WO2020108079A1 - 一种量子点的制备方法 - Google Patents

一种量子点的制备方法 Download PDF

Info

Publication number
WO2020108079A1
WO2020108079A1 PCT/CN2019/109072 CN2019109072W WO2020108079A1 WO 2020108079 A1 WO2020108079 A1 WO 2020108079A1 CN 2019109072 W CN2019109072 W CN 2019109072W WO 2020108079 A1 WO2020108079 A1 WO 2020108079A1
Authority
WO
WIPO (PCT)
Prior art keywords
quantum dots
composite material
oil
pamam dendrimer
initial
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.)
Ceased
Application number
PCT/CN2019/109072
Other languages
English (en)
French (fr)
Inventor
程陆玲
杨一行
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TCL Technology Group Co Ltd
Original Assignee
TCL Technology Group Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by TCL Technology Group Co Ltd filed Critical TCL Technology Group Co Ltd
Publication of WO2020108079A1 publication Critical patent/WO2020108079A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • 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
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/54—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing zinc or cadmium
    • 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/55—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing beryllium, magnesium, alkali metals or alkaline earth metals
    • 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/57—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing manganese or rhenium
    • 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/58—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing copper, silver or gold
    • 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/62—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing gallium, indium or thallium
    • 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/64—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing aluminium
    • 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/66—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing germanium, tin or lead
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/89—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing mercury
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots

Definitions

  • the present disclosure relates to the field of quantum dots, and in particular to a method for preparing quantum dots.
  • quantum dots There are many techniques for preparing quantum dots. No matter what way the quantum dots are prepared, there will be corresponding anion and cation defects on the surface layer, that is, the surface growth is not very good; the anion and cation defects on the surface of the quantum dots will be to a certain extent.
  • the exciton trapping causes quenching.
  • the anion defects on the surface of quantum dots can be compensated and improved by surface ligand modifiers, while the cationic defects on the surface of quantum dots in the prior art mainly use organic metal cation precursors to passivate the surface of quantum dots.
  • the treatment of the technical solution will cause further anion defects on the surface of the quantum dot, so the existing technology needs to be improved.
  • the purpose of the present disclosure is to provide a quantum dot and its preparation method, and quantum dot light-emitting diode, aiming to solve the problem that the prior art cannot effectively remove the cation defects on the surface of the quantum dot.
  • a method for preparing quantum dots which includes the steps of:
  • a composite material including PAMAM dendrimers and metal ions bound in the cavity of the PAMAM dendrimers;
  • the oil-soluble composite material and the initial quantum dots are mixed in a non-polar solvent to ionize the metal ions in the oil-soluble composite material and combine with the cation vacancies on the surface of the initial quantum dots to obtain the quantum dots.
  • the present disclosure provides a method for preparing quantum dots.
  • PAMAM dendrimers combined with metal ions in the cavity as a passivation precursor, surface passivation treatment of the initial quantum dots can produce fewer surface cation defects Quantum dots.
  • FIG. 1 is a flow chart of a preferred embodiment of a method for preparing quantum dots of the present disclosure.
  • the present disclosure provides a method for preparing quantum dots. To make the objectives, technical solutions, and effects of the present disclosure clearer and more specific, the present disclosure will be described in further detail below. It should be understood that the specific embodiments described herein are only used to explain the present disclosure and are not intended to limit the present disclosure.
  • the present disclosure provides a flow chart of a preferred embodiment of a method for preparing quantum dots. As shown in the figure, the method includes the following steps:
  • PAMAM dendrimers with metal ions incorporated in the cavity are used as precursors for the passivation element, and surface passivation treatment of the initial quantum dots can produce quantum dots with fewer surface cation defects.
  • the mechanism for achieving the above effects is as follows:
  • Quantum dots prepared by conventional oil phase technology usually have more cation vacancies on the surface, and the cation vacancies on the quantum dot surface are prone to coordination effects when they encounter metal ions again in a certain solution environment.
  • the modified oil-soluble composite material and the initial quantum dots are mixed in a non-polar solvent.
  • the metal ions in the oil-soluble composite material are ionized, and the initial quantum dots with cation vacancies on the surface are It is easier to produce chemical coordination when encountering free metal ions, so that free metal ions are bound to the cation vacancies on the surface of the initial quantum dots.
  • the metal ions in the PAMAM dendrimer can be ionized to fill the cation vacancies on the surface of the initial quantum dots, thereby reducing the defect states on the surface of the quantum dots.
  • the method for preparing the composite material includes the steps of: providing a PAMAM dendrimer; adding the PAMAM dendrimer to a metal ion solution, and mixing the N atoms in the PAMAM dendrimer cavity with The metal ions are coordinated and combined to obtain a composite material.
  • the PAMAM (polyamide-amine) dendrimer is obtained by reacting different molecular units A (ethylenediamine) and molecular units B (methyl acrylate), and the PAMAM dendrimer can be obtained by a divergent method Synthesis, the first step is the reaction of ethylenediamine and methyl acrylate to produce carboxylic acid ester. The second step is to react the obtained carboxylic acid ester with excess ethylenediamine. After the above two steps, the first generation of PAMAM can be prepared For dendrimers, repeat the above two steps to obtain higher algebraic PAMAM dendrimers.
  • the general formulas of molecular unit A and molecular unit B contained in PAMAM dendrimers of different algebras are: A(2 n +2 n-1 +...+2 n-3 )+B(2 n+1 +2 n + ....+2 n-1 ), where the value of n is 3-10; in addition, the general formula of the first generation PAMAM dendrimer containing molecular unit A and molecular unit B is A+4B, the second generation PAMAM dendrimer The general formula of the molecule containing molecular unit A and molecular unit B is 5A+8B.
  • the number of metal ions that can be combined by different generations of PAMAM dendrimers is different.
  • the main reason is that different generations of PAMAM dendrimers can coordinate metal ions.
  • the generation of PAMAM dendrimers is from the first generation to In the fourth generation, due to its low density of terminal functional groups (amine groups), it is not easy to be used as a carrier for adsorbing metal ions.
  • the PAMAM dendrimer is selected from the fifth generation PAMAM dendrimer (G5), the sixth generation PAMAM dendrimer (G6), the seventh generation PAMAM dendrimer (G7), and the eighth generation PAMAM One or more of dendrimer (G8), ninth generation PAMAM dendrimer (G9), tenth generation PAMAM dendrimer (G10), etc.
  • the algebra of the PAMAM dendrimer is G5-G10
  • the functional groups and functional groups can form a complete and The closed cavity, so the PAMAM dendrimers of the G5-G10 generation can be used as candidate materials for the coordination with metal ions.
  • the elemental species of the metal ion is selected from the group consisting of Mn, Zn, Cd, Hg, Pb, In, Ag, Mg, Au, Cu, Li, Al, Cd, In, Cs, Ga, and Gd One or more, but not limited to this.
  • the terminal functional groups of the PAMAM dendrimer in the composite material are modified to convert the amine groups in the PAMAM dendrimer into oil-soluble groups
  • the step of obtaining an oil-soluble composite material includes: After the composite material is dissolved in a polar solvent, an end group modifier is added, so that the amine functional group on the PAMAM dendrimer in the composite material reacts with the end group modifier to transform into an oil-soluble group to obtain the oil-soluble property Composite materials.
  • the composite material can be stably stored and dissolved In a polar solvent, a composite material solution is prepared. Adding an excessive amount of end-group modifier to the composite material solution under an inert atmosphere and rapidly stirring can make the amine functional group on the PAMAM dendrimer react with the end-group modifier to transform into oil-soluble groups to prepare oil Soluble composite material.
  • the end group modifier is selected from p-toluenesulfonyl chloride, o-toluenesulfonyl chloride, m-toluenesulfonyl chloride, p-dimethylaminobenzenesulfonyl chloride, o-dimethylbenzenesulfonyl chloride and m-dimethylaminobenzene
  • p-toluenesulfonyl chloride o-toluenesulfonyl chloride, m-toluenesulfonyl chloride, p-dimethylaminobenzenesulfonyl chloride, o-dimethylbenzenesulfonyl chloride and m-dimethylaminobenzene
  • the Dendrimer-NH 2 is a PAMAM dendrimer of the G5-G10 generation. After being modified with end groups, the composite material can be effectively dispersed in a non-polar solvent.
  • the end group modifier is added after dissolving the composite material in a polar solvent under the condition of 20-50°C, so that the amine functional group and the end group on the PAMAM dendrimer in the composite material The modifier reacts to transform into oil-soluble groups to obtain the oil-soluble composite material.
  • the oil-soluble composite material and the initial quantum dots are added to a non-polar solvent according to a predetermined ratio, and mixed to ionize the metal ions in the oil-soluble composite material to the cation vacancies on the surface of the initial quantum dots Coordinate bonding to obtain the quantum dots.
  • the metal ions in the oil-soluble composite material described in this embodiment can efficiently coordinate with the cation vacancy on the surface of the quantum dot, and will not introduce other unnecessary anions to affect the passivation effect of the quantum dot.
  • the amount of PAMAM dendrimers of different generations bound to metal ions is different, so the oil-soluble composite material and the initial quantum
  • the molar mass ratio of points is related to the algebra of PAMAM dendrimers.
  • the PAMAM dendrimer in the composite material is the fifth generation PAMAM dendrimer
  • the molar ratio to the initial quantum dot mass ratio is 1 mmol: (1-100) mg, and the oil-soluble composite material and the initial quantum dot are mixed in a non-polar solvent.
  • the molar ratio of the sixth-generation PAMAM dendrimer to the initial quantum dot mass ratio is 1 mmol: (10-150) mg
  • the oil-soluble composite material and the initial quantum dots are mixed in a non-polar solvent.
  • the molar ratio of the seventh-generation PAMAM dendrimer to the initial quantum dot mass ratio is 1 mmol: (50-200) mg
  • the oil-soluble composite material and the initial quantum dots are mixed in a non-polar solvent.
  • the molar ratio of the eighth-generation PAMAM dendrimer to the initial quantum dot mass ratio is 1 mmol: (100-250) mg.
  • the oil-soluble composite material and the initial quantum dots are mixed in a non-polar solvent.
  • the molar ratio of the ninth-generation PAMAM dendrimer to the initial quantum dot mass ratio is 1 mmol: (150-300) mg,
  • the oil-soluble composite material and the initial quantum dots are mixed in a non-polar solvent.
  • the molar ratio of the molar amount of the tenth generation PAMAM dendrimer to the initial quantum dot is 1 mmol: (200-500) mg
