WO2020134141A1 - Method for preparing quantum dot - Google Patents

Method for preparing quantum dot Download PDF

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WO2020134141A1
WO2020134141A1 PCT/CN2019/103207 CN2019103207W WO2020134141A1 WO 2020134141 A1 WO2020134141 A1 WO 2020134141A1 CN 2019103207 W CN2019103207 W CN 2019103207W WO 2020134141 A1 WO2020134141 A1 WO 2020134141A1
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quantum dot
precursor
trialkylamine
cationic precursor
quantum dots
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French (fr)
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程陆玲
杨一行
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Tcl科技集团股份有限公司
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    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • C09K11/881—Chalcogenides
    • C09K11/883—Chalcogenides with zinc or cadmium
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    • B82—NANOTECHNOLOGY
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    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/62—Luminescent, e.g. electroluminescent, chemiluminescent materials 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
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements

Definitions

  • the present disclosure relates to the field of quantum dots, and in particular to a method for preparing quantum dots.
  • Nanomaterials are hailed as the most promising materials in the 21st century. Quantum dots have an important application and research value as an important branch of the field of nanomaterials.
  • quantum dots because of their special optical and electrical properties, they can be used in many fields such as light-emitting diodes, solar cells, fluorescent biomarkers, and lighting.
  • the preparation of the quantum dot material itself will involve the growth of the core and shell, where the growth of the shell layer has a greater impact on the photoelectric properties of the quantum dot, and for the quantum dot alloyed shell layer, it will involve the rate between different precursors Competition, the competition of this rate mainly depends on the concentration ratio of different precursors to adjust. However, this concentration-based adjustment of the reaction rate between different precursors will not only cause unnecessary waste of raw materials, but also cause defects such as lattice mismatch on the surface of the quantum dot shell.
  • the purpose of the present disclosure is to provide a method for preparing quantum dots, aiming to solve the problem that the prior art is likely to cause waste of raw materials and the existence of the surface of the generated quantum dot shell during the process of preparing quantum dot shell The problem of lattice mismatch.
  • a method for preparing quantum dots which includes the steps of:
  • the cationic precursor complex, the anionic precursor and the quantum dot core are mixed, and shell growth is performed on the surface of the quantum dot core to prepare the quantum dot.
  • the present disclosure provides a method for preparing quantum dots.
  • a cationic precursor complex is prepared, and then the The cationic precursor complex, the anionic precursor and the quantum dot core are mixed in an organic solvent, and the cationic precursor complex and the anionic precursor are reacted on the surface of the quantum dot core to form a quantum dot shell, thereby preparing the Quantum dots.
  • the covalent binding energy of the metal atom and the organic acid is reduced, thereby reducing the pyrolysis energy of the cationic precursor, that is, improving the cationic precursor
  • the activation energy of the body therefore, when the cationic precursor complex after the activation energy is increased and the anion precursor react to form a quantum dot shell, the growth temperature of the quantum dot shell can be effectively reduced and the quantum dot shell can be improved Lattice defects and lattice mismatch can also effectively reduce the use of cationic precursor materials.
  • FIG. 1 is a flowchart of a preferred embodiment of a method for preparing quantum dots disclosed in 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:
  • the method for preparing quantum dots provided in this embodiment can effectively reduce the lattice defects and lattice mismatch of the quantum dot shell, and reduce the raw material cost.
  • the mechanism for achieving the above effect is as follows:
  • the charge balance of the cation changes due to the presence of the dipolar charge effect, resulting in a reduction in the covalent binding energy of the metal atom and the organic acid, thereby reducing the cationic precursor’s Pyrolysis energy, that is, the activation energy of the cationic precursor is improved; therefore, when the cationic precursor complex and the anionic precursor after the activation energy are mixed and reacted to form a quantum dot shell, the quantum dot shell can be effectively reduced Growth temperature and improve the lattice defects and lattice mismatch of the quantum dot shell, at the same time, it can also effectively reduce the use of cationic precursor materials.
  • the cationic precursor and the trialkylamine are mixed under the condition of 40-250° C. to combine the cationic precursor and the trialkylamine to prepare a cationic precursor complex. In some embodiments, the cationic precursor and the trialkylamine are mixed under an inert atmosphere for 10-60 minutes to combine the cationic precursor with the trialkylamine to prepare a cationic precursor complex.
  • the cationic precursor and the trialkylamine are mixed according to the molar ratio of the cationic precursor and the trialkylamine to be 1:1 to combine the cationic precursor and the trialkylamine to prepare Cationic precursor complex.
  • the cationic precursor is selected from one or more of zinc oleate, cadmium oleate, lead oleate, indium oleate, and copper oleate, but is not limited thereto.
  • the trialkylamine is selected from one or more of trioctylamine, triheptylamine, trihexylamine, tripentylamine, tributylamine, and tripropylamine, but is not limited thereto.
  • the trialkylamine is trioctylamine, and the trioctylamine is more non-polar and has a higher boiling point, which is more suitable for the synthesis of quantum dot shells in different temperature ranges .
  • the cationic precursor complex, the anionic precursor and the quantum dot core are mixed at 100-300°C, so that the cationic precursor complex and the anionic precursor are on the surface of the quantum dot core
  • the reaction generates a quantum dot shell to prepare the quantum dot.
  • the growth temperature of the shell layer and the concentration of the cation precursor are usually used to reduce the lattice defects and lattice loss during the growth process of the quantum dot shell layer; in this embodiment, due to the cation
  • a cationic precursor complex with stronger activation energy is generated, and the cationic precursor complex with the enhanced activation energy is mixed with an anionic precursor to form a quantum dot shell.
