CN112011330B - Perovskite quantum dot, preparation method thereof and quantum dot device - Google Patents
Perovskite quantum dot, preparation method thereof and quantum dot device Download PDFInfo
- Publication number
- CN112011330B CN112011330B CN201910460072.7A CN201910460072A CN112011330B CN 112011330 B CN112011330 B CN 112011330B CN 201910460072 A CN201910460072 A CN 201910460072A CN 112011330 B CN112011330 B CN 112011330B
- Authority
- CN
- China
- Prior art keywords
- quantum dot
- acid
- perovskite quantum
- halide
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002096 quantum dot Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- -1 ammonium halide Chemical class 0.000 claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 29
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 25
- 239000003960 organic solvent Substances 0.000 claims abstract description 25
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 23
- 150000002367 halogens Chemical class 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 21
- 150000001412 amines Chemical class 0.000 claims abstract description 18
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 13
- 150000005309 metal halides Chemical class 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 15
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 13
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 12
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 12
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000005642 Oleic acid Substances 0.000 claims description 12
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 12
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 8
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 8
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 3
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000004020 luminiscence type Methods 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 239000012264 purified product Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229960002703 undecylenic acid Drugs 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000003446 ligand Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 28
- 229940049964 oleate Drugs 0.000 description 23
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 18
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 12
- 230000002194 synthesizing effect Effects 0.000 description 12
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 10
- 229910052794 bromium Inorganic materials 0.000 description 10
- NAJCQJKJQOIHSH-UHFFFAOYSA-L [Pb](Br)Br.[Cs] Chemical compound [Pb](Br)Br.[Cs] NAJCQJKJQOIHSH-UHFFFAOYSA-L 0.000 description 9
- 229940102001 zinc bromide Drugs 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OGJOCASXPRMNAK-UHFFFAOYSA-L cesium;dichlorolead Chemical compound [Cs].Cl[Pb]Cl OGJOCASXPRMNAK-UHFFFAOYSA-L 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/181—Metal complexes of the alkali metals and alkaline earth metals
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Organic Chemistry (AREA)
- Optics & Photonics (AREA)
- Biophysics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention provides perovskite quantum dots, a preparation method thereof and a quantum dot device. The preparation method comprises the following steps: carrying out halogen precursor preparation reaction on metal halide, fatty amine and acid to obtain a first mixed solution containing ammonium halide and metal acid salt; and carrying out coordination reaction on the lead carboxylate, cesium carboxylate, the first mixed solution and the first organic solvent to obtain the perovskite quantum dot. Ammonium halide R-NH upon perovskite formation 3 + Has better coordination ability, thus adopting ammonium halide R-NH 3 + The fluorescent quantum efficiency of the perovskite quantum dots can be improved for ligands; meanwhile, the existence of the metal salt is beneficial to greatly improving the stability of the perovskite quantum dot, reducing the surface defects of the perovskite quantum dot and improving the fluorescence quantum efficiency. In addition, in the preparation method, the amount of the halogen precursor can be adjusted, and excessive halogen ions can also effectively eliminate the surface defects of the perovskite quantum dots, so that the fluorescence quantum efficiency is improved.
Description
Technical Field
The invention relates to the field of quantum dot synthesis, in particular to a perovskite quantum dot, a preparation method thereof and a quantum dot device.
Background
In recent years, perovskite quantum dots have been receiving a great deal of attention in the fields of solar cells, quantum dot films, light emitting diodes, and the like, due to their optical and physical properties, such as high photoelectric conversion efficiency and low manufacturing cost. Up to now, the highest photoelectric conversion efficiency of the reported quantum dots is 23.3%, which is already exceeding the silicon solar cells widely used in the market at present. And compared with the traditional inorganic semiconductor quantum dots (such as CdSe, cdS and the like), the perovskite quantum dots are used as a luminescent material, and the full-color-gamut coverage can be achieved by adjusting the element proportion and the element type in the perovskite quantum dots. However, perovskite quantum dots still have many disadvantages, such as thermal stability, high light intensity stability against water and resistance, and the like, which have limited application.