  • the oil-soluble composite material and the initial quantum dots are mixed in a non-polar solvent.
  • the PAMAM dendrimer is selected from one or both of the fifth generation PAMAM dendrimer and the sixth generation PAMAM dendrimer. Because the metal ions in the composite material will form a chemical bond with multiple N atoms in the gap of the terminal functional group of the PAMAM dendrimer, this makes the pyrolysis rate of the metal ion in the composite material slower than that of the organometallic precursor More; and the PAMAM dendrimers containing metal ions have larger corresponding viscosities as the algebraic number increases, and the greater the viscosity makes the metal ions and the cation vacancy coordination binding efficiency on the surface of the initial quantum dots decrease.
  • the PAMAM dendrimer is selected from the fifth generation PAMAM dendrimer and the sixth generation PAMAM dendrimer One or two of the molecules.
  • the oil-soluble composite material and quantum dots are added to a non-polar solvent and mixed at 80-300°C to combine the metal ions in the oil-soluble composite material with cation vacancies on the surface of the quantum dots.
  • Get quantum dots When the temperature of the PAMAM dendrimer (oil-soluble composite material) modified with end groups and containing metal ions in a nonpolar solvent is higher than a certain value, the metal ions will leave the dendrimer and enter the nonpolar solvent to participate in other chemical reactions.
  • the temperature range of the metal ions in PAMAM dendrimers of different algebras can be separated from PAMAM dendrimers is 800-300°C. Therefore, in order to ensure that the metal ions in the oil-soluble composite material can coordinately coordinate with the cation vacancy on the surface of the quantum dot, the oil-soluble composite material and the quantum dot are mixed under the condition of 80-300°C.
  • the oil-soluble composite material and the quantum dot are added to a non-polar solvent, wherein the metal ion in the oil-soluble composite material and the cation on the surface of the quantum dot are the same element.
  • the metal ion coordinated to the N atom in the gap of the terminal functional group of the PAMAM dendrimer in the oil-soluble composite material is Zn 2+ .
  • the effect after passivation can effectively reduce the defect on the surface of the quantum dot and improve the fluorescence intensity of the light-emitting quantum dot.
  • the metal ion in the oil-soluble composite material and the cation on the surface of the quantum dot are different elements.
  • the metal ion in the oil-soluble composite material is Zn 2+ .
  • the metal ion in the oil-soluble composite material is different from the cationic element on the surface of the quantum dot, if the band gap of the passivated quantum dot surface layer compound is greater than the band gap of the inner shell layer, it can not only enhance the quantum dot fluorescence intensity It can also improve the stability of quantum dots.
  • the quantum dots are selected from one of single-type quantum dots, core-shell quantum dots, or alloy structure quantum dots.
  • the group III-V single quantum dot is selected from one or more of GaN, GaP, GaAs, InP, InAs, InAsP, GaAsP, InGaP, InGaAs, and InGaAsP.
  • the group II-VI single quantum dot is selected from one or more of CdSe, CdS, CdTe, ZnSe, ZnS, ZnTe, HgSe, HgS, and HgTe.
  • the group III-V and group II-VI alloy structure quantum dots are selected from one or more of InPZnS, InPZnSe, InPZnSeS, InGaPZnSe, InGaPZnS and InGaPZnSeS.
  • the group II-VI core-shell quantum dots are selected from one or more of CdHgTe/CdS, CdTe/CdS, CdSe/ZnS, CdSeS/CdS and ZnSe/ZnS.
  • the present disclosure also provides a quantum dot, which is prepared by the method of the present disclosure.
  • the present disclosure also provides a quantum dot light emitting diode, including a quantum dot light emitting layer, wherein the material of the quantum dot light emitting layer is a quantum dot prepared by the preparation method of the present disclosure.
  • quantum dots with fewer surface defects prepared in the present disclosure can effectively improve the fluorescence intensity of the quantum dot light emitting diode.
  • the quantum dot light-emitting diode includes an anode, a hole transport layer, a quantum dot light-emitting layer, an electron transport layer, and a cathode that are stacked, wherein the material of the quantum dot light-emitting layer is prepared by the preparation method of the present disclosure Quantum dots.
  • the present disclosure is not limited to the quantum dot light-emitting diode of the above structure, and may further include an interface function layer or an interface modification layer, including but not limited to an electron blocking layer, a hole blocking layer, an electrode modification layer, and an isolation protection layer One or more.
  • the quantum dot light emitting diode of the present disclosure may be partially encapsulated, fully encapsulated, or unencapsulated.
  • QLED quantum dot light-emitting diode
  • the QLEDs can be divided into a QLED with a formal structure and a QLED with a flip structure.
  • the QLED of the formal structure includes an anode layered from the bottom up (the anode layered layer is disposed on the substrate), a hole transport layer, a quantum dot light emitting layer, an electron transport layer, and a cathode , wherein the quantum dot light emitting layer material is a quantum dot prepared by the preparation method of the present disclosure.
  • the flip-chip QLED includes a cathode stacked from the bottom up (the cathode stack is disposed on the substrate), an electron transport layer, a quantum dot light emitting layer, a hole transport layer, and An anode, wherein the material of the quantum dot light emitting layer is a quantum dot prepared by the preparation method of the present disclosure.
  • the material of the anode is selected from doped metal oxides; wherein, the doped metal oxides include but are not limited to indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), Antimony-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), indium-doped zinc oxide (IZO), magnesium-doped zinc oxide (MZO), aluminum-doped magnesium oxide One or more of (AMO).
  • ITO indium-doped tin oxide
  • FTO fluorine-doped tin oxide
  • ATO Antimony-doped tin oxide
  • AZO aluminum-doped zinc oxide
  • GZO gallium-doped zinc oxide
  • IZO indium-doped zinc oxide
  • MZO magnesium-doped zinc oxide
  • AMO aluminum-doped magnesium oxide
  • AMO aluminum-doped magnesium oxide
  • the material of the hole transport layer is selected from organic materials with good hole transport capabilities, such as but not limited to poly(9,9-dioctylfluorene-CO-N-(4- (Butylphenyl) diphenylamine) (TFB), polyvinylcarbazole (PVK), poly(N,N'bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine) ( Poly-TPD), poly(9,9-dioctylfluorene-co-bis-N,N-phenyl-1,4-phenylenediamine) (PFB), 4,4',4”-tri(carb Azole-9-yl) triphenylamine (TCTA), 4,4'-bis(9-carbazole) biphenyl (CBP), N,N'-diphenyl-N,N'-bis(3-methyl Phenyl)-1,1'-biphenyl-4,4'
  • the material of the cathode is selected from one or more of conductive carbon materials, conductive metal oxide materials and metal materials; wherein the conductive carbon materials include but are not limited to doped or undoped carbon nanotubes , One or more of doped or undoped graphene, doped or undoped graphene oxide, C60, graphite, carbon fiber and porous carbon; conductive metal oxide materials include but are not limited to ITO, FTO, ATO And one or more of AZO; metal materials include, but are not limited to, Al, Ag, Cu, Mo, Au, or their alloys; wherein, among the metal materials, their morphologies include but are not limited to dense thin films, nanowires, One or more of nanospheres, nanorods, nanocones and hollow nanospheres.
  • the present disclosure also provides a method for preparing a QLED with a hole-transporting layer in a formal structure, including the following steps:
  • the quantum dot light-emitting layer material is a quantum dot prepared by the preparation method of the present disclosure
  • a cathode is prepared on the electron transport layer to obtain QLED.
  • the present disclosure also provides a method for preparing a flip-chip structured QLED containing a hole transport layer, including the following steps:
  • the quantum dot light-emitting layer material is a quantum dot prepared by the preparation method of the present disclosure
  • An anode was prepared on the hole transport layer to obtain QLED.
  • the preparation method of the above layers may be a chemical method or a physical method, wherein the chemical method includes but is not limited to one of chemical vapor deposition method, continuous ion layer adsorption and reaction method, anodizing method, electrolytic deposition method, co-precipitation method or A variety of; physical methods include but are not limited to physical coating method or solution method, wherein the solution method includes but not limited to spin coating method, printing method, blade coating method, dipping method, dipping method, spraying method, roll coating method, casting Method, slot coating method, strip coating method; physical coating method includes but not limited to thermal evaporation coating method, electron beam evaporation coating method, magnetron sputtering method, multi-arc ion coating method, physical vapor deposition method, One or more of atomic layer deposition and pulsed laser deposition.
  • the chemical method includes but is not limited to one of chemical vapor deposition method, continuous ion layer adsorption and reaction method, anodizing method, electrolytic deposition method, co-pre
  • the present disclosure provides a method for preparing quantum dots.
  • Surface cation defects can be prepared by surface passivating the initial quantum dots by using PAMAM dendrimers combined with metal ions in the cavity as passivation precursors Fewer quantum dots.
  • using the quantum dots as the material of the quantum dot light emitting layer of the quantum dot light emitting diode can effectively increase the fluorescence intensity of the quantum dot light emitting diode.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Optics & Photonics (AREA)
  • Biophysics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Composite Materials (AREA)
  • Luminescent Compositions (AREA)

