WO2020085174A1 - Film mince nanocristallin de pérovskite, procédé de production de film mince nanocristallin de pérovskite, élément électroluminescent, élément de conversion photoélectrique, dispositif d'affichage et dispositif électronique - Google Patents
Film mince nanocristallin de pérovskite, procédé de production de film mince nanocristallin de pérovskite, élément électroluminescent, élément de conversion photoélectrique, dispositif d'affichage et dispositif électronique Download PDFInfo
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- WO2020085174A1 WO2020085174A1 PCT/JP2019/040788 JP2019040788W WO2020085174A1 WO 2020085174 A1 WO2020085174 A1 WO 2020085174A1 JP 2019040788 W JP2019040788 W JP 2019040788W WO 2020085174 A1 WO2020085174 A1 WO 2020085174A1
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- perovskite
- thin film
- nanocrystals
- ligand
- perovskite nanocrystal
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- 239000002159 nanocrystal Substances 0.000 title claims abstract description 310
- 239000010409 thin film Substances 0.000 title claims abstract description 157
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- 239000000126 substance Substances 0.000 claims abstract description 14
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 13
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 13
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 13
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- 239000002243 precursor Substances 0.000 claims description 25
- 238000000151 deposition Methods 0.000 claims description 2
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- 239000002096 quantum dot Substances 0.000 description 11
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- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 4
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- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 3
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- 229910052786 argon Inorganic materials 0.000 description 2
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
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- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- GEWWCWZGHNIUBW-UHFFFAOYSA-N 1-(4-nitrophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C([N+]([O-])=O)C=C1 GEWWCWZGHNIUBW-UHFFFAOYSA-N 0.000 description 1
- YPSXFMHXRZAGTG-UHFFFAOYSA-N 4-methoxy-2-[2-(5-methoxy-2-nitrosophenyl)ethyl]-1-nitrosobenzene Chemical compound COC1=CC=C(N=O)C(CCC=2C(=CC=C(OC)C=2)N=O)=C1 YPSXFMHXRZAGTG-UHFFFAOYSA-N 0.000 description 1
- FNFKHBDVQJIAKL-UHFFFAOYSA-N 9-[4-(4-carbazol-9-ylphenyl)phenyl]carbazole Chemical group c1ccc2c(c1)n(-c1ccc(cc1)-c1ccc(cc1)-n1c3ccccc3c3ccccc13)c1ccccc21.c1ccc2c(c1)n(-c1ccc(cc1)-c1ccc(cc1)-n1c3ccccc3c3ccccc13)c1ccccc21 FNFKHBDVQJIAKL-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical compound NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 description 1
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- NAJCQJKJQOIHSH-UHFFFAOYSA-L [Pb](Br)Br.[Cs] Chemical compound [Pb](Br)Br.[Cs] NAJCQJKJQOIHSH-UHFFFAOYSA-L 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
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- QWANGZFTSGZRPZ-UHFFFAOYSA-N aminomethylideneazanium;bromide Chemical compound Br.NC=N QWANGZFTSGZRPZ-UHFFFAOYSA-N 0.000 description 1
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- FVUCJMMROXQUQR-UHFFFAOYSA-N hexadecan-2-amine Chemical compound CCCCCCCCCCCCCCC(C)N FVUCJMMROXQUQR-UHFFFAOYSA-N 0.000 description 1
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- MJFXORGVTOGORM-UHFFFAOYSA-L lead(2+) methanamine dibromide Chemical compound [Pb+2].[Br-].CN.[Br-] MJFXORGVTOGORM-UHFFFAOYSA-L 0.000 description 1
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- GIDDQKKGAYONOU-UHFFFAOYSA-N octylazanium;bromide Chemical compound Br.CCCCCCCCN GIDDQKKGAYONOU-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C211/03—Monoamines
- C07C211/07—Monoamines containing one, two or three alkyl groups, each having the same number of carbon atoms in excess of three
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/65—Metal complexes of amines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C57/03—Monocarboxylic acids
- C07C57/12—Straight chain carboxylic acids containing eighteen carbon atoms
-
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/74—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing arsenic, antimony or bismuth
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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
- C09K11/74—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing arsenic, antimony or bismuth
- C09K11/75—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing arsenic, antimony or bismuth containing antimony
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/26—Materials of the light emitting region
Definitions
- the present invention relates to a perovskite nanocrystal thin film, a method for manufacturing a perovskite nanocrystal thin film, a light emitting element, a photoelectric conversion element, a display device, and an electronic device, for example, a light emitting diode using a lead halide perovskite nanocrystal thin film, a solar cell, and light detection. It is suitable for application to elements, display devices, and the like.
- Perovskites are excellent in that they can be easily synthesized from inexpensive precursors, have a wide range of emission colors, can obtain narrow-band photoluminescence (PL), and have a large diffusion length of photogenerated charge carriers. It has optical and electrical properties. For this reason, development of solar cells, lasers, light emitting diodes (LEDs), and the like using quantum dots made of perovskite nanocrystals is underway (see, for example, Patent Documents 1 to 3).
- perovskite nanocrystals When quantum dots using perovskite nanocrystals are applied to solar cells, LEDs, etc., it is thought that if a thin film in which perovskite nanocrystals are arranged can be used, the structure and manufacturing of solar cells, LEDs, etc. will be simplified, which is desirable. .