In 2015, the Maksym v.kovalenko group reported for the first time that a novel all-inorganic perovskite quantum dot cesium-lead halogen compound (CsPbX 3 X is Cl, br, I or a halogen mixture with a certain proportion (such as Cl, br, I and the like), and the development of inorganic perovskite quantum dot synthesis is led. They injected cesium oleate solution into a mixed solution containing lead halide, oleic acid and oleylamine at a certain temperature (140-200 ℃), reacted for 5 seconds and immediately cooled with ice water. However, the perovskite quantum dots prepared by the method have extremely poor thermal stability. To date, almost all inorganic perovskite quantum dot synthesis methods are similar.
Among all inorganic perovskite quantum dots reported in the prior literature, the fluorescence quantum efficiency of red-green quantum dots is generally about 60-80%, and the fluorescence quantum efficiency of blue-light emission perovskite quantum dots is generally about 10%. Although the fluorescence quantum efficiency can be improved by the subsequent treatments (including doping and addition of metal salts, etc.), a method of improving the fluorescence quantum efficiency by the synthetic means alone has not been reported for a while. In particular, blue light quantum dots are easy to generate surface defect states due to the wide energy band. The main reason for the low fluorescence quantum efficiency is that lead ions are excessive in the process of synthesizing perovskite quantum dots, and excessive lead can form defects, so that the fluorescence quantum efficiency is reduced. These are disadvantageous for convenient application of all-inorganic perovskite quantum dots in devices and the like. Therefore, the existing synthesis scheme of the all-inorganic perovskite quantum dot has low fluorescence quantum efficiency, poor thermal stability, difficult control of the reaction process and poor experimental repeatability.
On the basis, a new preparation method of the perovskite quantum dot is necessary to be developed so as to improve the fluorescence quantum efficiency and the thermal stability of the perovskite quantum dot.
Disclosure of Invention
The invention mainly aims to provide a perovskite quantum dot, a preparation method thereof and a quantum dot device, so as to solve the problems of low fluorescence quantum efficiency and poor thermal stability of the existing all-inorganic perovskite quantum dot synthesis scheme.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method of preparing perovskite quantum dots, the method comprising: carrying out halogen precursor preparation reaction on metal halide, fatty amine and acid to obtain a first mixed solution containing ammonium halide and metal acid salt; and carrying out coordination reaction on the lead carboxylate, cesium carboxylate, the first mixed solution and the first organic solvent to obtain the perovskite quantum dot.
Further, the reaction temperature of the halogen precursor preparation reaction is 100-200 ℃, preferably 120-180 ℃; the reaction temperature of the coordination reaction is 20 to 300 ℃, preferably 50 to 250 ℃.
Further, the molar ratio of the lead carboxylate to cesium carboxylate is (0.2-5): 1, and the molar ratio of the lead element in the lead carboxylate to the halogen in the ammonium halide is less than 1:3.
Further, the lead carboxylate is selected from one or more of lead carboxylates with carbon chain lengths of 8-22; preferably, cesium carboxylate is selected from cesium carboxylates having a carbon chain length of 8 to 22.
Further, the metal halide is selected from one or more of the group consisting of cadmium halide, zinc halide, indium halide, copper halide, iron halide, tin halide, and manganese halide.
Further, the fatty amine is selected from organic amines having a carbon chain length of 1 to 22; preferably, the fatty amine is selected from one or more of the group consisting of oleylamine, octylamine, hexylamine, octadecylamine and 1, 4-butanediamine.
Further, the acid is an organic acid and/or an inorganic acid; preferably, the mineral acid is selected from sulfuric acid and/or nitric acid; preferably, the organic acid is selected from one or more of the group consisting of oleic acid, formic acid, acetic acid, undecylenic acid and oxalic acid.
Further, the preparation method further comprises the following steps: purifying the product system of the coordination reaction, and mixing the purified product with a second organic solvent to obtain a mixed solution; and (3) reacting the mixed solution with ammonia water and ethyl orthosilicate to obtain the perovskite quantum dot.
Further, the first organic solvent and the second organic solvent are non-coordinating organic solvents; preferably, the first organic solvent and the second organic solvent are each independently selected from one or more of the group consisting of octadecene, octane and dodecane.
The perovskite quantum dot is prepared by the preparation method.
