CN112011330A - 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
- CN112011330A CN112011330A CN201910460072.7A CN201910460072A CN112011330A CN 112011330 A CN112011330 A CN 112011330A CN 201910460072 A CN201910460072 A CN 201910460072A CN 112011330 A CN112011330 A CN 112011330A
- Authority
- CN
- China
- Prior art keywords
- quantum dot
- perovskite quantum
- acid
- halide
- preparation
- 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.)
- Granted
Links
- 239000002096 quantum dot Substances 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- -1 ammonium halide Chemical class 0.000 claims abstract description 63
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 25
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 25
- 239000003960 organic solvent Substances 0.000 claims abstract description 25
- 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 20
- 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
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 35
- 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
- 150000001412 amines Chemical class 0.000 claims description 9
- 238000000034 method Methods 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
- 150000007522 mineralic acids Chemical class 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
- 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
- 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
- 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 18
- 230000007547 defect Effects 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000003446 ligand Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 29
- 229940049964 oleate Drugs 0.000 description 23
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 16
- 229910052794 bromium Inorganic materials 0.000 description 14
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 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
- 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 7
- 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
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 235000012239 silicon dioxide Nutrition 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
- 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
- 230000035484 reaction time Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002904 solvent Substances 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
- 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
- 230000008859 change Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 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
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010791 quenching Methods 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
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 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 a perovskite quantum dot, 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, aliphatic amine and acid to obtain a first mixed solution containing ammonium halide and metal acid salt; and carrying out coordination reaction on lead carboxylate, cesium carboxylate, the first mixed solution and the first organic solvent to obtain the perovskite quantum dot. In the formation of perovskites, ammonium halides R-NH3 +Has better coordination capacity, so ammonium halide R-NH is used3 +The ligand can improve the fluorescence quantum efficiency of the perovskite quantum dot; meanwhile, the existence of the metal salt is beneficial to greatly improving the stability of the perovskite quantum dots and reducing the surface defects of the perovskite quantum dots,and the fluorescence quantum efficiency is improved. In addition, in the preparation method, the amount of the halogen precursor can be adjusted, and the 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 attracted much 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 higher photoelectric conversion efficiency, and lower production cost. The highest photoelectric conversion efficiency of quantum dots reported to date is 23.3%, which has exceeded the silicon solar cells widely used in the market today. 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 coverage of the whole color gamut can be achieved by adjusting the element proportion and the element type in the perovskite quantum dots. However, perovskite quantum dots still have many defects, such as thermal stability, stability against water and high light intensity, and the like, so that the application of the perovskite quantum dots is limited.
In 2015, a novel all-inorganic perovskite quantum dot cesium lead halogen compound (CsPbX) was reported for the first time by Maksym V.Kovalenko subject group3X is Cl, Br, I or halogen mixture (such as Cl and Br, Br and I) in a certain proportion, and the like), and the development of the synthesis of the inorganic perovskite quantum dot is led. They injected a cesium oleate solution into a mixed solution containing lead halide, oleic acid and oleylamine at a certain temperature (140-. However, the thermal stability of the perovskite quantum dots prepared by the method is extremely poor. Almost all inorganic perovskite quantum dot synthesis methods are similar to these so far.
In all-inorganic perovskite quantum dots reported in the existing literature, the fluorescence quantum efficiency of red and green quantum dots is generally about 60-80%, and the fluorescence quantum efficiency of blue light emission perovskite quantum dots is generally only about 10%. Although the fluorescence quantum efficiency can be improved by subsequent treatment (including doping and metal salt addition, etc.), no relevant report has been made for a while only by a synthetic method to improve the fluorescence quantum efficiency. Especially, blue quantum dots are prone to surface defect states due to their wide energy bands. At present, the main reason that the fluorescence quantum efficiency is not high is that lead ions are excessive in the process of synthesizing the perovskite quantum dots, and the excessive lead can form defects, so that the fluorescence quantum efficiency is reduced. These are not favorable for convenient application of all-inorganic perovskite quantum dots in devices and the like. Therefore, the existing synthetic 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 needs to be developed, so that the fluorescence quantum efficiency and the thermal stability of the perovskite quantum dot are improved.
Disclosure of Invention
The invention mainly aims to provide a perovskite quantum dot, a preparation method thereof and a quantum dot device, and aims 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 for preparing a perovskite quantum dot, the method comprising: carrying out halogen precursor preparation reaction on metal halide, aliphatic amine and acid to obtain a first mixed solution containing ammonium halide and metal acid salt; and carrying out coordination reaction on 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 ℃, and preferably 120-180 ℃; the reaction temperature of the coordination reaction is 20-300 ℃, and preferably 50-250 ℃.