- the problem to be solved by the present invention is to use as a quantum dot array, a perovskite nanocrystal thin film in which perovskite nanocrystals are arranged, and a manufacturing method capable of easily producing such a perovskite nanocrystal thin film.
- Another object of the present invention is to provide a light emitting device, a photoelectric conversion device, a display device and an electronic device using the perovskite nanocrystal thin film.
- the ligand that binds the perovskite nanocrystals to each other is appropriately selected according to the set distance between the perovskite nanocrystals.
- the ligand may be monodentate or multidentate, such as bidentate.
- the length of the ligand is generally selected to be 3.7 nm or less from the viewpoint of obtaining the interaction between the perovskite nanocrystals bound by the ligand.
- the lower limit of the length of the ligand is not particularly limited, but the length of the ligand is generally 0.87 nm or more.
- oleic acid CH 3 (CH 2 ) 7 CH ⁇ CH (CH 2 ) 7 COOH
- the length of these ligands is used.
- this perovskite nanocrystal thin film is not particularly limited, and it can be used for various devices using a quantum dot array, but preferably, a light emitting layer that emits light by light irradiation or current injection, or a current or voltage by light irradiation. Used as a photoelectric conversion layer capable of taking out. If necessary, a plurality of layers of the same or different perovskite nanocrystal thin films may be laminated and used.
- the emission color can be controlled by selecting A, B, and X forming ABX 3 and a ligand that determines the distance between the perovskite nanocrystals. .
- A, B, X and the ligand that compose ABX 3 are selected according to the emission color.
- the size of the perovskite nanocrystal is selected according to need, but is generally 5 nm or more and 15 nm or less, and typically 8 nm or more and 12 nm or less.
- the distance between the perovskite nanocrystals is generally 2 nm or more and 5 nm or less, but is not limited thereto.
- the shape of the perovskite nanocrystal is not particularly limited, but is generally cubic.
- a perovskite nanocrystal thin film comprising a perovskite nanocrystal represented by: Attaching a solution in which the perovskite nanocrystals bound with the ligand are dispersed in a solvent to a substrate, Drying the solution attached to the substrate to self-assemble the perovskite nanocrystals bound with the ligand to form a thin film of the perovskite nanocrystals bound to each other via the ligand.
- a method for producing a characteristic perovskite nanocrystal thin film is
- the concentration of the solution in which the ligand-bound perovskite nanocrystals are dispersed in the solvent is too low, it is difficult to obtain a thin film composed of perovskite nanocrystals bound to each other via the ligand. Therefore, the concentration is preferably larger than 0.5 mg / mL. On the other hand, if it is too high, ligand-bound perovskite nanocrystals may aggregate, so it is preferably selected at 1.5 mg / mL or less.
- An aprotic solvent is preferably used as the solvent in which the perovskite nanocrystals to which the ligand is bound are dispersed.
- the aprotic solvent is, for example, toluene, hexane, dichloroethylene, trichloroethylene, chloroform, chlorobenzene, dichlorobenzene, styrene, dimethylformamide, dimethylsulfoxide, xylene, cyclohexene, isopropyl alcohol and the like.
- the perovskite nanocrystal to which the ligand is bound can be formed by various methods, and the forming method is selected as necessary.
- AX, BX 2 , Y— (CH 2 ) n —NH 2 and oleic acid are dissolved in a solvent to prepare a precursor solution, and a ligand is bound from the precursor solution.
- the perovskite nanocrystals to which the ligand is bound are formed.
- a solvent for dissolving AX, BX 2 , Y- (CH 2 ) n- NH 2 and oleic acid for example, N-dimethylformamide (DMF) is used, but it is not limited thereto.
- DMF N-dimethylformamide
- the precursor solution is mixed with another solvent different from the solvent of the precursor solution, and the perovskite nanocrystals to which the ligand is bound are precipitated therefrom.
- the aprotic solvent described above is preferably used.
- the light emitting element is a light emitting diode or a laser, and electrodes are provided on both sides of the perovskite nanocrystal thin film that constitutes the light emitting layer (active layer in laser), and light emission is caused by passing an electric current between these electrodes.
- the photoelectric conversion element is, for example, a solar cell, a light detection element (photodiode, etc.), or the like.
- the display device is used for an electronic device such as a television, a monitor for PC, a digital camera, a digital video camera, a smartphone, or a part thereof.
- the electronic device may be basically any type, and includes both a portable type and a stationary type, but specific examples thereof are a mobile phone, a mobile device, a robot, and a personal computer. , In-vehicle equipment, various home appliances, etc.
- the perovskite nanocrystal thin film when used as the photoelectric conversion layer, the electric power obtained by using the photoelectric conversion layer can be used in the electronic device.
- the perovskite nanocrystal thin film can be used for display in this display device.
- this perovskite nanocrystal thin film can be used as a quantum dot array in which quantum dots made of perovskite nanocrystals are arranged.
- this perovskite nanocrystal thin film as a photoelectric conversion layer of a photoelectric conversion element, not only highly efficient photoelectric conversion can be performed but also high light durability can be obtained. As described above, a high-performance light emitting element, photoelectric conversion element, display device, and electronic device can be realized.
