CN110129027B - Quantum dot composite film and preparation method thereof - Google Patents

Quantum dot composite film and preparation method thereof Download PDF

Info

Publication number
CN110129027B
CN110129027B CN201910471044.5A CN201910471044A CN110129027B CN 110129027 B CN110129027 B CN 110129027B CN 201910471044 A CN201910471044 A CN 201910471044A CN 110129027 B CN110129027 B CN 110129027B
Authority
CN
China
Prior art keywords
quantum dot
hydrogel
layer
composite film
hydrogel layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910471044.5A
Other languages
Chinese (zh)
Other versions
CN110129027A (en
Inventor
邢泽咏
王允军
刘思锦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou Xingshuo Nanotech Co Ltd
Original Assignee
Suzhou Xingshuo Nanotech Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Suzhou Xingshuo Nanotech Co Ltd filed Critical Suzhou Xingshuo Nanotech Co Ltd
Priority to CN201910471044.5A priority Critical patent/CN110129027B/en
Publication of CN110129027A publication Critical patent/CN110129027A/en
Application granted granted Critical
Publication of CN110129027B publication Critical patent/CN110129027B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • 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
    • C09K11/88—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

Landscapes

  • 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 quantum dot composite film, which comprises: a quantum dot-hydrogel layer; and the water-resistant layer is coated on the surface of the quantum dot-hydrogel layer. According to the invention, the hydrogel in the quantum dot-hydrogel layer has a protection effect on the quantum dots dispersed in the hydrogel layer, so that the adverse effect of water vapor and oxygen in the external environment on the quantum dots is reduced, the water-blocking layer coated on the surface of the quantum dot-hydrogel layer further blocks the permeation of external water vapor and oxygen, and the stable physical state of the quantum dot-hydrogel layer is maintained, so that the quantum dot composite film with low sensitivity to factors such as water vapor and oxygen and high stability is finally obtained. The preparation method is low in cost, mild in conditions and suitable for large-scale production and popularization.