Further, the perovskite quantum dot has a luminescence wavelength range of 400-700 nm, a fluorescence quantum efficiency of not less than 90%, and a half-peak width of 10-30 nm.
Still another aspect of the present application provides a quantum dot device comprising the perovskite quantum dot described above.
By applying the technical scheme of the invention, when perovskite is generated, ammonium halide R-NH 3 + Has better coordination ability, thus adopting ammonium halide R-NH 3 + The fluorescent quantum efficiency of the perovskite quantum dots can be improved for ligands; meanwhile, the existence of the metal salt is beneficial to greatly improving the stability of the perovskite quantum dot, reducing the surface defects of the perovskite quantum dot and improving the fluorescence quantum efficiency. In addition, in the preparation method, the amount of the halogen precursor can be adjusted, and excessive halogen ions can also effectively eliminate the surface defects of the perovskite quantum dots, so that the fluorescence quantum efficiency is improved.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present invention will be described in detail with reference to examples.
As described in the background art, the existing all-inorganic perovskite quantum dot synthesis scheme has the problems of low fluorescence quantum efficiency and poor thermal stability. In order to solve the technical problems, the application provides a preparation method of perovskite quantum dots, which comprises the following steps: carrying out halogen precursor preparation reaction on metal halide, fatty amine and acid to obtain a first mixed solution containing ammonium halide and metal acid salt; and carrying out coordination reaction on the lead carboxylate, cesium carboxylate, the first mixed solution and the first organic solvent to obtain the perovskite quantum dot.
The reaction principle is as follows: first the acid reacts with the metal halide to form the metal acid salt and the hydrogen halide, and then the hydrogen halide reacts with the aliphatic amine to form the halogen precursor, ammonium halide R-NH 3 + X - (wherein X is Cl, br or I, -R is hydrocarbyl); and then in a first organic solvent, carrying out coordination reaction with lead carboxylate and cesium carboxylate by taking ammonium halide as a ligand to obtain the perovskite quantum dot.
Ammonium halide R-NH upon perovskite formation 3 + Has better coordination ability, thus adopting ammonium halide R-NH 3 + The fluorescent quantum efficiency of the perovskite quantum dots can be improved for ligands; meanwhile, the existence of the metal acid salt is beneficial to greatly improving the stability of the perovskite quantum dot, reducing the surface defects of the perovskite quantum dot and improving the fluorescence quantum efficiency. Therefore, the preparation method can greatly improve the fluorescence quantum efficiency and the thermal stability.
In addition, in other embodiments of the preparation method, the amount of the halogen precursor can be adjusted, and excessive halogen ions can also effectively eliminate the surface defects of the perovskite quantum dots, so that the fluorescence quantum efficiency is further improved.
In some embodiments, a metal halide, a fatty amine, and an acid are subjected to a halogen precursor preparation reaction to obtain a first mixed solution containing an ammonium halide and a metal acid salt, a lead carboxylate and a cesium carboxylate are dissolved in a first organic solvent to obtain a second mixed solution, and then the first mixed solution is mixed with the second mixed solution, so that the lead carboxylate, the cesium carboxylate, and the first mixed solution are subjected to a coordination reaction to obtain the perovskite quantum dot. In other embodiments, a metal halide, a fatty amine, and an acid are subjected to a halogen precursor preparation reaction to obtain a first mixed solution containing an ammonium halide and a metal acid salt, and then lead carboxylate, cesium carboxylate, and a first organic solvent are directly added to the first mixed solution to carry out a coordination reaction to obtain perovskite quantum dots. I.e. embodiments which enable mixed contact of lead and cesium carboxylates with the first mixed solution are within the scope of the present application.
In order to increase the conversion of the halogen precursor, in a preferred embodiment, the reaction temperature of the halogen precursor preparation reaction is 100 to 200 ℃, more preferably 120 to 180 ℃.
In a preferred embodiment, the reaction temperature of the complexation reaction is from 20 to 300 ℃. The reaction temperature of the coordination reaction is limited to the above range, which is advantageous in improving the stability and yield of the perovskite quantum dot, and more preferably, the reaction temperature of the coordination reaction is 50 to 250 ℃.
