CN108587598B - Quantum dot dispersion system - Google Patents

Quantum dot dispersion system Download PDF

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CN108587598B
CN108587598B CN201810244619.5A CN201810244619A CN108587598B CN 108587598 B CN108587598 B CN 108587598B CN 201810244619 A CN201810244619 A CN 201810244619A CN 108587598 B CN108587598 B CN 108587598B
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quantum dot
ligand
group
protective layer
dispersion system
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CN108587598A (en
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李鑫
王允军
宋研君
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Suzhou Xingshuo Nanotech Co Ltd
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Suzhou Xingshuo Nanotech Co Ltd
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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
    • C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
    • C09K11/562—Chalcogenides
    • C09K11/565—Chalcogenides with zinc 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, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
    • 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
    • C09K11/881—Chalcogenides
    • C09K11/883—Chalcogenides with zinc or cadmium

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Abstract

The invention relates to a quantum dot dispersion system. The quantum dot dispersion system comprises: the quantum dot comprises a body, a protective layer formed on the outer surface of the body, and a first ligand connected to the protective layer, wherein the first ligand is provided with a first group connected with the protective layer and a second group having affinity with the nonpolar organic solvent. In the quantum dot dispersion system, the quantum dots not only have good stability, but also can be dissolved in common nonpolar organic solvents, so that the quantum dots can be well used.

