CN113023764A - Preparation method of copper-based perovskite nanocrystalline film - Google Patents
Preparation method of copper-based perovskite nanocrystalline film Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 38
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims description 22
- 238000005245 sintering Methods 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 32
- 239000010408 film Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000010409 thin film Substances 0.000 claims abstract description 23
- 238000003825 pressing Methods 0.000 claims abstract description 16
- 235000015895 biscuits Nutrition 0.000 claims abstract description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 8
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001125 extrusion Methods 0.000 claims abstract description 5
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 40
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 23
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 21
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 21
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 21
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000005642 Oleic acid Substances 0.000 claims description 21
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 18
- 229910052792 caesium Inorganic materials 0.000 claims description 15
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 229940049964 oleate Drugs 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 14
- 239000005457 ice water Substances 0.000 claims description 12
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 11
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 150000004820 halides Chemical class 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 5
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 5
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 5
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 5
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 5
- 229940045803 cuprous chloride Drugs 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 239000002096 quantum dot Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- HENDMPXHKSEXLO-KVVVOXFISA-M cesium;(z)-octadec-9-enoate Chemical compound [Cs+].CCCCCCCC\C=C/CCCCCCCC([O-])=O HENDMPXHKSEXLO-KVVVOXFISA-M 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002159 nanocrystal Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 6
- 230000008707 rearrangement Effects 0.000 abstract description 2
- 238000004227 thermal cracking Methods 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000001514 detection method Methods 0.000 description 5
- 230000005855 radiation Effects 0.000 description 4
- 238000002059 diagnostic imaging Methods 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000007689 inspection Methods 0.000 description 2
- 238000005424 photoluminescence Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/006—Compounds containing, besides copper, two or more other elements, with the exception of oxygen or hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
- C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
- C09K11/615—Halogenides
- C09K11/616—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
- H01L31/02—Details
- H01L31/0232—Optical elements or arrangements associated with the device
- H01L31/02322—Optical elements or arrangements associated with the device comprising luminescent members, e.g. fluorescent sheets upon the device
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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
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- Inorganic Chemistry (AREA)
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- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
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Abstract
The invention discloses a method for preparing a copper-based perovskite nanocrystalline film, which comprises the steps of putting dry perovskite nanocrystalline powder into a mold cavity in the process of sintering the perovskite nanocrystalline powder into the perovskite film, and pressing the dry perovskite nanocrystalline powder into a cylindrical biscuit with the diameter of phi 20mm multiplied by 10mm in a nitrogen atmosphere by using a cold pressing method; inserting the pressed cylindrical voxel blank into a Mo crucible; the multi-anvil unit was then loaded and six-axis extrusion was performed axially from 6 tungsten carbide anvils. The ultrahigh pressure can greatly reduce the sintering temperature, so that the copper-based perovskite nanocrystalline powder can form a molten state below a thermal cracking temperature point, meanwhile, the ultrahigh pressure can promote the rearrangement of the copper-based perovskite nanocrystalline particles, the preferred orientation enables the free energy of a system to be carried out in a lower direction, and finally, the copper-based perovskite thin film with the thickness of millimeter level is obtained.
Description
Technical Field
The invention relates to the technical field of perovskite thin film preparation, in particular to a preparation method of a copper-based perovskite nanocrystalline thin film.
Background
The X-ray detection material has the capability of converting X-rays into electronic signals or optical signals, so that the X-ray detection material has important significance in customs security inspection, nuclear reaction monitoring, medical imaging and the like, and is particularly important for obtaining the X-ray detection material with high sensitivity and high detection efficiency. In recent years, all-inorganic cesium-lead-halide perovskite (Cs)3Cu2X5X = Cl, Br, I) Quantum Dots (QDs) have been widely studied for their high luminous efficiency, their simple tunability of photoluminescence in the visible range, their sensitivity to X-rays, and other properties. For example, in X-ray radiation detection and medical imaging, due to its excellent radiation luminescence properties, it is considered as the most promising X-ray imaging material in the future, and on the other hand, the photoluminescence quantum yield (PLQY) of all-inorganic cesium-halogen perovskite thin film currently exceedsConventional fluorescent materials have therefore received increasing attention and use.