Further, the molar ratio of the lead carboxylate to the 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 length of 8-22; preferably, the cesium carboxylate is selected from cesium carboxylates with carbon chain lengths of 8-22.
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 with carbon chain length of 1-22; 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 also comprises the following steps: purifying a product system of the coordination reaction, and mixing a purified product with a second organic solvent to obtain a mixed solution; and reacting the mixed solution with ammonia water and ethyl orthosilicate to obtain the perovskite quantum dots.
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.
Furthermore, the light-emitting wavelength range of the perovskite quantum dots is 400-700 nm, the fluorescence quantum efficiency is not lower than 90%, and the half-peak width is 10-30 nm.
In yet another aspect, the present application also provides a quantum dot device comprising the above perovskite quantum dots.
By applying the technical scheme of the invention, when the perovskite is generated, ammonium halide R-NH3 +Has better coordination capacity, so ammonium halide R-NH is used3 +The ligand can improve the fluorescence quantum efficiency of the perovskite quantum dot; meanwhile, the existence of the metal salt is beneficial to greatly improving the stability of the perovskite quantum dots, reducing the surface defects of the perovskite quantum dots and improving the fluorescence quantum efficiency. In addition, in the preparation method, the amount of the halogen precursor can be adjusted, and the 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 the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background, the existing synthesis schemes of all-inorganic perovskite quantum dots have the problems of low fluorescence quantum efficiency and poor thermal stability. In order to solve the technical problem, the present application provides a preparation method of a perovskite quantum dot, including: carrying out halogen precursor preparation reaction on metal halide, aliphatic amine and acid to obtain a first mixed solution containing ammonium halide and metal acid salt; and carrying out coordination reaction on 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, acid and metal halide react to produce metal acid salt and hydrogen halide, and then the hydrogen halide reacts with aliphatic amine to form halogen precursor-ammonium halide R-NH3 +X-(wherein X is Cl, Br or I, -R is a hydrocarbyl group); and then, in a first organic solvent, taking ammonium halide as a ligand to perform a coordination reaction with lead carboxylate and cesium carboxylate to prepare the perovskite quantum dot.
In the formation of perovskites, ammonium halides R-NH3 +Has better coordination capacity, so ammonium halide R-NH is used3 +The ligand can improve the fluorescence quantum efficiency of the perovskite quantum dot; 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 fluorescent quantum efficiency and the thermal stability can be greatly improved by adopting the preparation method.
In addition, in other embodiments of the preparation method, the amount of the halogen precursor can be adjusted, and the 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, an aliphatic 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 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, cesium carboxylate, and the first mixed solution undergo a coordination reaction to obtain a perovskite quantum dot. In other embodiments, a metal halide, an aliphatic 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 perform a coordination reaction to obtain a perovskite quantum dot. That is, embodiments as long as mixed contact of lead carboxylate and cesium carboxylate with the first mixed solution can be achieved are within the scope of the present application.
In order to increase the conversion rate of the halogen precursor, in a preferred embodiment, the reaction temperature of the halogen precursor preparation reaction is 100 to 200 ℃, and more preferably 120 to 180 ℃.
In a preferred embodiment, the reaction temperature of the coordination reaction is 20 to 300 ℃. Limiting the reaction temperature of the coordination reaction within the above range is advantageous for improving the stability and yield of the perovskite quantum dots, and more preferably, the reaction temperature of the coordination reaction is 50 to 250 ℃.
In a preferred embodiment, the molar ratio of the lead carboxylate to the cesium carboxylate is (0.2-5) to 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. Limiting the molar ratio of lead carboxylate to cesium carboxylate and the molar ratio of lead element to halogen in the above ranges is advantageous for improving the fluorescence quantum efficiency of the perovskite quantum dot.
In a preferred embodiment, the lead carboxylates include, but are not limited to, one or more of lead carboxylates having a carbon chain length of 8 to 22; preferably, the cesium carboxylate includes, but is not limited to, cesium carboxylate with a carbon chain length of 8-22. The use of lead carboxylate and cesium carboxylate having the above chain length ranges is advantageous in improving the activity of the perovskite-forming reaction.
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. Several of the above metal halides have better solubility in acids and fatty amines than other metal halides.
The aliphatic amine used in the above preparation method may be a saturated or unsaturated primary amine commonly used in the art. In a preferred embodiment, the aliphatic 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 above chain length range is advantageous for increasing the activity of the perovskite growth reaction, and more preferably, the 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 preparation method may be an inorganic acid, and/or a saturated or unsaturated organic acid; preferably, the inorganic acids include, but are 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 organic acids are beneficial to improving the activity of the perovskite growth reaction.