Description

Quantum dot dispersion system
Technical Field
The application belongs to the technical field of quantum dots, and particularly relates to a quantum dot dispersion system.
Background
Quantum dots, also known as semiconductor nanocrystals, have very narrow half-peak widths of their emission spectra, and thus have very broad applications in the fields of electroluminescence, photoluminescence, and biomarkers.
The quantum dot composite is generally formed by coating a protective layer (e.g., aluminum hydroxide) on the surface of the quantum dot, whereby the stability of the quantum dot can be improved. However, the quantum dot coated with aluminum hydroxide is insoluble in common organic solvents such as toluene, liquid alkane, etc., which makes it difficult to use such quantum dot well.
Disclosure of Invention
In view of the above technical problems, the present application provides a quantum dot dispersion system. In the quantum dot dispersion system, the quantum dots not only have the protective layer, but also are connected with groups which are compatible with a nonpolar organic solvent, so that the quantum dots not only have good stability, but also can be dissolved in a common nonpolar organic solvent, and thus the quantum dots can be well used.
The quantum dot dispersion according to the present application comprises: a non-polar organic solvent, and quantum dots dispersed in the non-polar organic solvent. The quantum dot comprises a body, a protective layer formed on the outer surface of the body, and a first ligand connected to the protective layer. The first ligand has a first group attached to the protective layer and a second group that is compatible with the non-polar organic solvent.
The protective layer can protect the quantum dots, and the first ligand has the second group which is compatible with the nonpolar organic solvent, so that the quantum dots not only have good stability, but also can be dissolved in the common nonpolar organic solvent, and the quantum dots can be well used.
In one embodiment, the protective layer is aluminum hydroxide. In another embodiment, the first group is a carboxyl group or an amino group. The inventors have surprisingly found that stable linkage can be rapidly formed between carboxyl or amino groups and aluminium hydroxide, and that such linkage can be formed without the need for heat, special catalysts, extreme acidity and basicity, which enables rapid automatic attachment of ligands to quantum dots even when ligands containing carboxyl or amino groups are added directly to dispersions containing quantum dots, which greatly simplifies experimental operations.
In one embodiment, the second group is an aliphatic hydrocarbon group of C6-C22.
In a preferred embodiment, the aliphatic hydrocarbon group further has a substituent group which is a substituted or unsubstituted alicyclic hydrocarbon group of C4-C22, and/or a substituted or unsubstituted aromatic hydrocarbon group of C6-C22.
In the present application, the term "substituted" refers to a compound, group or moiety wherein at least one of its hydrogen atoms is replaced by a substituent selected from the group consisting of: C1-C30 alkyl, C2-C30 alkynyl, C6-C30 aryl, C7-C30 alkylaryl, C1-C30 alkoxy, C1-C30 heteroalkyl, C3-C30 heteroalkylaryl, C3-C30 cycloalkyl, C3-C15 cycloalkenyl, C6-C30 cycloalkynyl, C2-C30 heterocycloalkyl, halogen (-F, -Cl, -Br, or-I), aldehyde (-C (═ O) H), carbamoyl (-C) NH (O)2) An ester group (-C (═ O) OR, where R is a C1-C6 alkyl group OR a C6-C12 aryl group), and combinations thereof.
The term "substituted" may also refer to compounds, groups or moieties wherein at least one of its hydrogen atoms is replaced by a substituent selected from the group consisting of: hydroxyl (-OH), amino (-NRR ', wherein R and R' are independently hydrogen or C1-C6 alkyl), thiol (-SH), carboxylic acid (-COOH) or its salt (-C (═ O) OM, wherein M is an organic or inorganic cation), sulfonic acid (-SO), or its salt3H) Or a salt thereof (-SO)3M, wherein M is an organic or inorganic cation), a phosphate group (-PO)3H2) Or a salt thereof (-PO)3MH or-PO3M2Where M is an organic or inorganic cation), and combinations thereof.
The substitution pattern of these substituents, the number of substituents, is well known to those skilled in the art to ensure the affinity of the second group for non-polar organic solvents.
In a more preferred embodiment, the first ligand is oleic acid or oleylamine.
In one embodiment, the non-polar organic solvent is toluene or a liquid alkane.
In one embodiment, the content of the quantum dots is 1.2% to 3.6% by mass, the content of the first ligand is 2% to 4% by mass, and the balance is the non-polar organic solvent. It is generally believed that the greater the amount of first ligand, the more favorable the quantum dot is for dissolution in the non-polar solvent. However, the inventors have surprisingly found that in the solution of the present application, the content of the first ligand in the quantum dot dispersion is not linearly related to the solubility of the quantum dot in the dispersion. When the content of the quantum dots is 1.2-3.6% by mass and the content of the first ligand is less than 2% by mass, part of the quantum dots cannot be dissolved; and when the content of the first ligand is more than 4%, partial quantum dots are separated out. And when the content of the quantum dots is 1.2-3.6% by mass, the content of the first ligand is 2-4% by mass and the balance is the nonpolar organic solvent, the quantum dots can be stably dissolved in the nonpolar solvent, so that a stable quantum dot dispersion system is formed.
In one embodiment, the surface of the body is further coupled with a second ligand, and the protective layer covers the second ligand. In one embodiment, the second ligand is one or more of oleic acid, oleylamine, thiol, trioctylphosphine. In the case of synthesized quantum dots, a ligand (equivalent to the second ligand in the present application) is generally attached to the surface thereof so that the quantum dots can be stably dispersed or dissolved in a solvent. In the scheme of the present application, even if the second ligand is present, the protective layer and the first ligand are not adversely affected, thereby greatly simplifying the preparation of the quantum dot dispersion system of the present application.
Compared with the prior art, the application has the advantages that: the protective layer of the quantum dot can protect the quantum dot, and the first ligand has the second group which is compatible with the nonpolar organic solvent, so that the quantum dot not only has good stability, but also can be dissolved in the common nonpolar organic solvent, and the quantum dot can be well used.
Drawings
FIG. 1a is a TEM photograph of a sample of example 1;
FIG. 1b is the emission spectra of the quantum dots of example 1 before and after dissolution;
FIG. 2a is a TEM photograph of a sample of example 2;
fig. 2b is the emission spectra of the quantum dots of example 2 before and after dissolution;
FIG. 3a is a TEM photograph of a sample of example 3;
fig. 3b is the emission spectra of the quantum dots of example 3 before and after dissolution;
FIG. 4a is a TEM photograph of a sample of example 3; and
fig. 4b is the emission spectra of the quantum dots of example 4 before and after dissolution.
In the drawings like parts are provided with the same reference numerals. The figures show embodiments of the application only schematically.
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.
Example 1:
selecting 120mg of quantum dot composite CdSe/Al (OH)3I.e., CdSe as a bulk and Al (OH) as a protective layer3. The second ligand is oleic acid. The nonpolar organic solvent is toluene, the volume is 5 ml. The quantum dot composite and toluene are mixed to form a first mixed system. At this time, the quantum dot complex exists in the form of a precipitate in toluene.
And adding 200 mu L of oleic acid into the first mixed system, and dissolving the quantum dot composite to form a stable quantum dot dispersion system after simple shaking. A TEM photograph was taken of the quantum dots in the quantum dot dispersion, as in fig. 1 a. In FIG. 1a, the dark portion 11 is the bulk of the quantum dot and the light portion 12 is the protective layer Al (OH)3。
The emission spectra (i.e., PL) of the quantum dot complexes before and after dissolution were also tested using fluorescence spectroscopy, as shown in fig. 1 b. In fig. 1b, curve 13 is the emission spectrum of the quantum dot composite before dissolution, and curve 14 is the emission spectrum of the quantum dot composite after dissolution. As can be seen from fig. 1b, the emission spectrum hardly changes before and after the dissolution of the quantum dot complex, thereby facilitating the use of the quantum dots.
Example 2:
selecting 72mg quantum dot composite InP/Al (OH)3I.e., InP as a bulk and Al (OH) as a protective layer3. The second ligand is n-dodecyl mercaptan. The non-polar organic solvent is n-octane, the volume of which is 6 ml. And mixing the quantum dot composite and n-octane to form a first mixed system. At this time, the quantum dot complex exists as a precipitate in n-octane.
And adding 120 mu L of oleic acid into the first mixed system, and dissolving the quantum dot composite to form a stable quantum dot dispersion system after simple shaking. A TEM photograph was taken of the quantum dots in the quantum dot dispersion, as in fig. 2 a. In FIG. 2a, the dark portion 21 is the bulk of the quantum dot and the light portion 22 is the protective layer Al (OH)3。
The emission spectra (i.e., PL) of the quantum dot complexes before and after dissolution were also tested using fluorescence spectroscopy, as shown in fig. 2 b. In fig. 2b, curve 23 is the emission spectrum of the quantum dot composite before dissolution and curve 24 is the emission spectrum of the quantum dot composite after dissolution. As can be seen from fig. 2b, the emission spectrum hardly changes before and after the dissolution of the quantum dot complex, thereby facilitating the use of the quantum dots.
Example 3:
selecting 48mg quantum dot composite CdS/Al (OH)3That is, the body is CdS and the protective layer is Al (OH)3. The second ligand is oleylamine. The nonpolar organic solvent was chloroform, and the volume was 4 ml. The quantum dot composite and chloroform are mixed to form a first mixed system. At this time, the quantum dot complex exists as a precipitate in chloroform.
And adding 80 mu L of oleylamine into the first mixed system, and dissolving the quantum dot composite to form a stable quantum dot dispersion system after simple shaking. A TEM photograph was taken of the quantum dots in the quantum dot dispersion, as in fig. 3 a. In FIG. 3a, the dark portion 31 is the bulk of the quantum dot and the light portion 32 is the protective layer Al (OH)3。
The emission spectra (i.e., PL) of the quantum dot complexes before and after dissolution were also tested using fluorescence spectroscopy, as shown in fig. 3 b. In fig. 3b, curve 33 is the emission spectrum of the quantum dot composite before dissolution and curve 34 is the emission spectrum of the quantum dot composite after dissolution. As can be seen from fig. 3b, the emission spectrum hardly changes before and after the dissolution of the quantum dot complex, thereby facilitating the use of the quantum dots.
Example 4:
144mg of quantum dot composite ZnSe/Al (OH) is selected3That is, the main body is ZnSe, the protective layer is Al (OH)3. The second ligand is trioctyloxyphosphine. The nonpolar organic solvent was n-heptane, a volume of 4 ml. The quantum dot composite and n-heptane are mixed to form a first mixed system. At this time, the quantum dot complex exists as a precipitate in n-heptane.
160 mu L oleylamine is added into the first mixed system, and after simple shaking, the quantum dot compound is dissolved to form stable quantumA dot dispersion system. A TEM photograph was taken of the quantum dots in the quantum dot dispersion, as in fig. 4 a. In FIG. 4a, dark portions 41 are the bulk of the quantum dots and light portions 42 are the protective layers Al (OH)3。
The emission spectra (i.e., PL) of the quantum dot complexes before and after dissolution were also tested using fluorescence spectroscopy, as shown in fig. 4 b. In fig. 4b, curve 43 is the emission spectrum of the quantum dot composite before dissolution, and curve 44 is the emission spectrum of the quantum dot composite after dissolution. As can be seen from fig. 4b, the emission spectrum hardly changes before and after the dissolution of the quantum dot complex, thereby facilitating the use of the quantum dots.
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 (6)