  • the growth temperature of the quantum dot shell layer can be effectively reduced and the lattice defects and lattice mismatch of the quantum dot shell layer can be improved.
  • the material of the cationic precursor can also be effectively reduced.
  • the cationic precursor complex and the quantum dot core are mixed in an organic solvent and heated to 100-300°C, and then an appropriate dropping rate is applied to the cationic precursor complex
  • An anion precursor is injected into the mixed solution with the quantum dot core, and the cationic precursor complex and the anion precursor are reacted on the surface of the quantum dot core to generate a quantum dot shell, thereby preparing the quantum dot.
  • the cationic precursor complex, the anionic precursor, and the quantum dot core are mixed at a molar mass ratio of the cationic precursor complex to the quantum dot core of 0.5-10 mmol: 100 mg.
  • the cationic precursor complex, the anionic precursor, and the quantum dot core are mixed at a molar mass ratio of the anionic precursor to the quantum dot core of 0.5-10 mmol: 100 mg.
  • the anionic precursor is selected from S-ODE, S-TOP, S-OA, Se-TOP, S-OLA, S-TBP, Se-TBP, Te-ODE, Te-OA, Te -One or more of TOP and Te-TBP, but not limited thereto.
  • the organic solvent is selected from one or more of octadecene, diphenyl ether, and paraffin oil, but is not limited thereto.
  • the quantum dot core is selected from one or more of binary phase quantum dots, ternary phase quantum dots, and quaternary phase quantum dots, but is not limited thereto.
  • the binary phase quantum dots include CdS, CdSe, CdTe, InP, AgS, PbS, PbSe, HgS, etc., but not limited thereto;
  • the ternary phase quantum dots include ZnCdS, CuInS, ZnCdSe, ZnSeS, ZnCdTe , PbSeS, etc., but not limited thereto;
  • the quaternary phase quantum dots include ZnCdS/ZnSe, CuInS/ZnS, ZnCdSe/ZnS, CuInSeS, ZnCdTe/ZnS, PbSeS/ZnS, etc., but are not limited thereto.
  • a preparation method of CdSe/ZnS core-shell quantum dots includes steps:
  • CdSe/ZnS core-shell quantum dots disperse 10 mmol of S in 5 ml of TOP at 80°C to dissolve and disperse it, and then cool to room temperature to prepare an S-TOP (anionic precursor) solution; take 100 mg of CdSe
  • S-TOP anionic precursor
  • the quantum dot core is dispersed into a three-necked flask containing 10ml of ODE for inert gas exhaust, and then 5ml of the zinc ion precursor complex solution in 1) is added to the CdSe quantum dot core solution, and then the temperature of the solution is increased
  • 3ml of S-TOP solution was gradually added dropwise to the CdSe quantum dot core solution containing zinc ion precursor complex for ZnS shell growth, and finally a certain thickness of CdSe/ZnS core-shell quantum was grown. point.
  • a preparation method of CdSe/InSe core-shell quantum dots includes steps:
  • CdSe/InSe core-shell quantum dots disperse 10 mmol of Se in 5 ml of TBP at 80° C. to dissolve and disperse it, and then cool to room temperature to prepare a Se-TBP (anionic precursor) solution; take 100 mg of CdSe
  • the quantum dot core is dispersed into a three-necked flask containing 10ml of ODE for inert gas exhaust, and then 5ml of the indium ion precursor complex solution in 1) is added to the CdSe quantum dot core solution, and then the temperature of the solution is increased
  • 3ml of Se-TBP solution was gradually added dropwise to the CdSe quantum dot core solution containing indium ion precursor complex for InSe shell growth, and finally a certain thickness of CdSe/InSe core-shell quantum was grown point.
  • a preparation method of CdSe/PbTe core-shell quantum dots includes steps:
  • Preparation of cationic precursor complex Take 8mmol of lead acetate, 4ml of OA, 8ml of ODE and add them to a three-necked flask. After heating at 200°C for 30 minutes, the temperature of the solution is reduced to 150°C, and then the zinc oleate solution Add 3ml of tripropylamine to maintain 200 °C heating and stirring for 20min, and then maintain to 100 °C, to prepare lead ion precursor complex solution;
  • CdSe/PbTe core-shell quantum dots Disperse 10 mmol of Te in 5 ml of TOP at 80°C to dissolve and disperse it, then cool to room temperature to prepare a Te-TOP (anionic precursor) solution; take 100 mg of CdSe
  • Te-TOP anionic precursor
  • the quantum dot core was dispersed into a three-necked flask containing 10ml of ODE for inert gas exhaust, and then 5ml of the lead ion precursor complex solution in 1) was added to the CdSe quantum dot core solution, and then the temperature of the solution was increased
  • 3ml of Te-TOP solution was gradually added dropwise to the CdSe quantum dot core solution containing lead ion precursor complex for PbTe shell growth, and finally a certain thickness of CdSe/PbTe core-shell quantum was grown. point.
  • the present disclosure provides a method for preparing quantum dots, by mixing a cationic precursor with a trialkylamine in advance to combine the cationic precursor with a trialkylamine to prepare a cationic precursor complex, and then The cationic precursor complex, the anionic precursor and the quantum dot core are mixed in an organic solvent, and the cationic precursor complex and the anionic precursor are reacted on the surface of the quantum dot core to form a quantum dot shell layer to prepare The quantum dots.
  • the covalent binding energy of the metal atom and the organic acid is reduced, thereby reducing the pyrolysis energy of the cationic precursor, that is, improving the cationic precursor
  • the activation energy of the body therefore, when the cationic precursor complex after the activation energy is increased and the anion precursor react to form a quantum dot shell, the growth temperature of the quantum dot shell can be effectively reduced and the quantum dot shell can be improved Lattice defects and lattice mismatch can also effectively reduce the use of cationic precursor materials.