In a preferred embodiment, the preparation method further comprises: purifying a product system of the coordination reaction, and mixing a purified product with a second organic solvent to form a mixed solution; and reacting the mixed solution with ammonia water and ethyl orthosilicate to prepare the perovskite quantum dots coated by 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 strong 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 in the art that "high temperatures quench fluorescence". By utilizing the phenomenon, the perovskite quantum dots can be applied to thermosensitive sensors, confidentiality of character colors and the like.
In the above 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 light-emitting wavelength range of the perovskite quantum dot is 400-700 nm, the fluorescence quantum efficiency is not lower than 90%, and the half-peak width is 10-30 nm.
In yet another aspect, the present application also provides a quantum dot device comprising the above perovskite quantum dots. 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 also has good high-temperature resistance. Therefore, the quantum dot device containing the perovskite quantum dot has high luminous efficiency and service life.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Preparation of 0.5mmol/mL bromine precursor:
4.5g (0.020mol) of zinc bromide, 50mmol of oleic acid and 70mmol of oleylamine were placed in a 100mL three-necked flask, and the temperature was raised to 120 ℃ to react for 30 minutes. The preparation of other halogen precursors or the preparation of halogen precursors using different metal halides is possible with only a change in the amount.
Example 1
Cesium lead bromide (CsPbBr)3) And (3) synthesis of perovskite quantum dots. 0.4mL of a 0.5mmol/mL lead oleate solution, 1mL of a 0.2mmol/mL cesium oleate solution, and 10mL of ODE were placed in a 100mL three-necked flask and the temperature was raised to 260 ℃. 1.8mL of 0.5mmol/mL prepared bromine precursor (prepared from zinc bromide, oleic acid and oleylamine) was injected, the reaction was stopped after 1 min.
Example 2
Cesium lead chloride (CsPbCl)3) And (3) synthesis of perovskite quantum dots. Taking 0.4mL of 0.5mmol/mL lead oleate solution, 1mL of 0.2mmol/mL cesium oleate solution and 10mL of ODE in a 100mL three-neck flask,the temperature was increased to 260 ℃. 1.8mL of 0.5mmol/mL prepared chlorine precursor (prepared from zinc chloride, oleic acid and oleylamine) was injected, the reaction was stopped after 1 minute.
Example 3
Cesium lead chloride (CsPbI)3) And (3) synthesis of perovskite quantum dots. 0.4mL of a 0.5mmol/mL lead oleate solution, 1mL of a 0.2mmol/mL cesium oleate solution, and 10mL of ODE were placed in a 100mL three-necked flask and the temperature was raised to 260 ℃. 1.8mL of 0.5mmol/mL prepared iodine precursor (prepared from zinc iodide, oleic acid and oleylamine) was injected, reacted for 1 minute, and the reaction was stopped.
Example 4
Cesium lead bromide (CsPbBr)3) And (3) synthesis of perovskite quantum dots. 0.4mL of 0.5mmol/mL lead oleate solution, 1mL of 0.2mmol/mL cesium oleate solution and 10mL of ODE are placed in a 100mL three-necked flask, and the temperature is kept at normal temperature. 1.8mL of 0.5mmol/mL prepared bromine precursor (prepared from zinc bromide, oleic acid and oleylamine) was injected, reacted for 5 minutes, and the reaction was stopped.
Example 5
Cesium lead bromide (CsPbBr)3) And (3) synthesis of perovskite quantum dots. 0.4mL of a 0.5mmol/mL lead oleate solution, 1mL of a 0.2mmol/mL cesium oleate solution, and 10mL of ODE were placed in a 100mL three-necked flask and the temperature was raised to 150 ℃. 1.8mL of 0.5mmol/mL prepared bromine precursor (prepared from zinc bromide, acetic acid and oleylamine) was injected, the reaction was stopped after 1 min.
Example 6
Cesium lead bromide (CsPbBr)3) And (3) synthesis of perovskite quantum dots. 0.4mL of a 0.5mmol/mL lead oleate solution, 1mL of a 0.2mmol/mL cesium oleate solution, and 10mL of ODE were placed in a 100mL three-necked flask and the temperature was raised to 150 ℃. 1.8mL of 0.5mmol/mL prepared bromine precursor (prepared from zinc bromide, oleic acid and octylamine) was injected, the reaction was stopped after 1 min.
