CN112391162A - Luminescent material and quantum dot film and preparation method thereof - Google Patents

Luminescent material and quantum dot film and preparation method thereof Download PDF

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CN112391162A
CN112391162A CN201910757313.4A CN201910757313A CN112391162A CN 112391162 A CN112391162 A CN 112391162A CN 201910757313 A CN201910757313 A CN 201910757313A CN 112391162 A CN112391162 A CN 112391162A
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aromatic amine
quantum dot
halogenated aromatic
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聂志文
刘文勇
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TCL Corp
TCL Research America Inc
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Abstract

The invention belongs to the technical field of quantum dots, and particularly relates to a luminescent material, a quantum dot film and a preparation method thereof. The luminescent material comprises quantum dots and halogenated aromatic amine combined on the surfaces of the quantum dots; wherein the halogenated aromatic amine contains unsaturated chain hydrocarbon groups, and halogen elements in the halogenated aromatic amine substitute for hydrogen on an amine group. When the luminescent material is used for the quantum dot light-emitting diode, the quantum dot can be effectively prevented from being influenced by the outside on the premise of improving the conductivity of the quantum dot light-emitting diode due to the large pi bond, the stability of the luminescent material is improved, and therefore the efficiency and the service life of a device are further improved.

Description

Luminescent material and quantum dot film and preparation method thereof
Technical Field
The invention belongs to the technical field of quantum dots, and particularly relates to a luminescent material, a quantum dot film and a preparation method thereof.
Background
Quantum dots, also known as semiconductor nanocrystals, refer to semiconductor nanomaterials having particle sizes that are smaller than or close to the exciton Bohr radius, with the elemental composition typically being II-VI or III-V elements. The preparation method has the advantages of simple preparation, controllable size, narrow half-peak width, high luminous efficiency, good low-temperature solution film preparation and the like, thereby showing excellent optical performance and having wide application prospect in the fields of photoelectric devices, biological imaging, fluorescent labeling and the like. Particularly in the field of optoelectronic devices, for example: the efficiency and life index of alloyed red-green QLED devices represented by II-VI groups tend to be applied in commercialization, which is the firmest step for promoting the wide application of quantum dots in the display field.
Over thirty years of research and development, the synthesis method of the quantum dot tends to mature. High quality quantum dot synthesis processes are typically performed in organic phases, which are mostly long chain ligands, such as: oleic acid, oleylamine, trioctylphosphine and trioctyloxyphosphine, and the like. The existence of the long-chain ligands can control the nucleation and growth process of the quantum dots; meanwhile, agglomeration between adjacent quantum dots can be prevented, and the solubility and the dispersibility of the quantum dots in different solvents are improved. However, due to the large steric hindrance between the long-chain ligands, a large number of uncoordinated dangling bonds are easily generated on the surface of the quantum dot. Moreover, after the quantum dot solution is prepared into a thin film, due to the poor conductivity of the long-chain organic ligand between adjacent quantum dots in the thin film, carriers generated after the quantum dots are excited by light or electricity cannot be effectively transmitted between the quantum dots, so that the photocurrent density of the device is greatly inhibited, and the luminous efficiency and the service life of the device are low. Therefore, the prior art is in need of improvement.
Disclosure of Invention
The invention aims to provide a luminescent material, a quantum dot film and a preparation method thereof, and aims to solve the technical problems that dangling bonds are easily generated on the surface of the existing quantum dot and the conductivity of the quantum dot after film forming is not high.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a luminescent material, which comprises quantum dots and halogenated aromatic amine combined on the surfaces of the quantum dots; wherein the halogenated aromatic amine contains unsaturated chain hydrocarbon groups, and halogen elements in the halogenated aromatic amine substitute for hydrogen on an amine group.
The luminescent material provided by the invention comprises quantum dots and halogenated aromatic amine combined on the surfaces of the quantum dots, on one hand, halogen negative ions in the halogenated aromatic amine can be effectively combined with cation defect states on the surfaces of the quantum dots, and simultaneously, ammonium positive ions can be combined with anion defect states on the surfaces of the quantum dots, so that dangling bonds on the surfaces of the quantum dots are reduced, perfect coating of the surfaces of the quantum dots is realized, and the fluorescence efficiency of the luminescent material is improved. On the other hand, the halogenated aromatic amine ligand on the surface of the quantum dot has a pi-conjugated ligand, so that the conductivity of the halogenated aromatic amine ligand can be obviously improved.