Description

Quantum dot composite film and preparation method thereof
Technical Field
The application relates to the field of luminescent materials, in particular to a quantum dot composite film and a preparation method thereof.
Background
The quantum dot has the excellent performances of narrow half-peak width, high luminous purity, adjustable emission wavelength along with size and the like. The quantum dot film is used as a wavelength conversion element, can remarkably improve the color gamut of a display and the utilization efficiency of backlight, and has a wide application range in the display field.
If the existing quantum dot film is placed in the air without being protected by a diaphragm and the like, the quantum dots in the quantum dot film are easily influenced by water vapor and oxygen in the external environment, so that the quantum dots are damaged, the optical performance is reduced, the failure of the quantum dot film is caused, and the market application requirements can not be met.
Disclosure of Invention
In view of the above technical problems, an object of the present application is to provide a quantum dot composite film with high stability and a method for preparing the same.
According to a first aspect of the present application, there is provided a quantum dot composite film comprising:
a quantum dot-hydrogel layer; and
and the water-resistant layer is coated on the surface of the quantum dot-hydrogel layer.
Further, the quantum dot-hydrogel layer includes a hydrogel, and quantum dots dispersed in the hydrogel.
Further, the water-blocking layer contains SiO2Poly-silicon oxideAt least one alkane.
According to another aspect of the present application, there is provided a method of preparing a quantum dot film, including the steps of:
s1, providing a quantum dot-hydrogel layer;
s2, coating a silanization reagent on the surface of the quantum dot-hydrogel layer;
s3, standing the coated quantum dot-hydrogel layer for a period of time, and forming a layer containing SiO on the surface of the quantum dot-hydrogel layer2And/or a water-resistant layer of polysiloxane to obtain the quantum dot composite film.
Further, the coating manner of S2 includes: and soaking the quantum dot-hydrogel layer in a silanization reagent for a period of time, and taking out.
Further, the coating manner of S2 includes: and spraying and/or sprinkling the silanization reagent on the surface of the quantum dot-hydrogel layer.
Further, the silanization reagent comprises methyl orthosilicate, ethyl orthosilicate, trimethoxy silane, triethoxy silane and N, at least one of O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, dimethyldichlorosilane, 1,1,1,3,3, 3-hexamethyldisilane, N- (tert-butyldimethylsilyl) -N-methyltrifluoroacetamide, tert-butyldimethylchlorosilane, trimethylchlorosilane, trimethylsilyldiethylamine, trimethylsilylimidazole, long-chain alkyltrimethoxysilane, long-chain alkyltriethoxysilane, 3-aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and vinyltriethoxysilane.
Further, S1 includes the steps of:
s1-1, mixing the quantum dots, the hydrogel material and a first solvent to obtain a quantum dot-hydrogel mixed system;
s1-2, coating the quantum dot-hydrogel mixed system on a substrate material;
s1-3, carrying out curing treatment on the coated substrate material to form a cured quantum dot-hydrogel mixture;
and S1-4, separating the cured quantum dot-hydrogel mixture from the substrate material to obtain a quantum dot-hydrogel layer.
Further, the hydrogel material includes at least one of a natural polymer hydrogel, a synthetic polymer hydrogel, and a natural and synthetic polymer hybrid hydrogel.
Furthermore, the hydrogel material accounts for 0.1-50 wt% of the quantum dot-hydrogel mixed system.
Borrow by above-mentioned scheme, the beneficial effect of this application lies in:
1) the quantum dot-hydrogel layer is wrapped with the water-resistant layer on the surface, and the quantum dot composite film with low sensitivity to factors such as water, oxygen and the like and high stability is obtained.
2) The preparation method is low in cost, mild in conditions and suitable for large-scale production and popularization.
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 quantum dot composite film, which comprises a quantum dot-hydrogel layer and a water-blocking layer coated on the surface of the quantum dot-hydrogel layer.
According to some preferred embodiments of the present application, the quantum dot-hydrogel layer includes a hydrogel, and quantum dots dispersed in the hydrogel.
According to some preferred embodiments of the present application, the water resistant layer comprises SiO2And a polysiloxane.
The quantum dot composite film comprises a quantum dot-hydrogel layer and a water-resistant layer coated on the surface of the quantum dot-hydrogel layer. The hydrogel in the quantum dot-hydrogel layer has a protection effect on the quantum dots dispersed in the hydrogel layer, the adverse effect of water vapor and oxygen in the external environment on the quantum dots is reduced, then, the water-blocking layer wrapped on the surface of the quantum dot-hydrogel layer further blocks the permeation of external water vapor and oxygen, and simultaneously, the stable physical state of the quantum dot-hydrogel layer is kept, so that the quantum dot composite film with low sensitivity to factors such as water vapor and oxygen and high stability is finally obtained.
The application also provides a preparation method of the quantum dot composite film, which comprises the following steps:
s1, providing a quantum dot-hydrogel layer;
s2, coating a silanization reagent on the surface of the quantum dot-hydrogel layer;
s3, standing the coated quantum dot-hydrogel layer for a period of time, and forming a layer containing SiO on the surface of the quantum dot-hydrogel layer2And/or a water-resistant layer of polysiloxane to obtain the quantum dot composite film.
In the application, the silanization reagent depends on moisture in the air or in the environment with certain humidity or the moisture lost from the hydrogel layer to carry out hydrolysis reaction to obtain the product containing SiO2And/or a water-resistant layer of polysiloxane wraps the surface of the quantum dot-hydrogel layer, so that water vapor and oxygen in the external environment are difficult to permeate into the quantum dots from the outside, the light degradation caused by the water and oxygen permeating from the outside is effectively prevented, and the stability of the quantum dot film is greatly improved. On the other hand, because the surface of the quantum dot-hydrogel layer is wrapped by the water-resistant layer, the water of the quantum dot-hydrogel layer is not easy to dissipate, so that the problem of failure of the quantum dot-hydrogel layer caused by water dissipation is avoided.
According to some preferred embodiments of the present application, the coating manner of S2 includes: and soaking the quantum dot-hydrogel layer in a silanization reagent for a period of time, and taking out.
According to some preferred embodiments of the present application, the coating manner of S2 includes: and spraying and/or sprinkling the silanization reagent on the surface of the quantum dot-hydrogel layer.
In the present application, the silylation agent is completely coated on the surface of the quantum dot-hydrogel layer, so that each surface of the quantum dot-hydrogel layer is "covered" and "soaked" by the silylation agent. By such an operation step, through a subsequent placing process, SiO is contained2And/or the water-resistant layer of polysiloxane is completely coated on the surface of the quantum dot-hydrogel layer,thereby effectively preventing the permeation of external water oxygen.
According to some preferred embodiments of the present application, the silylating agent comprises methyl orthosilicate, ethyl orthosilicate, trimethoxysilane, triethoxysilane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, dimethyldichlorosilane, 1,1,1,3,3, 3-hexamethyldisilane, N- (tert-butyldimethylsilyl) -N-methyltrifluoroacetamide, tert-butyldimethylchlorosilane, trimethylchlorosilane, trimethylsilyldiethylamine, trimethylsilylimidazole, long chain alkyltrimethoxysilane, long chain alkyltriethoxysilane, 3-aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N-bis (trimethylsilyl) acetamide, N, O-bis (trimethylsilyl) acetamide, dimethyldichlorosilane, N, 1,1,3, 3-hexamethyldisilane, N- (tert-butyldimethylsilyl) -N-methyltrifluoroacetamide, t-butyldimethylsilyl-chlorosilane, trimethylchlorosilane, trimethylsilyldiethylamine, trimethylsilylidine, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, p-ethoxysilane, and N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, At least one of vinyltriethoxysilane.
In a specific embodiment of the present application, the long chain alkyl trimethoxysilane, long chain alkyl triethoxysilane includes one of octyl trimethoxysilane, octyl triethoxysilane, decyl trimethoxysilane, decyl triethoxysilane, dodecyl trimethoxysilane, dodecyl triethoxysilane, hexadecyl trimethoxysilane, hexadecyl triethoxysilane, octadecyl trimethoxysilane, octadecyl triethoxysilane.
According to some preferred embodiments of the present application, S1 includes the steps of:
s1-1, mixing the quantum dots, the hydrogel material and a first solvent to obtain a quantum dot-hydrogel mixed system;
s1-2, coating the quantum dot-hydrogel mixed system on a substrate material;
s1-3, carrying out curing treatment on the coated substrate material to form a cured quantum dot-hydrogel mixture;
and S1-4, separating the cured quantum dot-hydrogel mixture from the substrate material to obtain a quantum dot-hydrogel layer.
In a specific embodiment, the preparation method of step S1-1 specifically includes:
s1-1-1, mixing and stirring the quantum dots and the first solvent to uniformly disperse the quantum dots in the first solvent to obtain a solution containing the quantum dots;
s1-1-2, dispersing the hydrogel material in the solution containing the quantum dots and stirring to uniformly mix and react the hydrogel material with the solution containing the quantum dots to obtain a quantum dot-hydrogel mixing system.
In the present application, hydrogel materials are a class of polymers having a spatial network structure. The inventors have found that the hydrogel material of the present application, when mixed with a solution comprising quantum dots, can absorb the solution comprising quantum dots by a swelling action, such that the solution comprising quantum dots swells into the hydrogel material. As the hydrogel protects the quantum dots, the influence of water vapor and oxygen in the external environment on the luminescent performance of the quantum dots can be effectively reduced, the stability of the quantum dots is improved, and the optical performance of the quantum dots is not affected.
According to some preferred embodiments of the present application, the hydrogel material comprises at least one of a natural polymer hydrogel, a synthetic polymer hydrogel, and a natural and synthetic polymer hybrid hydrogel.