- FIG. 1 is a schematic diagram showing a perovskite nanocrystal thin film according to a first embodiment of the present invention.
- FIG. 3 is a schematic diagram showing a ligand-bonded perovskite nanocrystal used for manufacturing the perovskite nanocrystal thin film according to the first embodiment of the present invention.
- FIG. 3 is a schematic diagram showing a solution in which a perovskite nanocrystal having a ligand bound thereto is dispersed, which is used for manufacturing a perovskite nanocrystal thin film according to the first embodiment of the present invention.
- 3 is a schematic diagram showing an absorption spectrum and a PL spectrum of a colloidal solution of MAPbBr 3 perovskite nanocrystals produced in Example 1.
- FIG. 3 is a schematic diagram showing an absorption spectrum and a PL spectrum of a colloidal solution of FAPbBr 3 perovskite nanocrystals produced in Example 3.
- FIG. 5 is a schematic diagram showing an absorption spectrum and a PL spectrum of a colloidal solution of CsPbBr 3 perovskite nanocrystals produced in Example 2.
- FIG. 3 is a schematic diagram showing PL attenuation profiles of MAPbBr 3 perovskite nanocrystals, FAPbBr 3 perovskite nanocrystals and CsPbBr 3 perovskite nanocrystals in a colloidal solution.
- MAPbBr 3 perovskite nanocrystals in the colloidal solution is a schematic diagram for explaining a method of determining the band gap of the FAPbBr 3 perovskite nanocrystals and CsPbBr 3 perovskite nanocrystals.
- 5 is a drawing-substituting photograph showing a transmission electron microscope image of the MAPbBr 3 perovskite nanocrystals produced in Example 1.
- MAPbBr 3 perovskite nanocrystals prepared in Example 1 is a schematic diagram illustrating a powder X-ray diffraction pattern of CsPbBr 3 perovskite nanocrystals prepared in FAPbBr 3 perovskite nanocrystals and Example 2 produced in Example 3.
- 5 is a schematic diagram showing a method of manufacturing the MAPbBr 3 perovskite nanocrystal thin film manufactured in Example 1.
- FIG. 6 is a drawing-substituting photograph showing a photograph of a MAPbBr 3 perovskite nanocrystal thin film produced in Example 1, under a UV lamp.
- FIG. 7 is a drawing-substituting photograph showing a change in amplified radiation when the intensity of incident photon flux on the MAPbBr 3 perovskite nanocrystal thin film produced in Example 1 is increased.
- 5 is a schematic diagram showing a change in PL spectrum when the laser fluence of the MAPbBr 3 perovskite nanocrystal thin film produced in Example 1 is changed.
- FIG. 5 is a schematic diagram showing a change in PL attenuation profile when the laser fluence on the MAPbBr 3 perovskite nanocrystal thin film produced in Example 1 is changed.
- FIG. 5 is a schematic diagram for explaining a change in a time-spectrum resolved photon measurement map when a laser fluence on a FAPbBr 3 perovskite nanocrystal thin film produced in Example 3 is changed.
- FIG. 5 is a schematic diagram for explaining a change in a time-spectrum resolved photon measurement map when a laser fluence on a FAPbBr 3 perovskite nanocrystal thin film produced in Example 3 is changed.
- FIG. 5 is a schematic diagram for explaining a change in a time-spectrum resolved photon measurement map when a laser fluence on a FAPbBr 3 perovskite nanocrystal thin film produced in Example 3 is changed.
- FIG. 5 is a schematic diagram for explaining a change in a time-spectrum resolved photon measurement map when a laser fluence on a FAPbBr 3 perovskite nanocrystal thin film produced in Example 3 is changed.
- FIG. 5 is a schematic diagram for explaining a change in a time-spectrum resolved photon measurement map when a laser fluence on a FAPbBr 3 perovskite nanocrystal thin film produced in Example 3 is changed.
- FIG. 5 is a schematic diagram showing a semi-logarithmic plot of the average PL lifetime and the number of photons measured when the laser fluence of the MAPbBr 3 perovskite nanocrystal thin film produced in Example 1 was changed.
- 6 is a schematic diagram showing a semi-logarithmic plot of the average PL lifetime and the number of photons measured when the laser fluence on the FAPbBr 3 perovskite nanocrystal thin film produced in Example 3 was changed.
- FIG. 5 is a schematic diagram showing a semilogarithmic plot of the average PL lifetime and the number of photons measured when the laser fluence on the CsPbBr 3 perovskite nanocrystal thin film produced in Example 2 was changed.
- FIG. 4 is a schematic diagram showing diffusion and recombination of charge carriers in a perovskite nanocrystal thin film at low laser fluence.
- FIG. 6 is a schematic diagram showing diffusion and recombination of charge carriers in a perovskite nanocrystal thin film at high laser fluence. It is an approximate line figure showing the method of performing time resolved PL measurement, when the irradiation field of a perovskite nanocrystal thin film is not masked.
- FIG. 5 is a schematic diagram showing integrated PL spectra from a non-irradiated region and an irradiated region of a FAPbBr 3 perovskite nanocrystal thin film manufactured in Example 3 under a low laser fluence.