Correspondingly, the preparation method of the luminescent material comprises the following steps:
providing an oil-soluble quantum dot solution and a halogenated aromatic amine; wherein, the halogenated aromatic amine contains unsaturated chain alkyl, and halogen elements in the halogenated aromatic amine substitute hydrogen on an amino group;
and mixing the halogenated aromatic amine with the oil-soluble quantum dot solution, and carrying out ligand exchange reaction to obtain the luminescent material.
The preparation method of the luminescent material provided by the invention is characterized in that halogenated aromatic amine and quantum dots in an oil-soluble quantum dot solution are subjected to ligand exchange reaction, the method is simple and effective to operate, and the original optical performance of the quantum dots is not damaged.
The invention provides a quantum dot film, which contains mutually cross-linked luminescent materials, wherein the luminescent materials comprise quantum dots and halogenated aromatic amine combined on the surfaces of the quantum dots; wherein the halogenated aromatic amine contains unsaturated chain hydrocarbon groups, and halogen elements in the halogenated aromatic amine substitute for hydrogen on an amine group.
The quantum dot film contains the mutually cross-linked luminescent materials, and the halogenated aromatic amine ligands containing unsaturated chain alkyl in the luminescent materials can be subjected to in-situ polymerization reaction to be mutually cross-linked, so that the formed quantum dot film has the characteristics of good stability, high luminous efficiency and high conductivity.
Correspondingly, the preparation method of the quantum dot film comprises the following steps:
providing a substrate;
depositing a quantum dot solution on the substrate to obtain an initial quantum dot film; halogenated aromatic amine is combined on the surface of the quantum dot in the quantum dot solution, the halogenated aromatic amine contains unsaturated chain alkyl, and halogen elements in the halogenated aromatic amine substitute hydrogen on an amino group;
and depositing a photopolymerization monomer containing unsaturated chain hydrocarbon groups and an initiator on the initial quantum dot film, and carrying out in-situ polymerization reaction to obtain the quantum dot film.
The preparation method of the quantum dot film provided by the invention has the characteristics of simple and effective operation and no damage to the original optical performance of the quantum dot, and the quantum dot film has the characteristics of good stability, high luminous efficiency and high conductivity, and can improve the luminous efficiency and prolong the service life of a device when being used for a quantum dot light-emitting diode.
Drawings
Fig. 1 is a schematic flow chart of a method for producing a luminescent material according to an embodiment of the present invention;
fig. 2 is a schematic flow chart of a method for preparing a quantum dot thin film according to an embodiment of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In one aspect, embodiments of the present invention provide a luminescent material, including a quantum dot and a halogenated aromatic amine bonded to a surface of the quantum dot; wherein the halogenated aromatic amine contains unsaturated chain hydrocarbon groups, and halogen elements in the halogenated aromatic amine substitute for hydrogen on an amine group.
The luminescent material provided by the embodiment of the invention comprises the quantum dots and the halogenated aromatic amine combined on the surfaces of the quantum dots, on one hand, the halogen negative ions in the halogenated aromatic amine can be effectively combined with the cation defect state on the surfaces of the quantum dots, and meanwhile, the ammonium positive ions can be combined with the anion defect state on the surfaces of the quantum dots, so that the dangling bonds on the surfaces of the quantum dots are reduced, the perfect coating of the surfaces of the quantum dots is realized, and the fluorescence efficiency of the luminescent material is improved. On the other hand, the halogenated aromatic amine ligand on the surface of the quantum dot has a pi-conjugated ligand, so that the conductivity of the halogenated aromatic amine ligand can be obviously improved.
In the luminescent material provided by the embodiment of the invention, the halogenated aromatic amine containing unsaturated chain hydrocarbon groups can be understood as carbon-carbon unsaturated bonds, and the halogen element in the halogenated aromatic amine substitutes hydrogen on the amine groups to form ammonium, so that the halogenated aromatic amine can be understood as aromatic ammonium halide containing carbon-carbon unsaturated bonds. In the halogenated aromatic amine, the halogenated aromatic amine is selected from at least one of halogenated 2-vinyl aniline, halogenated 3-vinyl aniline, halogenated 4-vinyl aniline, halogenated 2-isopropenylphenyl aniline, halogenated 4- [ N- (methylaminoethyl) aminomethyl ] styrene, halogenated 2-allyloxy-phenyl amine and halogenated 3, 5-dimethoxy-4- (allyloxy) phenethylamine; the halogen element in the halogenated aromatic amine is selected from at least one of F, Cl, Br and I.