In a preferred embodiment, the molar ratio of lead carboxylate to cesium carboxylate is (0.2-5) 1, and the molar ratio of lead element in the lead carboxylate to halogen in the ammonium halide is less than 1:3. Limiting the molar ratio of lead carboxylate and cesium carboxylate to the above-described range is advantageous for improving the fluorescence quantum efficiency of the perovskite quantum dot.
In a preferred embodiment, the lead carboxylate includes, but is not limited to, one or more of a lead carboxylate having a carbon chain length of 8 to 22; preferably, cesium carboxylates include, but are not limited to, cesium carboxylates having a carbon chain length of 8 to 22. The use of lead carboxylate and cesium carboxylate having the chain length ranges described above is advantageous for enhancing the activity of perovskite-forming reactions.
In a preferred embodiment, the metal halide includes, but is not limited to, one or more of the group consisting of cadmium halide, zinc halide, indium halide, copper halide, iron halide, tin halide, and manganese halide. The above-mentioned several metal halides have better solubility in acids and fatty amines than other metal halides.
The fatty amine used in the preparation method can be saturated or unsaturated primary amine commonly used in the field. In a preferred embodiment, the fatty amine includes, but is not limited to, an organic amine having a carbon chain length of 1 to 22. The use of fatty amines having the chain length ranges described above advantageously increases the activity of the perovskite growth reaction, more preferably fatty amines include, but are not limited to, one or more of the group consisting of oleylamine, octylamine, hexylamine, octadecylamine, and 1, 4-butanediamine.
The acid used in the above-mentioned production method may be an inorganic acid, and/or a saturated or unsaturated organic acid; preferably, the mineral acid includes, but is not limited to, sulfuric acid and/or nitric acid; preferably, the organic acid includes, but is not limited to, one or more of the group consisting of oleic acid, formic acid, acetic acid, undecylenic acid, and oxalic acid. Compared with other organic acids, the adoption of the organic acids is beneficial to improving the activity of perovskite growth reaction.
In a preferred embodiment, the method of preparation further comprises: purifying the product system of the coordination reaction, and mixing the purified product with a second organic solvent to form a mixed solution; and (3) reacting the mixed solution with ammonia water and ethyl orthosilicate to obtain the perovskite quantum dot coated with the silicon dioxide.
The perovskite quantum dot coated with the silicon dioxide is prepared by the method, the quantum dot coated with the silicon dioxide has stronger fluorescence (the color of the solution is green because of green fluorescence) at a certain temperature (such as 50 ℃), and the color of the solution is colorless and transparent when the fluorescence intensity is 0 after the temperature is reduced (such as 20 ℃). This is in contrast to the recognition that "high temperatures cause quenching of fluorescence" as is well known in the art. By utilizing the phenomenon, the perovskite quantum dot can be applied to aspects such as a thermal sensor or confidentiality of text color.
In the preparation method, the first organic solvent and the second organic solvent are non-coordinating organic solvents. Preferably, the first organic solvent and the second organic solvent each independently include, but are not limited to, one or more of the group consisting of octadecene, octane, and dodecane.
The perovskite quantum dot is prepared by the preparation method.
The perovskite quantum dot obtained by the preparation method has the advantages of high fluorescence quantum efficiency, narrow half-peak width, controllable reaction process, good repeatability and good high temperature resistance, and the synthesis of the doped perovskite quantum dot can be well carried out.
In a preferred embodiment, the perovskite quantum dot has a luminescence wavelength range of 400-700 nm, a fluorescence quantum efficiency of not less than 90%, and a half-width of 10-30 nm.
Still another aspect of the present application provides a quantum dot device comprising the perovskite quantum dot described above. The quantum dot device may be a thermal sensor, an image sensor, a display device, an optical device, or the like.
The perovskite quantum dot has the characteristics of high fluorescence quantum efficiency, narrow half-peak width, controllable reaction process and good repeatability, and simultaneously has good high temperature resistance. Therefore, the quantum dot device containing the perovskite quantum dot has higher luminous efficiency and service life.
The present application is described in further detail below in conjunction with specific embodiments, which should not be construed as limiting the scope of the claims.
