CN110129026A - Perovskite quantum dot dispersion - Google Patents

Perovskite quantum dot dispersion Download PDF

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CN110129026A
CN110129026A CN201910461123.8A CN201910461123A CN110129026A CN 110129026 A CN110129026 A CN 110129026A CN 201910461123 A CN201910461123 A CN 201910461123A CN 110129026 A CN110129026 A CN 110129026A
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perovskite quantum
quantum dot
additive
dispersion
dot dispersion
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CN110129026B (en
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邢泽咏
王允军
厉芙伶
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Suzhou Xingshuo Nanotech Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/66Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
    • C09K11/664Halogenides
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/66Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
    • C09K11/664Halogenides
    • C09K11/665Halogenides with alkali or alkaline earth metals

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Abstract

The invention discloses a kind of perovskite quantum dot dispersions, comprising: dispersion liquid;Perovskite quantum dot is dispersed in the dispersion liquid;Additive is dispersed in the dispersion liquid;Wherein, the chemical formula of additive isWherein, R1、R2It is independently selected from the alkane chain for C1-C20, R3Selected from the alkane chain for C2-C20.It include additive in perovskite quantum dot dispersion of the invention, under the action of the additive, perovskite quantum dot and dispersion liquid have good intermiscibility, to which dissolubility of the perovskite quantum dot in dispersion liquid be improved greatly, and after perovskite quantum dot dispersion of the invention is long placed in, quantum dot will not occur to sink to gather, and dispersion stabilization is good.