Accordingly, a method for preparing a luminescent material, as shown in fig. 1, comprises the following steps:
s01, providing an oil-soluble quantum dot solution and halogenated aromatic amine; wherein, the halogenated aromatic amine contains unsaturated chain alkyl, and halogen elements in the halogenated aromatic amine substitute hydrogen on an amino group;
and S02, mixing the halogenated aromatic amine with the oil-soluble quantum dot solution, and carrying out ligand exchange reaction to obtain the luminescent material.
The preparation method of the luminescent material provided by the embodiment of the invention is characterized in that halogenated aromatic amine and quantum dots in an oil-soluble quantum dot solution are subjected to ligand exchange reaction, the method is simple and effective to operate, and the original optical performance of the quantum dots is not damaged.
In one embodiment, the ligand exchange reaction is conducted under inert atmosphere conditions; the temperature of the ligand exchange reaction is 80-250 ℃; the time of the ligand exchange reaction is 1-24 h. In one embodiment, the ligand exchange reaction is performed according to the mass ratio of the halogenated aromatic amine to the quantum dots being 0.1-5: 1. In one embodiment, the halogenated aromatic amine is mixed with an oil-soluble quantum dot solution, and the ligand exchange reaction is carried out under the condition of a non-coordinating solvent. Wherein the non-coordinating solvent is selected from at least one of olefin, alkane, ether hydrocarbon and aromatic compound; the solvent in the oil-soluble quantum dot solution is at least one selected from chloroform, tetrahydrofuran, chlorobenzene, acetonitrile, cyclohexane and toluene; and in one embodiment, the volume ratio of the non-coordinating solvent to the solvent in the oil-soluble quantum dot solution is 1-20: 1. The mass concentration of the quantum dots in the oil-soluble quantum dot solution is 1-100 mg/ml.
After ligand exchange is completed, precipitating, centrifugally separating and drying a product to obtain the luminescent material: quantum dots grafted with a target ligand (i.e., a halogenated aromatic amine). The quantum dots comprise CdSe, CdS, CdTe, ZnSe, ZnS, CdTe and ZnTe of II-VI groups; CdZnS, CdZnSe, CdZnTe, ZnSeS, ZnSeTe, ZnTeS, CdSeS, CdSeTe, CdTeS; CdZnSeS, CdZnSeTe, CdZnSTe; or III-V group InP, InAs, GaP, GaAs, GaSb, AlN, or a mixture thereof,AlP; InAsP; InNP, InNSb, GaAlNP, InAlNP, or I-III-VI2Group of CuInS2、CuInSe2、AgInS2Any one or more of the above in combination.
In one embodiment, the method for preparing the halogenated aromatic amine comprises: dissolving aromatic amine and halide in an alcohol solvent, and carrying out substitution reaction at the temperature of 0-4 ℃; wherein the aromatic amine contains unsaturated chain hydrocarbon group. Wherein the aromatic amine is selected from 2-vinylaniline, 3-vinylaniline, 4-vinylaniline, 2-isopropenylphenylaniline, 4- [ N- (methylaminoethyl) aminomethyl]At least one of styrene, 2-allyloxy-phenylamine and 3, 5-dimethoxy-4- (allyloxy) phenethylamine; the halide is selected from HF and NH4F、HCl、NH4Cl、HBr、NH4Br、LiF、KF、NaF、BeF2、MgF2、CaF2、AlF3、InF3、LiCl、NaCl、MgCl2、CaCl2、ZnCl2、AlCl3、GaCl3、InCl3、LiBr、NaBr、MgBr2、CaBr2、ZnBr2、AlBr3、GaBr3、InBr3、LiI、NaI、MgI2、CaI2、ZnI2、AlBr3、GaI3And InI3At least one of; the alcohol solvent is selected from at least one of methanol, ethanol, propanol, butanol and isopropanol.
In one embodiment, the halogenated arylamine ligand precursor is prepared as follows:
(1) aromatic amine and alcohol were placed in a three-necked flask. Stirring at 0 ℃, then adding equimolar halide, and reacting for 1-4 h at the temperature. After the reaction is finished, the product is dissolved and precipitated by ethanol and ether, and the halogenated aromatic amine ligand is finally obtained.
(2) Dissolving the halogenated aromatic amine ligand in methyl acetate to obtain a halogenated aromatic amine ligand precursor.
The embodiment of the invention provides a quantum dot film, which contains mutually cross-linked luminescent materials, wherein the luminescent materials comprise quantum dots and halogenated aromatic amine combined on the surfaces of the quantum dots; wherein the halogenated aromatic amine contains unsaturated chain hydrocarbon groups, and halogen elements in the halogenated aromatic amine substitute for hydrogen on an amine group.