- 6 is a schematic diagram showing a change in PL spectrum when the density of perovskite nanocrystals of the FAPbBr 3 perovskite nanocrystal thin film produced in Example 3 is changed.
- FIG. 5 is a schematic diagram showing a change in PL attenuation profile when the density of perovskite nanocrystals of the FAPbBr 3 perovskite nanocrystal thin film produced in Example 3 is changed.
- FIG. 5 is a schematic diagram for explaining a change in a time-spectrum resolved photon measurement map when a laser fluence on a CsPbBr 3 perovskite nanocrystal thin film produced in Example 2 is changed.
- FIG. 5 is a schematic diagram for explaining a change in a time-spectrum resolved photon measurement map when a laser fluence on a CsPbBr 3 perovskite nanocrystal thin film produced in Example 2 is changed.
- FIG. 5 is a schematic diagram for explaining a change in a time-spectrum resolved photon measurement map when a laser fluence on a CsPbBr 3 perovskite nanocrystal thin film produced in Example 2 is changed.
- FIG. 5 is a schematic diagram for explaining a change in a time-spectrum resolved photon measurement map when a laser fluence on a CsPbBr 3 perovskite nanocrystal thin film produced in Example 2 is changed.
- FIG. 5 is a schematic diagram for explaining a change in a time-spectrum resolved photon measurement map when a laser fluence on a CsPbBr 3 perovskite nanocrystal thin film produced in Example 2 is changed.
- FIG. 7 is a schematic diagram showing an absorption spectrum and a PL spectrum of a colloidal solution of MAPbI 3 perovskite nanocrystals produced in Example 4.
- FIG. 6 is a schematic diagram showing a PL spectrum of a colloidal solution of MAPbI 3 perovskite nanocrystals immediately after synthesis prepared in Example 4 and a PL spectrum of a colloidal solution of MAPbI 3 perovskite nanocrystals after 2 months from the synthesis.
- FIG. 7 is a schematic diagram showing an absorption spectrum and a PL spectrum of a colloidal solution of MAPbCl 3 perovskite nanocrystals produced in Example 5.
- FIG. 5 is a schematic diagram showing an absorption spectrum and a PL spectrum of a colloidal solution of MAPbBr 3 perovskite nanocrystals produced in Example 5.
- FIG. 5 is a schematic diagram showing an absorption spectrum and a PL spectrum of a colloidal solution of MAPbI 3 perovskite nanocrystals produced in Example 5.
- FIG. It is a perspective view which shows the light emitting diode by the 2nd Embodiment of this invention.
- FIG. 1 shows a perovskite nanocrystal thin film according to the first embodiment.
- the perovskite nanocrystal thin film has a plurality of chemical formulas ABX 3 (A, B, and X are as described above) that are bound to each other via a ligand 10 and are arranged in a two-dimensional or three-dimensional manner. It consists of the perovskite nanocrystals 20 represented.
- FIG. 1 the case where the perovskite nanocrystals 20 are two-dimensionally arranged is shown.
- One perovskite nanocrystal 20 constitutes a quantum dot, and thus this perovskite nanocrystal thin film constitutes a quantum dot array.
- the perovskite nanocrystal 20 may have a shape other than a cube, such as a rectangular parallelepiped, a sphere, or an ellipsoid.
- the distance between two adjacent perovskite nanocrystals 20 is determined by the length of the ligand 10.
- the size (length of one side) of the perovskite nanocrystal 20 is generally 5 nm or more and 15 nm or less, and typically 8 nm or more and 12 nm or less.
- the distance between the perovskite nanocrystals 20 is generally 2 nm or more and 5 nm or less.
- This perovskite nanocrystal thin film can generate photoluminescence (PL) by performing light irradiation and can be used as a light emitting layer.
- the emission color of this perovskite nanocrystal thin film can be selected by selecting A, B, X in ABX 3 constituting the perovskite nanocrystal 20, the size of the perovskite nanocrystal 20, the molecule used as the ligand 10, and the like. The method of selecting the emission color will be described more specifically.
- ABX 3 specifically, for example, Cl as X, given the Br ABCl 3-n Br n, consider Br, an I as X when ABBr 3-n I n.
- a perovskite nanocrystal 20 to which a ligand 10 (Y— (CH 2 ) n —NH 2 10a and oleic acid 10b) is bound is prepared.
- a precipitation method, a hot injection method, or the like can be used for the production.
- AX and BX 2 are used as a raw material of perovskite nanocrystals.
- AX, BX 2 , Y— (CH 2 ) n —NH 2 and oleic acid are dissolved in a solvent such as DMF and stirred to prepare a precursor solution.
- the precursor solution thus prepared is mixed with another solvent such as anhydrous toluene and stirred to precipitate the perovskite nanocrystals 20.
- another solvent such as anhydrous toluene and stirred to precipitate the perovskite nanocrystals 20.
- the ligand 10 is bound to the perovskite nanocrystal 20.
- the perovskite nanocrystals 20 bound with the thus-deposited ligand 10 are washed to remove the unbound ligand 10.
- the perovskite nanocrystals 20 to which the ligand 10 is bound are dispersed in a solvent such as toluene, and this dispersion is attached onto a substrate and dried.