The perovskite method for preparing the thin film is generally divided into a solution method and a vacuum method. The film is prepared by a conventional solution method, so that the solvent is volatilized in the preparation process, cavities are easy to form, and the quality of the film is common; the other method is a vacuum method film preparation process, the vacuum method is mostly concentrated in the preparation of the film, and the problem of serious component segregation often occurs in the preparation of the perovskite film, so that the prepared perovskite film is impure, and in addition, crystals cannot grow in a large area, so the vacuum method is not the preferred method in the preparation of the perovskite film.
Disclosure of Invention
The invention aims to provide a preparation method of a copper-based perovskite nanocrystalline film, which firstly provides that the copper-based perovskite nanocrystalline film with millimeter-scale thickness is prepared under the melting temperature point of the copper-based perovskite nanocrystalline through an ultrahigh pressure sintering process.
In order to realize the purpose, the invention provides a preparation method of an ultrahigh-pressure copper-based perovskite nanocrystalline film, which adopts the technical scheme that: in the process of sintering perovskite nanocrystalline powder into a perovskite film, dry perovskite nanocrystalline powder is firstly placed into a mold cavity and pressed into a cylindrical biscuit with the diameter of phi 20mm multiplied by 10mm in a nitrogen atmosphere by using a cold pressing method; inserting the pressed cylindrical voxel blank into a Mo crucible; the multi-anvil unit was then loaded and six-axis extrusion was performed axially from 6 tungsten carbide anvils.
The pressure sintering process is carried out at different sintering temperatures, and the sintering temperature range is 200-230 ℃; sequentially applying high pressure to the sample at a corresponding sintering temperature, wherein the pressure distribution range is 1.5-2.0 GPa; a heating rate of
150K/min, and the stay heat preservation and pressure maintaining sintering time is 10-15 min.
The optimized preparation steps for preparing the raw material perovskite nanocrystalline powder of the copper-based perovskite nanocrystalline film are as follows:
firstly, preparing a precursor solution of cesium oleate: 2.92g (9 mm) of cesium carbonate, 0.95ml of Oleic Acid (OA) and 15ml of Octadecene (ODE) were sequentially added to a 50ml three-necked flask and filled with nitrogen to remove the air in the flask; putting the three-necked flask into an oil bath pot, heating to 120 ℃, and keeping for 1h to remove residual water in OA and ODE and fully react cesium carbonate to produce cesium oleate; placing the generated caesium oleate precursor solution in an oil bath kettle at 120 ℃ to keep a transparent molten state for direct use in the following steps;
secondly, synthesizing perovskite quantum dots: cuprous halide and 10ml ODE are added into another three-neck flask with the specification of 50ml, and nitrogen is introduced to remove air in the flask; putting the three-neck flask into an oil bath pot, heating to 120 ℃, and keeping for 1h to remove residual water in ODE; then slowly reducing the temperature, quickly injecting the cesium oleate precursor solution prepared in the first step when the temperature is reduced stably to 70 ℃, and fully oscillating the three-neck flask for 20-30 s; finally, immediately putting the crystal grains into an ice water bath for cooling to promote the crystal grains not to continue to grow;
thirdly, centrifugally purifying perovskite nanocrystalline powder: adding a precursor solution cooled by an ice water bath into the mixed solution according to the volume ratio of 1: 1-1: 3, centrifuging at 5000-8000 rpm/min for 5-8 min, discarding supernatant, adding 5-10 ml of organic solution such as toluene or normal hexane or cyclohexane into the precipitate, centrifuging at 5000-8000 rpm/min for 5-8 min, taking the centrifuged precipitate, placing the precipitate on a pure glass slide, and putting the precipitate into a vacuum drying oven at 60-70 ℃ for vacuum drying for 24h to obtain the perovskite nanocrystal powder.
It should be added that, as a preferred parameter in the first step and the second step, cesium carbonate and cuprous halide are selected in a molar ratio of 3: 2.
it should be further added that the cuprous halide used in the second step may be one or more of cuprous chloride (CuCl), cuprous bromide (CuBr), and cuprous iodide (CuI).