The quantum dot film contains the mutually cross-linked luminescent materials, the halogenated aromatic amine ligands containing unsaturated chain alkyl groups in the luminescent materials can be subjected to in-situ polymerization reaction to be mutually cross-linked, the quantum dot film formed by the raw materials containing the special luminescent materials through in-situ polymerization cross-linking has the characteristics of good stability, high luminous efficiency and high conductivity, and when the quantum dot film is used for a quantum dot light-emitting diode, due to the fact that the quantum dot film has large pi bonds, the quantum dot film can effectively avoid the quantum dots from being influenced by the outside on the premise of improving the conductivity of the quantum dot light-emitting diode, the stability of the quantum dot film is improved, and therefore the efficiency and the service life of the device are further improved.
Accordingly, a method for preparing a quantum dot thin film, as shown in fig. 2, comprises the following steps:
e01 providing a substrate;
e02, depositing the quantum dot solution on the substrate to obtain an initial quantum dot film; halogenated aromatic amine is combined on the surface of the quantum dot in the quantum dot solution, the halogenated aromatic amine contains unsaturated chain alkyl, and halogen elements in the halogenated aromatic amine substitute hydrogen on an amino group;
and E03, depositing a photopolymerization monomer containing unsaturated chain hydrocarbon groups and an initiator on the initial quantum dot film, and carrying out in-situ polymerization reaction to obtain the quantum dot film.
The preparation method of the quantum dot film provided by the embodiment of the invention has the characteristics of simple and effective operation and no damage to the original optical performance of the quantum dot, and the quantum dot film has the characteristics of good stability, high luminous efficiency and high conductivity, and can improve the luminous efficiency and prolong the service life of a device when being used for a quantum dot light-emitting diode.
Specifically, the photopolymerizable monomer is selected from at least one of styrene, 2-vinylaniline, 3-vinylaniline, 4-vinylaniline, 2-isopropenylphenylaniline, 4- [ N- (methylaminoethyl) aminomethyl ] styrene, 2-allyloxy-phenylamine and 3, 5-dimethoxy-4- (allyloxy) phenylethylamine; the initiator is at least one selected from benzophenone, hydroxybenzophenone, benzyl dimethyl ketal, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether. The mass ratio of the photopolymerization monomer to the quantum dots is 0.1-10: 1; the mass ratio of the initiator to the quantum dots is 0.01-1: 1.
The embodiment of the invention also provides a QLED device which comprises the quantum dot film. In an embodiment, the QLED device is a positive QLED device, and includes, from bottom to top, a substrate, a bottom electrode, a hole injection layer, a hole transport layer, a quantum dot light emitting layer, an electron transport layer, and a top electrode in this order.
The specific preparation process of the QLED device comprises the following steps:
and dissolving the quantum dots subjected to ligand exchange by adopting a nonpolar solvent to form a quantum dot solution. Then, a quantum dot light-emitting layer is deposited on the hole transport layer. Then adding a certain amount of a photopolymerizable monomer having a carbon-carbon unsaturated bond and an initiator, and then washing with methyl acetate or ethyl acetate. The electron transport layer and top electrode preparation then continues.
The substrate comprises a rigid, flexible substrate.
The bottom electrode comprises Al, Cu, Mo, Au, Ag or their alloys
The hole injection layer includes PEODT: PSS, WoO3、MoO3、HATCN、NiO、HATCN、CuS CuO、V2O5And the like.
The hole transport layer can be a small molecular organic matter or a high molecular conductive polymer, and comprises TFB, PVK, Poly-TBP, Poly-TPD, NPB, TCTA, TAPC, CBP and PEODT: PSS, MoO3、WoO3、NiO、CuO、V2O5CuS, and the like.
The electron transport layer comprises ZnO, ZrO, TiO2、Alq3TAZ, TPBI, PBD, BCP, Bphen.
The top electrode comprises ITO, FTO or ZTO.
The thickness of the bottom electrode is 30-110 nm; the thickness of the hole injection layer is 30-100 nm; the thickness of the hole transport layer is 30-100 nm; the thickness of the quantum dot light-emitting layer is 30-100 nm; the thickness of the electron transmission layer is 10-100 nm; the thickness of the top electrode is 90-110 nm;
photopolymerizable monomers having carbon-carbon unsaturation include styrene, 2-vinylaniline, 3-vinylaniline, 4-vinylaniline, 2-isopropenylphenylaniline, 4- [ N- (methylaminoethyl) aminomethyl ] styrene, 2-allyloxy-phenylamine, 3, 5-dimethoxy-4- (allyloxy) phenethylamine, and combinations thereof
Photoinitiators include benzophenone, hydroxybenzophenone, benzyl dimethyl ketal, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether.