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Abstract

Disclosed is a method for preparing a quantum dot, comprising mixing a cation precursor with a trialkylamine to allow the cation precursor and the trialkylamine to combine to prepare a cation precursor complex, and mixing the cation precursor complex, an anion precursor and a quantum dot core in an organic solvent to allow the cation precursor complex and the anion precursor to react on a surface of the quantum dot core to form a quantum dot shell layer, thus preparing the quantum dot. After the trialkylamine combines with the cation precursor, the presence of a dipole charge effect results in a reduction in covalent binding energy between a metal atom and an organic acid, which decreases thermolysis energy of the cation precursor and increases activation energy of the cation precursor. Reaction of the cation precursor complex having increased activation energy with the anion precursor to form the quantum dot shell layer is advantageous in that a growth temperature of the quantum dot shell layer can be effectively decreased, a lattice defect and a lattice mismatch associated with the quantum dot shell layer can be effectively ameliorated, and the amount of the cation precursor used can be effectively reduced.

Description

一种量子点的制备方法Method for preparing quantum dots 技术领域Technical field
本公开涉及量子点领域，尤其涉及一种量子点的制备方法。The present disclosure relates to the field of quantum dots, and in particular to a method for preparing quantum dots.
背景技术Background technique
纳米材料被誉为21世纪最具有前途的材料，量子点作为纳米材料领域的一个重要分支也有很重要的应用和研究价值。Nanomaterials are hailed as the most promising materials in the 21st century. Quantum dots have an important application and research value as an important branch of the field of nanomaterials.
对于发光量子点而言，由于其具有较特殊的光学和电学性能而能够应用在发光二极管、太阳能电池、荧光生物标记以及照明等多个领域。For light-emitting quantum dots, because of their special optical and electrical properties, they can be used in many fields such as light-emitting diodes, solar cells, fluorescent biomarkers, and lighting.
量子点材料本身的制备会涉及到核壳的生长，其中，壳层的生长对于量子点的光电特性影响较大，对于量子点合金化壳层而言，会涉及到不同前驱体之间的速率竞争，该速率的竞争主要是依靠不同前驱物的浓度比例来调节。然而，这种依靠浓度来调节不同前驱体之间的反应速率不仅会造成不必要的原料浪费，而且也会使生成的量子点壳层表面存在晶格失配等缺陷。The preparation of the quantum dot material itself will involve the growth of the core and shell, where the growth of the shell layer has a greater impact on the photoelectric properties of the quantum dot, and for the quantum dot alloyed shell layer, it will involve the rate between different precursors Competition, the competition of this rate mainly depends on the concentration ratio of different precursors to adjust. However, this concentration-based adjustment of the reaction rate between different precursors will not only cause unnecessary waste of raw materials, but also cause defects such as lattice mismatch on the surface of the quantum dot shell.
因此，现有技术还有待于改进。Therefore, the existing technology needs to be improved.
发明内容Summary of the invention
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的制备方法，旨在解决现有技术在制备量子点壳层的过程中易造成原料浪费以及生成的量子点壳层表面存在晶格失配的问题。In view of the above-mentioned shortcomings of the prior art, the purpose of the present disclosure is to provide a method for preparing quantum dots, aiming to solve the problem that the prior art is likely to cause waste of raw materials and the existence of the surface of the generated quantum dot shell during the process of preparing quantum dot shell The problem of lattice mismatch.
本公开的技术方案如下：The technical solutions of the present disclosure are as follows:
一种量子点的制备方法，其中，包括步骤：A method for preparing quantum dots, which includes the steps of:
将阳离子前驱体和三烷基胺混合，使阳离子前驱体与三烷基胺之间结合，制得阳离子前驱体络合物；Mixing the cationic precursor and the trialkylamine to combine the cationic precursor and the trialkylamine to prepare a cationic precursor complex;
将所述阳离子前驱体络合物、阴离子前驱体以及量子点核混合，在所述量子点核表 面进行壳层生长，制得所述量子点。The cationic precursor complex, the anionic precursor and the quantum dot core are mixed, and shell growth is performed on the surface of the quantum dot core to prepare the quantum dot.
有益效果：本公开提供一种量子点的制备方法，通过预先将阳离子前驱体与三烷基胺混合，使阳离子前驱体与三烷基胺结合，制得阳离子前驱体络合物，然后将所述阳离子前驱体络合物、阴离子前驱体以及量子点核混合在有机溶剂中，使所述阳离子前驱体络合物和阴离子前驱体在量子点核表面反应生成量子点壳层，制得所述量子点。所述三烷基胺与阳离子前驱体结合后，由于偶极电荷效应的存在促使了金属原子与有机酸的共价结合能降低，从而减少了阳离子前驱体的热解能，即提升了阳离子前驱体的活化能；因此，将所述活化能提升后的阳离子前驱体络合物与阴离子前驱体反应生成量子点壳层时，可有效降低量子点壳层的生长温度并改善量子点壳层的晶格缺陷和晶格失配，同时还可有效减少阳离子前驱体的用料。Beneficial effect: The present disclosure provides a method for preparing quantum dots. By mixing a cationic precursor with a trialkylamine in advance to combine the cationic precursor with a trialkylamine, a cationic precursor complex is prepared, and then the The cationic precursor complex, the anionic precursor and the quantum dot core are mixed in an organic solvent, and the cationic precursor complex and the anionic precursor are reacted on the surface of the quantum dot core to form a quantum dot shell, thereby preparing the Quantum dots. After the trialkylamine is combined with the cationic precursor, due to the presence of the dipole charge effect, the covalent binding energy of the metal atom and the organic acid is reduced, thereby reducing the pyrolysis energy of the cationic precursor, that is, improving the cationic precursor The activation energy of the body; therefore, when the cationic precursor complex after the activation energy is increased and the anion precursor react to form a quantum dot shell, the growth temperature of the quantum dot shell can be effectively reduced and the quantum dot shell can be improved Lattice defects and lattice mismatch can also effectively reduce the use of cationic precursor materials.
