CN116199253A - Seleno perovskite and preparation method and application thereof - Google Patents
Seleno perovskite and preparation method and application thereof Download PDFInfo
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- CN116199253A CN116199253A CN202310173169.6A CN202310173169A CN116199253A CN 116199253 A CN116199253 A CN 116199253A CN 202310173169 A CN202310173169 A CN 202310173169A CN 116199253 A CN116199253 A CN 116199253A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 134
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 claims abstract description 89
- 239000000243 solution Substances 0.000 claims abstract description 70
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000012047 saturated solution Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 14
- 239000000725 suspension Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 12
- 238000002189 fluorescence spectrum Methods 0.000 claims description 4
- 230000005693 optoelectronics Effects 0.000 claims description 4
- 238000000862 absorption spectrum Methods 0.000 claims description 3
- 241000258957 Asteroidea Species 0.000 claims 1
- 229910052711 selenium Inorganic materials 0.000 abstract description 21
- 239000011669 selenium Substances 0.000 abstract description 21
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 abstract description 20
- 238000002347 injection Methods 0.000 abstract description 12
- 239000007924 injection Substances 0.000 abstract description 12
- 238000000975 co-precipitation Methods 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 description 32
- 239000000047 product Substances 0.000 description 28
- 239000000843 powder Substances 0.000 description 24
- 239000011521 glass Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 239000006228 supernatant Substances 0.000 description 7
- 238000009777 vacuum freeze-drying Methods 0.000 description 7
- 238000004020 luminiscence type Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 3
- 238000009849 vacuum degassing Methods 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L tin(ii) bromide Chemical compound Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- VDFAFONHYZMTOX-UHFFFAOYSA-N [Sn].[Cs] Chemical compound [Sn].[Cs] VDFAFONHYZMTOX-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
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/006—Compounds containing, besides tin, two or more other elements, with the exception of oxygen or hydrogen
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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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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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
- C09K11/664—Halogenides
- C09K11/665—Halogenides with alkali or alkaline earth metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
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- 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
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention discloses a seleno perovskite and a preparation method and application thereof, and relates to the technical field of luminescent materials. The preparation method of the seleno perovskite comprises the following steps: under the inert gas atmosphere, the SnBr is dropwise added into the CsBr ethanol saturated solution 2 Ethanol solution, uniformly mixed and SnBr 2 And after the ethanol solution is completely dripped, standing the suspension until all the product particles are settled, and drying the product particles to obtain the seleno perovskite. Preparation of seleno perovskite of the inventionThe method is obviously different from the existing hot injection method, does not need a high-temperature heating process, and more importantly, the CsBr ethanol saturated solution and the SnBr 2 The selenium-based perovskite is prepared by the coprecipitation of the ethanol solution, and ethanol can be adsorbed on the surface of the selenium-based perovskite in the coprecipitation process, so that the stability of the selenium-based perovskite is comprehensively improved, the selenium-based perovskite has excellent oxidation resistance, and can be stably placed in the air for more than 6 days.
Description
Technical Field
The invention relates to the technical field of luminescent materials, in particular to a seleno perovskite and a preparation method and application thereof.