Description

Perovskite quantum dot dispersion system
Technical Field
The application belongs to the field of nano materials, and particularly relates to a perovskite quantum dot dispersion system.
Background
Perovskite quantum dots have excellent optical properties such as easy tuning of light emission, narrow emission line, high quantum efficiency, and the like, and have recently received wide attention from academic and industrial fields.
The existing dispersion liquid containing perovskite quantum dots has poor solubility and low concentration of the quantum dots, is easy to generate coagulation after being placed for a long time, and is not beneficial to subsequent application.
Disclosure of Invention
In view of the above technical problems, the present application provides a perovskite quantum dot dispersion system, which improves the solubility and dispersion stability of perovskite quantum dots in a dispersion liquid.
According to one aspect of the present application, there is provided a perovskite quantum dot dispersion comprising: a dispersion liquid; perovskite quantum dots dispersed in the dispersion liquid; an additive dispersed in the dispersion; the chemical formula of the additive is
Wherein R is1、R2Each independently selected from C1-C20 alkane chains, R3Is selected from C2-C20 alkane chains.
Further, R in the chemical formula of the additive described herein1、R2Each independently selected from linear alkanes of C1-C20, and R3 is selected from linear alkanes of C2-C20.
Further, the additive comprises at least one of triethylamine, tributylamine, trihexylamine, triheptylamine, trioctylamine, N-dimethyldecylamine, N-dimethyldodecylamine, N-dimethyltetradecylamine and N, N-dimethylhexadecylamine.
Further, this application dispersion includes at least one in polymer resin, monomer resin, ultraviolet curing glue, the heat-cure glue.
Further, the dispersion liquid comprises an organic solvent, and the organic solvent comprises at least one of alkane solvents, aromatic solvents and ester solvents.
Further, the alkane solvent comprises a branched or straight-chain saturated aliphatic hydrocarbon organic solvent CnH2n+2Or naphthenic organic solvents CmH2mWherein n and m are positive integers, n is more than or equal to 6 and m is less than or equal to 18.
Furthermore, the structural general formula of the perovskite quantum dot is ABX3Wherein a is at least one monovalent organic cation, at least one monovalent inorganic cation, or any combination thereof; b is at least one divalent inorganic cation; x is at least one monovalent anion.
Further, A is Rb+、Cs+、(R4R5R6R7N)+Or (R)4R5N=C(R6)-NR7R8)+At least one of; b is Pb2+、Ge2+、Sn2+At least one of; x is at least one of halogen anions.
Further, the molar mass ratio of the perovskite quantum dots to the additive ranges from 1: (0.01-100).
Further, the molar mass ratio of the perovskite quantum dots to the additive ranges from 1: (0.1-10).
Has the advantages that:
the perovskite quantum dot dispersion system comprises the additive, and under the action of the additive, the perovskite quantum dot and the dispersion liquid have good intermiscibility, so that the solubility of the perovskite quantum dot in the dispersion liquid is greatly improved, and after the perovskite quantum dot dispersion system is used for a long time, the quantum dot cannot be precipitated, and the dispersion stability is good.
Detailed Description
The technical solutions in the examples of the present application will be described in detail below with reference to the embodiments of the present application. It should be noted that the described embodiments are only some embodiments of the present application, and not all embodiments.
The application provides a perovskite quantum dot disperse system, including: a dispersion liquid; perovskite quantum dots dispersed in the dispersion liquid; an additive dispersed in the dispersion; the chemical formula of the additive is
Wherein R is1、R2Each independently selected from C1-C20 alkane chains, R3Is selected from C2-C20 alkane chains.
The perovskite quantum dot dispersion system comprises the additive, and under the action of the additive, the perovskite quantum dot and the dispersion liquid have good intermiscibility, so that the perovskite quantum dot dispersion system overcomes the problem that the perovskite quantum dot is poor in solubility in the dispersion liquid, and the technical effect that the perovskite quantum dot has good solubility in the dispersion liquid is achieved.
In the prior art, perovskite quantum dots are generally directly dispersed in a toluene solvent, the dispersion concentration is about 5%, the perovskite quantum dot dispersion system with low dispersion concentration has poor effect in subsequent application, for example, when the perovskite quantum dot film is prepared by using the perovskite quantum dot dispersion system through ink-jet printing, the film has low light conversion efficiency and low brightness. The inventor finds that the additive is added into the perovskite quantum dot dispersion system, so that the dispersion concentration of the perovskite quantum dots can be improved to a great extent, the perovskite quantum dots cannot be precipitated after a long time, and the dispersion stability is good.