附图说明BRIEF DESCRIPTION
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。FIG. 1 is a flowchart of a preferred embodiment of a method for preparing quantum dots disclosed in the present disclosure.
具体实施方式detailed description
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。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.
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：Please refer to FIG. 1, 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:
S100、将阳离子前驱体和三烷基胺混合，使阳离子前驱体与三烷基胺之间结合，制得阳离子前驱体络合物；S100. Mixing the cationic precursor and the trialkylamine to combine the cationic precursor and the trialkylamine to prepare a cationic precursor complex;
S200、将所述阳离子前驱体络合物、阴离子前驱体以及量子点核混合，在所述量子点核表面进行壳层生长，制得所述量子点。S200. Mix the cationic precursor complex, the anionic precursor and the quantum dot core, and perform shell growth on the surface of the quantum dot core to prepare the quantum dot.
本实施例提供的量子点制备方法能够有效降低量子点壳层的晶格缺陷以及晶格失配，并降低原料成本。实现上述效果的机理具体如下：The method for preparing quantum dots provided in this embodiment can effectively reduce the lattice defects and lattice mismatch of the quantum dot shell, and reduce the raw material cost. The mechanism for achieving the above effect is as follows:
由于三烷基胺中的N原子中具有一对孤对电子，所述阳离子前驱体络合物的化学结构式为(R1) 3N：M(R2COO -)，其中，三个R1基团独立地选自碳原子数为2-10的烷基，R2为碳原子数为12-20的烷基，M为金属离子作为举例，当所述阳离子前驱体为油酸锌时，则其与三烷基胺形成的阳离子前驱体络合物的化学结构式为(R1) 3N：Zn(OA) 2。由于所述三烷基胺与阳离子前驱体结合后由于偶极电荷效应的存在使得阳离子所处的电荷平衡发生变化，导致金属原子与有机酸的共价结合能降低，从而减少了阳离子前驱体的热解能，即提升了阳离子前驱体的活化能；因此，将所述活化能提升后的阳离子前驱体络合物与阴离子前驱体混合反应生成量子点壳层时，可有效降低量子点壳层的生长温度并改善量子点壳层的晶格缺陷和晶格失配，同时还可有效减少阳离子前驱体的用料。 Since trialkyl amine N atom having one lone pair of electrons, said cationic precursor complex chemical structural formula (R1) 3 N: M ( R2COO -), wherein three of R1 groups are independently It is selected from alkyl groups with 2-10 carbon atoms, R2 is alkyl group with 12-20 carbon atoms, M is a metal ion as an example, when the cationic precursor is zinc oleate, it is The chemical structural formula of the cationic precursor complex formed by the base amine is (R1) 3 N:Zn(OA) 2 . After the trialkylamine is combined with the cationic precursor, the charge balance of the cation changes due to the presence of the dipolar charge effect, resulting in a reduction in the covalent binding energy of the metal atom and the organic acid, thereby reducing the cationic precursor’s Pyrolysis energy, that is, the activation energy of the cationic precursor is improved; therefore, when the cationic precursor complex and the anionic precursor after the activation energy are mixed and reacted to form a quantum dot shell, the quantum dot shell can be effectively reduced Growth temperature and improve the lattice defects and lattice mismatch of the quantum dot shell, at the same time, it can also effectively reduce the use of cationic precursor materials.
在一些实施方式中，将阳离子前驱体和三烷基胺在40-250℃的条件下混合，使阳离子前驱体与三烷基胺之间结合，制得阳离子前驱体络合物。在一些实施方式中，在惰性气氛条件下将所述阳离子前驱体和三烷基胺混合10-60min，使阳离子前驱体与三烷基胺结合，制得阳离子前驱体络合物。In some embodiments, the cationic precursor and the trialkylamine are mixed under the condition of 40-250° C. to combine the cationic precursor and the trialkylamine to prepare a cationic precursor complex. In some embodiments, the cationic precursor and the trialkylamine are mixed under an inert atmosphere for 10-60 minutes to combine the cationic precursor with the trialkylamine to prepare a cationic precursor complex.
在一些实施方式中，按照阳离子前驱体与三烷基胺的摩尔量比为1:1-2，将阳离子前驱体和三烷基胺混合，使阳离子前驱体与三烷基胺结合，制得阳离子前驱体络合物。In some embodiments, the cationic precursor and the trialkylamine are mixed according to the molar ratio of the cationic precursor and the trialkylamine to be 1:1 to combine the cationic precursor and the trialkylamine to prepare Cationic precursor complex.
在一些实施方式中，所述阳离子前驱体选自油酸锌、油酸镉、油酸铅、油酸铟和油酸铜中的一种或多种，但不限于此。在一些实施方式中，所述三烷基胺选自三辛胺、三庚胺、三己胺、三戊胺、三丁胺和三丙胺中的一种或多种，但不限于此。In some embodiments, the cationic precursor is selected from one or more of zinc oleate, cadmium oleate, lead oleate, indium oleate, and copper oleate, but is not limited thereto. In some embodiments, the trialkylamine is selected from one or more of trioctylamine, triheptylamine, trihexylamine, tripentylamine, tributylamine, and tripropylamine, but is not limited thereto.