- This dispersion is schematically shown in FIG. 3 (solvent is not shown).
- the perovskite nanocrystals 20 in the dispersion are arranged by self-assembly, and a perovskite nanocrystal thin film is obtained as shown in FIG.
- the length of the ligand 10 determines the distance between the perovskite nanocrystals 20.
- the formation of the perovskite nanocrystal thin film by self-assembly of the perovskite nanocrystals 20 to which the ligands 10 are bound is promoted by the hydrophobic interaction between the ligands 10.
- the perovskite nanocrystal 20 when the perovskite nanocrystal 20 has a cubic shape of 10 nm ⁇ 10 nm ⁇ 10 nm, when green light emission is obtained, the perovskite nanocrystal 20 may be made of ABBr 3 , and ABr + BBr 2 is used as a raw material thereof. it can. Further, when red light emission is obtained, the perovskite nanocrystal 20 may be made of ABI 3 , and AI + BI 2 can be used as a raw material thereof. Further, when violet emission is obtained, the perovskite nanocrystal 20 may be made of ABCl 3 , and ACl + BCl 2 can be used as a raw material thereof.
- Example 1 A MAPbBr 3 (Methylammonium Lead Bromide, CH 3 NH 3 PbBr 3 ) perovskite nanocrystal thin film was prepared as follows.
- MAPbBr 3 perovskite nanocrystals were synthesized by a precipitation method.
- CH 3 NH 3 Br 28 mg, 0.25 mmol
- PbBr 2 100 mg, 0.25 mmol
- oleic acid 80 ⁇ L, 0.25 mmol
- hexadecylamine 46 mg, 0.19 mmol
- the solution was dissolved by repeating stirring and heating alternately until a transparent precursor solution was formed on a water bath set at 60 ° C.
- the transparent precursor solution thus obtained was poured into 50 mL of anhydrous toluene and vigorously stirred.
- the solution first changed from colorless to green, gradually became cloudy with mixing, and exhibited an orange-yellow color, indicating that MAPbBr 3 perovskite nanocrystals were precipitated.
- the resulting product was centrifuged at 10,000 rpm for 5 minutes and the clear supernatant was discarded.
- the precipitate was washed with n-butanol to remove excess unbound ligand.
- the final precipitate was ultrasonically dispersed again in toluene and centrifuged at 5000 rpm for 5 minutes to separate large particles.
- a room temperature drop molding technique was used to form a thin film on a glass substrate using the MAPbBr 3 perovskite nanocrystals synthesized as described above. That is, the synthesized MAPbBr 3 perovskite nanocrystals were dispersed in toluene to prepare a concentrated colloidal solution of perovskite nanocrystals (1 mg / mL), which was formed on a slide glass of size 24 ⁇ 50 mm 2 in the atmosphere. 50 ⁇ L of this concentrated colloidal solution was injected into the circular hole formed in the center of the square silicone rubber, and dried to form a MAPbBr 3 perovskite nanocrystal thin film.
- Example 2 A CsPbBr 3 (Cesium Lead Bromide) perovskite nanocrystal thin film was prepared as follows.
- CsPbBr 3 perovskite nanocrystals were synthesized by the hot injection method.
- PbBr 2 (690 mg, 1.88 mmol), oleic acid (4 mL), hexadecylamine (3.670 g) and 1-hexadecene (90 mL) were placed in a 500 mL two-necked flask and dried in vacuum at 120 ° C. for 1 hour. did.
- cesium acetate (96 mg, 0.5 mmol) in 1-hexadecene (10 mL) was also dried at 120 ° C. in vacuum.
- To the above solution was added 1 mL of oleic acid to completely dissolve the cesium salt.
- the argon was repeatedly discharged in vacuum every 20 minutes during drying. After complete dissolution of the lead salt, the temperature was raised to 170 ° C. in an argon atmosphere. A dry cesium acetate solution was injected into the hot solution under argon. After 5 seconds, the reaction was quenched by placing the reaction mixture in an ice-water bath. The reaction mixture was centrifuged at 6000 rpm for 25 minutes and the yellow supernatant was discarded. The precipitate was collected and washed with hexane and n-butanol.
- FAPbBr 3 perovskite nanocrystals were synthesized by the method described in Non-Patent Document 1. That is, the precursors, formamidinium bromide (0.20 mmol) and lead (II) bromide (0.12 mmol), were separately dissolved in dry DMF. These solutions are called precursor solution A and precursor solution B, respectively. Similarly, octyl ammonium bromide (0.12 mmol) and oleic acid (0.6 mmol) as ligands were dissolved in octadecene (ligand solution) at 80 ° C. with continuous stirring. Precursor solutions A and B were added to these ligand solutions. FAPbBr 3 perovskite nanocrystals were precipitated by adding dry acetone to the mixture of the ligand and the precursor. The mixture was centrifuged at 7000 rpm for 10 minutes and the supernatant was discarded.
- FAPbBr 3 perovskite nanocrystal thin film was prepared in the same manner as in Example 1.
- Example 4 A MAPbI 3 (Methylammonium Lead Iodide, CH 3 NH 3 PbI 3 ) perovskite nanocrystal thin film was prepared as follows.