The mass ratio of the photopolymerization monomer with carbon-carbon unsaturated bonds to the quantum dots is 0.1-10: 1, and the mass ratio of the photoinitiator to the quantum dots is 0.01-1: 1.
The invention is described in further detail with reference to a part of the test results, which are described in detail below with reference to specific examples.
Example 1
1. Preparation of halogenated aromatic amine ligand precursor:
(1) 1g of 4-vinylaniline and 20ml of ethanol were placed in a three-necked flask. Stirring was carried out at 0 ℃ and then an equimolar amount of aqueous hydrogen bromide (48%) was added and reacted at this temperature for 1 h. After the reaction is finished, the product is dissolved and precipitated by ethanol and ether, and the halogenated aromatic amine ligand is finally obtained.
(2) Dissolving the halogenated aromatic amine ligand in methyl acetate to obtain a halogenated aromatic amine ligand precursor.
2. Quantum dot ligand exchange:
(1) 10ml CdZnS/ZnS quantum dot solution (solvent n-octane) with a concentration of 20mg/ml was provided. And then mixing the halogenated aromatic amine ligand precursor with 50ml of octadecene, and reacting for 30min at 100 ℃ under an argon atmosphere. And centrifugally separating the final product to obtain the ligand-exchanged quantum dots.
Preparing a QLED device:
a bottom electrode, a hole injection layer, a hole transport layer, a quantum dot light emitting layer, an electron transport layer and a top electrode are sequentially prepared on a substrate. Wherein the substrate is a glass substrate; the bottom electrode is ITO with the thickness of 100 nm; PSS, the thickness of the hole injection layer is 40 nm; the hole transport layer is TFB and is 80nm thick; the quantum dot light-emitting layer is obtained by in-situ polymerization of the quantum dots after ligand exchange, and the thickness is 100 nm; the electron transmission layer is ZnO and has the thickness of 60 nm; the top electrode was Al and the thickness was 50 nm.
After the deposition of the quantum dot light emitting layer is finished, 200mg of styrene and 2mg of hydroxybenzophenone are irradiated for 30 seconds under 365nm ultraviolet light, and then the surface is cleaned by methyl acetate.
Example 2
1. Preparing halogenated aromatic amine precursor:
(1) 1g of 4-vinylaniline and 20ml of ethanol were placed in a three-necked flask. Stirring was carried out at 0 ℃ and then an equimolar amount of aqueous hydrogen bromide (48%) was added and reacted at this temperature for 1 h. After the reaction is finished, the product is dissolved and precipitated by ethanol and ether, and the halogenated aromatic amine ligand is finally obtained.
(2) Dissolving the halogenated aromatic amine ligand in methyl acetate to obtain a halogenated aromatic amine ligand precursor.
2. Quantum dot ligand exchange:
(1) 10ml CdZnSe/ZnS quantum dot solution (solvent n-octane) with a concentration of 20mg/ml were provided. And then mixing the halogenated aromatic amine ligand precursor with 50ml of octadecene, and reacting for 30min at 100 ℃ under an argon atmosphere. And centrifugally separating the final product to obtain the ligand-exchanged quantum dots.
Preparing a QLED device:
a bottom electrode, a hole injection layer, a hole transport layer, a quantum dot light emitting layer, an electron transport layer and a top electrode are sequentially prepared on a substrate. Wherein the substrate is a glass substrate; the bottom electrode is ITO with the thickness of 100 nm; PSS, the thickness of the hole injection layer is 40 nm; the hole transport layer is TFB and is 80nm thick; the quantum dot light-emitting layer is obtained by in-situ polymerization of the quantum dots after ligand exchange, and the thickness is 100 nm; the electron transmission layer is ZnO and has the thickness of 60 nm; the top electrode was Al and the thickness was 50 nm.
After the deposition of the quantum dot light emitting layer is finished, 200mg of styrene and 2mg of hydroxybenzophenone are irradiated for 30 seconds under 365nm ultraviolet light, and then the surface is cleaned by methyl acetate.
Example 3
1. Preparation of halogenated aromatic amine ligand precursor:
(1) 1g of 3-vinylaniline and 20ml of ethanol were placed in a three-necked flask. Stirring was carried out at 0 ℃ and then an equimolar amount of aqueous hydrogen bromide (48%) was added and reacted at this temperature for 1 h. After the reaction is finished, the product is dissolved and precipitated by ethanol and ether, and the halogenated aromatic amine ligand is finally obtained.