The invention has the advantages that: at present, the difficulty in preparing high-quality void-free perovskite thin films is still a great obstacle limiting the wide application of the perovskite thin films, and more importantly, the perovskite thin films prepared by the conventional method are generally in the nanometer-level thickness and cannot completely attenuate X rays. The invention firstly provides a copper-based perovskite nanocrystalline film with millimeter-scale thickness prepared by adopting an ultrahigh pressure sintering method, the film prepared by the method is compact and has no gap, the thickness reaches millimeter level, X rays can be completely absorbed, the signal to noise ratio is improved, the dose rate is greatly reduced, the radiation dose of ray application places such as medical imaging and nondestructive inspection is effectively reduced, and the radiation damage to a human body is reduced to be within a safe range.
Detailed Description
The preparation method of the copper-based perovskite nanocrystalline film comprises the following steps:
firstly, putting dry perovskite nanocrystalline powder into a mold cavity, and pressing the perovskite nanocrystalline powder into a cylindrical biscuit with the diameter of phi 20mm multiplied by 10mm by using a cold pressing method in a nitrogen atmosphere; inserting the pressed cylindrical voxel blank into a Mo crucible; the multi-anvil unit was then loaded and six-axis extrusion was performed axially from 6 tungsten carbide anvils.
The pressure sintering process is carried out at different sintering temperatures, and the sintering temperature range is 200-230 ℃; sequentially applying high pressure to the sample at a corresponding sintering temperature, wherein the pressure distribution range is 1.5-2.0 GPa; the heating rate is 150K/min, and the stay heat preservation pressure maintaining sintering time is 10-15 min.
The preparation method of the raw material perovskite nanocrystalline powder for preparing the copper-based perovskite nanocrystalline film comprises the following steps:
firstly, preparing a precursor solution of cesium oleate: 2.93g (9 mm) of cesium carbonate, 0.95ml of Oleic Acid (OA) and 15ml of Octadecene (ODE) were sequentially added to a 50ml three-necked flask and filled with nitrogen to remove the air in the flask; putting the three-necked flask into an oil bath pot, heating to 120 ℃, and keeping for 1h to remove residual water in OA and ODE and fully react cesium carbonate to produce cesium oleate; placing the generated caesium oleate precursor solution in an oil bath kettle at 120 ℃ to keep a transparent molten state for direct use in the following steps;
secondly, synthesizing perovskite quantum dots: cuprous halide and 10ml ODE are added into another three-neck flask with the specification of 50ml, and nitrogen is introduced to remove air in the flask; putting the three-neck flask into an oil bath pot, heating to 120 ℃, and keeping for 1h to remove residual water in ODE; then slowly reducing the temperature, quickly injecting the cesium oleate precursor solution prepared in the first step when the temperature is reduced stably to 70 ℃, and fully oscillating the three-neck flask for 20-30 s; finally, immediately putting the crystal grains into an ice water bath for cooling to promote the crystal grains not to continue to grow;
thirdly, centrifugally purifying perovskite nanocrystalline powder: adding a precursor solution cooled by an ice water bath into the mixed solution according to the volume ratio of 1: 1-1: 3, centrifuging at 5000-8000 rpm/min for 5-8 min, discarding supernatant, adding 5-10 ml of organic solution such as toluene or normal hexane or cyclohexane into the precipitate, centrifuging at 5000-8000 rpm/min for 5-8 min, taking the centrifuged precipitate, placing the precipitate on a pure glass slide, and putting the precipitate into a vacuum drying oven at 60-70 ℃ for vacuum drying for 24h to obtain the perovskite nanocrystal powder.
The first concrete embodiment of the preparation method of the copper-based perovskite nanocrystalline thin film is as follows: preparation of Cs3Cu2Cl5The method of the nanocrystalline thin film comprises the following steps:
(1) 2.93g (9 mm) of Cs were added in this order2CO30.95ml of oleic acid OA and 15ml of octadecene ODE are added into a three-neck flask with the specification of 50ml, and nitrogen is introduced;
(2) heating the three-necked flask to 120 ℃ in an oil bath pan, and drying for 1 h;
(3) the heating temperature is raised to 150 ℃ and the nitrogen is continuously introduced until Cs2CO3The oleic acid OA and octadecene ODE are completely reacted;
note: cesium oleate precipitates at room temperature and needs to be heated to 120 ℃ for use before thermal injection.