在一种具体的实施方式中，所述三烷基胺为三辛胺，所述三辛胺的非极性较强且具有较高的沸点，更加适合不同温度范围的量子点壳层的合成。In a specific embodiment, the trialkylamine is trioctylamine, and the trioctylamine is more non-polar and has a higher boiling point, which is more suitable for the synthesis of quantum dot shells in different temperature ranges .
在一些实施方式中，将所述阳离子前驱体络合物、阴离子前驱体以及量子点核在100-300℃条件下混合，使所述阳离子前驱体络合物和阴离子前驱体在量子点核表面反应生成量子点壳层，制得所述量子点。现有技术在制备量子点壳层时通常会采用提高壳层生长温度和阳离子前驱体的浓度来降低量子点壳层生长过程中的晶格缺陷以及晶格缺失；而本实施方式中，由于阳离子前驱体经过所述三烷基胺的处理后生成了活化能更 强的阳离子前驱体络合物，将所述活化能提升后的阳离子前驱体络合物与阴离子前驱体混合反应生成量子点壳层时，可有效降低量子点壳层的生长温度并改善量子点壳层的晶格缺陷和晶格失配，同时还可有效减少阳离子前驱体的用料。In some embodiments, the cationic precursor complex, the anionic precursor and the quantum dot core are mixed at 100-300°C, so that the cationic precursor complex and the anionic precursor are on the surface of the quantum dot core The reaction generates a quantum dot shell to prepare the quantum dot. In the prior art, when preparing the quantum dot shell layer, the growth temperature of the shell layer and the concentration of the cation precursor are usually used to reduce the lattice defects and lattice loss during the growth process of the quantum dot shell layer; in this embodiment, due to the cation After the precursor is treated with the trialkylamine, a cationic precursor complex with stronger activation energy is generated, and the cationic precursor complex with the enhanced activation energy is mixed with an anionic precursor to form a quantum dot shell. When the layer is used, the growth temperature of the quantum dot shell layer can be effectively reduced and the lattice defects and lattice mismatch of the quantum dot shell layer can be improved. At the same time, the material of the cationic precursor can also be effectively reduced.
在一些具体的实施方式中，将所述阳离子前驱体络合物和量子点核混合在有机溶剂中并升温至100-300℃，然后采用适当的滴加速率向所述阳离子前驱体络合物和量子点核的混合溶液中注入阴离子前驱体，使所述阳离子前驱体络合物和阴离子前驱体在量子点核表面反应生成量子点壳层，制得所述量子点。In some specific embodiments, the cationic precursor complex and the quantum dot core are mixed in an organic solvent and heated to 100-300°C, and then an appropriate dropping rate is applied to the cationic precursor complex An anion precursor is injected into the mixed solution with the quantum dot core, and the cationic precursor complex and the anion precursor are reacted on the surface of the quantum dot core to generate a quantum dot shell, thereby preparing the quantum dot.
在一些实施方式中，按阳离子前驱体络合物与量子点核的摩尔质量比为0.5-10mmol：100mg，将所述阳离子前驱体络合物、阴离子前驱体以及量子点核混合。In some embodiments, the cationic precursor complex, the anionic precursor, and the quantum dot core are mixed at a molar mass ratio of the cationic precursor complex to the quantum dot core of 0.5-10 mmol: 100 mg.
在一些实施方式中，按阴离子前躯体与量子点核的摩尔质量比为0.5-10mmol：100mg，将所述阳离子前驱体络合物、阴离子前驱体以及量子点核混合。In some embodiments, the cationic precursor complex, the anionic precursor, and the quantum dot core are mixed at a molar mass ratio of the anionic precursor to the quantum dot core of 0.5-10 mmol: 100 mg.
在一些实施方式中，所述阴离子前驱体选自S-ODE、S-TOP、S-OA、Se-TOP、S-OLA、S-TBP、Se-TBP、Te-ODE、Te-OA、Te-TOP和Te-TBP中的一种或多种，但不限于此。在一些实施方式中，所述有机溶剂选自十八稀、二苯醚和石蜡油中的一种或多种，但不限于此。In some embodiments, the anionic precursor is selected from S-ODE, S-TOP, S-OA, Se-TOP, S-OLA, S-TBP, Se-TBP, Te-ODE, Te-OA, Te -One or more of TOP and Te-TBP, but not limited thereto. In some embodiments, the organic solvent is selected from one or more of octadecene, diphenyl ether, and paraffin oil, but is not limited thereto.
在一些实施方式中，所述量子点核选自二元相量子点、三元相量子点和四元相量子点中的一种或多种，但不限于此。作为举例，所述二元相量子点包括CdS、CdSe、CdTe、InP、AgS、PbS、PbSe、HgS等，但不限于此；所述三元相量子点包括ZnCdS、CuInS、ZnCdSe、ZnSeS、ZnCdTe、PbSeS等，但不限于此；所述四元相量子点包括ZnCdS/ZnSe、CuInS/ZnS、ZnCdSe/ZnS、CuInSeS、ZnCdTe/ZnS、PbSeS/ZnS等，但不限于此。In some embodiments, the quantum dot core is selected from one or more of binary phase quantum dots, ternary phase quantum dots, and quaternary phase quantum dots, but is not limited thereto. As an example, the binary phase quantum dots include CdS, CdSe, CdTe, InP, AgS, PbS, PbSe, HgS, etc., but not limited thereto; the ternary phase quantum dots include ZnCdS, CuInS, ZnCdSe, ZnSeS, ZnCdTe , PbSeS, etc., but not limited thereto; the quaternary phase quantum dots include ZnCdS/ZnSe, CuInS/ZnS, ZnCdSe/ZnS, CuInSeS, ZnCdTe/ZnS, PbSeS/ZnS, etc., but are not limited thereto.