Background
At present, the luminescent seleno perovskite CsSnBr is mainly prepared by a thermal injection method 3 . The "hot injection" needs to be performed in a closed three-necked flask, water and oxygen in the flask need to be removed by vacuum degassing and nitrogen filling throughout the process, and is heavily dependent on expensive and highly toxic long chain hydrocarbons such as oleylamine, trioctylphosphine. Besides the harsh reaction conditions, complex synthesis steps and the use of toxic organic reagents, the synthesized product is extremely easy to oxidize in air. Typical thermal injection methods are disclosed in the literature (JELLICTE T C, RICHTER J M, GLASS H F, et al Synthesis and Optical Properties of Lead-Free Cesium Tin Halide Perovskite Nanocrystals [ J ]]J Am Chem Soc,2016,138 (9): 2941-4.): 0.8mL of oleic acid, 0.8mL of oleylamine and 24mL of 1-octadecene were charged into a three-necked flask, heated to 80℃and degassed under vacuum at 80℃for 1 hour. Thereafter, 0.26g CsCO was added to the reaction vessel 3 Vacuum degassing was continued for 1 hour. Nitrogen is filled and heated to 100 ℃, and the temperature is kept for 1 hour until CsCO 3 All dissolved. Subsequently, the reaction mixture was heated to a reaction temperature of 170℃and 5mL of SnBr at a concentration of 1M 2 The tri-n-octylphosphine solution was rapidly injected into the mixed solution in the above three-necked flask. After the reaction was kept for 1min, the three-necked flask was ice-water-cooled. The crude product suspension obtained in the three-necked flask was transferred to a glove box filled with nitrogen, an equal volume of n-butanol was added, and then redispersed in n-hexane, and the process was repeated twice. Finally, csSnBr is contained 3 The n-hexane suspension of perovskite was centrifuged at 4 rpm for 2min and then filtered through a 200nm PTFE filter. The prepared CsSnBr 3 The perovskite is put in the air and oxidized after 5 min. The hot injection method has the defects of strong toxicity, complex operation steps, harsh reaction conditions and the like, and the prepared product is extremely easy to oxidize in the air.
The prior art discloses a preparation method of a lead-free all-inorganic perovskite film by one-step chemical vapor deposition, and provides a preparation method of the lead-free all-inorganic perovskite film by one-step chemical vapor deposition aiming at the problem of crystal quality of the lead-free all-inorganic perovskite film, so as to obtain the lead-free all-inorganic perovskite film with high crystallinity and good uniformity. However, the preparation method does not solve the problems that perovskite products are easy to oxidize and have poor stability.
Disclosure of Invention
The invention aims to overcome the defect of the prior seleno perovskite CsSnBr 3 The selenium-based perovskite preparation method has the defects of easy oxidation and poor stability of the product by the hot injection method, is simple to operate, does not need high-temperature heating, is more stable, is not easy to oxidize, and can be stably placed in the air for 6 days.
It is another object of the present invention to provide a seleno perovskite.
It is a further object of the present invention to provide the use of a seleno perovskite for the preparation of light emitting LEDs, solar cells and photodetectors.
Another object of the present invention is to provide an optoelectronic device whose luminescent material is the seleno perovskite
The above object of the present invention is achieved by the following technical scheme:
a method for preparing seleno perovskite, comprising the following steps:
under the inert gas atmosphere, the SnBr is dropwise added into the CsBr ethanol saturated solution 2 Ethanol solution, uniformly mixed and SnBr 2 And after the ethanol solution is completely dripped, standing the suspension until all the product particles are settled, and drying the product particles to obtain the seleno perovskite.
The following are to be described:
the preparation method of the seleno perovskite is different from the hot injection method in the prior art, and the seleno perovskite can be prepared at normal temperature without high-temperature heating. More importantly, the invention provides a novel preparation method of the seleno perovskite, wherein CsBr ethanol saturated solution and SnBr 2 Ethanol solution is subjected to coprecipitation to prepare seleno perovskite, csBr and SnBr 2 The solution is prepared by using ethanol as solvent, and the ethanol has reducibility and can prevent seleno perovskite from being damagedAnd (5) oxidizing. In the coprecipitation process, the ethanol can be adsorbed on the surfaces of the selenium-based perovskite particles, so that the generated selenium-based perovskite is further prevented from being oxidized, the stability of the selenium-based perovskite is comprehensively improved, and the selenium-based perovskite has excellent oxidation resistance and can be stably placed in the air for more than 6 days.
Wherein the CsBr ethanol solution is saturated CsBr ethanol solution, the solubility of CsBr in ethanol is low, and the lower concentration can lead to CsSnBr 3 Cannot be generated. And SnBr 2 The ethanol solution must be added dropwise, otherwise the generated seleno perovskite has weak luminescence property and cannot be used.