Abstract

量子点的制备方法，包括以下步骤：提供一种包括PAMAM树形分子以及结合在PAMAM树形分子腔体内的金属离子的复合材料，使复合材料中的PAMAM树形分子中的胺基转变为油溶性基团得到油溶性复合材料，将油溶性复合材料和初始量子点在非极性溶剂中混合、使油溶性复合材料中的金属离子电离后与初始量子点表面的阳离子空位配位结合进而得到量子点。

Description

一种量子点的制备方法 技术领域
本公开涉及量子点领域，尤其涉及一种量子点的制备方法。
背景技术
量子点的制备技术有很多种，无论何种方式制备得到的量子点在表层都会存在相应的阴阳离子缺陷，也即是表面生长的不是很完好；量子点表层存在的阴阳离子缺陷会在一定程度上造成激子捕获引起猝灭。
针对量子点表面的阴离子缺陷可以通过表面配体修饰剂进行弥补改善，而针对量子点表面的阳离子缺陷在现有技术中主要是采用有机金属阳离子前躯体对量子点表面进行钝化处理，而采用该技术方案处理会造成量子点表面进一步的产生阴离子缺陷，因此现有技术有待改进。
发明内容
鉴于上述现有技术的不足，本公开的目的在于提供一种量子点及其制备方法、量子点发光二极管，旨在解决现有技术无法有效去除量子点表面阳离子缺陷的问题。
本公开的技术方案如下：
一种量子点的制备方法，其中，包括步骤：
提供一种复合材料，所述复合材料包括PAMAM树形分子以及结合在所述PAMAM树形分子腔体内的金属离子；
对所述复合材料中的PAMAM树形分子末梢官能团进行改性处理，使PAMAM树形分子中的胺基转变为油溶性基团，得到油溶性复合材料；
将所述油溶性复合材料和初始量子点在非极性溶剂中混合，使油溶性复合材料中的金属离子电离后与初始量子点表面的阳离子空位结合，得到所述量子点。
有益效果：本公开提供一种量子点的制备方法，通过利用腔体内结合有金属离子的PAMAM树形分子作为钝化前驱体，对初始量子点进行表面钝化处理可制得表面阳离子缺陷较少的量子点。
附图说明
图1为本公开一种量子点的制备方法较佳实施例的流程图。
具体实施方式
本公开提供一种量子点的制备方法，为使本公开的目的、技术方案及效果更加清楚、明确，以下对本公开进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本公开，并不用于限定本公开。
请参阅图1，本公开提供一种量子点的制备方法较佳实施例的流程图，其中，如图所示，包括步骤：
S100、提供一种复合材料，所述复合材料包括PAMAM树形分子以及结合在所述PAMAM树形分子腔体内的金属离子；
S200、对所述复合材料中的PAMAM树形分子末梢官能团进行改性处理，使PAMAM树形分子中的胺基转变为油溶性基团，得到油溶性复合材料；
S300、将所述油溶性复合材料和初始量子点在非极性溶剂中混合，使油溶性复合材料中的金属离子电离后与初始量子点表面的阳离子空位结合，得到所述量子点。
本实施例利用腔体内结合有金属离子的PAMAM树形分子作为钝化元素的前驱体，对初始量子点进行表面钝化处理可制得表面阳离子缺陷较少的量子点。实现上述效果的机理具体如下：
采用常规的油相技术方案制备得到的量子点表面通常存在较多的阳离子空位，而量子点表面的阳离子空位在一定的溶液环境中再次遇到金属离子时容易发生配位效应。本实施例将经过改性处理得到的油溶性复合材料与初始量子点混合在非极性溶剂中，所述油溶性复合材料中的金属离子会发生电离，而表面存在阳离子空位的初始量子点在遇到游离的金属离子时比较容易产生化学配位作用，使游离的金属离子结合到初始量子点表面的阳离子空位中。因此，本实施例利用油溶性复合材料与量子点进行混合后，PAMAM树形分子中的金属离子电离后可填补初始量子点表面的阳离子空位，从而降低量子点表面的缺陷态。
在一些实施方式中，所述复合材料的制备方法包括以下步骤：提供一种PAMAM树形分子；向金属离子溶液中加入所述PAMAM树形分子，混合使 PAMAM树形分子腔体内的N原子与金属离子配位结合，得到复合材料。
本实施例中，所述PAMAM(聚酰胺-胺)树形分子是由不同的分子单元A(乙二胺)和分子单元B(丙烯酸甲酯)反应得到，所述PAMAM树形分子可由发散法合成，第一步由乙二胺和丙烯酸甲酯反应生成羧酸酯，第二步将得到的羧酸酯与过量的乙二胺反应，经过上述两步反应后即可制得第一代PAMAM树形分子，重复上述两步反应即可得到更高代数的PAMAM树形分子。不同代数的PAMAM树形分子所含有的分子单元A和分子单元B的通式为：A(2 n+2 n-1+…+2 n-3)+B(2 n+1+2 n+….+2 n-1)，其中n的取值为3-10；另外，第一代PAMAM树形分子含有分子单元A和分子单元B的通式为A+4B，第二代PAMAM树形分子含有分子单元A和分子单元B的通式为5A+8B。
不同代数的PAMAM树形分子能够结合的金属离子的数量不同，其主要原因是不同代数的PAMAM树形分子能够配位金属离子的能力不同，当所述PAMAM树形分子的代数为第一代至第四代时，由于其末梢官能团(胺基)密集度较低，因此不易作为吸附金属离子的载体。
本实施例中，所述PAMAM树形分子选自第五代PAMAM树形分子(G5)、第六代PAMAM树形分子(G6)、第七代PAMAM树形分子(G7)、第八代PAMAM树形分子(G8)、第九代PAMAM树形分子(G9)和第十代PAMAM树形分子(G10)等中的一种或多种。当所述PAMAM树形分子的代数为G5-G10时，由于其外围具有较多的官能团(胺基)且具有电负性，所述官能团与官能团之间通过产生静电相互作用能够形成完整而又封闭的空腔，因此G5-G10代的PAMAM树形分子可以作为制备与金属离子配位结合的候选材料。
在一些实施方式中，所述金属离子的元素种类选自Mn、Zn、Cd、Hg、Pb、In、Ag、Mg、Au、Cu、Li、Al、Cd、In、Cs、Ga和Gd中的一种或多种，但不限于此。