(2) Dissolving the halogenated aromatic amine ligand in methyl acetate to obtain a halogenated aromatic amine ligand precursor.
2. Quantum dot ligand exchange:
(1) 10ml CdZnS/ZnS quantum dot solution (solvent n-octane) with a concentration of 20mg/ml was provided. Then, the unsaturated aromatic ammonium halide ligand precursor and 50ml of octadecene are mixed and reacted for 30min at 100 ℃ under an argon atmosphere. And centrifugally separating the final product to obtain the ligand-exchanged quantum dots.
Preparing a QLED device:
a bottom electrode, a hole injection layer, a hole transport layer, a quantum dot light emitting layer, an electron transport layer and a top electrode are sequentially prepared on a substrate. Wherein the substrate is a glass substrate; the bottom electrode is ITO with the thickness of 100 nm; PSS, the thickness of the hole injection layer is 40 nm; the hole transport layer is TFB and is 80nm thick; the quantum dot light-emitting layer is obtained by in-situ polymerization of the quantum dots after ligand exchange, and the thickness is 100 nm; the electron transmission layer is ZnO and has the thickness of 60 nm; the top electrode was Al and the thickness was 50 nm.
After the deposition of the quantum dot light emitting layer is finished, 200mg of styrene and 2mg of hydroxybenzophenone are irradiated for 30 seconds under 365nm ultraviolet light, and then the surface is cleaned by methyl acetate.
Example 4
1. Preparation of halogenated aromatic amine ligand precursor:
(1) 1g of 3-vinylaniline and 20ml of ethanol were placed in a three-necked flask. Stirring was carried out at 0 ℃ and then an equimolar amount of aqueous hydrogen bromide (48%) was added and reacted at this temperature for 1 h. After the reaction is finished, the product is dissolved and precipitated by ethanol and ether, and the halogenated aromatic amine ligand is finally obtained.
(2) Dissolving the halogenated aromatic amine ligand in methyl acetate to obtain a halogenated aromatic amine ligand precursor.
2. Quantum dot ligand exchange:
(1) 10ml CdZnSe/ZnS quantum dot solution (solvent n-octane) with a concentration of 20mg/ml were provided. And then mixing the halogenated aromatic amine ligand precursor with 50ml of octadecene, and reacting for 30min at 100 ℃ under an argon atmosphere. And centrifugally separating the final product to obtain the ligand-exchanged quantum dots.
Preparing a QLED device:
a bottom electrode, a hole injection layer, a hole transport layer, a quantum dot light emitting layer, an electron transport layer and a top electrode are sequentially prepared on a substrate. Wherein the substrate is a glass substrate; the bottom electrode is ITO with the thickness of 100 nm; PSS, the thickness of the hole injection layer is 40 nm; the hole transport layer is TFB and is 80nm thick; the quantum dot light-emitting layer is obtained by in-situ polymerization of the quantum dots after ligand exchange, and the thickness is 100 nm; the electron transmission layer is ZnO and has the thickness of 60 nm; the top electrode was Al and the thickness was 50 nm.
After the deposition of the quantum dot light emitting layer is finished, 200mg of styrene and 2mg of hydroxybenzophenone are irradiated for 30 seconds under 365nm ultraviolet light, and then the surface is cleaned by methyl acetate.
Example 5
1. Preparation of halogenated aromatic amine ligand precursor:
(1) 1g of 4-vinylaniline and 20ml of ethanol were placed in a three-necked flask. Stirring was carried out at 0 ℃ and then an equimolar amount of potassium bromide solution was added and the reaction was carried out at this temperature for 1 h. After the reaction is finished, the product is dissolved and precipitated by ethanol and ether, and the halogenated aromatic amine ligand is finally obtained.
(2) Dissolving the halogenated aromatic amine ligand in methyl acetate to obtain a halogenated aromatic amine ligand precursor.
2. Quantum dot ligand exchange:
(1) 10ml CdZnS/ZnS quantum dot solution (solvent n-octane) with a concentration of 20mg/ml was provided. And then mixing the halogenated aromatic amine ligand precursor with 50ml of octadecene, and reacting for 30min at 100 ℃ under an argon atmosphere. And centrifugally separating the final product to obtain the ligand-exchanged quantum dots.
