CN110467918A - Quantum dot and preparation method thereof - Google Patents

Quantum dot and preparation method thereof Download PDF

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Publication number
CN110467918A
CN110467918A CN201910718464.9A CN201910718464A CN110467918A CN 110467918 A CN110467918 A CN 110467918A CN 201910718464 A CN201910718464 A CN 201910718464A CN 110467918 A CN110467918 A CN 110467918A
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Prior art keywords
quantum dot
ligand
group
application
dispersion
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CN201910718464.9A
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Chinese (zh)
Inventor
邢泽咏
刘思锦
厉芙伶
王允军
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Suzhou Xingshuo Nanotech Co Ltd
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Suzhou Xingshuo Nanotech Co Ltd
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Priority to CN201910718464.9A priority Critical patent/CN110467918A/en
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
    • C09K11/664—Halogenides
    • C09K11/665—Halogenides with alkali or alkaline earth metals

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

Abstract

This application discloses a kind of quantum dots, are combined with ligand thereon, wherein ligand has R group, and R group is selected from least one of ester group, epoxy group, amide groups, fragrant ring group.The ligand with R group is combined on the quantum dot of the application, so that quantum dot dissolubility with higher, so that the intermiscibility with dispersion is good, and quantum dot is not susceptible to heavy poly-, more conducively subsequent applications use in dispersion.