1. A quantum dot dispersion comprising: a non-polar organic solvent, and quantum dots dispersed in the non-polar organic solvent,
the quantum dot comprises a body, a protective layer formed on the outer surface of the body, and a first ligand connected to the protective layer,
the first ligand is provided with a first group connected with the protective layer and a second group having affinity with the nonpolar organic solvent, the protective layer is aluminum hydroxide, the first group is carboxyl or amino,
the surface of the body is also connected with a second ligand, the protective layer covers the second ligand, and the second ligand is one or more of oleic acid, oleylamine, mercaptan, trioctylphosphine and trioctylphosphine.
2. The quantum dot dispersion system of claim 1, wherein the second group is an aliphatic hydrocarbon group of C6-C22.
3. The quantum dot dispersion system according to claim 2, wherein the aliphatic hydrocarbon group further has a substituent group thereon,
the substituent group is a substituted or unsubstituted alicyclic hydrocarbon group of C4-C22 and/or a substituted or unsubstituted aromatic hydrocarbon group of C6-C22.
4. The quantum dot dispersion system according to any one of claims 1 to 3, wherein the first ligand is oleic acid or oleylamine.
5. The quantum dot dispersion system according to any one of claims 1 to 3, wherein the non-polar organic solvent is toluene, chloroform or a liquid alkane.
6. The quantum dot dispersion system according to any one of claims 1 to 3, wherein the content of the quantum dots is 1.2% to 3.6% by mass, the content of the first ligand is 2% to 4% by mass, and the balance is the non-polar organic solvent.
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WO2019161588A1 (en) * 2018-02-22 2019-08-29 苏州星烁纳米科技有限公司 Quantum dot composite, preparation method therefor and quantum dot composite dispersion system
CN111352298B (en) * 2018-12-21 2023-09-01 苏州星烁纳米科技有限公司 Dispersion, photoresist composition, color film substrate and display device
CN111378447B (en) * 2018-12-27 2021-12-14 Tcl科技集团股份有限公司 Post-processing method of quantum dots