下面通过具体实施例对本公开一种量子点固态膜的制备方法做进一步的解释说明：The following further explains the preparation method of a quantum dot solid film of the present disclosure through specific embodiments:
实施例1Example 1
一种CdSe/ZnS核壳量子点的制备方法包括步骤：A preparation method of CdSe/ZnS core-shell quantum dots includes steps:
1)、阳离子前驱体络合物的制备：取8mmol的醋酸锌、4ml OA、8ml ODE一起加入到三口烧瓶中，200℃加热排气30min后使溶液温度降低至150℃，然后向油酸锌溶液中加入3ml的三庚胺维持150℃加热搅拌30min，然后维持至100℃，制得锌离子前 驱体络合物溶液；1). Preparation of cationic precursor complex: 8mmol of zinc acetate, 4ml of OA, and 8ml of ODE were added to a three-necked flask, and the temperature of the solution was reduced to 150°C after heating and exhausting at 200°C for 30min, and then to zinc oleate Add 3ml of triheptylamine to the solution to maintain 150 ℃ heating and stirring for 30min, and then maintain to 100 ℃, to prepare zinc ion precursor complex solution;
2)、CdSe/ZnS核壳量子点的制备：取10mmol的S分散到5ml的TOP中80℃使其溶解分散，然后冷却至室温制得S-TOP(阴离子前驱体)溶液；取100mg的CdSe量子点核分散到含有10ml的ODE的三口烧瓶中进行惰性气体排气，然后再取1)中锌离子前驱体络合物溶液5ml添加到含有CdSe量子点核溶液中，然后使溶液温度升高到250℃，再取3ml的S-TOP溶液逐步滴加道到含有锌离子前驱体络合物的CdSe量子点核溶液中进行ZnS壳层生长，最后得到生长一定厚度的CdSe/ZnS核壳量子点。2). Preparation of CdSe/ZnS core-shell quantum dots: disperse 10 mmol of S in 5 ml of TOP at 80°C to dissolve and disperse it, and then cool to room temperature to prepare an S-TOP (anionic precursor) solution; take 100 mg of CdSe The quantum dot core is dispersed into a three-necked flask containing 10ml of ODE for inert gas exhaust, and then 5ml of the zinc ion precursor complex solution in 1) is added to the CdSe quantum dot core solution, and then the temperature of the solution is increased At 250°C, 3ml of S-TOP solution was gradually added dropwise to the CdSe quantum dot core solution containing zinc ion precursor complex for ZnS shell growth, and finally a certain thickness of CdSe/ZnS core-shell quantum was grown. point.
实施例2Example 2
一种CdSe/InSe核壳量子点的制备方法包括步骤：A preparation method of CdSe/InSe core-shell quantum dots includes steps:
1)、阳离子前驱体络合物的制备：取8mmol的醋酸铟、4ml OA、8ml ODE一起加入到三口烧瓶中，200℃加热排气30min后使溶液温度降低至150℃，然后向油酸锌溶液中加入3ml的三辛胺维持100℃加热搅拌50min，然后维持至100℃，制得铟离子前驱体络合物溶液；1). Preparation of cationic precursor complex: 8mmol of indium acetate, 4ml OA, 8ml ODE were added into a three-necked flask, heated at 200 ℃ for 30min, the solution temperature was reduced to 150 ℃, and then to zinc oleate Add 3ml of trioctylamine to the solution to maintain 100 ℃ heating and stirring for 50min, and then maintain to 100 ℃, to prepare an indium ion precursor complex solution;
2)、CdSe/InSe核壳量子点的制备：取10mmol的Se分散到5ml的TBP中80℃使其溶解分散，然后冷却至室温制得Se-TBP(阴离子前驱体)溶液；取100mg的CdSe量子点核分散到含有10ml的ODE的三口烧瓶中进行惰性气体排气，然后再取1)中铟离子前驱体络合物溶液5ml添加到含有CdSe量子点核溶液中，然后使溶液温度升高到200℃，再取3ml的Se-TBP溶液逐步滴加道到含有铟离子前驱体络合物的CdSe量子点核溶液中进行InSe壳层生长，最后得到生长一定厚度的CdSe/InSe核壳量子点。2). Preparation of CdSe/InSe core-shell quantum dots: disperse 10 mmol of Se in 5 ml of TBP at 80° C. to dissolve and disperse it, and then cool to room temperature to prepare a Se-TBP (anionic precursor) solution; take 100 mg of CdSe The quantum dot core is dispersed into a three-necked flask containing 10ml of ODE for inert gas exhaust, and then 5ml of the indium ion precursor complex solution in 1) is added to the CdSe quantum dot core solution, and then the temperature of the solution is increased At 200°C, 3ml of Se-TBP solution was gradually added dropwise to the CdSe quantum dot core solution containing indium ion precursor complex for InSe shell growth, and finally a certain thickness of CdSe/InSe core-shell quantum was grown point.