Description

Quantum dot and preparation method thereof
Technical field
The application belongs to field of nanometer material technology more particularly to a kind of quantum dot and preparation method thereof.
Background technique
Quantum dot has the easily tuning that shines, the excellent optical property such as the spectral line of emission is narrow, quantum efficiency is high, in recent years by The extensive concern of academia and industrial circle.
The dissolubility of the quantum dot of the prior art is simultaneously bad, and the concentration in dispersion is often all relatively low, dispersion Stability is also bad, places to be easy to happen to sink for a long time and gather, is highly detrimental to subsequent applications.
Summary of the invention
In view of the above technical problems, the application provides a kind of with ligand modified quantum dot, in dispersion Dissolution dispersity is good, is conducive to subsequent applications and uses.
According to the one aspect of the application, a kind of quantum dot is provided, is combined with ligand thereon, the ligand has R base Group, the R group are selected from least one of ester group, epoxy group, amide groups, fragrant ring group.
Further, the boiling point of the ligand is not less than 120 DEG C.
Further, the ligand is sour ligand.
Further, the ligand is amine ligand.
Further, the ligand is sour ligand and amine ligand.
Further, the quantum dot is perovskite quantum dot.
Further, the general structure of the perovskite quantum dot is ABX3, wherein A is at least one organic sun of unit price Ion, at least one monovalent inorganic cation or any combination thereof；B is at least one divalent inorganic cations；X is at least one Monovalent anion.
Further, by percentage to the quality, the ligand accounts for the 5~60% of the gross mass of the quantum dot.
Further, by percentage to the quality, the ligand accounts for the 8~30% of the gross mass of the quantum dot.
According to further aspect of the application, a kind of preparation method of quantum dot is provided, comprising steps of in predetermined temperature Under, it mixes the precursor for synthesizing quantum dot with ligand, obtains the ligand modified quantum dot, wherein the ligand has R base Group, the R group are selected from least one of ester group, epoxy group, amide groups, fragrant ring group.
According to the above aspect of the present invention, the beneficial effects of the present application are as follows:
The ligand with R group is combined on the quantum dot of the application, wherein R group is selected from ester group, epoxy group, amide At least one of base, fragrant ring group, quantum dot dissolubility with higher so that the intermiscibility with dispersion is good, and are measured Son point is not susceptible to heavy poly-, more conducively subsequent applications use in dispersion.
The preparation method of the application quantum dot is simple, technique is controllable, meets the needs of large-scale production.
Specific embodiment
Below in conjunction with the application embodiment, technical solutions in the embodiments of the present application is described in detail.It answers It is noted that described embodiment is only a part of embodiment of the application, rather than whole embodiments.
The application provides firstly a kind of quantum dot, is combined with ligand thereon, which has R group, and R group is selected from ester At least one of base, epoxy group, amide groups, fragrant ring group.
According to a kind of preferred embodiment of the application, the boiling point of ligand is not less than 120 DEG C.
In a preferred embodiment of the present application, the boiling point of ligand is not less than 180 DEG C.
According to a kind of preferred embodiment of the application, ligand is sour ligand, has R group thereon, and R group is selected from ester At least one of base, epoxy group, amide groups, fragrant ring group.
In a preferred embodiment of the present application, ligand is selected from monoethyl malonate, single-ethyl succinate, 2,2- diformazan Propylmalonic acid mono ethyl ester, 2,2- dimethyl malonic acid mono-methyl, glycidic acid, 3- propylene oxide carboxylic acid, succinamic acid, Malaysia acyl At least one of amino acid, oxamic acid, benzoic acid.
According to a kind of preferred embodiment of the application, ligand is amine ligand, has R group thereon, and R group is selected from ester At least one of base, epoxy group, amide groups, fragrant ring group.
In a preferred embodiment of the present application, ligand is selected from 3- oxa- ring butylamine, 3- amine Ethyloxetane, 2- At least one of oxetanes methylamine, glycine methyl ester, aniline.
According to a kind of preferred embodiment of the application, ligand is sour ligand and amine ligand, on sour ligand and amine ligand all With R group, R group is selected from least one of ester group, epoxy group, amide groups, fragrant ring group.
In this application, inventors have found that combining the ligand with R group over the qds, under the action of the ligand, Quantum dot can show good dissolution dispersity in dispersion, so that the intermiscibility of quantum dot and dispersion is good, Thus the problem of quantum dot dissolution dispersity difference in dispersion is overcome.
According to a kind of preferred embodiment of the application, quantum dot is perovskite quantum dot.
In the prior art, perovskite quantum dot is generally directly dispersing in toluene system, dispersion concentration about 5% or so, The perovskite quantum dot solution of this lower dispersion concentration is ineffective in subsequent applications.For example, using the perovskite When quantum dot solution carries out inkjet printing and prepares perovskite quantum dot film, the light conversion efficiency of film is low, and emitting brightness is low.At this In application, inventors have found that combining the ligand of the application on perovskite quantum dot, perovskite can be largely improved The dispersion concentration of quantum dot, and be long placed in rear perovskite quantum dot will not occur it is heavy poly-.
According to a kind of preferred embodiment of the application, the general structure of perovskite quantum dot is ABX3, wherein A is extremely A kind of few monovalent organic cation, at least one monovalent inorganic cation or any combination thereof；B is at least one divalent inorganic sun Ion；X is at least one monovalent anion.
In a preferred embodiment of the present application, A Rb+、Cs+、(R4R5R6R7N)+Or (R4R5N=C (R6)- NR7R8)+At least one of, wherein R4To R8It is each independently selected from hydrogen, deuterium ,-F ,-Cl ,-Br ,-I, hydroxyl, substitution or not Substituted C1-C60Alkyl, substituted or unsubstituted C2-C60Alkenyl, substituted or unsubstituted C2-C60It is alkynyl, substituted or unsubstituted C1-C60Alkoxy, substituted or unsubstituted C6-C60Aryl.
In a preferred embodiment of the present application, B can be a kind of divalent inorganic cations or at least two different two The combination of valence inorganic cation.Further, B can be the bivalent cation of rare earth metal, the bivalent cation of alkaline-earth metal, mistake Cross the bivalent cation of metal, the bivalent cation of late transition metal, or any combination thereof.For example, B can be Pb2+、Ge2+、Sn2+ At least one of.
In a preferred embodiment of the present application, X can be a kind of monovalent anion or at least two different unit price yin The combination of ion.Further, X can be at least one of halide anion, for example, X can be F-、Cl-、Br-Or I-.Alternatively, X can be the combination of at least one halide anion or at least two different halide anions.
In a specific embodiment, perovskite quantum dot is selected from CH3NH3PbI3、CH3NH3PbBr3、CH3NH3PbCl3、 CH3NH3PbIBr2、CH3NH3PbI2Br、CH3NH3PbBrCl2、CH3NH3PbBr2Cl、[CH(NH2)2]PbI3、[CH(NH2)2] PbBr3、[CH(NH2)2]PbCl3、[CH(NH2)2]PbIBr2、[CH(NH2)2]PbI2Br、[CH(NH2)2]PbBrCl2、[CH (NH2)2]PbBr2Cl、CsPbI3、CsPbBr3、CsPbCl3、RbPbI3、RbPbBr3、RbPbCl3、CsPbIBr2、CsPbI2Br、 CsPbBrCl2、CsPbBr2At least one of Cl.
In a preferred embodiment of the present application, perovskite quantum dot is core-shell structure, specifically includes perovskite quantum The core of point and the shell of the perovskite quantum dot different from core.
According to a kind of preferred embodiment of the application, by percentage to the quality, ligand account for the gross mass of quantum dot 5~ 60%.
In this application, inventors have found that quantum dot has in dispersion when ligand is within the scope of aforementioned proportion Preferable dissolubility, quantum dot is not easy to generate precipitating in dispersion, to effectively inhibit quantum dot in dispersion Sink poly- phenomenon.
In a preferred embodiment of the present application, by percentage to the quality, ligand account for the gross mass of quantum dot 8~ 30%.
Present invention also provides a kind of preparation methods of quantum dot, comprising steps of making to synthesize quantum dot under predetermined temperature Precursor mixed with ligand, obtain ligand modified quantum dot, wherein ligand have R group, R group be selected from ester group, epoxy At least one of base, amide groups, fragrant ring group.
According to a kind of preferred embodiment of the application, the range of predetermined temperature is at 120~280 DEG C.
Hereinafter, embodiments of the present invention are described in more detail referring to embodiment.However, they are of the invention show Example property embodiment, and the invention is not limited thereto.
Embodiment 1
Quantum dot, is combined with ligand thereon, and ligand is 3- oxa- ring butylamine.
Wherein, quantum dot CsPbCl3Quantum dot, ligand account for the 10% of quantum dot gross mass.
Embodiment 2
Quantum dot, is combined with ligand thereon, and ligand is monomethyl succinate.
Wherein, quantum dot CH3NH3PbBr3Quantum dot, ligand account for the 20% of quantum dot gross mass.
Embodiment 3
Quantum dot, is combined with ligand thereon, and ligand includes oleic acid and aniline.
Wherein, quantum dot CsPbBr3Quantum dot, ligand account for the 20% of quantum dot gross mass.
Embodiment 4
Quantum dot, is combined with ligand thereon, and ligand includes 2,2- dimethyl malonic acid mono ethyl ester and 2- oxetanes first Amine.
Wherein, quantum dot CsPbBr3Quantum dot, ligand account for the 25% of quantum dot gross mass.
Comparative example 1
Quantum dot, is combined with ligand thereon, and ligand includes oleic acid.
Wherein, quantum dot CsPbBr3Quantum dot, ligand account for the 10% of quantum dot gross mass.
Comparative example 2
Quantum dot, is combined with ligand thereon, and ligand includes oleic acid and oleyl amine.
Wherein, quantum dot CH3NH3PbBr3Quantum dot, ligand account for the 30% of quantum dot gross mass.
Test characterization
Example 1 is dispersed in respectively to each 0.2mmol of quantum dot in embodiment 4, comparative example 1, comparative example 2 In the toluene solution of 50mL, quantum dot dispersion is obtained.To quantum dot in each quantum dot dispersion with the presence or absence of precipitating It is evaluated, the results listed in the following table.
In order in testing example 1 to embodiment 4, comparative example 1, comparative example 2 in quantum dot dispersion quantum dot point Stability is dissipated, above-mentioned quantum dot dispersion is stood into 120h under room temperature, is to quantum dot in each quantum dot dispersion No to be evaluated again in the presence of precipitating, the results listed in the following table.
As seen from the table, the embodiment of the present invention 1 does not occur before and after standing to the quantum dot dispersion in embodiment 4 Precipitating, and there is precipitating after standing 120h in the quantum dot dispersion of comparative example 1, comparative example 2, to illustrate the application reality It applies mode and combines the ligand with R group over the qds, can make quantum dot that there is higher dissolubility, thus in dispersion Good intermiscibility and dispersion stabilization are shown in system.
Although inventor has done more detailed elaboration to the technical solution of the application and has enumerated, it should be understood that for For those skilled in the art, above-described embodiment is modified and/or the flexible or equivalent alternative solution of use is obvious , cannot all be detached from the essence of the application spirit, the term occurred in the application be used for elaboration to technical scheme and Understand, the limitation to the application can not be constituted.