(4) 0.594 g of CuCl (6 mm) and 10ml of octadecene ODE are weighed and added into another three-neck flask with the specification of 50ml, and nitrogen is introduced to remove air in the flask;
(5) putting the three-necked flask obtained in the step 4) into an oil bath pot, heating to 120 ℃, keeping the temperature for 1h, and drying to remove residual moisture in the octadecene ODE;
(6) slowly reducing the temperature of the three-neck flask obtained in the step 5) to ensure that the temperature is reduced and stabilized at 70 ℃; finally, immediately putting the crystal grains into an ice water bath for cooling to promote the crystal grains not to continue to grow;
(7) quickly injecting 4ml of the cesium oleate precursor solution prepared in the step 3), and fully oscillating the three-neck flask for 20-30 s;
(8) after 30s, the reaction mixture was quickly cooled to room temperature in an ice-water bath;
(9) adding ethyl acetate into the mixture according to a volume ratio of 1: 1, adding the mixture into the solution obtained in the step 8), then centrifuging the mixture at 5000 rpm/min for 3min, and discarding the supernatant;
(10) washing the precipitate with toluene twice, pouring onto quartz plate, and drying in vacuum drying oven at 60 deg.C for 24 hr;
(11) collecting 10 g of the powder dried in the step 10), introducing the powder into a mold cavity, and pressing the powder into a cylindrical biscuit with the diameter of phi 20mm multiplied by 10mm by a cold pressing method in a nitrogen atmosphere;
(12) inserting the pressed cylindrical voxel blank into a Mo crucible;
(13) loading into a multi-anvil device, and performing pressure sintering by 6 tungsten carbide anodes under the environment condition of multi-axial pressing, wherein the sintering temperature is 200 ℃, the sintering pressure is 1.5GPa, and the pressure maintaining time is 10 min;
(14) slowly cooling to room temperature and carefully taking out from the die cavity to obtain Cs with the film thickness of about 2mm3Cu2Cl5A nanocrystalline thin film.
The following is a specific example II based on the preparation method of the copper-based perovskite nanocrystalline thin film of the invention: preparation of Cs3Cu2Br5The method for preparing the quasi-single crystal thin film comprises the following steps:
(1) 2.93g (9 mm) of Cs were added in this order2CO30.95ml of oleic acid OA and 15ml of octadecene ODE are added into a three-neck flask with the specification of 50ml, and nitrogen is introduced;
(2) heating the three-necked flask to 120 ℃ in an oil bath pan, and drying for 1 h;
(3) the heating temperature is raised to 150 ℃ and the nitrogen is continuously introduced until Cs2CO3The oleic acid OA and octadecene ODE are completely reacted;
note: cesium oleate precipitates at room temperature and needs to be heated to 120 ℃ for use before thermal injection.
(4) 0.861g of CuBr (6 mm) and 10ml of octadecene ODE are weighed and added into another three-neck flask with the specification of 50ml, and nitrogen is introduced to remove air in the flask;
(5) putting the three-necked flask obtained in the step 4) into an oil bath pot, heating to 120 ℃, keeping the temperature for 1h, and drying to remove residual moisture in the octadecene ODE;
(6) slowly reducing the temperature of the three-neck flask obtained in the step 5) to ensure that the temperature is reduced and stabilized at 70 ℃; finally, immediately putting the crystal grains into an ice water bath for cooling to promote the crystal grains not to continue to grow;
(7) quickly injecting 4ml of the cesium oleate precursor solution prepared in the step 3), and fully oscillating the three-neck flask for 20-30 s;
(8) after 30s, the reaction mixture was quickly cooled to room temperature in an ice-water bath;
(9) adding ethyl acetate into the mixture according to a volume ratio of 1: 1, adding the mixture into the solution obtained in the step 8), then centrifuging the mixture at 5000 rpm/min for 3min, and discarding the supernatant;
(10) washing the precipitate with toluene twice, pouring onto quartz plate, and drying in vacuum drying oven at 60 deg.C for 24 hr;
(11) collecting 6g of the powder dried in the step 10), introducing the powder into a mold cavity, and pressing the powder into a cylindrical biscuit with the diameter of phi 20mm multiplied by 6mm by a cold pressing method in a nitrogen atmosphere;
(12) inserting the pressed cylindrical voxel blank into a Mo crucible;
(13) loading into a multi-anvil device, and performing pressure sintering by 6 tungsten carbide anodes under the environment condition of multi-axial pressing, wherein the sintering temperature is 220 ℃, the sintering pressure is 1.8GPa, and the pressure maintaining time is 15 min;
(14) slowly cooling to room temperature and carefully taking out from the die cavity to obtain Cs with the film thickness of about 1.5mm3Cu2Br5A nanocrystalline thin film.