According to a preferred embodiment of the present application, R in the chemical formula of the additive is1、R2Each independently selected from C1-C20 straight-chain alkane, R3Is selected from linear alkanes of C2-C20. The inventors found that the additive having such a chemical formula has an appropriate chain length and small steric hindrance, and thus the distance between the perovskite quantum dots can be made to be within an appropriate range, thereby maintaining a good dispersion state of the perovskite quantum dots in a dispersion liquid.
According to a preferred embodiment of the present application, the additive comprises at least one of triethylamine, tributylamine, trihexylamine, triheptylamine, trioctylamine, N-dimethyldecylamine, N-dimethyldodecylamine, N-dimethyltetradecylamine, N-dimethylhexadecylamine.
According to a preferred embodiment of the present application, the dispersion includes at least one of a polymer resin, a monomer resin, an ultraviolet-curable adhesive, and a thermal-curable adhesive.
According to a preferred embodiment of the present application, the dispersion comprises an organic solvent comprising at least one of an alkane solvent, an aromatic solvent, an ester solvent.
In a particular embodiment, the alkane solvent comprises a branched and linear saturated aliphatic hydrocarbon organic solvent CnH2n+2And a cycloalkane organic solvent CmH2mWherein n and m are positive integers, n is more than or equal to 6 and m is less than or equal to 18. For example, alkane solvents include, but are not limited to, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, cyclodecane, and the like, cycloundecane, and isomers thereof.
In a specific embodiment, the aromatic hydrocarbon solvent includes, but is not limited to, toluene, ethylbenzene, o-xylene (o-), m-xylene (m-), p-xylene (p-), o-chlorotoluene, p-chlorotoluene, m-chlorotoluene, o-diethylbenzene (o-), m-diethylbenzene (m-), p-diethylbenzene (p-), o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, trimethylbenzene, tetramethylbenzene, tripentylbenzene, pentyltoluene, 1-methylnaphthalene, dihexylbenzene, butylbenzene, sec-butylbenzene, tert-butylbenzene, isobutylbenzene, dibutylbenzene, isopropylbenzene, p-diisopropylbenzene, pentylbenzene, dipentylbenzene, dodecylbenzene, tetrahydronaphthalene, cyclohexylbenzene, 1,3, 5-trimethylbenzene cyclohexylbenzene, 1-chloronaphthalene, 1-tetralone, 3-phenoxytoluene, p-xylene, p-diisopropylbenzene, pentylbenzene, dipentylbenzene, dodecylbenzene, tetrahydronaphthalene, cyclohexylbenzene, 1, 1-methoxynaphthalene, dimethylnaphthalene, 3-isopropylbiphenyl, 1,2, 4-trimethylbenzenebiphenyl, benzyl benzoate, benzyl ether, benzyl benzoate, indene, benzylbenzene, divinylbenzene, indane, styrene oxide, and the like, or any mixture thereof.
According to a preferred embodiment of the present application, the perovskite quantum dots have the general structural formula ABX3Wherein a is at least one monovalent organic cation, at least one monovalent inorganic cation, or any combination thereof; b is at least one divalent inorganic cation; x is at least one monovalent anion.
In a specific embodiment, a is Rb+、Cs+、(R4R5R6R7N)+Or (R)4R5N=C(R6)-NR7R8)+Wherein R is4To R8Each independently selected from hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxy, substituted or unsubstituted C1-C60Alkyl, substituted or unsubstituted C2-C60Alkenyl, substituted or unsubstituted C2-C60Alkynyl, substituted or unsubstituted C1-C60Alkoxy, substituted or unsubstituted C6-C60And (4) an aryl group.
In a particular embodiment, B may be one divalent inorganic cation or a combination of at least two different divalent inorganic cations. Further, B may be a divalent cation of a rare earth metal, a divalent cation of an alkaline earth metal, a divalent cation of a transition metal, a divalent cation of a late transition metal, or any combination thereof. For example, B can be Pb2+、Ge2+、Sn2+At least one of (1). However, the exemplary embodiments of the present application are not limited thereto.
In a particular embodiment, X may be one monovalent anion or a combination of at least two different monovalent anions. Further, X may be at least one of halide anions, for example, X may be F-、Cl-、Br-Or I-. Alternatively, X can be at least one halide anion or a combination of at least two different halide anions. However, the exemplary embodiments of the present application are not limited thereto.
According to a preferred embodiment of the present application, the molar mass ratio of perovskite quantum dots to the additive is in the range of 1: (0.01-100). The inventors found that the molar mass ratio between the perovskite quantum dots and the additive was in the range of 1: (0.01-100), the perovskite quantum dots have better solubility in the dispersion liquid, so that the perovskite quantum dots are not easy to precipitate in the dispersion system, and the precipitation phenomenon of the perovskite quantum dots in the dispersion liquid is effectively inhibited.