- MAI Metal Iodide
- PbI 2 ⁇ -butyrolactone
- GBL ⁇ -butyrolactone
- hexadecylamine and oleic acid were dissolved in toluene and kept at 80 ° C. with continuous stirring to prepare a monodentate ligand solution.
- the amounts of precursor, ligand and solvent used are as follows.
- the precursor solution thus obtained was rapidly injected into the ligand solution, and the mixture was kept at 80 ° C. for 15 minutes with continuous stirring to carry out the reaction.
- the solution turned dark brown after the precursor addition, indicating that MAPbI 3 perovskite nanocrystals had precipitated.
- This mixture was centrifuged at 7000 rpm for 3 minutes, and the residue and supernatant were collected and evaluated.
- MAPbI 3 perovskite nanocrystals synthesized as described above were dispersed in toluene to prepare a colloidal solution of MAPbI 3 perovskite nanocrystals.
- This colloidal solution was spin-coated on a slide glass at 500 rpm and then dried to prepare a MAPbI 3 perovskite nanocrystal thin film.
- X Cl
- MAX and PbX 2 were mixed in a mixed solvent of 250 ⁇ L DMF and 250 ⁇ L dimethylsulfoxide (DMSO) to prepare a transparent precursor solution.
- DMSO dimethylsulfoxide
- 1,12-dodecanedioic acid and 1,12-diaminododecane were dissolved in 500 ⁇ L of DMF to prepare a bidentate ligand.
- a solution was made.
- the amounts of precursor, ligand and solvent used are as follows.
- a MAPbX 3 perovskite nanocrystal thin film was prepared in the same manner as in Example 4.
- MAPbBr 3 perovskite nanocrystals FAPbBr 3 perovskite nanocrystals and CsPbBr synthesized as described above by ultraviolet-visible (UV-Vis) absorption and PL spectroscopy, transmission electron microscopy, powder X-ray diffraction and time-resolved PL measurement.
- UV-Vis ultraviolet-visible
- UV-Vis absorption spectra were recorded using Thermo Fischer Scientific using a colloidal solution in which the synthesized perovskite nanocrystals were dispersed in toluene.
- the PL spectrum was recorded using a fluorescence spectrometer (FL4100) manufactured by Hitachi, Ltd. using the same colloidal solution. During the measurement of the PL spectrum, the colloidal solution was excited with light having a wavelength of 365 nm.
- As the transmission electron microscope HD-2000 transmission electron microscope manufactured by Hitachi, Ltd. with an acceleration voltage of 200 kV was used.
- the sample for observation was prepared by dispersing the synthesized perovskite nanocrystals in toluene, centrifuging at 5000 rpm for 5 minutes to remove large particles, and dropping the supernatant onto a STEM Cu100P grid, followed by vacuum molding. It was made by drying.
- the powder sample was prepared by grinding the precipitate of perovskite nanocrystals in a mortar.
- the excitation source used for the time-resolved PL measurement was a 400 nm (150 fs) pulse generated from an SHG crystal of an optical parametric amplifier (Coherent OPA9400).
- the OPA was pumped at 200 kHz by a regenerative amplifier (Coherent RegA 9000) using a mode-locked Ti: sapphire laser (Coherent Mira 900F) as a seed laser.
- the fluorescence lifetime system is a combination of a polychromator (Chromex, model250IS) and a photon measuring streak camera (Hamamatsu Photonics, model C4334).
- the fluorescence signal from the sample was passed through a 440 nm low-pass filter, focused on the entrance slit of the polychromator, and detected using a streak camera.
- the laser power was modulated using neutral filters with different transmissions.
- Example CsPbBr 3 perovskite nanocrystals made with 2 3 shows a UV-Vis absorption spectrum and a PL spectrum of a colloidal solution in which is dispersed in toluene.
- FIG. 7 shows the PL decay profiles of these colloidal solutions.
- MAPbBr 3 perovskite nanocrystals of these colloidal solution CsPbBr 3 perovskite nanocrystals and FAPbBr 3 perovskite nano these MAPbBr 3 perovskite nanocrystals a band gap of the crystal
- the Tauc plot of CsPbBr 3 perovskite nanocrystals and FAPbBr 3 perovskite nanocrystals It was decided by carrying out. That is, the bandgap is given by the energy value on the x-axis corresponding to the intersection obtained by extrapolation of the Tauc plot at the sharp edge, as shown in FIG.
- MAPbBr 3 perovskite nanocrystals derived from the absorption spectra of CsPbBr 3 perovskite nanocrystals and FAPbBr 3 perovskite nanocrystals.
- the resulting band gap, FAPbBr 3 perovskite nanocrystals, MAPbBr 3 respectively perovskite nanocrystals and CsPbBr 3 perovskite nanocrystals, 2.18eV, was 2.22eV and 2.36 eV.
- FIG. 9 shows a transmission electron microscope image of MAPbBr 3 perovskite nanocrystals. From FIG. 9, cubic nanocrystals having a clearly uniform size distribution (about 10 nm) are observed.
- FIG. 10 shows a powder X-ray diffraction pattern. From this powder X-ray diffraction pattern, the synthesized MAPbBr 3 perovskite nanocrystals, FAPbBr 3 perovskite nanocrystals and CsPbBr 3 perovskite nanocrystals can be classified into the cubic system of the space group Pm3m.