在一些实施方式中，对所述复合材料中的PAMAM树形分子末梢官能团进行改性处理，使PAMAM树形分子中的胺基转变为油溶性基团，得到油溶性复合材料步骤包括：将所述复合材料溶解在极性溶剂后加入端基修饰剂，使所述复合材料中的PAMAM树形分子上的胺基官能团与端基修饰剂发生反应转变为油溶性基团，得到所述油溶性复合材料。
本实施例中，由于PAMAM树形分子为亲水性有机分子，且金属离子与所述PAMAM树形分子中的末梢官能团的N原子以配位键结合，因此所述复合材料能够稳定存放并溶解在极性溶剂中，制得复合材料溶液。在惰性气氛下向所述复合材料溶液中加入过量的端基修饰剂并快速搅拌，可使PAMAM树形分子上的胺基官能团与端基修饰剂发生反应转变为油溶性基团，制得油溶性复合材料。在一些实施方式中，所述端基修饰剂选自对甲苯磺酰氯、邻甲苯磺酰氯、间甲苯磺酰氯、对二甲氨基苯磺酰氯、邻二甲基苯磺酰氯和间二甲氨基苯磺酰氯中的一种或多种，但不限于此。作为举例，当向复合材料溶液中加入对二甲氨基苯磺酰氯时，其反应式为：Dendrimer-NH 2+(CH 3) 2-N-C 10H 6-SOCl→Dendrimer-NHOS-C 10H 6-N-(CH 3) 2+HCl；当向复合材料溶液中加入对甲磺酰氯时，其反应式为Dendrimer-NH 2+CH 3-C 6H 4-SOOCl→Dendrimer-NHSOO-C 6H 4-CH 3；所述Dendrimer-NH 2为G5-G10代的PAMAM树形分子。所述复合材料在经过端基修饰后能够有效分散在非极性溶剂中。
在一些实施方式中，在20-50℃条件下，将所述复合材料溶解在极性溶剂后加入端基修饰剂，使所述复合材料中的PAMAM树形分子上的胺基官能团与端基修饰剂发生反应转变为油溶性基团，得到所述油溶性复合材料。
在一些实施方式中，按照预定比例将所述油溶性复合材料和初始量子点加入到非极性溶剂中，混合使油溶性复合材料中的金属离子电离后与所述初始量子点表面的阳离子空位配位结合，得到所述量子点。
本实施例中所述油溶性复合材料中的金属离子能够高效地与量子点表面的阳离子空位配位结合，而且不会引入其它不必要的阴离子影响量子点的钝化效果。
在一些实施方式中，由于不同代数的PAMAM树形分子能够配位金属离子的能力不同，使得不同代数的PAMAM树形分子结合金属离子的量不同，因此所述油溶性复合材料与所述初始量子点的摩尔质量比与PAMAM树形分子的代数有关。以PAMAM树形分子配位结合金属离子的数量达到最大化为例，当所述复合材料中的PAMAM树形分子为第五代PAMAM树形分子时，按所述第五代PAMAM树形分子的摩尔量与初始量子点的质量比为1mmol：(1-100)mg，将所述油溶性复合材料和初始量子点在非极性溶剂中混合。当复合材料中的PAMAM树形分子为第六代PAMAM树形分子时，按所述第六代PAMAM树形 分子的摩尔量与初始量子点的质量比为1mmol：(10-150)mg，将所述油溶性复合材料和初始量子点在非极性溶剂中混合。当复合材料中的PAMAM树形分子为第七代PAMAM树形分子时，按所述第七代PAMAM树形分子的摩尔量与初始量子点的质量比为1mmol：(50-200)mg，将所述油溶性复合材料和初始量子点在非极性溶剂中混合。当复合材料中的PAMAM树形分子为第八代PAMAM树形分子时，按所述第八代PAMAM树形分子的摩尔量与初始量子点的质量比为1mmol：(100-250)mg，将所述油溶性复合材料和初始量子点在非极性溶剂中混合。当复合材料中的PAMAM树形分子为第九代PAMAM树形分子时，按所述第九代PAMAM树形分子的摩尔量与初始量子点的质量比为1mmol：(150-300)mg，将所述油溶性复合材料和初始量子点在非极性溶剂中混合。当复合材料中的PAMAM树形分子为第十代PAMAM树形分子时，按所述第十代PAMAM树形分子的摩尔量与初始量子点的质量比为1mmol：(200-500)mg，将所述油溶性复合材料和初始量子点在非极性溶剂中混合。
在一些实施方式中，所述PAMAM树形分子选自第五代PAMAM树形分子和第六代PAMAM树形分子中的一种或两种。由于复合材料中的金属离子会与PAMAM树形分子末梢官能团缝隙内的多个N原子产生化学键，这使得复合材料中金属离子的热解速率相比于有机金属前驱体的热解速率要缓慢得多；且所述含有金属离子的PAMAM树形分子随着代数的增大其相应的粘度也越大，粘度越大使得所述金属离子与初始量子点表面的阳离子空位配位结合效率降低。因此，本实施例为了保证复合材料中的金属离子能够更高效地与量子点表面的阳离子空位配位结合，所述PAMAM树形分子选自第五代PAMAM树形分子和第六代PAMAM树形分子中的一种或两种。
在一些实施方式中，所述油溶性复合材料与量子点加入到非极性溶剂中，在80-300℃的条件下混合使油溶性复合材料中的金属离子与量子点表面的阳离子空位结合，得到量子点。经过端基修饰且含有金属离子的PAMAM树形分子(油溶性复合材料)在非极性溶剂中的温度高于一定值时，金属离子会脱离树形分子进入非极性溶剂参与其它化学反应，不同代数的PAMAM树形分子中的金属离子能够脱离PAMAM树形分子的温度范围为800-300℃。因此，为了保证油溶性复合材料中的金属离子能够与量子点表面的阳离子空位配位结合，在80-300℃的 条件下对油溶性复合材料和量子点进行混合。
在一些实施方式中，将所述油溶性复合材料和量子点加入到非极性溶剂中，其中，所述油溶性复合材料中的金属离子与所述量子点表面的阳离子为相同元素。作为举例，当所述待钝化处理的量子点表面阳离子为Zn 2+时，则所述油溶性复合材料中与PAMAM树形分子末梢官能团缝隙内N原子配位结合的金属离子为Zn 2+。当所述油溶性复合材料中的金属离子与所述量子点表面的阳离子为相同元素时，钝化后的效果能够有效减少量子点表面的缺陷并改善发光量子点的荧光强度。