Preferably, the SnBr 2 The concentration of the ethanol solution is 0.2-0.5 mol/L.
By controlling the drop wise addition of SnBr 2 The concentration of the ethanol solution can control the morphology of the generated seleno perovskite, for example, can control the generation of starfish-shaped seleno perovskite, rod-shaped seleno perovskite, spherical seleno perovskite or cubic blocky seleno perovskite. And drop wise added SnBr 2 The concentration control of the ethanol solution can further improve the crystallinity of the seleno perovskite material, form a high-crystallization product, reduce the surface defects of seleno perovskite and improve the luminous performance. SnBr 2 The concentration of the ethanol solution is more than 0.55mol/L, and the product may contain CsSn as an impurity 2 Cl 5 。
In particular embodiments, it may be further preferred that the SnBr 2 The concentration of the ethanol solution is 0.4-0.5 mol/L.
In a specific embodiment, csBr ethanol saturated solution and drop-by-drop SnBr 2 The ethanol solution can be uniformly mixed by adopting various embodiments, for example, snBr can be dropwise added under stirring 2 The ethanol solution can be stirred by adding magnetic stirring, mechanical stirring, shaking and blending.
In a specific embodiment, the stirring speed may be in the range of 450 to 1300rpm.
The invention also specifically protects the selenium-based perovskite material prepared by the preparation method of the selenium-based perovskite.
The selenium-based perovskite material can be prepared by dropwise adding SnBr in a preparation process 2 The concentration control of the ethanol solution forms a different morphology, in some embodiments a starfish-like seleno-perovskite, in some embodiments a rod-like seleno-perovskite, in some embodiments a sphere-like seleno-perovskite, in some embodiments a block-like seleno-perovskite, in some embodiments a cube-like seleno-perovskite.
In a specific embodiment, the selenium-based perovskite material has a fluorescence emission spectrum of 650-800nm, an absorption spectrum of 300-700nm, and a luminous intensity of 647934counts.
The selenium-based perovskite material has excellent oxidation resistance, good stability and excellent luminescence property, can be widely applied to the application fields of various luminescent materials, and also specifically protects the application of the selenium-based perovskite material in preparing luminescent LEDs, solar cells and photodetectors.
The invention also specifically protects the photoelectric equipment, and the luminescent material of the photoelectric equipment is selenium-based perovskite.
In a specific embodiment, the optoelectronic device may be any one of a light emitting LED, a solar cell, and a photodetector.
The photovoltaic device is not limited to the above list, and the seleno perovskite material may be used in any device requiring a stable light-emitting material and having excellent oxidation resistance.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of the seleno perovskite is obviously different from the existing hot injection method, does not need a high-temperature heating process, and more importantly, is that CsBr ethanol saturated solution and SnBr are adopted 2 The selenium-based perovskite is prepared by the coprecipitation of the ethanol solution, and ethanol can be adsorbed on the surface of the selenium-based perovskite in the coprecipitation process, so that the stability of the selenium-based perovskite is comprehensively improved, the selenium-based perovskite has excellent oxidation resistance, and can be stably placed in the air for more than 6 days.
Drawings
FIG. 1 shows CsSnBr prepared by hot injection 3 CsSnBr prepared by (above) the synthetic method of the invention 3 (lower) color change contrast plot placed in air.
FIG. 2 shows different SnBr 2 The concentration gives a fluorescence emission spectrum of the product.
FIG. 3 shows different SnBr 2 And obtaining a scanning electron microscope image of the product by concentration.
FIG. 4 shows the one-time addition of 0.5mol/L SnBr to a CsBr precursor solution 2 Emission spectra of the precursor solution.
FIG. 5 shows the one-time addition of 0.5mol/L SnBr to a CsBr precursor solution 2 Scanning electron microscope image of the precursor solution.