Preparation of 0.5mmol/mL bromine precursor:
4.5g (0.020 mol) of zinc bromide, 50mmol of oleic acid and 70mmol of oleylamine were taken in a 100mL three-necked flask, the temperature was raised to 120℃and the reaction was carried out for 30 minutes. The preparation of other halogen precursors or the preparation of halogen precursors using different metal halides may be carried out with varying amounts.
Example 1
Cesium lead bromide (CsPbBr) 3 ) And (3) synthesizing perovskite quantum dots. 0.4mL of a lead oleate solution, 1mL of a cesium oleate solution, 0.2mmol/mL, 10mL ODE was taken in a 100mL three-necked flask, and the temperature was raised to 260 ℃. 1.8mL of the prepared bromine precursor (prepared by zinc bromide, oleic acid and oleylamine) was injected and reacted for 1 minute, and the reaction was stopped.
Example 2
Cesium lead chloride (CsPbCl) 3 ) And (3) synthesizing perovskite quantum dots. 0.4mL of a lead oleate solution, 1mL of a cesium oleate solution, 0.2mmol/mL, 10mL ODE was taken in a 100mL three-necked flask, and the temperature was raised to 260 ℃. 1.8mL of the prepared chlorine precursor (prepared by zinc chloride, oleic acid and oleylamine) was injected and reacted for 1 minute, and the reaction was stopped.
Example 3
Cesium lead chloride (CsPbI) 3 ) And (3) synthesizing perovskite quantum dots. 0.4mL of a lead oleate solution, 1mL of a cesium oleate solution, 0.2mmol/mL, 10mL ODE was taken in a 100mL three-necked flask, and the temperature was raised to 260 ℃. 1.8mL of the prepared iodine precursor (prepared by zinc iodide, oleic acid and oleylamine) was injected and reacted for 1 minute, and the reaction was stopped.
Example 4
Cesium lead bromide (CsPbBr) 3 ) And (3) synthesizing perovskite quantum dots. 0.4mL of a lead oleate solution of 0.5mmol/mL, 1mL of a cesium oleate solution of 0.2mmol/mL, and 10mL ODE were taken in a 100mL three-necked flask, and the temperature was kept at room temperature. 1.8mL of the prepared bromine precursor (prepared by zinc bromide, oleic acid and oleylamine) was injected and reacted for 5 minutes, and the reaction was stopped.
Example 5
Cesium lead bromide (CsPbBr) 3 ) And (3) synthesizing perovskite quantum dots. 0.4mL of a lead oleate solution, 1mL of a cesium oleate solution, 0.2mmol/mL, 10mL ODE was taken in a 100mL three-necked flask, and the temperature was raised to 150 ℃. 1.8mL of the prepared bromine precursor (prepared by zinc bromide, acetic acid and oleylamine) was injected and reacted for 1 minute, and the reaction was stopped.
Example 6
Cesium lead bromide (CsPbBr) 3 ) And (3) synthesizing perovskite quantum dots. 0.4mL of a lead oleate solution, 1mL of a cesium oleate solution, 0.2mmol/mL, 10mL ODE was taken in a 100mL three-necked flask, and the temperature was raised to 150 ℃. 1.8mL of the prepared bromine precursor (prepared by zinc bromide, oleic acid and octylamine) was injected and reacted for 1 minute, and the reaction was stopped.
Example 7
Cesium lead bromide (CsPbBr) 3 ) And (3) synthesizing perovskite quantum dots. 0.4mL of a lead oleate solution, 1mL of a cesium oleate solution, 0.2mmol/mL, 10mL ODE was taken in a 100mL three-necked flask, and the temperature was raised to 260 ℃. 1.8mL of the prepared bromine precursor (prepared by copper bromide, oleic acid and oleylamine) was injected and reacted for 1 minute, and the reaction was stopped.
Example 8
Cesium lead bromide (CsPbBr) 3 ) And (3) synthesizing perovskite quantum dots. Taking 0.4mL of lead oleate solution with the concentration of 0.5mmol/mL, 1mL of cesium oleate with the concentration of 0.2mmol/mL10mL ODE was placed in a 100mL three-necked flask and the temperature was raised to 150 ℃. 1.8mL of the prepared bromine precursor (prepared by zinc bromide, sulfuric acid and octylamine) was injected and reacted for 1 minute, and the reaction was stopped.