实施例3Example 3
一种CdSe/PbTe核壳量子点的制备方法包括步骤：A preparation method of CdSe/PbTe core-shell quantum dots includes steps:
1)、阳离子前驱体络合物的制备：取8mmol的醋酸铅、4ml OA、8ml ODE一起加入到三口烧瓶中，200℃加热排气30min后使溶液温度降低至150℃，然后向油酸锌溶液中加入3ml的三丙胺维持200℃加热搅拌20min，然后维持至100℃，制得铅离子前驱体络合物溶液；1). Preparation of cationic precursor complex: Take 8mmol of lead acetate, 4ml of OA, 8ml of ODE and add them to a three-necked flask. After heating at 200℃ for 30 minutes, the temperature of the solution is reduced to 150℃, and then the zinc oleate solution Add 3ml of tripropylamine to maintain 200 ℃ heating and stirring for 20min, and then maintain to 100 ℃, to prepare lead ion precursor complex solution;
2)、CdSe/PbTe核壳量子点的制备：取10mmol的Te分散到5ml的TOP中80℃使 其溶解分散，然后冷却至室温制得Te-TOP(阴离子前驱体)溶液；取100mg的CdSe量子点核分散到含有10ml的ODE的三口烧瓶中进行惰性气体排气，然后再取1)中铅离子前驱体络合物溶液5ml添加到含有CdSe量子点核溶液中，然后使溶液温度升高到300℃，再取3ml的Te-TOP溶液逐步滴加道到含有铅离子前驱体络合物的CdSe量子点核溶液中进行PbTe壳层生长，最后得到生长一定厚度的CdSe/PbTe核壳量子点。2). Preparation of CdSe/PbTe core-shell quantum dots: Disperse 10 mmol of Te in 5 ml of TOP at 80°C to dissolve and disperse it, then cool to room temperature to prepare a Te-TOP (anionic precursor) solution; take 100 mg of CdSe The quantum dot core was dispersed into a three-necked flask containing 10ml of ODE for inert gas exhaust, and then 5ml of the lead ion precursor complex solution in 1) was added to the CdSe quantum dot core solution, and then the temperature of the solution was increased At 300℃, 3ml of Te-TOP solution was gradually added dropwise to the CdSe quantum dot core solution containing lead ion precursor complex for PbTe shell growth, and finally a certain thickness of CdSe/PbTe core-shell quantum was grown. point.
综上所述，本公开提供一种量子点的制备方法，通过预先将阳离子前驱体与三烷基胺混合，使阳离子前驱体与三烷基胺结合，制得阳离子前驱体络合物，然后将所述阳离子前驱体络合物、阴离子前驱体以及量子点核混合在有机溶剂中，使所述阳离子前驱体络合物和阴离子前驱体在量子点核表面反应生成量子点壳层，制得所述量子点。所述三烷基胺与阳离子前驱体结合后，由于偶极电荷效应的存在促使了金属原子与有机酸的共价结合能降低，从而减少了阳离子前驱体的热解能，即提升了阳离子前驱体的活化能；因此，将所述活化能提升后的阳离子前驱体络合物与阴离子前驱体反应生成量子点壳层时，可有效降低量子点壳层的生长温度并改善量子点壳层的晶格缺陷和晶格失配，同时还可有效减少阳离子前驱体的用料。In summary, the present disclosure provides a method for preparing quantum dots, by mixing a cationic precursor with a trialkylamine in advance to combine the cationic precursor with a trialkylamine to prepare a cationic precursor complex, and then The cationic precursor complex, the anionic precursor and the quantum dot core are mixed in an organic solvent, and the cationic precursor complex and the anionic precursor are reacted on the surface of the quantum dot core to form a quantum dot shell layer to prepare The quantum dots. After the trialkylamine is combined with the cationic precursor, due to the presence of the dipole charge effect, the covalent binding energy of the metal atom and the organic acid is reduced, thereby reducing the pyrolysis energy of the cationic precursor, that is, improving the cationic precursor The activation energy of the body; therefore, when the cationic precursor complex after the activation energy is increased and the anion precursor react to form a quantum dot shell, the growth temperature of the quantum dot shell can be effectively reduced and the quantum dot shell can be improved Lattice defects and lattice mismatch can also effectively reduce the use of cationic precursor materials.
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。It should be understood that the application of the present disclosure is not limited to the above examples, and those of ordinary skill in the art may make improvements or changes based on the above description, and all such improvements and changes shall fall within the protection scope of the claims appended to the present disclosure.

Claims (15)

  1. 一种量子点的制备方法，其特征在于，包括步骤：A method for preparing quantum dots, characterized in that it includes the steps of:
    将阳离子前驱体和三烷基胺混合，使阳离子前驱体与三烷基胺之间结合，制得阳离子前驱体络合物；Mixing the cationic precursor and the trialkylamine to combine the cationic precursor and the trialkylamine to prepare a cationic precursor complex;
    将所述阳离子前驱体络合物、阴离子前驱体以及量子点核混合，在所述量子点核表面进行壳层生长，制得所述量子点。The cationic precursor complex, the anionic precursor and the quantum dot core are mixed, and shell growth is performed on the surface of the quantum dot core to prepare the quantum dot.
  2. 根据权利要求1所述量子点的制备方法，其特征在于，将阳离子前驱体和三烷基胺在40-250℃的条件下混合，使阳离子前驱体与三烷基胺发生结合，制得阳离子前驱体络合物。The method for preparing quantum dots according to claim 1, characterized in that the cationic precursor and the trialkylamine are mixed under the condition of 40-250°C to combine the cationic precursor and the trialkylamine to prepare the cation Precursor complex.
  3. 根据权利要求1所述量子点的制备方法，其特征在于，在惰性气氛条件下将所述阳离子前驱体和三烷基胺混合10-60min，使阳离子前驱体与三烷基胺结合，制得阳离子前驱体络合物。The method for preparing quantum dots according to claim 1, characterized in that the cationic precursor and the trialkylamine are mixed under an inert atmosphere for 10-60 min to combine the cationic precursor and the trialkylamine to prepare Cationic precursor complex.