Preparing a QLED device:
a bottom electrode, a hole injection layer, a hole transport layer, a quantum dot light emitting layer, an electron transport layer and a top electrode are sequentially prepared on a substrate. Wherein the substrate is a glass substrate; the bottom electrode is ITO with the thickness of 100 nm; PSS, the thickness of the hole injection layer is 40 nm; the hole transport layer is PVK and is 80nm thick; the quantum dot light-emitting layer is obtained by in-situ polymerization of the quantum dots after ligand exchange, and the thickness is 100 nm; the electron transmission layer is ZnO and has the thickness of 60 nm; the top electrode was Al and the thickness was 50 nm.
After the deposition of the quantum dot light emitting layer is finished, 200mg of styrene and 2mg of hydroxybenzophenone are irradiated for 30 seconds under 365nm ultraviolet light, and then the surface is cleaned by methyl acetate.
Example 6
1. Preparation of halogenated aromatic amine ligand precursor:
(1) 1g of 4-vinylaniline and 20ml of ethanol were placed in a three-necked flask. Stirring was carried out at 0 ℃ and then an equimolar amount of potassium bromide solution was added and the reaction was carried out at this temperature for 1 h. After the reaction is finished, the product is dissolved and precipitated by ethanol and ether, and the halogenated aromatic amine ligand is finally obtained.
(2) Dissolving the halogenated aromatic amine ligand in methyl acetate to obtain a halogenated aromatic amine ligand precursor.
2. Quantum dot ligand exchange:
(1) 10ml CdZnSe/ZnS quantum dot solution (solvent n-octane) with a concentration of 20mg/ml were provided. And then mixing the halogenated aromatic amine ligand precursor with 50ml of octadecene, and reacting for 30min at 100 ℃ under an argon atmosphere. And centrifugally separating the final product to obtain the ligand-exchanged quantum dots.
Preparing a QLED device:
a bottom electrode, a hole injection layer, a hole transport layer, a quantum dot light emitting layer, an electron transport layer and a top electrode are sequentially prepared on a substrate. Wherein the substrate is a glass substrate; the bottom electrode is ITO with the thickness of 100 nm; PSS, the thickness of the hole injection layer is 40 nm; the hole transport layer is PVK and is 80nm thick; the quantum dot light-emitting layer is obtained by in-situ polymerization of the quantum dots after ligand exchange, and the thickness is 100 nm; the electron transmission layer is ZnO and has the thickness of 60 nm; the top electrode was Al and the thickness was 50 nm.
After the deposition of the quantum dot light emitting layer is finished, 200mg of styrene and 2mg of hydroxybenzophenone are irradiated for 30 seconds under 365nm ultraviolet light, and then the surface is cleaned by methyl acetate.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (10)

1. A luminescent material, wherein the luminescent material comprises a quantum dot and a halogenated aromatic amine bonded to the surface of the quantum dot; wherein the halogenated aromatic amine contains unsaturated chain hydrocarbon groups, and halogen elements in the halogenated aromatic amine substitute for hydrogen on an amine group.
2. The light-emitting material according to claim 1, wherein the halogenated aromatic amine is at least one selected from the group consisting of halogenated 2-vinylaniline, halogenated 3-vinylaniline, halogenated 4-vinylaniline, halogenated 2-isopropenylphenylaniline, halogenated 4- [ N- (methylaminoethyl) aminomethyl ] styrene, halogenated 2-allyloxy-phenylamine and halogenated 3, 5-dimethoxy-4- (allyloxy) phenethylamine; and/or the presence of a gas in the gas,
the halogen element in the halogenated aromatic amine is selected from at least one of F, Cl, Br and I.
3. A preparation method of a luminescent material is characterized by comprising the following steps:
providing an oil-soluble quantum dot solution and a halogenated aromatic amine; wherein, the halogenated aromatic amine contains unsaturated chain alkyl, and halogen elements in the halogenated aromatic amine substitute hydrogen on an amino group;
and mixing the halogenated aromatic amine with the oil-soluble quantum dot solution, and carrying out ligand exchange reaction to obtain the luminescent material.
4. The method for producing a light-emitting material according to claim 3, wherein the ligand exchange reaction is performed under an inert atmosphere; and/or the presence of a gas in the gas,
the temperature of the ligand exchange reaction is 80-250 ℃; and/or the presence of a gas in the gas,
the time of the ligand exchange reaction is 1-24 h; and/or the presence of a gas in the gas,
performing the ligand exchange reaction according to the mass ratio of the halogenated aromatic amine to the quantum dots being 0.1-5: 1; and/or the presence of a gas in the gas,
and mixing the halogenated aromatic amine with the oil-soluble quantum dot solution, and carrying out ligand exchange reaction under the condition of a non-coordination solvent.