Example 9
Cesium lead bromide (CsPbBr) 3 ) And (3) synthesizing perovskite quantum dots. 0.4mL of a lead oleate solution, 1mL of a cesium oleate solution, 0.2mmol/mL, 10mL ODE was taken in a 100mL three-necked flask, and the temperature was raised to 150 ℃. 1.8mL of the prepared bromine precursor (prepared by zinc bromide, oxalic acid and octylamine) was injected and reacted for 1 minute, and the reaction was stopped.
Example 10
Cesium lead bromide (CsPbBr) 3 ) And (3) synthesizing perovskite quantum dots. 0.4mL of a lead oleate solution, 1mL of a cesium oleate solution, 0.2mmol/mL, 10mL ODE was taken in a 100mL three-necked flask, and the temperature was raised to 150 ℃. 1.8mL of the prepared bromine precursor (prepared by zinc bromide, oleic acid and 1, 4-butanediamine) was injected and reacted for 1 minute, and the reaction was stopped.
Example 11
The differences from example 1 are: the molar ratio of the lead carboxylate to the cesium carboxylate is 2:1, and the molar ratio of the lead element in the lead carboxylate to the halogen in the ammonium halide is 1:5.
Example 12
The differences from example 1 are: the reaction time was prolonged to 1 hour.
Example 13
Cesium lead bromide (CsPbBr) 3 )/SiO 2 And (3) synthesizing perovskite quantum dots. 0.4mL of a lead oleate solution, 1mL of a cesium oleate solution, 0.2mmol/mL, and 10mLODE were taken in a 100mL three-necked flask, and the temperature was raised to 260 ℃. 1.8mL of 0.5mmol/mL of the prepared bromine precursor (prepared by zinc bromide) was injected and reacted for 1 minute to stop the reaction. Cooling to 50 ℃, injecting 0.198g of ammonia water solution, dropwise adding 0.5mL of 1mmol/mL of ethyl orthosilicate-n-octane solution (dropwise adding is completed in 2 minutes), reacting for 20 minutes, and stopping the reaction.
The test results of the fluorescence emission peak wavelength, half-width, and quantum efficiency of the perovskite quantum dots of the above examples are shown in table 1. The fluorescence emission spectrometer is adopted to test the fluorescence emission peak and half-peak width of the perovskite quantum dot of each embodiment, and the quantum efficiency detection method comprises the following steps: and using a 450nm blue LED lamp as a backlight spectrum, respectively testing the blue backlight spectrum and the spectrum of the transmitted quantum dot solution by using an integrating sphere, and calculating the luminous efficiency of the quantum dot by using the integral area of the spectrogram. Quantum efficiency = (quantum dot emission peak area)/(blue backlight peak area-blue peak area not absorbed through quantum dot solution) ×100%.
TABLE 1
| Fluorescence emission peak/nm | Half width/nm | Quantum efficiency/% | |
| Example 1 | 517 | 15 | 96 |
| Example 2 | 410 | 11 | 95 |
| Example 3 | 660 | 28 | 93 |
| Example 4 | 486 | 18 | 97 |
| Example 5 | 518 | 18 | 94 |
| Example 6 | 508 | 19 | 96 |
| Example 7 | 493 | 15 | 97 |
| Example 8 | 518 | 19 | 95 |
| Example 9 | 519 | 20 | 93 |
| Example 10 | 515 | 21 | 91 |
| Example 11 | 517 | 16 | 97 |
| Example 12 | 517 | 15 | 96 |
| Example 13 | 520 | 19 | 91 |
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects: the perovskite quantum dot prepared by the method provided by the application has higher fluorescence quantum efficiency. In particular, in example 12, the reaction time is prolonged to 1 hour, and the fluorescence quantum efficiency of the prepared perovskite quantum dot is still unchanged, which indicates that the perovskite quantum dot obtained by the preparation method has good stability in a solvent at high temperature. Therefore, the perovskite quantum dot prepared by the method provided by the application has higher fluorescence quantum efficiency and good solvent thermal stability.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (11)
1. A method for preparing perovskite quantum dots, which is characterized by comprising the following steps:
carrying out halogen precursor preparation reaction on metal halide, fatty amine and acid to obtain a first mixed solution containing ammonium halide and metal acid salt; wherein the reaction temperature of the halogen precursor preparation reaction is 100-200 ℃;
carrying out coordination reaction on lead carboxylate, cesium carboxylate, the first mixed solution and a first organic solvent to obtain the perovskite quantum dot; the reaction temperature of the coordination reaction is 20-300 ℃;
the lead carboxylate is selected from one or more of lead carboxylates with carbon chain length of 8-22; the cesium carboxylate is selected from cesium carboxylates with carbon chain lengths of 8-22;
the metal halide is selected from one or more of the group consisting of cadmium halide, zinc halide, indium halide, copper halide, iron halide, tin halide and manganese halide;
the fatty amine is selected from organic amine with carbon chain length of 1-22;
the acid is an organic acid and/or an inorganic acid;
the first organic solvent is a non-coordinating solvent.