Citations (4)

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CN101003732A (en) * 2007-01-12 2007-07-25 中国科学院上海技术物理研究所 Method for preparing hud quant point of semiconductor in II VI families capable of adjusting and controlling wavelength of fluorescence
CN101168663A (en) * 2007-11-30 2008-04-30 中国科学院上海技术物理研究所 Method for preparing cadmium selenide/cadmium sulfide /zinc sulfide core-shell quantum dots
CN103361066A (en) * 2013-06-28 2013-10-23 上海纳米技术及应用国家工程研究中心有限公司 Preparation method for synthesizing CdSe/CdS core-shell structure quantum dots through one step
CN105199735A (en) * 2015-08-31 2015-12-30 江汉大学 Preparing method for solid quantum dots

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101003732A (en) * 2007-01-12 2007-07-25 中国科学院上海技术物理研究所 Method for preparing hud quant point of semiconductor in II VI families capable of adjusting and controlling wavelength of fluorescence
CN101168663A (en) * 2007-11-30 2008-04-30 中国科学院上海技术物理研究所 Method for preparing cadmium selenide/cadmium sulfide /zinc sulfide core-shell quantum dots
CN103361066A (en) * 2013-06-28 2013-10-23 上海纳米技术及应用国家工程研究中心有限公司 Preparation method for synthesizing CdSe/CdS core-shell structure quantum dots through one step
CN105199735A (en) * 2015-08-31 2015-12-30 江汉大学 Preparing method for solid quantum dots

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