在一些实施方式中，所述油溶性复合材料中的金属离子与所述量子点表面的阳离子为不同元素。作为举例，当所述待钝化处理的量子点表面阳离子为Cd 2+时，所述油溶性复合材料中的金属离子为Zn 2+。当所述油溶性复合材料中的金属离子与量子点表面的阳离子元素不相同时，钝化后的量子点表层化合物的带隙如果大于内壳层的带隙，则不仅能够增强量子点荧光强度而且也能够提高量子点的稳定性。
在一些实施方式中，所述所述量子点选自单一型量子点、核壳量子点或合金结构量子点中的一种。作为举例，所述III-V族单一量子点选自GaN、GaP、GaAs、InP、InAs、InAsP、GaAsP、InGaP、InGaAs和InGaAsP中的一种或多种。所述II-VI族单一量子点选自CdSe、CdS、CdTe、ZnSe、ZnS、ZnTe、HgSe、HgS和HgTe中的一种或多种。所述III-V族和II-VI族合金结构量子点选自InPZnS、InPZnSe、InPZnSeS、InGaPZnSe、InGaPZnS和InGaPZnSeS中的一种或多种。所述II-VI族核壳量子点选自CdHgTe/CdS、CdTe/CdS、CdSe/ZnS、CdSeS/CdS和ZnSe/ZnS中的一种或多种。
本公开还提供一种量子点，其中，采用本公开方法制备而成。
本公开还提供一种量子点发光二极管，包括量子点发光层，其中，所述量子点发光层材料为本公开制备方法制备的量子点。
由于本公开提供的量子点表面阳离子缺陷较少，将本公开制得的表面缺陷较少的量子点作为量子点发光二极管的量子点发光层材料，可以有效提升量子点发光二极管的荧光强度。
在一些实施方式中，所述量子点发光二极管包括层叠设置的阳极、空穴传输 层、量子点发光层、电子传输层以及阴极，其中，所述量子点发光层材料为本公开制备方法制备的量子点。
需说明的是，本公开不限于上述结构的量子点发光二极管，还可进一步包括界面功能层或界面修饰层，包括但不限于电子阻挡层、空穴阻挡层、电极修饰层、隔离保护层中的一种或多种。本公开所述量子点发光二极管可以部分封装、全封装或不封装。
下面对含空穴传输层的量子点发光二极管(QLED)结构及其制备方法作详细说明：
根据所述QLED发光类型的不同，所述QLED可以分为正装结构的QLED和倒装结构的QLED。
在一些实施方式中，所述正装结构的QLED包括从下往上叠层设置的阳极(所述阳极叠层设置于衬底上)、空穴传输层、量子点发光层、电子传输层和阴极，其中，所述量子点发光层材料为本公开制备方法制备的量子点。
在一些实施方式中，所述倒装结构的QLED包括从下往上叠层设置的阴极(所述阴极叠层设置于衬底上)、电子传输层、量子点发光层、空穴传输层和阳极，其中，所述量子点发光层材料为本公开制备方法制备的量子点。
在一些实施方式中，所述阳极的材料选自掺杂金属氧化物；其中，所述掺杂金属氧化物包括但不限于铟掺杂氧化锡(ITO)、氟掺杂氧化锡(FTO)、锑掺杂氧化锡(ATO)、铝掺杂氧化锌(AZO)、镓掺杂氧化锌(GZO)、铟掺杂氧化锌(IZO)、镁掺杂氧化锌(MZO)、铝掺杂氧化镁(AMO)中的一种或多种。
在一些实施方式中，所述空穴传输层的材料选自具有良好空穴传输能力的有机材料，例如可以为但不限于聚(9,9-二辛基芴-CO-N-(4-丁基苯基)二苯胺)(TFB)、聚乙烯咔唑(PVK)、聚(N,N'双(4-丁基苯基)-N,N'-双(苯基)联苯胺)(Poly-TPD)、聚(9,9-二辛基芴-共-双-N,N-苯基-1,4-苯二胺)(PFB)、4,4’,4”-三(咔唑-9-基)三苯胺(TCTA)、4,4'-二(9-咔唑)联苯(CBP)、N,N’-二苯基-N,N’-二(3-甲基苯基)-1,1’-联苯-4,4’-二胺(TPD)、N,N’-二苯基-N,N’-(1-萘基)-1,1’-联苯-4,4’-二胺(NPB)、掺杂石墨烯、非掺杂石墨烯和C60中的一种或多种。
在一些实施方式中，所述阴极的材料选自导电碳材料、导电金属氧化物材料和金属材料中的一种或多种；其中导电碳材料包括但不限于掺杂或非掺杂碳纳米 管、掺杂或非掺杂石墨烯、掺杂或非掺杂氧化石墨烯、C60、石墨、碳纤维和多孔碳中的一种或多种；导电金属氧化物材料包括但不限于ITO、FTO、ATO和AZO中的一种或多种；金属材料包括但不限于Al、Ag、Cu、Mo、Au、或它们的合金；其中所述金属材料中，其形态包括但不限于致密薄膜、纳米线、纳米球、纳米棒、纳米锥和纳米空心球中的一种或多种。
本公开还提供一种正装结构的含空穴传输层的QLED的制备方法，包括如下步骤：
提供含阳极的衬底，在阳极上制备空穴传输层；
在空穴传输层上制备量子点发光层，所述量子点发光层材料为本公开制备方法制备的量子点；
在量子点发光层上制备电子传输层；
在电子传输层上制备阴极，得到QLED。
本公开还提供一种倒装结构的含空穴传输层的QLED的制备方法，包括如下步骤：
提供含有阴极的衬底，在所述阴极上制备电子传输层；
在电子传输层上制备量子点发光层，所述量子点发光层材料为本公开制备方法制备的量子点；
在量子点发光层上制备空穴传输层；
在空穴传输层上制备阳极，得到QLED。
上述各层的制备方法可以是化学法或物理法，其中化学法包括但不限于化学气相沉积法、连续离子层吸附与反应法、阳极氧化法、电解沉积法、共沉淀法中的一种或多种；物理法包括但不限于物理镀膜法或溶液法，其中溶液法包括但不限于旋涂法、印刷法、刮涂法、浸渍提拉法、浸泡法、喷涂法、滚涂法、浇铸法、狭缝式涂布法、条状涂布法；物理镀膜法包括但不限于热蒸发镀膜法、电子束蒸发镀膜法、磁控溅射法、多弧离子镀膜法、物理气相沉积法、原子层沉积法、脉冲激光沉积法中的一种或多种。
综上所述，本公开提供一种量子点的制备方法，通过利用腔体内结合有金属离子的PAMAM树形分子作为钝化前驱体，对初始量子点进行表面钝化处理可制得表面阳离子缺陷较少的量子点。进一步地，将所述量子点作为量子点发光二 极管的量子点发光层材料，可以有效提高量子点发光二极管的荧光强度。
应当理解的是，本公开的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本公开所附权利要求的保护范围。