- MAPbBr 3 perovskite nano crystal thin film was formed on a glass substrate. That is, as shown in FIG. 11A, a square silicone rubber having a circular well-shaped hole at the center was formed on a slide glass. Then, 50 ⁇ L of a perovskite nanocrystal solution (1 mg / mL) prepared by dispersing MAPbBr 3 perovskite nanocrystals in toluene was injected into the hole of the silicone rubber, and a cover glass (not shown) was placed thereon. After covering, it was dried.
- a perovskite nanocrystal solution (1 mg / mL) prepared by dispersing MAPbBr 3 perovskite nanocrystals in toluene was injected into the hole of the silicone rubber, and a cover glass (not shown) was placed thereon. After covering, it was dried.
- FIG. 11B is a photograph of a MAPbBr 3 perovskite nanocrystal thin film taken under an ultraviolet lamp (UV lamp). It was observed that the whole circular MAPbBr 3 perovskite nanocrystal thin film emitted green light.
- UV lamp ultraviolet lamp
- the MAPbBr 3 perovskite nanocrystal thin film formed on the slide glass was photoexcited with a femtosecond laser of 400 nm to investigate the behavior.
- the fluence (energy per unit area) of the incident laser beam was systematically increased from 0.017 MWcm -2 to 170 MWcm -2.
- FIG. 12 it was observed that the intensity of green light emission gradually increased as the incident photon flux increased.
- this increase was recorded as a change in PL spectrum depending on the incident photon flux of the MAPbBr 3 perovskite nanocrystal thin film.
- the laser fluence-dependent increase in PL intensity indicates an increase in the concentration of charge carriers or electron-hole (eh) pairs generated by light irradiation and the rate of radiative recombination.
- radiative recombination becomes the dominant process, which is evidenced by amplified radiation above a threshold power of approximately 2 MWcm -2 (see Figures 13 and 16-18).
- Amplified emission is due to an increase in carrier density between perovskite nanocrystals and an increase in the rate of non-geminate radiative recombination between accumulated carriers. Narrowing of the spectrum or lasing is not observed here due to the collective excitation of the nanocrystals.
- Fluorescence masking and non-masking experiments were performed to verify the above mechanism of incident photon flux controlled charge carrier accumulation in perovskite nanocrystalline thin films. This experiment was performed using a designed and assembled device for performing time-resolved PL measurements by collecting photons generated from selected areas. As shown in FIG. 20A, during the unmasked experiment, photons were collected from the central iris-controlled irradiation area (radius about 50 ⁇ m). On the other hand, as shown in FIG. 20B, during the masking experiment, the central irradiation area (width: 75 ⁇ m) was masked with black paper mounted on a slide glass, and photons generated from the outer non-irradiation area were collected. .
- the time-resolved PL measurement of the FAPbBr 3 perovskite nanocrystal thin film was performed, as shown in FIG. 19A and FIG. Was selectively collected.
- FAPbBr 3 perovskite by controlling the concentration of the colloidal solution of nanocrystals, dense FAPbBr 3 perovskite nano crystal thin film and density of four different low density FAPbBr 3 perovskite A nanocrystal thin film was prepared.
- the concentration of the colloidal solution used to prepare the high-density FAPbBr 3 perovskite nanocrystal thin film was 1 mg / mL
- the concentration of the colloidal solution used to prepare the low-density FAPbBr 3 perovskite nanocrystal thin film was 0 in order from the highest density.
- FIG. 24 shows PL spectra of these high-density FAPbBr 3 perovskite nanocrystal thin films and low-density FAPbBr 3 perovskite nanocrystal thin films.
- FAPbBr 3 perovskite PL spectrum of a low density low density FAPbBr 3 perovskite nanocrystals films of the nanocrystals is always shifted to a higher energy side, but, FAPbBr 3 perovskite nano dense density FAPbBr 3 crystals
- the PL spectrum of the perovskite nanocrystal thin film always shifts to the low energy side.
- the corresponding PL decay profile is shown in FIG.
- the red-shifted PL spectrum is always accompanied by an increase in PL lifetime.
- 26A, 26B, 26C and 26D show changes in the time-spectral resolved photon measurement map when the laser fluence of the CsPbBr 3 perovskite nanocrystal thin film prepared in Example 2 was changed to 4 levels.
- CsPbBr 3 perovskite nano PL lifetime with increasing incident laser fluence to the crystal thin film is reduced, PL intensity increases, which is consistent with PL characteristics of MAPbBr 3 perovskite nano crystal thin film and FAPbBr 3 perovskite nano crystal thin film
- the maximum PL lifetime (50 ns) estimated for CsPbBr 3 perovskite nanocrystal thin films is two orders of magnitude lower than for inorganic-organic perovskites.
- A-site cations such as Cs + , MA + or FA + , that occupy the voids formed by the PbBr 6 4- octahedron sharing the apex on the modulation of the minimum of the conduction band of perovskite nanocrystals is unknown, The relationship of cations to PL lifetime has not been clarified.