In a specific embodiment, the molar mass ratio of perovskite quantum dots to the additive is in the range of 1: (0.1-10).
Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. However, they are exemplary embodiments of the present invention, and the present invention is not limited thereto.
Example 1
A perovskite quantum dot dispersion comprising:
dispersion liquid: 50mL of toluene solvent;
perovskite quantum dots: 0.1mmol of CsPbBr3Quantum dots;
additive: 0.05mmol of N, N-dimethyldecylamine.
Wherein the molar mass ratio of the perovskite quantum dots to the additive is 2: 1.
Example 2
A perovskite quantum dot dispersion comprising:
dispersion liquid: 50mL of a mixed solvent of 1-methylundecane and cyclohexylbenzene, wherein the volume ratio of the 1-methylundecane to the cyclohexylbenzene is 4: 1;
perovskite quantum dots: 0.1mmol of CH3NH3PbBr3Quantum dots;
additive: 0.1mmol of triethylamine.
Wherein the molar mass ratio of the perovskite quantum dots to the additive is 1: 1.
Example 3
A perovskite quantum dot dispersion comprising:
dispersion liquid: 30mL of ultraviolet curing adhesive;
perovskite quantum dots: 0.2mmol of CH3NH3PbI3Quantum dots;
additive: 0.4mmol of trioctylamine.
Wherein the molar mass ratio of the perovskite quantum dots to the additive is 1: 2.
Example 4
A perovskite quantum dot dispersion comprising:
dispersion liquid: 50mL of a mixed solvent of 1-methylundecane and propylene glycol methyl ether acetate, wherein the volume ratio of the 1-methylundecane to the propylene glycol methyl ether acetate is 1: 4;
perovskite quantum dots: 0.2mmol of CsPbI3Quantum dots;
additive: 1.0mmol of N, N-dimethyldecylamine.
Wherein the molar mass ratio of the perovskite quantum dots to the additive is 1: 5.
Example 5
A perovskite quantum dot dispersion comprising:
dispersion liquid: 30mL of tripropylene glycol diacrylate;
perovskite quantum dots: 0.1mmol of CsPbCl3Quantum dots;
additive: 0.01mmol of triethylamine.
Wherein the molar mass ratio of the perovskite quantum dots to the additive is 10: 1.
Comparative example 1
A perovskite quantum dot dispersion comprising:
dispersion liquid: 50mL of a mixed solvent of 1-methylundecane and cyclohexylbenzene, wherein the volume ratio of the 1-methylundecane to the cyclohexylbenzene is 4: 1;
perovskite quantum dots: 0.1mmol of CH3NH3PbBr3And (4) quantum dots.
Comparative example 2
A perovskite quantum dot dispersion comprising:
dispersion liquid: 50mL of toluene solvent;
perovskite quantum dots: 0.1mmol of CsPbBr3And (4) quantum dots.
Comparative example 3
A perovskite quantum dot dispersion comprising:
dispersion liquid: 30mL of ultraviolet curing adhesive;
perovskite quantum dots: 0.2mmol of CH3NH3PbI3And (4) quantum dots.
Comparative example 4
A perovskite quantum dot dispersion comprising:
dispersion liquid: 50mL of a mixed solvent of 1-methylundecane and propylene glycol methyl ether acetate, wherein the volume ratio of the 1-methylundecane to the propylene glycol methyl ether acetate is 1: 4;
perovskite quantum dots: 0.2mmol of CsPbI3And (4) quantum dots.
Comparative example 5
A perovskite quantum dot dispersion comprising:
dispersion liquid: 30mL of tripropylene glycol diacrylate;
perovskite quantum dots: 0.1mmol of CsPbCl3And (4) quantum dots.
In order to test the dispersion stability of the quantum dots in the perovskite quantum dot dispersion systems of examples 1 to 5 and comparative examples 1 to 5, after the perovskite quantum dot dispersion systems were prepared, each perovskite quantum dot dispersion system was left at normal temperature for 24 hours, and whether the quantum dots in each perovskite quantum dot dispersion system precipitated or not was evaluated, and the results are shown in the following table.
Whether or not there is a precipitate Whether or not there is a precipitate
Example 1 Whether or not Comparative example 1 Is that
Example 2 Whether or not Comparative example 2 Is that
Example 3 Whether or not Comparative example 3 Is that
Example 4 Whether or not Comparative example 4 Is that
Example 5 Whether or not Comparative example 5 Is that
As can be seen from the table, the perovskite quantum dot dispersion systems in examples 1 to 5 of the present invention have no precipitation, while the perovskite quantum dot dispersion systems in comparative examples 1 to 5 have precipitation, so that the addition of the additive to the perovskite quantum dot dispersion system in this embodiment can provide good compatibility and dispersion stability to the perovskite quantum dot dispersion liquid.
Although the present disclosure has been described and illustrated in greater detail by the inventors, it should be understood that modifications and/or alterations to the above-described embodiments, or equivalent substitutions, will be apparent to those skilled in the art without departing from the spirit of the disclosure, and that no limitations to the present disclosure are intended or should be inferred therefrom.