Claims (10)

1. a kind of quantum dot, ligand is combined on the quantum dot, which is characterized in that the ligand has R group, the R base Group is selected from least one of ester group, epoxy group, amide groups, fragrant ring group.
2. quantum dot according to claim 1, which is characterized in that the boiling point of the ligand is not less than 120 DEG C.
3. quantum dot according to claim 1, which is characterized in that the ligand is sour ligand.
4. quantum dot according to claim 1, which is characterized in that the ligand is amine ligand.
5. quantum dot according to claim 1, which is characterized in that the ligand is sour ligand and amine ligand.
6. quantum dot according to claim 1, which is characterized in that the quantum dot is perovskite quantum dot.
7. quantum dot according to claim 6, which is characterized in that the general structure of the perovskite quantum dot is ABX3, In,
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 cations；
X is at least one monovalent anion.
8. quantum dot according to claim 1, which is characterized in that by percentage to the quality, the ligand accounts for the quantum The 5~60% of the gross mass of point.
9. quantum dot according to claim 8, which is characterized in that by percentage to the quality, the ligand accounts for the quantum The 8~30% of the gross mass of point.
10. a kind of preparation method of quantum dot, which is characterized in that comprising steps of making before synthesizing quantum dot under predetermined temperature Body is mixed with ligand, obtains the ligand modified quantum dot；
Wherein, the ligand has a R group, the R group in ester group, epoxy group, amide groups, fragrant ring group at least one Kind.
CN201910718464.9A 2019-08-05 2019-08-05 Quantum dot and preparation method thereof Withdrawn CN110467918A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113088275A (en) * 2021-03-05 2021-07-09 苏州星烁纳米科技有限公司 Quantum dot, quantum dot composition, quantum dot color film prepared from quantum dot composition and display device
WO2023050214A1 (en) * 2021-09-29 2023-04-06 京东方科技集团股份有限公司 Quantum dot ligand, quantum dot-ligand system, and quantum dot material

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113088275A (en) * 2021-03-05 2021-07-09 苏州星烁纳米科技有限公司 Quantum dot, quantum dot composition, quantum dot color film prepared from quantum dot composition and display device
WO2023050214A1 (en) * 2021-09-29 2023-04-06 京东方科技集团股份有限公司 Quantum dot ligand, quantum dot-ligand system, and quantum dot material

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