2. The preparation method according to claim 1, wherein the reaction temperature of the halogen precursor preparation reaction is 120 to 180 ℃;
the reaction temperature of the coordination reaction is 50-250 ℃.
3. The method according to claim 1, wherein the molar ratio of the lead carboxylate to the cesium carboxylate is (0.2 to 5) 1, and the molar ratio of the lead element in the lead carboxylate to the halogen in the ammonium halide is less than 1:3.
4. The method of claim 1, wherein the fatty amine is one or more selected from the group consisting of oleylamine, octylamine, hexylamine, octadecylamine, and 1, 4-butanediamine.
5. A process according to any one of claim 1 to 3,
the inorganic acid is selected from sulfuric acid and/or nitric acid;
the organic acid is selected from one or more of the group consisting of oleic acid, formic acid, acetic acid, undecylenic acid and oxalic acid.
6. A production method according to any one of claims 1 to 3, characterized in that the production method further comprises:
purifying the product system of the coordination reaction, and mixing the purified product with a second organic solvent to obtain a mixed solution;
and (3) reacting the mixed solution with ammonia water and ethyl orthosilicate to obtain the perovskite quantum dot.
7. The method of claim 6, wherein the second organic solvent is a non-coordinating organic solvent.
8. The method according to claim 7, wherein the first organic solvent and the second organic solvent are each independently selected from one or more of the group consisting of octadecene, octane, and dodecane.
9. A perovskite quantum dot, characterized in that it is produced by the production method according to any one of claims 1 to 8.
10. The perovskite quantum dot according to claim 9, wherein the perovskite quantum dot has a luminescence wavelength range of 400-700 nm, a fluorescence quantum efficiency of not less than 90%, and a half-width of 10-30 nm.
11. A quantum dot device comprising the perovskite quantum dot of claim 9 or 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910460072.7A CN112011330B (en) | 2019-05-29 | 2019-05-29 | Perovskite quantum dot, preparation method thereof and quantum dot device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910460072.7A CN112011330B (en) | 2019-05-29 | 2019-05-29 | Perovskite quantum dot, preparation method thereof and quantum dot device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112011330A CN112011330A (en) | 2020-12-01 |
| CN112011330B true CN112011330B (en) | 2024-04-12 |
Family
ID=73501830
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910460072.7A Active CN112011330B (en) | 2019-05-29 | 2019-05-29 | Perovskite quantum dot, preparation method thereof and quantum dot device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112011330B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113340948A (en) * | 2021-06-09 | 2021-09-03 | 重庆大学 | Preparation method of high-response humidity sensor based on halogenated perovskite microcrystal and product thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106833635A (en) * | 2017-01-22 | 2017-06-13 | 山东工商学院 | Large scale perovskite CsPbBr3The preparation method of six square piece circular pieces |
| CN108929671A (en) * | 2018-08-06 | 2018-12-04 | 湖北文理学院 | Nano particle, preparation method and the photoelectric nano material of coated with silica perovskite quantum dot |
| CN108998004A (en) * | 2018-08-01 | 2018-12-14 | 北京苏瑞同创科技有限公司 | A kind of preparation method of high stability quantum dot microsphere |
| CN109810704A (en) * | 2019-04-09 | 2019-05-28 | 厦门大学 | A kind of perovskite nanometer sheet material and its preparation method and application |
-
2019
- 2019-05-29 CN CN201910460072.7A patent/CN112011330B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106833635A (en) * | 2017-01-22 | 2017-06-13 | 山东工商学院 | Large scale perovskite CsPbBr3The preparation method of six square piece circular pieces |
| CN108998004A (en) * | 2018-08-01 | 2018-12-14 | 北京苏瑞同创科技有限公司 | A kind of preparation method of high stability quantum dot microsphere |