Example 7
Cesium lead bromide (CsPbBr)3) And (3) synthesis of perovskite quantum dots. 0.4mL of a 0.5mmol/mL lead oleate solution, 1mL of a 0.2mmol/mL cesium oleate solution, and 10mL of ODE were placed in a 100mL three-necked flask and the temperature was raised to 260 ℃. Injecting 1.8mL of 0.5mmol/mL prepared bromine precursor (prepared by copper bromide, oleic acid and oleylamine)) After 1 minute of reaction, the reaction was stopped.
Example 8
Cesium lead bromide (CsPbBr)3) And (3) synthesis of perovskite quantum dots. 0.4mL of a 0.5mmol/mL lead oleate solution, 1mL of a 0.2mmol/mL cesium oleate solution, and 10mL of ODE were placed in a 100mL three-necked flask and the temperature was raised to 150 ℃. 1.8mL of 0.5mmol/mL prepared bromine precursor (prepared from zinc bromide, sulfuric acid and octylamine) was injected, the reaction was stopped after 1 min.
Example 9
Cesium lead bromide (CsPbBr)3) And (3) synthesis of perovskite quantum dots. 0.4mL of a 0.5mmol/mL lead oleate solution, 1mL of a 0.2mmol/mL cesium oleate solution, and 10mL of ODE were placed in a 100mL three-necked flask and the temperature was raised to 150 ℃. 1.8mL of 0.5mmol/mL prepared bromine precursor (prepared from zinc bromide, oxalic acid and octylamine) was injected, the reaction was stopped after 1 min.
Example 10
Cesium lead bromide (CsPbBr)3) And (3) synthesis of perovskite quantum dots. 0.4mL of a 0.5mmol/mL lead oleate solution, 1mL of a 0.2mmol/mL cesium oleate solution, and 10mL of ODE were placed in a 100mL three-necked flask and the temperature was raised to 150 ℃. 1.8mL of 0.5mmol/mL prepared bromine precursor (prepared from zinc bromide, oleic acid and 1, 4-butanediamine) was injected, the reaction was stopped after 1 min.
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 extended to 1 hour.
Example 13
Cesium lead bromide (CsPbBr)3)/SiO2And (3) synthesis of perovskite quantum dots. 0.4mL of 0.5mmol/mL lead oleate solution, 1mL of 0.2mmol/mL cesium oleate solution, and 10mL of LODE were placed 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 using zinc bromide) was injected and reacted for 1 min, and the reaction was stopped. Cooling to 50 ℃, injecting 0.198g of ammonia water solution, and dropwise adding 0.5mL of 1mmol/mL ethyl orthosilicate-n-octaneThe solution was added dropwise over 2 minutes, and the reaction was stopped after 20 minutes.
The test results of the fluorescence emission peak wavelength, half-peak 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 the half-peak width of the perovskite quantum dots of the above embodiments, and the detection method of the quantum efficiency comprises the following steps: the 450nm blue LED lamp is used as a backlight spectrum, the integrating sphere is used for respectively testing the blue backlight spectrum and the spectrum penetrating through the quantum dot solution, and the quantum dot luminous efficiency is calculated by using the integral area of a spectrogram. Quantum efficiency ═ 100% for (quantum dot emission peak area)/(blue backlight peak area-blue peak area not absorbed through quantum dot solution).
TABLE 1
| Fluorescence emission peak/nm | Half peak 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-described embodiments of the present invention achieve the following technical effects: the perovskite quantum dots prepared by the method have high 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 remains unchanged, which indicates that the perovskite quantum dot prepared by the preparation method of the present application has good stability in a solvent at high temperature. Therefore, the perovskite quantum dots prepared by the method have high fluorescence quantum efficiency and good solvent thermal stability.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (12)
1. A preparation method of perovskite quantum dots is characterized by comprising the following steps:
carrying out halogen precursor preparation reaction on metal halide, aliphatic amine and acid to obtain a first mixed solution containing ammonium halide and metal acid salt;
and carrying out coordination reaction on lead carboxylate, cesium carboxylate, the first mixed solution and a first organic solvent to obtain the perovskite quantum dot.
2. The method according to claim 1, wherein the reaction temperature of the halogen precursor preparation reaction is 100 to 200 ℃, preferably 120 to 180 ℃;
the reaction temperature of the coordination reaction is 20-300 ℃, and preferably 50-250 ℃.
3. The preparation method according to claim 1 or 2, wherein the molar ratio of the lead carboxylate to the 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.