Claims (20)

  1. 一种量子点的制备方法，其特征在于，包括步骤：
    提供一种复合材料，所述复合材料包括PAMAM树形分子以及结合在所述PAMAM树形分子腔体内的金属离子；
    对所述复合材料中的PAMAM树形分子末梢官能团进行改性处理，使PAMAM树形分子中的胺基转变为油溶性基团，得到油溶性复合材料；
    将所述油溶性复合材料和初始量子点在非极性溶剂中混合，使油溶性复合材料中的金属离子电离后与初始量子点表面的阳离子空位结合，得到所述量子点。
  2. 根据权利要求1所述量子点的制备方法，其特征在于，所述PAMAM树形分子选自第五代至第十代PAMAM树形分子中的一种或多种。
  3. 根据权利要求1所述量子点的制备方法，其特征在于，所述PAMAM树形分子选自第五代和第六代PAMAM树形分子中的一种或两种。
  4. 根据权利要求1所述量子点的制备方法，其特征在于，所述金属离子的元素种类选自Mn、Zn、Cd、Hg、Pb、In、Ag、Mg、Au、Cu、Li、Al、Cd、In、Cs、Ga和Gd中的一种或多种。
  5. 根据权利要求1所述量子点的制备方法，其特征在于，所述对所述复合材料中的PAMAM树形分子末梢官能团进行改性处理，使PAMAM树形分子中的胺基转变为油溶性基团的步骤包括：
    将所述复合材料溶解在极性溶剂后加入端基修饰剂，使所述复合材料中的PAMAM树形分子上的胺基官能团与端基修饰剂发生反应转变为油溶性基团，得到所述油溶性复合材料。
  6. 根据权利要求5所述量子点的制备方法，其特征在于，所述端基修饰剂选自对甲苯磺酰氯、邻甲苯磺酰氯、间甲苯磺酰氯、对二甲氨基苯磺酰氯、邻二甲基苯磺酰氯和间二甲氨基苯磺酰氯中的一种或多种。
  7. 根据权利要求5所述量子点的制备方法，其特征在于，在20-50℃条件下，将所述复合材料溶解在极性溶剂后加入端基修饰剂，使所述复合材料中的PAMAM树形分子上的胺基官能团与端基修饰剂发生反应转变为油溶性基团，得到所述油溶性复合材料。
  8. 根据权利要求7所述量子点的制备方法，其特征在于，在80-300℃条件下，将所述油溶性复合材料和初始量子点在非极性溶剂中混合，使油溶性复合材 料中的金属离子电离后与初始量子点表面的阳离子空位配位结合，得到所述量子点。
  9. 根据权利要求8所述量子点的制备方法，其特征在于，所述油溶性复合材料中的金属离子与所述初始量子点表面的阳离子为相同元素。
  10. 根据权利要求8所述量子点的制备方法，其特征在于，所述油溶性复合材料中的金属离子与所述初始量子点表面的阳离子为不同元素。
  11. 根据权利要求2所述量子点的制备方法，其特征在于，当复合材料中的PAMAM树形分子为第五代PAMAM树形分子时，按所述第五代PAMAM树形分子的摩尔量与初始量子点的质量比为1mmol：(1-100)mg，将所述油溶性复合材料和初始量子点加入到非极性溶剂中混合。
  12. 根据权利要求2所述量子点的制备方法，其特征在于，当复合材料中的PAMAM树形分子为第六代PAMAM树形分子时，按所述第六代PAMAM树形分子的摩尔量与初始量子点的质量比为1mmol：(10-150)mg，将所述油溶性复合材料和初始量子点加入到非极性溶剂中混合。
  13. 根据权利要求2所述量子点的制备方法，其特征在于，当复合材料中的PAMAM树形分子为第七代PAMAM树形分子时，按所述第七代PAMAM树形分子的摩尔量与初始量子点的质量比为1mmol：(50-200)mg，将所述油溶性复合材料和初始量子点加入到非极性溶剂中混合。
  14. 根据权利要求2所述量子点的制备方法，其特征在于，当复合材料中的PAMAM树形分子为第八代PAMAM树形分子时，按所述第八代PAMAM树形分子的摩尔量与初始量子点的质量比为1mmol：(100-250)mg，将所述油溶性复合材料和初始量子点加入到非极性溶剂中混合。
  15. 根据权利要求2所述量子点的制备方法，其特征在于，当复合材料中的PAMAM树形分子为第九代PAMAM树形分子时，按所述第九代PAMAM树形分子的摩尔量与初始量子点的质量比为1mmol：(150-300)mg，将所述油溶性复合材料和初始量子点加入到非极性溶剂中混合。
  16. 根据权利要求2所述量子点的制备方法，其特征在于，当复合材料中的PAMAM树形分子为第十代PAMAM树形分子时，按所述第十代PAMAM树形分子的摩尔量与初始量子点的质量比为1mmol：(200-500)mg，将所述油溶性 复合材料和初始量子点加入到非极性溶剂中混合。
  17. 根据权利要求1所述量子点的制备方法，其特征在于，所述初始量子点为单一型量子点、核壳量子点或合金结构量子点。
  18. 根据权利要求17所述量子点的制备方法，其特征在于，所述单一型量子点选自GaN、GaP、GaAs、InP、InAs、InAsP、GaAsP、InGaP、InGaAs、InGaAsP、CdSe、CdS、CdTe、ZnSe、ZnS、ZnTe、HgSe、HgS和HgTe中的一种或多种。
  19. 根据权利要求17所述量子点的制备方法，其特征在于，所述核壳量子点选自CdHgTe/CdS、CdTe/CdS、CdSe/ZnS、CdSeS/CdS和ZnSe/ZnS中的一种或多种。
  20. 根据权利要求17所述量子点的制备方法，其特征在于，所述合金结构量子点选自InPZnS、InPZnSe、InPZnSeS、InGaPZnSe、InGaPZnS和InGaPZnSeS中的一种或多种。
PCT/CN2019/109072 2018-11-28 2019-09-29 一种量子点的制备方法 Ceased WO2020108079A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201811432312.4A CN111234802A (zh) 2018-11-28 2018-11-28 一种量子点的制备方法
CN201811432312.4 2018-11-28