Detailed Description
The invention will be further described with reference to the following specific embodiments, but the examples are not intended to limit the invention in any way. Raw materials reagents used in the examples of the present invention are conventionally purchased raw materials reagents unless otherwise specified.
Example 1
A method for preparing seleno perovskite, comprising the following steps:
41mmol of CsBr powder was added to 500mL of absolute ethanol, and the mixture was stirred in a glove box for 12 hours to dissolve the CsBr powder sufficiently and then allowed to stand for half an hour, thereby obtaining a CsBr saturated precursor solution.
0.2mmol SnBr was taken 2 Adding the powder into 1mL of absolute ethanol, stirring to dissolve completely to obtain SnBr 2 Precursor solution, snBr 2 The concentration of the ethanol solution was 0.2mol/L.
6mL of CsBr ethanol saturated solution was placed in a glass vial, and the magnet was placed. Dropwise adding 0.2mol/L SnBr under the rotation of a magnet at 450rpm 2 And (3) after 1mL of the precursor solution is completely dripped, standing the suspension until all the product particles are settled at the bottom of the glass vial. Then sucking out the supernatant ethanol, and drying the bottom product in a vacuum freeze drying oven to obtain CsSnBr with starfish-like morphology 3 Perovskite.
Example 2
A method for preparing seleno perovskite, comprising the following steps:
41mmol of CsBr powder was added to 500mL of absolute ethanol, and the mixture was stirred in a glove box for 12 hours to dissolve the CsBr powder sufficiently and then allowed to stand for half an hour, thereby obtaining a CsBr saturated precursor solution.
0.3mmol SnBr was taken 2 Adding the powder into 1mL of absolute ethanol, stirring to dissolve completely to obtain SnBr 2 Precursor solution, snBr 2 The concentration of the ethanol solution was 0.3mol/L.
6mL of CsBr ethanol saturated solution was placed in a glass vial, and the magnet was placed. Dropwise adding 0.3mol/L SnBr under the rotation of a magnet at 450rpm 2 And (3) after 1mL of the precursor solution is completely dripped, standing the suspension until all the product particles are settled at the bottom of the glass vial. Then sucking out the supernatant ethanol, and drying the bottom product in a vacuum freeze drying oven to obtain CsSnBr with short bar or ball shape 3 Perovskite.
Example 3
A method for preparing seleno perovskite, comprising the following steps:
41mmol of CsBr powder was added to 500mL of absolute ethanol, and the mixture was stirred in a glove box for 12 hours to dissolve the CsBr powder sufficiently and then allowed to stand for half an hour, thereby obtaining a CsBr saturated precursor solution.
0.4mmol SnBr was taken 2 Adding the powder into 1mL of absolute ethanol, stirring to dissolve completely to obtain SnBr 2 Precursor solution, snBr 2 The concentration of the ethanol solution was 0.4mol/L.
6mL of CsBr ethanol saturated solution was placed in a glass vial, and the magnet was placed. Dropwise adding 0.4mol/L SnBr under the rotation of a magnet at 450rpm 2 And (3) after 1mL of the precursor solution is completely dripped, standing the suspension until all the product particles are settled at the bottom of the glass vial. Then sucking out the supernatant ethanol, and drying the bottom product in a vacuum freeze drying oven to obtain CsSnBr with a building block-like appearance 3 Perovskite.
Example 4
A method for preparing seleno perovskite, comprising the following steps:
41mmol of CsBr powder was added to 500mL of absolute ethanol, and the mixture was stirred in a glove box for 12 hours to dissolve the CsBr powder sufficiently and then allowed to stand for half an hour, thereby obtaining a CsBr saturated precursor solution.
0.5mmol SnBr was taken 2 Adding the powder into 1mL of absolute ethanol, stirring to dissolve completely to obtain SnBr 2 Precursor solution, snBr 2 The concentration of the ethanol solution was 0.5mol/L.