4. The preparation method according to claim 1, wherein the lead carboxylate is selected from one or more of lead carboxylates with carbon chain length of 8-22; preferably, the cesium carboxylate is selected from cesium carboxylate with carbon chain length of 8-22.
5. The production method according to any one of claims 1 to 4, wherein the metal halide is one or more selected from the group consisting of cadmium halide, zinc halide, indium halide, copper halide, iron halide, tin halide, and manganese halide.
6. The method according to any one of claims 1 to 4, wherein the aliphatic 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.
7. The production method according to any one of claims 1 to 4, characterized in that the acid is an organic acid and/or an inorganic acid;
preferably, the inorganic 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.
8. The production method according to any one of claims 1 to 7, characterized by further comprising:
purifying the product system of the coordination reaction, and mixing the purified product with a second organic solvent to obtain a mixed solution;
and reacting the mixed solution with ammonia water and ethyl orthosilicate to obtain the perovskite quantum dot.
9. The production method according to claim 8, wherein 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.
10. A perovskite quantum dot, wherein the perovskite quantum dot is prepared by the preparation method according to any one of claims 1 to 9.
11. The perovskite quantum dot according to claim 10, wherein the luminescent wavelength range of the perovskite quantum dot is 400-700 nm, the fluorescence quantum efficiency is not less than 90%, and the half-peak width is 10-30 nm.
12. A quantum dot device, characterized in that it comprises a perovskite quantum dot as claimed in claim 10 or 11.
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 true CN112011330A (en) | 2020-12-01 |
| CN112011330B 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) |
Cited By (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》, vol. 7, no. 6, pages 1 * |
| JAVAD SHAMSI等: "Colloidal CsX (X = Cl, Br, I) Nanocrystals and Their Transformation to CsPbX3 Nanocrystals by Cation Exchange", 《CHEMISTRY OF MATERIALS》, vol. 30, no. 1, pages 2 * |
Cited By (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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112011330B (en) | 2024-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108251109B (en) | Perovskite quantum dot material and preparation method thereof | |
| CN111117601B (en) | Red light perovskite quantum dot with stable luminescence property and preparation method thereof | |
| CN110257063B (en) | Blue-light perovskite with high quantum yield and preparation method and application thereof | |
| CN110526277A (en) | The preparation method of doped zinc oxide nano crystalline substance, electron transfer layer, luminescent device | |
| CN113150768B (en) | Perovskite quantum dot and preparation method thereof, quantum dot composition and quantum dot device | |
| CN114540010B (en) | Preparation method of blue-light perovskite quantum dot | |
| CN112011330B (en) | Perovskite quantum dot, preparation method thereof and quantum dot device | |
| CN112521933B (en) | Core-shell perovskite quantum dot and preparation method thereof, quantum dot composition and quantum dot device with quantum dot composition | |
| CN114031506B (en) | Novel copper-based halogen perovskite fluorescent powder and preparation method thereof | |
| KR20030060697A (en) | Green-emitting phosphor for long wavelength ultraviolet and a preparation method thereof | |
| CN112011334B (en) | Perovskite quantum dot, preparation method thereof and quantum dot device | |
| CN110257065B (en) | Red fluorescent powder with waterproof performance and preparation method thereof | |
| CN114736670B (en) | Preparation method of halogen perovskite quantum dot | |
| CN115368888A (en) | Aluminum ion surface-passivated cesium chloride lead perovskite quantum dot and preparation method and application thereof | |
| CN116285979A (en) | Te doped Rb 2 SnCl 6 Preparation method and application of vacancy ordered double perovskite fluorescent powder | |
| CN112480927B (en) | Quantum dot composite material and preparation method thereof | |
| CN114214063A (en) | Preparation method of single-matrix white light emitting carbon dot fluorescent powder | |
| CN112143493B (en) | Preparation method of zinc sulfide or zinc selenide coated perovskite quantum dot and quantum dot device | |
| CN113736448A (en) | Modified halogen perovskite quantum dot and preparation method thereof | |
| CN108929677B (en) | Double-emission two-dimensional perovskite fluorescent powder and preparation method thereof | |
| CN112724968A (en) | Preparation method of heavy atom doped long-life room temperature phosphorescent carbon quantum dot | |
| CN113150779A (en) | Perovskite quantum dot and preparation method thereof, quantum dot composition and quantum dot device | |
| KR101036504B1 (en) | Method of preparing oxynitride fluorescent substance | |
| CN108129505B (en) | aluminum organic complex and graphene oxide doped aluminum organic complex fluorescent material thereof | |
| CN1236012C (en) | Making process of high-luminance pink LED |
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 |