  4. 根据权利要求1所述量子点的制备方法，其特征在于，按照阳离子前驱体与三烷基胺的摩尔量比为1:1-2，将阳离子前驱体和三烷基胺混合，使阳离子前驱体与三烷基胺结合，制得阳离子前驱体络合物。The method for preparing quantum dots according to claim 1, characterized in that the cationic precursor and the trialkylamine are mixed according to the molar ratio of the cationic precursor and the trialkylamine to be 1:1 to make the cationic precursor The body is combined with trialkylamine to prepare a cationic precursor complex.
  5. 根据权利要求1-4任一所述量子点的制备方法，其特征在于，所述阳离子前驱体络合物的化学结构式为(R1) 3N：M(R2COO -)，其中，三个R1独立地选自碳原子数为2-10的烷基，R2为碳原子数为12-20的烷基，M为金属离子。 Prepared according to the method of a quantum dot of any of claims 1-4, characterized in that the cationic precursor complex chemical structural formula (R1) 3 N: M ( R2COO -), wherein three of R1 is independently It is selected from alkyl groups with 2-10 carbon atoms, R2 is alkyl group with 12-20 carbon atoms, and M is a metal ion.
  6. 根据权利要求1所述量子点的制备方法，其特征在于，所述阳离子前驱体选自油酸锌、油酸镉、油酸铅、油酸铟和油酸铜中的一种或多种。The method for preparing quantum dots according to claim 1, wherein the cationic precursor is selected from one or more of zinc oleate, cadmium oleate, lead oleate, indium oleate, and copper oleate.
  7. 根据权利要求1所述量子点的制备方法，其特征在于，所述三烷基胺选自三辛胺、三庚胺、三己胺、三戊胺、三丁胺和三丙胺中的一种或多种。The method for preparing quantum dots according to claim 1, wherein the trialkylamine is selected from one of trioctylamine, triheptylamine, trihexylamine, tripentylamine, tributylamine and tripropylamine Or more.
  8. 根据权利要求6所述量子点的制备方法，其特征在于，所述三烷基胺为三辛胺。The method for preparing quantum dots according to claim 6, wherein the trialkylamine is trioctylamine.
  9. 根据权利要求1所述量子点的制备方法，其特征在于，将所述阳离子前驱体络合物、阴离子前驱体以及量子点核在100-300℃条件下混合，在所述量子点核表面进行壳层生长，制得所述量子点。The method for preparing quantum dots according to claim 1, characterized in that the cationic precursor complex, the anionic precursor and the quantum dot core are mixed under the condition of 100-300°C, and are carried out on the surface of the quantum dot core The shell layer grows to produce the quantum dot.
  10. 根据权利要求1所述量子点的制备方法，其特征在于，将所述阳离子前驱体络 合物和量子点核混合在有机溶剂中并升温至100-300℃，向所述阳离子前驱体络合物和量子点核的混合溶液中注入阴离子前驱体，使所述阳离子前驱体络合物和阴离子前驱体在量子点核表面反应生成量子点壳层，制得所述量子点。The method for preparing quantum dots according to claim 1, characterized in that the cationic precursor complex and the quantum dot core are mixed in an organic solvent and heated to 100-300°C to complex the cationic precursor The anion precursor is injected into the mixed solution of the substance and the quantum dot core, and the cationic precursor complex and the anion precursor are reacted on the surface of the quantum dot core to generate a quantum dot shell, thereby preparing the quantum dot.
  11. 根据权利要去10所述量子点的制备方法，其特征在于，所述有机溶剂选自十八稀、二苯醚和石蜡油中的一种或多种。The method for preparing quantum dots according to claim 10, wherein the organic solvent is selected from one or more of octadecene, diphenyl ether, and paraffin oil.
  12. 根据权利要求1所述量子点的制备方法，其特征在于，按阳离子前驱体络合物与量子点核的摩尔质量比为0.5-10mmol：100mg，将所述阳离子前驱体络合物、阴离子前驱体以及量子点核混合。The method for preparing quantum dots according to claim 1, characterized in that the cationic precursor complex and the anionic precursor are mixed at a molar mass ratio of the cationic precursor complex to the quantum dot core of 0.5-10 mmol: 100 mg Volume and quantum dot nuclei are mixed.
  13. 根据权利要求1所述量子点的制备方法，其特征在于，按阴离子前躯体与量子点核的摩尔质量比为0.5-10mmol：100mg，将所述阳离子前驱体络合物、阴离子前驱体以及量子点核混合。The method for preparing quantum dots according to claim 1, characterized in that the cationic precursor complex, anionic precursor and quantum are mixed according to the molar mass ratio of the anion precursor to the quantum dot core of 0.5-10mmol: 100mg Point core mixing.
  14. 根据权利要求1所述量子点的制备方法，其特征在于，所述阴离子前驱体选自S-ODE、S-TOP、S-OA、Se-TOP、S-OLA、S-TBP、Se-TBP、Te-ODE、Te-OA、Te-TOP和Te-TBP中的一种或多种。The method for preparing quantum dots according to claim 1, wherein the anionic precursor is selected from S-ODE, S-TOP, S-OA, Se-TOP, S-OLA, S-TBP, Se-TBP , Te-ODE, Te-OA, Te-TOP and Te-TBP one or more.
  15. 根据权利要求1所述量子点的制备方法，其特征在于，所述量子点核选自二元相量子点、三元相量子点和四元相量子点中的一种或多种。The method for preparing quantum dots according to claim 1, wherein the quantum dot core is selected from one or more of binary phase quantum dots, ternary phase quantum dots and quaternary phase quantum dots.
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