- CsPbBr 3 it perovskite nano crystal thin film of short life enough unexpected compared to MAPbBr 3 perovskite nano crystal thin film and FAPbBr 3 perovskite nano crystal thin film of life,
- a site organic cation MA + or FA + is, perovskite nano It suggests that it is preferable for diffusion of charge over a wide range in the crystalline thin film.
- the MAPbI 3 perovskite nanocrystals produced in Example 4 were evaluated by the same UV-Vis absorption and PL spectroscopy as described above. Therefore, a colloidal solution was prepared in which the MAPbI 3 perovskite nanocrystal prepared in Example 4 was dispersed in toluene at a concentration of 10 ⁇ g / mL.
- FIG. 27 shows the UV-Vis absorption spectrum and PL spectrum of this colloidal solution.
- MAPbI 3 perovskite nanocrystals capped with hexadecylamine and oleic acid show particularly stable photoluminescence.
- FIG. 28 shows a PL spectrum of the colloidal solution of MAPbI 3 perovskite nanocrystals immediately after synthesis shown in FIG. 27 and a PL spectrum of the colloidal solution of MAPbI 3 perovskite nanocrystals measured after storage for 2 months from the synthesis. is there.
- the PL spectrum intensity and profile of the MAPbI 3 perovskite nanocrystal did not substantially change even after 2 months.
- the MAPbX 3 perovskite nanocrystals produced in Example 5 were evaluated by the same UV-Vis absorption and PL spectroscopy as described above.
- this perovskite nanocrystal thin film can be used as a quantum dot array, has a wide range of selection of emission colors, has high brightness and high light durability, and has high efficiency. It is possible to realize a photoelectric conversion element or a photovoltaic element such as a high-performance solar cell having high durability. In addition, this perovskite nanocrystal thin film can be easily manufactured.
- FIG. 32 shows a light emitting diode according to the second embodiment.
- This light emitting diode uses the perovskite nanocrystal thin film according to the first embodiment as a light emitting layer.
- the light emitting diode has a structure in which a perovskite nanocrystal thin film 100 used as a light emitting layer is sandwiched between a transparent electron injection layer 200 and a hole transport layer 300.
- a transparent electrode 400 is provided on the electron injection layer 200.
- An electrode 500 is provided on the hole transport layer 300.
- the electron injection layer 200 is made of ZnO, for example.
- the hole transport layer 300 is made of, for example, CBP / MoO 3 .
- CBP is 4,4′-bis (N-carbazolyl) -1,1′-biphenyl (4,4′-Bis (N-carbazolyl) -1,1′-biphenyl).
- the transparent electrode 400 is made of, for example, a glass substrate coated with indium-tin oxide (ITO).
- An electron injection layer 200, a perovskite nanocrystal thin film 100, a hole transport layer 300, and an electrode 500 are sequentially formed on the entire surface of the transparent electrode 400, and then these are patterned by lithography and etching to manufacture the light emitting diode shown in FIG. .
- a direct current voltage is applied between the transparent electrode 400 and the electrode 500 to cause a current to flow, thereby injecting electrons (e) from the electron injection layer 200 into the perovskite nanocrystal thin film 100 and at the same time, holes Holes (h) are injected from the transport layer 300.
- the electrons and holes thus injected into the perovskite nanocrystal thin film 100 are recombined in the perovskite nanocrystal 20 to generate light emission, whereby the perovskite nanocrystal thin film 100 emits light and the light is extracted to the outside through the transparent electrode 400.
- the perovskite nanocrystal thin film 100 is used as the light emitting layer, the emission color selection range is wide, and the high-performance novel light emission with high brightness and high light durability is provided.
- a diode can be realized.
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Abstract
L'invention concerne un film mince nanocristallin de pérovskite comprenant une pluralité de nanocristaux de pérovskite qui sont liés les uns aux autres par l'intermédiaire de ligands pour ainsi être agencés de manière bidimensionnelle ou tridimensionnelle, chacun des nanocristaux de pérovskite étant représenté par la formule chimique : ABX3 (dans laquelle A = CH3NH3, Cs ou CH(NH2)2 ; B = Pb, Cd, Sb, Bi ou Sn ; X = Cl, Br ou I). Les ligands sont l'acide oléique et Y-(CH2)n-NH2 (Y = H ou NH2; n = 6, 8 à 16, 18, 20, 21 ou 34). Le film mince nanocristallin de pérovskite est formé par fixation d'une solution préparée par dispersion des nanocristaux de pérovskite présentant les ligands fixés à ceux-ci dans un solvant sur un substrat, puis par séchage de la solution, ce qui permet d'autoassembler les nanocristaux de pérovskite présentant les ligands fixés à ceux-ci.
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CN113943575A (zh) * | 2021-10-11 | 2022-01-18 | 西安石油大学 | 一种荧光峰峰位可调的全无机铯铅溴钙钛矿纳米晶的制备方法 |
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CN113834856B (zh) * | 2020-06-24 | 2023-07-21 | 中国科学院福建物质结构研究所 | 一种大尺寸超晶格薄膜及其制备方法和用途 |
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CN112080276B (zh) * | 2020-09-30 | 2022-11-11 | 上海应用技术大学 | 一种高发光效率的铯铅卤族钙钛矿纳米晶薄膜的制备方法 |
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