The following is a third specific embodiment of the preparation method of the copper-based perovskite nanocrystalline thin film according to the invention: preparation of Cs3Cu2I5The method of the nanocrystalline thin film comprises the following steps:
(1) 2.93g (9 mm) of Cs were added in this order2CO30.95ml of oleic acid OA and 15ml of octadecene ODE were put into a 50ml three-necked flaskIntroducing nitrogen;
(2) heating the three-necked flask to 120 ℃ in an oil bath pan, and drying for 1 h;
(3) the heating temperature is raised to 150 ℃ and the nitrogen is continuously introduced until Cs2CO3The oleic acid OA and octadecene ODE are completely reacted;
note: cesium oleate precipitates at room temperature and needs to be heated to 120 ℃ for use before thermal injection.
(4) Weighing 1.143g of CuI (6 mm) and 10ml of octadecene ODE, adding into another three-neck flask with the specification of 50ml, and introducing nitrogen to remove air in the flask;
(5) putting the three-necked flask obtained in the step 4) into an oil bath pot, heating to 120 ℃, keeping the temperature for 1h, and drying to remove residual moisture in the octadecene ODE;
(6) slowly reducing the temperature of the three-neck flask obtained in the step 5) to ensure that the temperature is reduced and stabilized at 70 ℃; finally, immediately putting the crystal grains into an ice water bath for cooling to promote the crystal grains not to continue to grow;
(7) quickly injecting 4ml of the cesium oleate precursor solution prepared in the step 3), and fully oscillating the three-neck flask for 20-30 s;
(8) after 30s, the reaction mixture was quickly cooled to room temperature in an ice-water bath;
(9) adding ethyl acetate into the mixture according to a volume ratio of 1: 1, adding the mixture into the solution obtained in the step 8), then centrifuging the mixture at 5000 rpm/min for 3min, and discarding the supernatant;
(10) washing the precipitate with toluene twice, pouring onto quartz plate, and drying in vacuum drying oven at 70 deg.C for 24 hr;
(11) collecting 5g of the powder dried in the step 10), introducing the powder into a mold cavity, and pressing the powder into a cylindrical biscuit with the diameter of phi 20mm multiplied by 5mm by a cold pressing method in a nitrogen atmosphere;
(12) inserting the pressed cylindrical voxel blank into a Mo crucible;
(13) loading into a multi-anvil device, and performing pressure sintering by 6 tungsten carbide anodes under the environment condition of multi-axial pressing, wherein the sintering temperature is 230 ℃, the sintering pressure is 2GPa, and the pressure maintaining time is 15 min;
(14) slowly cooling to room temperature and carefully removing the moldTaking out the obtained product from the mold cavity to obtain Cs with a film thickness of about 1mm3Cu2I5A nanocrystalline thin film.
In the process of sintering perovskite nanocrystalline powder into a perovskite film, dry perovskite nanocrystalline powder is firstly placed into a mold cavity and pressed into a cylindrical biscuit with the diameter of phi 20mm multiplied by 10mm in a nitrogen atmosphere by using a cold pressing method; inserting the pressed cylindrical voxel blank into a Mo crucible; the multi-anvil unit was then loaded and six-axis extrusion was performed axially from 6 tungsten carbide anvils. The ultrahigh pressure can greatly reduce the sintering temperature, so that the copper-based perovskite nanocrystalline powder can form a molten state below a thermal cracking temperature point, meanwhile, the ultrahigh pressure can promote the rearrangement of copper-based perovskite nanocrystalline grains, the preferred orientation enables the free energy of a system to be carried out in a lower direction, and finally, the copper-based perovskite nanocrystalline film with the thickness of millimeter level is obtained.
The differences of the process parameters of sintering temperature, sintering pressure and heat-preservation and pressure-maintaining time can cause the differences of the compactness of the film and the quality and performance of X-ray imaging, and the process parameter range given in the method can prepare the thick film for high-performance X-ray imaging.
Claims (7)
1. A preparation method of a copper-based perovskite nanocrystalline film is characterized by comprising the following steps: in the process of sintering the perovskite nanocrystalline powder into a film, firstly, dry copper-based perovskite nanocrystalline powder is placed into a mould cavity, and is pressed into a cylindrical biscuit with the diameter of phi 20mm multiplied by 10mm in a nitrogen atmosphere by using a cold pressing method; inserting the pressed cylindrical voxel blank into a Mo crucible; then, the materials are loaded into a multi-anvil device, and six-axis extrusion is carried out on the 6 tungsten carbide anvils in the axial direction; the ultrahigh pressure sintering process is carried out at different temperatures, and the sintering temperature range is 200-230 ℃; sequentially applying ultrahigh pressure to the sample at a corresponding sintering temperature, wherein the pressure distribution range is 1.5-2.0 GPa; the heating rate is 150K/min, and the stay heat preservation pressure maintaining sintering time is 10-15 min.
2. The method for producing a copper-based perovskite nanocrystalline thin film according to claim 1, characterized in that: the pressure sintering process is carried out at different sintering temperatures, and the sintering temperature range is 200-230 ℃.
3. The method for producing a copper-based perovskite nanocrystalline thin film according to claim 1, characterized in that: and sequentially applying high pressure to the sample at the corresponding sintering temperature, wherein the pressure distribution range is 1.5-2.0 GPa.
4. The method for producing a copper-based perovskite nanocrystalline thin film according to claim 1, characterized in that: the heating rate is 150K/min, and the stay heat preservation pressure maintaining sintering time is 10-15 min.
5. The method for producing a copper-based perovskite nanocrystalline thin film according to claim 1, characterized in that:
the optimized preparation steps for preparing the raw material perovskite nanocrystalline powder of the copper-based perovskite nanocrystalline film are as follows:
firstly, preparing a precursor solution of cesium oleate: 0.305g (0.9 mm) of cesium carbonate, 0.95ml of Oleic Acid (OA), and 15ml of Octadecene (ODE) were sequentially added to a 50 ml-sized three-necked flask and the air in the flask was purged with nitrogen; putting the three-necked flask into an oil bath pot, heating to 120 ℃, and keeping for 1h to remove residual water in OA and ODE and fully react cesium carbonate to produce cesium oleate; placing the generated caesium oleate precursor solution in an oil bath kettle at 120 ℃ to keep a transparent molten state for direct use in the following steps;
secondly, synthesizing perovskite quantum dots: cuprous halide and 10ml ODE are added into another three-neck flask with the specification of 50ml, and nitrogen is introduced to remove air in the flask; putting the three-necked flask into an oil bath pot, heating to 120 ℃, and keeping for 1h to remove residual moisture in the octadecene ODE; then slowly reducing the temperature, quickly injecting the cesium oleate precursor solution prepared in the first step when the temperature is reduced stably to 70 ℃, and fully oscillating the three-neck flask for 20-30 s; then immediately putting the crystal grains into an ice water bath for cooling to promote the crystal grains not to continue to grow;
thirdly, centrifugally purifying perovskite nanocrystalline powder: adding a precursor solution cooled by an ice water bath into the mixed solution according to the volume ratio of 1: 1-1: 3, centrifuging at 5000-8000 rpm/min for 5-8 min, discarding supernatant, adding 5-10 ml of organic solution such as toluene or normal hexane or cyclohexane into the precipitate, centrifuging at 5000-8000 rpm/min for 5-8 min, taking the centrifuged precipitate, placing the precipitate on a pure glass slide, and putting the precipitate into a vacuum drying oven at 60-70 ℃ for vacuum drying for 24h to obtain the perovskite nanocrystal powder.
6. The method for producing a copper-based perovskite nanocrystalline thin film according to claim 5, characterized in that: when the raw material perovskite nanocrystalline powder of the copper-based perovskite nanocrystalline film is prepared, the mol ratio of cesium carbonate to cuprous halide is preferably 3: 2.
7. the method for producing a copper-based perovskite nanocrystalline thin film according to claim 5, characterized in that: the cuprous halide can be one or more of cuprous chloride (CuCl), cuprous bromide (CuBr) and cuprous iodide (CuI).
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