CN106938854A - A kind of preparation method of large scale lead halide caesium perovskite crystal - Google Patents
A kind of preparation method of large scale lead halide caesium perovskite crystal Download PDFInfo
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- CN106938854A CN106938854A CN201710150280.8A CN201710150280A CN106938854A CN 106938854 A CN106938854 A CN 106938854A CN 201710150280 A CN201710150280 A CN 201710150280A CN 106938854 A CN106938854 A CN 106938854A
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- perovskite crystal
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- 239000013078 crystal Substances 0.000 title claims abstract description 50
- 229910052792 caesium Inorganic materials 0.000 title claims abstract description 39
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 150000004820 halides Chemical class 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 4
- 238000001704 evaporation Methods 0.000 claims abstract description 4
- 230000008020 evaporation Effects 0.000 claims abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000004528 spin coating Methods 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- -1 caesium halide Chemical class 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 4
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 230000026030 halogenation Effects 0.000 claims description 4
- 238000005658 halogenation reaction Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 abstract description 3
- 229910052740 iodine Inorganic materials 0.000 abstract description 2
- 230000005622 photoelectricity Effects 0.000 abstract description 2
- 238000011160 research Methods 0.000 abstract description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000002017 high-resolution X-ray diffraction Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- 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
-
- 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
- H01L31/02—Details
- H01L31/0216—Coatings
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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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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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
- C01P2002/70—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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
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- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
Abstract
The invention discloses a kind of preparation method of large scale lead halide caesium perovskite crystal, crystal structure composition is CsPbX3, wherein X=Cl, Br or I.The present invention prepares large scale lead halide caesium perovskite crystal by evaporation at constant temperature, and whole process does not need protective gas, and equipment is simple, is produced on a large scale.Prepare gained large scale lead halide caesium perovskite crystal yield higher, good stability, available for solar cell, photo-detector, the photoelectricity research field such as light emitting diode.
Description
Technical field
The present invention relates to a kind of preparation method of large scale lead halide caesium perovskite crystal, belong to photoelectron material and prepare skill
Art field.
Background technology
In recent years, perovskite material causes as a kind of new Semiconductor Optoeletronic Materials in academia and industrial circle
Great interest.Metal halide perovskite, general structure is ABX3, wherein B is bivalent cation (Ge2+、Sn2+、pb2+),
X is halogen atom (F-、Cl-、Br-Or I-), A is monovalent cation (K+、Cs+、CH3NH3 +).Perovskite material is used as solar-electricity
The absorbed layer in pond, its electricity conversion has been able to mutually be equal to high performance indium gallium selenium and Commercial monocrystalline silicon solar cell
It is beautiful.Meanwhile, abundant raw materials, with low cost, carrier mobility needed for its preparation are high, the absorption coefficient of light is big, with significant
Performance and cost advantage.Except the absorbed layer as solar cell, perovskite material is in photovoltaic material, laser material and lights
Also great application value is shown in terms of material.
At present, the electricity conversion of perovskite solar cell has been over 20%, and with new material
Synthesis, the application of new device structure, it is contemplated that the electricity conversion of following Ca-Ti ore type solar cell can also be lifted constantly.Separately
On the one hand, in light emitting diode and field of lasers, perovskite material also shows original potentiality, lights and display field
Also therefore next application focus of perovskite material is become.However, perovskite material is also deposited due to its own design feature
In some defects and deficiency.Hybrid inorganic-organic perovskite material is very sensitive to air and water, holds in a humid environment
Easily adsorb the moisture in air and cause degraded, thus less stable.This defect, significantly limit perovskite material and exists
The practical application of optoelectronic areas.Therefore researcher focuses on to develop a kind of new perovskite material：Lead halide caesium full-inorganic calcium
Titanium ore (CsPbX3), because it is free of organic amine component, thus it is more stable in atmosphere.In recent years, full-inorganic perovskite by
Gradually become the study hotspot of perovskite material.On the other hand, CsPbX3Not only have luminance purity good, quantum dot efficiency height etc.
The advantage of traditional perovskite material；Meanwhile, its stability under air and wet environment is much better than hybrid inorganic-organic calcium titanium
Pit wood material.
The team that the Dalian Chemistry and Physics Institute of Chinese Academy of Sciences Liu Shengzhong researcher leads, using the crystallization method that heats up, prepares super large first
Size single crystal perovskite CH3NH3PbI3Crystal, more than 2 inches of its size (71 millimeters).This is to report that size surpasses first in the world
Cross 0.5 inch of perovskite monocrystalline.By high-resolution X-ray diffraction and optic test, CH is found3NH3PbX3(X=C1, Br, I)
Perovskite crystal material has very high crystalline quality and more preferable light abstraction width.On the other hand, monocrystal material is than film material
Material has higher heat endurance, therefore the perovskite solar cell made using monocrystalline, can obtain more preferable photoelectricity and turn
Change efficiency.Meanwhile, have benefited from perfection of crystal and its less defect, single crystal device is also thus with more preferable stability.
Because monocrystal material is the basis of modern semiconductors industry, electronics industry and optoelectronics industry, thus there is the big chi of premium properties
Very little perovskite monocrystal material is possible to realize the innovation to polycrystalline perovskite material device, promotes the new round leather of photoelectric device
Life.
So, large scale full-inorganic perovskite material (CsPbX3) be with a wide range of applications.Thus need extensive
Prepare large-sized full-inorganic perovskite material, but because its preparation needs protective gas and hot conditions, cause its high cost,
Low yield, it is impossible to extensive to prepare.This is current, and the research of large scale lead halide caesium perovskite crystal and one of application field are urgently
To be solved the problem of.
The content of the invention
It is not enough for more than, the invention provides a kind of preparation method of large scale lead halide caesium perovskite crystal, use
The product characteristicses prepared are stable, and preparation technology is simple, and yield is higher, can be with large-scale production.
Technical scheme is as follows：A kind of preparation method of large scale lead halide caesium perovskite crystal, step is as follows：
(1) lead halide is dissolved in dimethylformamide, stirring is to being completely dissolved；
(2) caesium halide is dissolved in dimethylformamide and adds surfactant, solution is heated into 150 DEG C keeps constant temperature anti-
Answer and room temperature is cooled to after 1h；
(3) gained halogenation lead solution in step (1) is taken to be preheated to 50 DEG C, afterwards by Cs+：Pb2+Mol ratio is 1：1 adds step
(2) gained caesium halide solution in, mixed solution is progressively warming up to after 70 DEG C, reaction 3h, is cooled to room temperature, obtains precursor liquid；
(4) precursor liquid of gained in step (3) is taken, it is instilled in poor solvent with 0.1ml/s speed, at the uniform velocity stirred
Afterwards, solution is progressively warming up to 50 DEG C, evaporation at constant temperature 5h is kept, its solution bottom gradually there are orange red coloured particles to separate out；
(5) resulting solution in step (4) is cooled to after room temperature, centrifugation purification drying obtains large scale full-inorganic halogen
Plain perovskite crystal；Consisting of CsPbX3, wherein X is Cl, Br, any one in I or two kinds of mixing, while caesium, lead with
The mol ratio of halogen is 1：1：3.
Further, the surfactant described in step (2) is oleic acid, oleyl amine mixed solution, and volume ratio is 2:1.
Further, the poor solvent described in step (4) is in toluene, n-hexane, normal heptane, normal octane or chloroform
Any one.
Further, the at the uniform velocity stir speed (S.S.) described in step (4) is 700~1000r/min.
Further, the heating rate described in step (4) is 10 DEG C/h.
Lead halide caesium perovskite crystal size obtained by the preparation method of the present invention is 200 nanometers~1 micron；Crystal
Glow peak continuously adjustabe between 300~700nm.
The invention also discloses a kind of preparation method preparation of large scale lead halide caesium perovskite crystal using the present invention
The crystal method for preparing film, comprise the following steps：
(1) large scale lead halide caesium perovskite crystal is dissolved in organic solvent, stirred to being completely dissolved, concentration is 0.1
~5mol/L；
(2) solution for obtaining step (1) stirs 2~24h under the conditions of 50~100 DEG C, lucifuge, obtain large scale completely without
Machine perovskite crystal solution；
(3) backing material is cleaned by ultrasonic, then dried up using nitrogen；
(4) backing material after processing is placed in 10~60min for the treatment of with irradiation in UV ozone cleaning device；
(5) the large scale full-inorganic perovskite crystal solution that the step of taking 50 μ L~150 μ L (2) obtains is laid in step
(4) in the substrate material surface after handling, spin coating 5~50 seconds, its spin speed is 3000~8000r/min；
(6) 10~100min is heated under the conditions of the backing material after spin coating being placed in into 50~150 DEG C, room is subsequently cooled to
Temperature, produces large scale full-inorganic perovskite crystal film.
The present invention has the following advantages that compared with prior art：
Large-size crystals structure prepared by the present invention is perovskite structure, and preparation is carried out at normal temperatures, it is not necessary to protected
Gas, equipment is simple, is produced on a large scale.Effectively change the size of crystal, and yield can be prepared with control heating-up temperature is crossed
It is higher.When it is Br to select halogen, launch green glow, launch wavelength is stable in properties in 520nm.Large scale halogen prepared by the present invention
Change lead caesium perovskite crystal, available for solar cell, laser, optical detection, the photoelectric field such as light emitting diode.
Brief description of the drawings
Fig. 1 is ESEM (SEM) figure using large scale lead halide caesium perovskite crystal produced by the present invention.
Fig. 2 is the XRD spectrum using large scale lead halide caesium perovskite crystal produced by the present invention.
Fig. 3 is the UV absorption visible spectrum and fluorescence using large scale lead halide caesium perovskite crystal produced by the present invention
Spectrogram.
Embodiment
The present invention is described in further detail with accompanying drawing with reference to embodiments
Embodiment 1
(1) 0.147g PbBr are weighed2It is dissolved in 5mL dimethylformamide (DMF), stirring is to being completely dissolved；
(2) 0.0851g CsBr are weighed to be dissolved in 5mL dimethylformamide (DMF) and add surfactant (0.5mL oil
Acid and 0.25mL oleyl amines), it is cooled to room temperature after solution is heated into 150 DEG C of holding isothermal reaction 1h；
(3) by the 5mLPbBr of gained2Solution is preheated to 50 DEG C, rear to add the 5ml caesium acid salt solutions (Cs prepared+：Pb2+Rub
You are than being 1：1), mixed solution is progressively warming up to after 70 DEG C, reaction 3h, obtains precursor liquid；
(4) 1mL precursor liquids are taken,, will be molten after at the uniform velocity stirring in the n-hexane that it is instilled to 10mL with 0.1ml/s speed
Liquid is progressively warming up to 50 DEG C, keeps evaporation at constant temperature 5h, solution bottom can be observed have reddish-orange crystals precipitation；
(5) after solution is cooled to room temperature, centrifugation purification drying obtains large scale CsPbBr3Perovskite crystal.Full mistake
Journey is carried out at normal temperatures and pressures, it is not necessary to protective gas, and obtained nanocrystal size is 1um, under 365nm photoexcitation
Glow peak is 520nm.
Embodiment 2
It is cleaned by ultrasonic backing material successively using detergent, deionized water, alcohol, acetone, isopropanol, is cleaned by ultrasonic every time
5 minutes.
(1) obtained large scale lead halide caesium perovskite crystal is dissolved in organic solvent, and magnetic agitation to completely it is molten
Solution, concentration is 0.1mol/L；
(2) above-mentioned solution is stirred into 24h under the conditions of 50 DEG C, lucifuge, obtains large scale lead halide caesium perovskite crystal molten
Liquid；
(3) backing material is cleaned by ultrasonic, then dried up with nitrogen；
(4) the thorough material after drying is placed in treatment with irradiation 10min in UV ozone cleaning device；
(5) 50 μ L large scale lead halide caesium perovskite crystal solution is laid on backing material bottom surface, spin coating 5s, revolved
It is 3000 revolutions per seconds to apply speed；
(6) material after spin coating is heated into 100min under the conditions of 50 DEG C, is subsequently cooled to room temperature, produce large scale halogenation
Lead caesium perovskite crystal film.
Embodiment 3
It is cleaned by ultrasonic backing material successively using detergent, deionized water, alcohol, acetone, isopropanol, is cleaned by ultrasonic every time
15 minutes.
(1) obtained large scale lead halide caesium perovskite crystal is dissolved in organic solvent, and magnetic agitation to completely it is molten
Solution, solubility is 5mol/L；
(2) above-mentioned solution is stirred into 2h under the conditions of 100 DEG C, lucifuge, obtains large scale lead halide caesium perovskite crystal molten
Liquid；
(3) backing material is cleaned by ultrasonic, then dried up with nitrogen；
(4) the thorough material after drying is placed in treatment with irradiation 60min in UV ozone cleaning device；
(5) 150 μ L large scale lead halide caesium perovskite crystal solution is laid on backing material bottom surface, spin coating 50s,
Spin speed is 3000 revolutions per seconds；
(6) material after spin coating is heated into 10min under the conditions of 150 DEG C, is subsequently cooled to room temperature, produce large scale halogenation
Lead caesium perovskite crystal film.The detailed presentation of the preferred embodiment of the present invention and explanation.It should be appreciated, however, that
Without departing from the spirit or scope of appended claims, it can make various changes and modifications.
Claims (6)
1. a kind of preparation method of large scale lead halide caesium perovskite crystal, it is characterised in that step is as follows：
(1) lead halide is dissolved in dimethylformamide, stirring is to being completely dissolved；
(2) caesium halide is dissolved in dimethylformamide and adds surfactant, solution is heated into 150 DEG C keeps isothermal reaction 1h
After be cooled to room temperature；
(3) gained halogenation lead solution in step (1) is taken to be preheated to 50 DEG C, afterwards by Cs+：Pb2+Mol ratio is 1：1 adds step (2)
Middle gained caesium halide solution, mixed solution is progressively warming up to after 70 DEG C, reaction 3h, is cooled to room temperature, obtains precursor liquid；
(4) precursor liquid of gained in step (3) is taken, it is instilled in poor solvent with 0.1ml/s speed, after at the uniform velocity stirring,
Solution is progressively warming up to 50 DEG C, evaporation at constant temperature 5h is kept, its solution bottom gradually there are orange red coloured particles to separate out；
(5) resulting solution in step (4) is cooled to after room temperature, centrifugation purification drying obtains large scale full-inorganic halogen calcium
Titanium ore crystal；Consisting of CsPbX3, wherein X is Cl, Br, any one in I or two kinds of mixing, while caesium, lead and halogen
Mol ratio be 1：1：3.
2. a kind of preparation method of large scale lead halide caesium perovskite crystal according to claim 1, it is characterised in that step
Suddenly the surfactant described in (2) is oleic acid, oleyl amine mixed solution, and volume ratio is 2:1.
3. a kind of preparation method of large scale lead halide caesium perovskite crystal according to claim 1, it is characterised in that step
Suddenly any one of the poor solvent described in (4) in toluene, n-hexane, normal heptane, normal octane or chloroform.
4. a kind of preparation method of large scale lead halide caesium perovskite crystal according to claim 1, it is characterised in that step
Suddenly the at the uniform velocity stir speed (S.S.) described in (4) is 700~1000r/min.
5. a kind of preparation method of large scale lead halide caesium perovskite crystal according to claim 1, it is characterised in that step
Suddenly the heating rate described in (4) is 10 DEG C/h.
6. a kind of a kind of preparation method system of large scale lead halide caesium perovskite crystal described in utilization claim any one of 1-5
The method that standby crystal prepares film, it is characterised in that comprise the following steps：
(1) large scale lead halide caesium perovskite crystal is dissolved in organic solvent, stirring to being completely dissolved, concentration is 0.1~
5mol/L；
(2) solution for obtaining step (1) stirs 2~24h under the conditions of 50~100 DEG C, lucifuge, obtains large scale full-inorganic calcium
Titanium ore crystalloid solution；
(3) backing material is cleaned by ultrasonic, then dried up using nitrogen；
(4) backing material after processing is placed in 10~60min for the treatment of with irradiation in UV ozone cleaning device；
(5) the large scale full-inorganic perovskite crystal solution that the step of taking 50 μ L~150 μ L (2) obtains is laid in step (4) place
In substrate material surface after reason, spin coating 5~50 seconds, its spin speed is 3000~8000r/min；
(6) 10~100min is heated under the conditions of the backing material after spin coating being placed in into 50~150 DEG C, room temperature is subsequently cooled to, i.e.,
Obtain large scale full-inorganic perovskite crystal film.
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