| CN108929671A (en) * | 2018-08-06 | 2018-12-04 | 湖北文理学院 | Nano particle, preparation method and the photoelectric nano material of coated with silica perovskite quantum dot |
| CN109810704A (en) * | 2019-04-09 | 2019-05-28 | 厦门大学 | A kind of perovskite nanometer sheet material and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| Ding, Hongwei等.Transition metal halide-doped, highly stable all-inorganic perovskite nanocrystals for fabrication of white light-emitting diodes.《JOURNAL OF MATERIALS CHEMISTRY C》.2019,第7卷(第6期), Supportting Information第1页. * |
| Javad Shamsi等.Colloidal CsX (X = Cl, Br, I) Nanocrystals and Their Transformation to CsPbX3 Nanocrystals by Cation Exchange.《CHEMISTRY OF MATERIALS》.2017,第30卷(第1期),Supportting Information第S2页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112011330A (en) | 2020-12-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110184056B (en) | Synthesis method of high-efficiency halogen perovskite quantum dot scintillator for X-ray imaging | |
| CN102079975B (en) | Coprecipitation preparation method of rare earth-doped yttrium aluminium garnet fluorescent powder | |
| CN110526277B (en) | Preparation method of doped zinc oxide nanocrystal, electron transport layer and light-emitting device | |
| CN111117601B (en) | Red light perovskite quantum dot with stable luminescence property and preparation method thereof | |
| CN109370587B (en) | Nitride near-infrared fluorescent material, the light emitting device containing nitride near-infrared fluorescent material | |
| CN113150768B (en) | Perovskite quantum dot and preparation method thereof, quantum dot composition and quantum dot device | |
| CN112011330B (en) | Perovskite quantum dot, preparation method thereof and quantum dot device | |
| Gong et al. | In-situ guanidinium bromide passivation treatment of CsPbBr3 perovskite quantum dots exhibiting high photoluminescence and environmental stability | |
| CN105601671B (en) | A kind of organometallic solid luminescent material and preparation method | |
| CN114540010B (en) | Preparation method of blue-light perovskite quantum dot | |
| CN112521933B (en) | Core-shell perovskite quantum dot and preparation method thereof, quantum dot composition and quantum dot device with quantum dot composition | |
| CN112126424B (en) | Perovskite nano material, preparation method thereof and photoelectric device containing perovskite nano material | |
| KR100458126B1 (en) | Green-emitting phosphor for long wavelength ultraviolet and a preparation method thereof | |
| CN114031506B (en) | Novel copper-based halogen perovskite fluorescent powder and preparation method thereof | |
| US20110001154A1 (en) | Method of preparing an oxynitride phosphor, oxynitride phosphor obtained using the method, and a white light-emitting device including the oxynitride phosphor | |
| Huang et al. | Visible-emitting hybrid sol–gel materials comprising lanthanide ions: thin film behaviour and potential use as phosphors for solid-state lighting | |
| CN112011334B (en) | Perovskite quantum dot, preparation method thereof and quantum dot device | |
| US9929321B2 (en) | Phosphor, producing method thereof and light-emitting device employing the phosphor | |
| CN110257065B (en) | Red fluorescent powder with waterproof performance and preparation method thereof | |
| CN115368888A (en) | Aluminum ion surface-passivated cesium chloride lead perovskite quantum dot and preparation method and application thereof | |
| CN114736670B (en) | Preparation method of halogen perovskite quantum dot | |
| CN112480927B (en) | Quantum dot composite material and preparation method thereof | |
| CN112143493B (en) | Preparation method of zinc sulfide or zinc selenide coated perovskite quantum dot and quantum dot device | |
| CN114214063A (en) | Preparation method of single-matrix white light emitting carbon dot fluorescent powder | |
| CN113150779A (en) | Perovskite quantum dot and preparation method thereof, quantum dot composition and quantum dot device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |