid solution.
2nd, prepared by material
Take precursor solution in step 1 in 4 10ml sample bottles, every bottle of each 2.5ml, the sample bottle of precursor solution will to be filled
It is put into 95 DEG C of oil bath constant temperature 3 hours, container bottom can separate out 0.5 ~ 10mm CH3NH3PbIBr2。
3、CH3NH3PbIBr2Material is cleaned, dries and collected
CH is cleaned with absolute ether3NH3PbIBr2Material, in vacuum drying chamber after 60 DEG C of dryings 24 hours, carry out vacuum packet
Dress.
Embodiment 4
CsPbBr3The preparation method of material：
1st, precursor solution is configured
Weigh 0.5854g cesium bromides（CsBr）, 1.835g lead bromides（PbBr2）In being put into the 50ml beakers of stirrer, add
Enter 10ml DMSOs（DMSO）, sealed with PM-996 and poly tetrafluoroethylene duplicature, with magnetic stirring apparatus at room temperature
Stirring more than 12 hours, can be dissolved with ultrasonic assistant, and the hydrogen bromine that 0.9ml concentration is 48wt% is added into the solution after stirring
Acid, the PTFE membrane filtration solution of 22 μm of diameter is used after stirring half an hour, obtains precursor solution.
2nd, prepared by material
Take precursor solution in step 1 in 4 10ml sample bottles, every bottle of each 2.5ml, the sample bottle of precursor solution will to be filled
It is put into 80 DEG C of oil bath constant temperature 3 hours, container bottom can separate out 0.5 ~ 10mm CsPbBr3。
3、CsPbBr3Material is cleaned, dries and collected
CsPbBr is cleaned with absolute ether3Material, in vacuum drying chamber 60 DEG C of dryings be vacuum-packed again after 24 hours.
Embodiment 5
CsSnBr3The preparation method of luminescent material：
1st, precursor solution is configured
Weigh 0.5854g cesium bromides（CsBr）, 1.393g stannous bromides（SnBr2）In being put into the 50ml beakers of stirrer,
Add 10ml DMSOs（DMSO）, sealed with PM-996 and poly tetrafluoroethylene duplicature, with magnetic stirring apparatus in room temperature
Lower stirring more than 12 hours, can be dissolved with ultrasonic assistant, and the hydrogen bromine that 1ml concentration is 48wt% is added into the solution after stirring
Acid, the PTFE membrane filtration solution of 22 μm of diameter is used after stirring half an hour, obtains precursor solution.
2nd, prepared by material
Take precursor solution in step 1 in 4 10ml sample bottles, every bottle of each 2.5ml, the sample bottle of precursor solution will to be filled
It is put into 80 DEG C of oil bath constant temperature 3 hours, container bottom can separate out 0.5 ~ 10mm CsSnBr3。
3、CsSnBr3Material is cleaned, dries and collected
CsSnBr is cleaned with absolute ether3Material, in vacuum drying chamber after 60 DEG C of dryings 24 hours, vacuum packaging.
Embodiment 6
CsPb0.5Sn0.5Br3The preparation method of luminescent material：
1st, precursor solution is configured
Weigh 0.5854g cesium bromides（CsBr）, 0.918g lead bromides（PbBr2）, 0.697g stannous bromides（SnBr2）In being put into
In the 50ml beakers of stirrer, 10ml DMSOs are added（DMF）, sealed with PM-996 and poly tetrafluoroethylene duplicature,
It is stirred at room temperature more than 12 hours, can be dissolved with ultrasonic assistant with magnetic stirring apparatus.Added into the solution after stirring
0.9ml concentration is 48wt% hydrobromic acid, and the PTFE membrane filtration solution of 22 μm of diameter is used after stirring half an hour, obtains presoma
Solution.
2nd, prepared by material
Take precursor solution in step 1 in 4 10ml sample bottles, every bottle of each 2.5ml, the sample of precursor solution will to be filled
Bottle is put into 80 DEG C of oil bath constant temperature 3 hours, and container bottom can separate out 0.5 ~ 10mm CsPb0.5Sn0.5Br3。
3、CsPb0.5Sn0.5Br3Material is cleaned, dries and collected
CsPb is cleaned with absolute ether0.5Sn0.5Br3Material, in vacuum drying chamber after 60 DEG C of dryings 24 hours, carry out vacuum packet
Dress.
In summary, a kind of reversal temperature method that the present invention points out prepares the technique of perovskite structure luminescent material, utilizes
The principle that solute solubility reduces with temperature in certain temperature range, the luminous material of perovskite structure is prepared by raising temperature
Expect ABX3, obtained perovskite structure luminescent material ABX3Purity is high, and luminous efficiency is high, and the cycle of production is short, during production
Energy consumption is low, simple to production equipment requirement.
Embodiments of the invention are the foregoing is only, are not intended to limit the scope of the invention, it is every to utilize this hair
The equivalent structure or equivalent flow conversion that bright description is made, or directly or indirectly it is used in other related technology necks
Domain, it is included within the scope of the present invention.
Claims (8)
1. a kind of reversal temperature method prepares the technique of perovskite structure luminescent material, for perovskite structure luminescent material ABX3's
Production, it is characterised in that comprise the following steps：
Step 1：A halides and the thing of metal halide containing B will be contained or oxide is dissolved in solvent M, obtained after resulting solution filtering
Precursor solution, the A are CH3NH3 +、Cs+、H2N-CH=NH2 +、(CH3)4N+、C7H7 +、C3H11SN3 2+In one or more mix
Close, one or more mixing in B Pb, Ge, Sn, X is one or more mixing in halogen Cl, Br, I, described molten
Agent M is to ABX3There are the single solvent or mixed solvent of larger solubility；
Step 2：The container for filling precursor solution is put into 50-200 DEG C of oil bath constant temperature 0.5-5 hours, container bottom
Separate out ABX3；
Step 3：By the ABX of precipitation3Cleaned, and sealed up for safekeeping after being dried in vacuo 0.5-48 hours at 20-200 DEG C, institute with solvent N
It is to ABX to state solvent N3Insoluble or slightly soluble, it can be dissolved each other with solvent M, there is certain volatile single solvent or mixed solvent.
2. the technique that reversal temperature method according to claim 1 prepares perovskite structure luminescent material, it is characterised in that institute
State solvent M and include but is not limited to water, halogen acids, DMSO, METHYLPYRROLIDONE, gamma-butyrolacton and N, N- diformazan
Base formamide.
3. the technique that reversal temperature method according to claim 1 prepares perovskite structure luminescent material, it is characterised in that institute
State, the solvent N includes but is not limited to dichloromethane, isopropanol, toluene, paraxylene, ethanol and ether.
4. the technique that reversal temperature method according to claim 1 prepares perovskite structure luminescent material, it is characterised in that institute
State ABX3Typical material chemical molecular formula include but is not limited to CH3NH3PbBr3、CH3NH3PbCl3、CH3NH3PbI3、
(CH3NH3)0.5Cs0.5PbBr3、CsPbBr3、CsPbI3、CsPbBrCl2、CsPbIBr2、CsSnBr3、CsGeBr3、
CsPb0.5Sn0.5Br3、(CH3NH3)0.5Cs0.5PbIBr2、(CH3NH3)0.5Cs0.5Pb0.5Sn0.5IBr2。
5. the technique that reversal temperature method according to claim 1 prepares perovskite structure luminescent material, it is characterised in that institute
Halides containing A are stated as one in the organic or inorganic halides containing the organic or inorganic ion that ionic radius is 1.5-2.5
Kind or a variety of mixing, including cesium chloride, cesium bromide, cesium iodide, chloromethane amine, chloromethane amidine, tetramethylamine chloride, chlorine are tall and erect, chloro 2-
Isothiourea, bromine methylamine, bromine carbonamidine, bromination tetramethylammonium, bromine Zhuo, bromo 2- isothioureas, iodine methylamine, iodine carbonamidine, iodate tetramethylammonium,
Iodine Zhuo and iodo 2- isothioureas.
6. the technique that reversal temperature method according to claim 1 prepares perovskite structure luminescent material, it is characterised in that institute
The thing of metal halide containing B or oxide are stated as one or more mixing in following compound：Lead chloride, lead bromide, lead iodide, vinegar
Lead plumbate, stannous chloride, butter of tin, stannous bromide, stannous iodide, stannous oxide, tin oxide, germanium chloride, bromination germanium, iodate
Germanium.
7. the technique that reversal temperature method according to claim 1 prepares perovskite structure luminescent material, it is characterised in that institute
It is 1 to state halides containing A and the mol ratio of the thing of metal halide containing B or oxide in precursor solution：0.2~2.
8. the technique that reversal temperature method according to claim 1 prepares perovskite structure luminescent material, it is characterised in that institute
The concentration for stating precursor solution is 0.01-5.0mol/L.
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| CN108110068A (en) * | 2017-12-19 | 2018-06-01 | 广东工业大学 | A kind of unleaded perovskite solar cell and preparation method thereof |
| CN108305945A (en) * | 2018-01-15 | 2018-07-20 | 南京信息工程大学 | A kind of perovskite precursor solution and the preparation method and application thereof |
| CN108455660A (en) * | 2018-03-13 | 2018-08-28 | 合肥国轩高科动力能源有限公司 | A kind of method that solid-liquid phase reaction prepares Two-dimensional Inorganic perovskite negative material |
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