Claims (10)

1. A perovskite quantum dot dispersion comprising:
a dispersion liquid;
perovskite quantum dots dispersed in the dispersion liquid;
an additive dispersed in the dispersion; the additive has a chemical formula of
Wherein,
R1、R2each is independentA vertical alkane chain selected from C1-C20, R3Is selected from C2-C20 alkane chains.
2. The perovskite quantum dot dispersion system of claim 1, wherein R is R1、R2Each independently selected from linear alkanes of C1-C20, R3Is selected from linear alkanes of C2-C20.
3. The perovskite quantum dot dispersion system of claim 1, wherein the additive comprises at least one of triethylamine, tributylamine, trihexylamine, triheptylamine, trioctylamine, N-dimethyldecylamine, N-dimethyldodecylamine, N-dimethyltetradecylamine, N-dimethylhexadecylamine.
4. The perovskite quantum dot dispersion system of claim 1, wherein the dispersion comprises at least one of a polymeric resin, a monomer, a monomeric resin, an ultraviolet light curable glue, and a heat curable glue.
5. The perovskite quantum dot dispersion system of claim 1, wherein the dispersion comprises an organic solvent comprising at least one of an alkane solvent, an aromatic solvent, an ester solvent.
6. The perovskite quantum dot dispersion system of claim 5, wherein the alkane solvent comprises a branched or straight chain saturated aliphatic organic solvent CnH2n+2Or naphthenic organic solvents CmH2mWherein n and m are positive integers, n is more than or equal to 6 and m is less than or equal to 18.
7. The perovskite quantum dot dispersion system of claim 1, wherein the perovskite quantum dot has a general structural formula of ABX3Wherein
a is at least one monovalent organic cation, at least one monovalent inorganic cation, or any combination thereof;
b is at least one divalent inorganic cation;
x is at least one monovalent anion.
8. The perovskite quantum dot dispersion system of claim 7, wherein A is Rb+、Cs+、(R4R5R6R7N)+Or (R)4R5N=C(R6)-NR7R8)+At least one of;
b is Pb2+、Ge2+、Sn2+At least one of;
x is at least one of halogen anions.
9. The perovskite quantum dot dispersion system of claim 1, wherein the molar mass ratio of the perovskite quantum dots to the additive is in the range of 1: (0.01-100).
10. The perovskite quantum dot dispersion system of claim 1, wherein the molar mass ratio of the perovskite quantum dots to the additive is in the range of 1: (0.1-10).
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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN113150768A (en) * 2020-01-07 2021-07-23 纳晶科技股份有限公司 Perovskite quantum dot and preparation method thereof, quantum dot composition and quantum dot device

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CN108091763A (en) * 2017-12-12 2018-05-29 南方科技大学 Quantum dot dispersion liquid, preparation method thereof and photoelectric detector comprising quantum dot dispersion liquid
CN108893104A (en) * 2018-07-13 2018-11-27 深圳信息职业技术学院 Composite perofskite quantum dot and preparation method thereof based on allyl based quaternary ammonium salt ligand
CN109651887A (en) * 2018-11-15 2019-04-19 苏州星烁纳米科技有限公司 Perovskite quantum dot ink and luminescent film

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Publication number Priority date Publication date Assignee Title
CN107489898A (en) * 2016-06-09 2017-12-19 三星显示有限公司 Luminaire with light conversion layer
CN108091763A (en) * 2017-12-12 2018-05-29 南方科技大学 Quantum dot dispersion liquid, preparation method thereof and photoelectric detector comprising quantum dot dispersion liquid
CN108893104A (en) * 2018-07-13 2018-11-27 深圳信息职业技术学院 Composite perofskite quantum dot and preparation method thereof based on allyl based quaternary ammonium salt ligand
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Publication number Priority date Publication date Assignee Title
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