5. The method for producing a luminescent material according to claim 4, wherein the non-coordinating solvent is at least one selected from the group consisting of olefins, alkanes, ether hydrocarbons, and aromatic compounds; and/or the presence of a gas in the gas,
the solvent in the oil-soluble quantum dot solution is at least one selected from chloroform, tetrahydrofuran, chlorobenzene, acetonitrile, cyclohexane and toluene; and/or the presence of a gas in the gas,
the volume ratio of the non-coordination solvent to the solvent in the oil-soluble quantum dot solution is 1-20: 1.
6. The method for producing a luminescent material according to any one of claims 3 to 5, wherein the method for producing the halogenated aromatic amine comprises: dissolving aromatic amine and halide in an alcohol solvent, and carrying out substitution reaction at the temperature of 0-4 ℃; wherein the aromatic amine contains unsaturated chain hydrocarbon group.
7. The method according to claim 6, wherein the aromatic amine is at least one selected from the group consisting of 2-vinylaniline, 3-vinylaniline, 4-vinylaniline, 2-isopropenylphenylaniline, 4- [ N- (methylaminoethyl) aminomethyl ] styrene, 2-allyloxy-phenylamine and 3, 5-dimethoxy-4- (allyloxy) phenethylamine; and/or the presence of a gas in the gas,
the halide is selected from HF and NH4F、HCl、NH4Cl、HBr、NH4Br、LiF、KF、NaF、BeF2、MgF2、CaF2、AlF3、InF3、LiCl、NaCl、MgCl2、CaCl2、ZnCl2、AlCl3、GaCl3、InCl3、LiBr、NaBr、MgBr2、CaBr2、ZnBr2、AlBr3、GaBr3、InBr3、LiI、NaI、MgI2、CaI2、ZnI2、AlBr3、GaI3And InI3At least one of; and/or the presence of a gas in the gas,
the alcohol solvent is selected from at least one of methanol, ethanol, propanol, butanol and isopropanol.
8. The quantum dot film is characterized by comprising luminescent materials which are mutually crosslinked, wherein the luminescent materials comprise quantum dots and halogenated aromatic amine combined on the surfaces of the quantum dots; wherein the halogenated aromatic amine contains unsaturated chain hydrocarbon groups, and halogen elements in the halogenated aromatic amine substitute for hydrogen on an amine group.
9. The preparation method of the quantum dot film is characterized by comprising the following steps:
providing a substrate;
depositing a quantum dot solution on the substrate to obtain an initial quantum dot film; halogenated aromatic amine is combined on the surface of the quantum dot in the quantum dot solution, the halogenated aromatic amine contains unsaturated chain alkyl, and halogen elements in the halogenated aromatic amine substitute hydrogen on an amino group;
and depositing a photopolymerization monomer containing unsaturated chain hydrocarbon groups and an initiator on the initial quantum dot film, and carrying out in-situ polymerization reaction to obtain the quantum dot film.
10. The method of preparing a quantum dot film according to claim 9, wherein the photopolymerizable monomer is at least one selected from the group consisting of styrene, 2-vinylaniline, 3-vinylaniline, 4-vinylaniline, 2-isopropenylphenylaniline, 4- [ N- (methylaminoethyl) aminomethyl ] styrene, 2-allyloxy-phenylamine and 3, 5-dimethoxy-4- (allyloxy) phenethylamine; and/or the presence of a gas in the gas,
the initiator is at least one selected from benzophenone, hydroxybenzophenone, benzyl dimethyl ketal, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether.
The mass ratio of the photopolymerization monomer to the quantum dots is 0.1-10: 1; and/or the presence of a gas in the gas,
the mass ratio of the initiator to the quantum dots is 0.01-1: 1.
CN201910757313.4A 2019-08-16 2019-08-16 Luminescent material and quantum dot film and preparation method thereof Pending CN112391162A (en)

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CN117148688A (en) * 2023-11-01 2023-12-01 长春理工大学 Method for processing quantum dots for direct lithography and dual-channel imaging chip

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CN109935709A (en) * 2017-12-15 2019-06-25 Tcl集团股份有限公司 Quantum dot film and preparation method thereof, QLED device and preparation method thereof

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CN109935709A (en) * 2017-12-15 2019-06-25 Tcl集团股份有限公司 Quantum dot film and preparation method thereof, QLED device and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116478693A (en) * 2023-04-23 2023-07-25 天津大学 Red light emitting material suitable for electroluminescent device without carrier injection and its prepn
CN117148688A (en) * 2023-11-01 2023-12-01 长春理工大学 Method for processing quantum dots for direct lithography and dual-channel imaging chip

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