Publications (1)

Publication Number Publication Date
WO2020108079A1 true WO2020108079A1 (zh) 2020-06-04

Family

ID=70853721

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/109072 Ceased WO2020108079A1 (zh) 2018-11-28 2019-09-29 一种量子点的制备方法

Country Status (2)

Country Link
CN (1) CN111234802A (zh)
WO (1) WO2020108079A1 (zh)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102703057A (zh) * 2012-05-18 2012-10-03 北京工商大学 一种聚酰胺-胺树形分子包覆的ZnX半导体量子点在指纹显现中的应用
CN106398680A (zh) * 2016-08-30 2017-02-15 Tcl集团股份有限公司 一种油溶性蓝光量子点及其制备方法
CN107359264A (zh) * 2017-08-03 2017-11-17 青岛海信电器股份有限公司 一种qled、制备方法及显示装置

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107936943A (zh) * 2017-12-05 2018-04-20 华南师范大学 一种基于树形分子的量子点荧光强度增强方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102703057A (zh) * 2012-05-18 2012-10-03 北京工商大学 一种聚酰胺-胺树形分子包覆的ZnX半导体量子点在指纹显现中的应用
CN106398680A (zh) * 2016-08-30 2017-02-15 Tcl集团股份有限公司 一种油溶性蓝光量子点及其制备方法
CN107359264A (zh) * 2017-08-03 2017-11-17 青岛海信电器股份有限公司 一种qled、制备方法及显示装置

Also Published As

Publication number Publication date
CN111234802A (zh) 2020-06-05

Similar Documents

Publication Publication Date Title
Zhang et al. PbS capped CsPbI3 nanocrystals for efficient and stable light-emitting devices using p–i–n structures
Zhou et al. Stabilized low-dimensional species for deep-blue perovskite light-emitting diodes with EQE approaching 3.4%
CN111384278B (zh) 一种量子点发光二极管及其制备方法
CN109390476B (zh) 一种具有氧化石墨烯界面层的qled器件及其制备方法
CN111244295B (zh) 一种量子点发光二极管及其制备方法
Chen et al. Passivation layer of potassium iodide yielding high efficiency and stable deep red perovskite light-emitting diodes
WO2023281639A1 (ja) 発光素子および発光装置
Shen et al. Silver–Bismuth Bilayer Anode for Perovskite Nanocrystal Light-Emitting Devices
CN111232931B (zh) 一种纳米金属氧化物及其制备方法、量子点发光二极管
Ye et al. Uncovering the performance enhancing mechanism of methanesulfonate ligands in perovskite quantum dots for light-emitting devices
CN113120952B (zh) 一种硫化锌纳米材料及其制备方法、硫化锌薄膜、量子点发光二极管
CN114695813B (zh) 一种复合材料及其制备方法、发光二极管
CN114188490B (zh) 量子点-半导体复合膜层及其制备方法、量子点发光器件
CN112542553B (zh) 一种复合物及其制备方法与量子点发光二极管
CN111234802A (zh) 一种量子点的制备方法
CN113046077B (zh) 一种复合材料、量子点发光二极管及其制备方法
KR20240006990A (ko) 금속 산화물 나노입자 및 이를 포함하는 양자점 발광 소자
CN111234804A (zh) 一种量子点的制备方法
CN114695810A (zh) 一种复合材料及其制备方法、量子点发光二极管
CN111244296B (zh) 一种量子点发光二极管及其制备方法
CN114695807B (zh) 一种复合材料及其制备方法、发光二极管
CN117623369B (zh) 锌基氧化物半导体纳米晶的对称掺杂方法及其应用
CN114520297B (zh) 纳米材料及其制备方法和量子点发光二极管
CN112542552A (zh) 一种复合物及其制备方法与量子点发光二极管
Lee et al. Light-Emitting Diodes with Cd-Free Quantum Dots Embedded in a Carrier Transport Matrix Grown by a Wet Process

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19891440

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19891440

Country of ref document: EP

Kind code of ref document: A1