6mL of CsBr ethanol saturated solution was placed in a glass vial, and the magnet was placed. Dropwise adding 0.5mol/L SnBr under the rotation of a magnet at 450rpm 2 And (3) after 1mL of the precursor solution is completely dripped, standing the suspension until all the product particles are settled at the bottom of the glass vial. Then sucking out the supernatant ethanol, and drying the bottom product in a vacuum freeze drying oven to obtain CsSnBr with cubic morphology 3 Perovskite.
Example 5
A method for preparing seleno perovskite, comprising the following steps:
41mmol of CsBr powder was added to 500mL of absolute ethanol, and the mixture was stirred in a glove box for 12 hours to dissolve the CsBr powder sufficiently and then allowed to stand for half an hour, thereby obtaining a CsBr saturated precursor solution.
0.1mmol SnBr was taken 2 Adding the powder into 1mL of absolute ethanol, stirring to dissolve completely to obtain SnBr 2 Precursor solution, snBr 2 The concentration of the ethanol solution was 0.1mol/L.
6mL of CsBr ethanol saturated solution was placed in a glass vial, and the magnet was placed. Dropwise adding 0.1mol/L SnBr under the rotation of a magnet at 450rpm 2 And (3) after 1mL of the precursor solution is completely dripped, standing the suspension until all the product particles are settled at the bottom of the glass vial. Then sucking out the supernatant ethanol, and drying the bottom product in a vacuum freeze drying oven to obtain CsSnBr with starfish-like morphology 3 Perovskite.
Example 6
A method for preparing seleno perovskite, comprising the following steps:
41mmol of CsBr powder was added to 500mL of absolute ethanol, and the mixture was stirred in a glove box for 12 hours to dissolve the CsBr powder sufficiently and then allowed to stand for half an hour, thereby obtaining a CsBr saturated precursor solution.
0.6mmol SnBr was taken 2 Adding the powder into 1mL of absolute ethanol, stirring to dissolve completely to obtain SnBr 2 Precursor solution, snBr 2 The concentration of the ethanol solution was 0.6mol/L.
6mL of CsBr ethanol saturated solution was placed in a glass vial, and the magnet was placed. Dropwise adding 0.6mol/L SnBr under the rotation of a magnet at 450rpm 2 And (3) after 1mL of the precursor solution is completely dripped, standing the suspension until all the product particles are settled at the bottom of the glass vial. Then sucking out the supernatant ethanol, and drying the bottom product in a vacuum freeze drying oven to obtain CsSnBr 3 Perovskite, the product contains CsSn as an impurity 2 Cl 5 。
Comparative example 1
A method for preparing seleno perovskite, comprising the following steps:
0.8mL of oleic acid, 0.8mL of oleylamine and 24mL of 1-octadecene were charged into a three-necked flask, heated to 80℃and degassed under vacuum at 80℃for 1 hour.
Thereafter, 0.26g CsCO was added to the reaction vessel 3 Vacuum degassing was continued for 1 hour. Nitrogen is filled and heated to 100 ℃, and the temperature is kept for 1 hour until CsCO 3 All dissolved.
Subsequently, the reaction mixture was heated to a reaction temperature of 170℃and 5mL of SnBr at a concentration of 1mol/L was added 2 The solution and tri-n-octylphosphine were rapidly injected into the mixed solution in the above three-necked flask. After the reaction was kept for 1min, the three-necked flask was ice-water-cooled.
The crude product solution obtained in the three-necked flask was transferred to a glove box filled with nitrogen, an equal volume of n-butanol was added, and then redispersed in n-hexane, and the process was repeated twice. Finally, csSnBr is contained 3 The n-hexane suspension of perovskite was centrifuged at 4 rpm for 2min and then filtered through a 200nm PTFE filter. The prepared CsSnBr 3 The perovskite is put in the air and oxidized after 5 min.
Comparative example 2
A method for preparing seleno perovskite, comprising the following steps:
41mmol of CsBr powder was added to 500mL of absolute ethanol, and the mixture was stirred in a glove box for 12 hours to dissolve the CsBr powder sufficiently and then allowed to stand for half an hour, thereby obtaining a CsBr saturated precursor solution.
0.5mmol SnBr was taken 2 Adding the powder into 1mL of absolute ethanol, stirring to dissolve completely to obtain SnBr 2 Precursor solution, snBr 2 The concentration of the ethanol solution was 0.5mol/L.
6mL of CsBr ethanol saturated solution was placed in a glass vial, and the magnet was placed. Under the rotation of a magnet at 450rpm, 0.5mol/L SnBr is added at one time 2 And (3) after 1mL of the precursor solution is completely dripped, standing the suspension until all the product particles are settled at the bottom of the glass vial. Then sucking out the supernatant ethanol, and drying the bottom product in a vacuum freeze drying oven to obtain CsSnBr 3 Perovskite, however, has poor crystallinity and weak luminescence.
Comparative example 3
A method for preparing seleno perovskite, comprising the following steps:
41mmol of CsBr powder was added to 500mL of water, stirred in a glove box for 12 hours, and allowed to stand still for half an hour after being sufficiently dissolved, to obtain a CsBr precursor solution.
0.2mmol SnBr was taken 2 Adding the powder into 1mL of water, stirring to dissolve completely to obtain SnBr 2 Precursor solution, snBr 2 The concentration of the ethanol solution was 0.2mol/L.
6mL of CsBr ethanol saturated solution was placed in a glass vial, and the magnet was placed. Under the rotation of a magnet at 450rpm, 1mL of 0.2mol/L SnBr2 precursor solution is dropwise added, and no product is produced after standing after all the adding is finished, so that CsSnBr can not be prepared 3 Perovskite.
Result detection
(1) Stability detection
The seleno perovskite nanocrystals obtained in comparative example 1 were dispersed in n-hexane, and the seleno perovskite powder obtained in example 4 was placed on a glass plate while being placed in air (temperature 24.2 to 25.8 ℃ C., humidity 63 to 78%), and the color change of both was observed, and the change of the luminous intensity of both with time was tested.
(2) Luminescence performance detection
The emission spectrum was measured by Edinburgh FLS1000 spectrum, excitation light was a 450nm xenon lamp, slit was (ExBW: 2, emBW: 2), step size was 1nm, integration time was 0.2s, and emission spectra in the range of 600-800nm were measured at room temperature. The absorption spectra were measured by a Cary 5000UV/vis/NIR spectrometer.
Wherein, csSnBr 3 The stability detection result of perovskite is shown in figure 1, and figure 1 shows that CsSnBr is prepared by hot injection method 3 CsSnBr prepared by (above) the synthetic method of the invention 3 As can be seen from FIG. 1, the CsSnBr prepared by the preparation method of the present invention 3 The perovskite was left in air for 6 days without a significant change in color. While CsSnBr prepared by the existing thermal injection method in comparative example 1 3 The perovskite starts to lighten after 5 minutes of standing and substantially disappears after 40 minutes.
FIG. 2 shows the preparation of examples of different SnBr 2 FIG. 4 is a fluorescence emission spectrum of a product obtained by concentration, in which 0.5mol/L SnBr is added to a CsBr precursor solution at one time in comparative example 2 2 The emission spectrum of the precursor solution is shown in Table 1.
The morphology scanning electron microscope of the selenium-based perovskite product prepared by the embodiment is shown in figure 3, and SnBr with different concentrations 2 Can prepare CsSnBr with different morphologies 3 Perovskite. FIG. 5 is a schematic illustration of comparative example 2 in which 0.5mol/L SnBr was added to a CsBr precursor solution at one time 2 The scanning electron microscope image of the precursor solution can be seen from FIG. 5, and CsSnBr prepared therefrom 3 Perovskite morphology crystallinity is poor, and further luminescence performance is poor.
Among them, the detection results concerning the light emission performance are shown in table 1.
TABLE 1
| Sequence number | Luminous intensity (counts) | Time to light stabilization |
| Example 1 | 124561 | For 6 days |
| Example 2 | 178772 | For 6 days |
| Example 3 | 440082 | For 6 days |
| Example 4 | 647934 | For 6 days |
| Example 5 | 110354 | For 6 days |
| Example 6 | 608431 | For 6 days |
| Comparative example 1 | 967825 | 40 minutes |
| Comparative example 2 | 14940 | For 6 days |
As can be seen from the data in Table 1 above, csSnBr of the present invention 3 The perovskite has high luminous intensity, is more stable, is not easy to oxidize, and can achieve the luminous stability time of 6 days.
In comparative example 1, a thermal injection method was used, but CsSnBr was prepared although the luminous intensity was still satisfactory 3 Perovskite is unstable and is easy to oxidize, and the luminescence stabilization time is only 40 minutes.
Comparative example 2 one-time addition of SnBr 2 Ethanol solution, severely affects CsSnBr 3 The luminous intensity of the perovskite.
Comparative example 3 CsBr solution and SnBr were prepared with water 2 The solution can not be prepared into CsSnBr at all 3 Perovskite.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (10)
1. A method for preparing seleno perovskite, which is characterized by comprising the following steps:
under the inert gas atmosphere, the SnBr is dropwise added into the CsBr ethanol saturated solution 2 Ethanol solution, uniformly mixed and SnBr 2 And after the ethanol solution is completely dripped, standing the suspension until all the product particles are settled, and drying the product particles to obtain the seleno perovskite.
2. The method of preparing a seleno-perovskite according to claim 1, wherein the SnBr 2 The concentration of the ethanol solution is 0.2-0.5 mol/L.
3. The method of preparing a seleno-perovskite according to claim 1, wherein the SnBr 2 The concentration of the ethanol solution is 0.4-0.5 mol/L.
4. The method for preparing seleno-perovskite according to claim 1, wherein SnBr is dropwise added under stirring 2 Ethanol solution.
5. The method of preparing a seleno-perovskite according to claim 4, wherein the stirring rate is between 450 and 1300rpm.
6. A seleno perovskite prepared by the method for preparing a seleno perovskite according to any one of claims 1 to 4.
7. The seleno-perovskite of claim 6, wherein the seleno-perovskite is any one of starfish, rod-like, spherical, or cubic.
8. The seleno-perovskite of claim 6, wherein the seleno-perovskite has a fluorescence emission spectrum of 650-800nm and an absorption spectrum of 300-700 nm.
9. Use of the seleno-perovskite of claim 6 for the preparation of luminescent LEDs, solar cells and photodetectors.
10. An optoelectronic device, wherein the luminescent material of the optoelectronic device is the seleno-perovskite according to claim 6.
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| CN111470528A (en) * | 2020-04-11 | 2020-07-31 | 上海科技大学 | Tin-containing semiconductor material and preparation method thereof |
| KR20210051833A (en) * | 2019-10-31 | 2021-05-10 | 중앙대학교 산학협력단 | Pb-free perovskite nanocrystals synthesis method and Pb-free perovskite nanocrystals synthesized thereby |
| CN113233496A (en) * | 2021-06-16 | 2021-08-10 | 辽宁科技大学 | Method for preparing tin-based perovskite nano powder by hydrothermal method |
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| CN111470528A (en) * | 2020-04-11 | 2020-07-31 | 上海科技大学 | Tin-containing semiconductor material and preparation method thereof |
| CN113233496A (en) * | 2021-06-16 | 2021-08-10 | 辽宁科技大学 | Method for preparing tin-based perovskite nano powder by hydrothermal method |
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