In one embodiment, the natural polymer hydrogel comprises polysaccharides such as starch, cellulose, alginate, hyaluronic acid, chitosan, agarose, etc., and at least one of polypeptides such as collagen, gelatin, poly-L-lysine, poly-L-glutamic acid. However, the exemplary embodiments of the present application are not limited thereto.
In one embodiment, the synthetic polymeric hydrogel comprises at least one of polyvinyl alcohol, polyethylene oxide, polyethylene glycol, poly-N-methyl pyrrolidone, acrylic acid and derivatives thereof (e.g., poly-25-carboxylic acid, polymethacrylic acid, polyacrylamide, poly-N-isopropylacrylamide, poly-2-hydroxyethyl methacrylate), and polyamines. However, the exemplary embodiments of the present application are not limited thereto.
In a specific embodiment, the natural and synthetic high molecular hybrid hydrogel comprises at least one of polyethylene glycol-polypeptide copolymer, alginic acid grafted polyethylene oxide-polypropylene oxide-polyethylene oxide, alginic acid-acrylic acid copolymer, hyaluronic acid grafted isopropyl acrylamide, and chitosan-polyisopropyl acrylamide crosslinked polymer. However, the exemplary embodiments of the present application are not limited thereto.
According to a preferred embodiment of the present application, the quantum dots are selected from at least one of group IIB-VIA, group IIIA-VA, group IVA-VIA, group IB-IIIA-VIA, group IIB-IVA-VIA, group IIA-IVB-VA, group VIII-VIA single or composite structure quantum dots, or perovskite quantum dots. However, the exemplary embodiments of the present application are not limited thereto.
In a particular embodiment, the quantum dots are selected from the group consisting of CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, MgSe, MgS, CdSeS, CdSeTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgSe, CdHgTe, HgZnSe, HgZnTe, MgZnSe, MgZnS, HgZnTeS, CdZnSeTe, CdZnSTe, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, AlgZnTe, GaN, InAs, GaInAsB, AlN, AlP, AlAs, AlGaInSb, AlGanGaAs, GanGanGanGanAs, AlNSNAP, AlnNAP, AlnGanNAP, AlnGanGanNAP, AlnGanNAP, AlnNAP, AlnGanGanNAP, AlnGanNAP, AlnNAP, AlnGanGanNAP, AlnGanGanGanGanNAP, AlnNAP, AlnGanNAP, AlnGanGanGanNAP, AlnNAP, AlnGanGanNAP, AlnNAP, AlnGanNAP, AlnGanGanGanGanGanGanGanGanGanGanNAP, AlnGanGanNAP, AlnNAP, AlnGanNAP, AlnNAP, AlnGanGanNAP, AlnNAP, AlnGanGanGanGanNAP, AlnNAP, AlnGanNAP, AlnGanGanGanP, AlnP, AlnNAP, AlnGanGanNAP, AlnGanNAP, AlnP, AlnGanGanP, AlnGanGanGanGanGanGanGanGanGanGanGanGanGanGanGanGanGanGanNAP, AlnGanNAP, AlnGanGanGanGanGanP, AlnGanGanGanGanGanGanGanGanNap, AlnGanGanGanGanGanGanNap, AlnGanNap, AlnGanGanNAP, AlnNAP, AlnNap, AlnGanGanNap, AlnNap, Al3(X ═ Cl, Br, I) or CH3NH3PbX3(X ═ Cl, Br, I) quantum dots.
According to a preferred embodiment of the present application, the quantum dots are water-soluble quantum dots.
In a specific embodiment, the water-soluble quantum dot surface is linked with a ligand, wherein the ligand comprises a hydrophilic functional group, and the hydrophilic functional group comprises at least one of, but not limited to, a carboxyl group, a hydroxyl group, an aldehyde group, an amide group, an amino group, a sulfonic acid group, a sulfinic acid group, and a phosphoric acid group.
According to a preferred embodiment of the present application, the first solvent includes at least one of deionized water, an alcohol solvent, and a basic solution. However, the exemplary embodiments of the present application are not limited thereto.
In a specific embodiment, the first solvent comprises at least one of deionized water, methanol, ethanol, and aqueous sodium hydroxide.
According to a preferred embodiment of the present application, the quantum dots are oil-soluble quantum dots.
In a specific embodiment, the surface of the oil-soluble quantum dot is connected with a ligand, and the ligand comprises at least one of saturated or unsaturated amine, saturated or unsaturated acid and alkyl phosphine with the carbon atom number of more than or equal to 6. However, the exemplary embodiments of the present application are not limited thereto. The inventors found that the ligand on the surface of the oil-soluble quantum dot contributes to improving the luminescent quality of the quantum dot complex and improving the luminescent efficiency of the quantum dot complex.
In a specific embodiment, the ligand comprises at least one of tetradecanoic acid, hexadecanoic acid, octadecanoic acid, eicosanoic acid, oleic acid, tributylamine, tri-n-octylamine, oleylamine, trioctylphosphine.
According to a preferred embodiment of the present application, the first solvent comprises at least one of alkanes, alkenes, halogenated hydrocarbons, aromatic hydrocarbons, ethers, amines, amides, ketones, esters having a boiling point in the range of 40 ℃ to 150 ℃. However, the exemplary embodiments of the present application are not limited thereto.
In a specific embodiment, the first solvent comprises at least one of N-hexane, N-heptane, chloroform, toluene, N-dimethylformamide.
According to some preferred embodiments of the present application, the hydrogel material comprises 0.1 wt% to 50 wt% of the quantum dot-hydrogel hybrid system.
In a specific embodiment, the hydrogel material accounts for 5 wt% to 20 wt% of the quantum dot-hydrogel hybrid system.
The inventor finds that the mass ratio of the hydrogel material has a key effect on the stability and the luminescence performance of the quantum dot composite film. If the mass ratio of the hydrogel material is too low, the water and oxygen barrier property of the quantum dot-hydrogel layer is deteriorated, so that the quantum dot cannot be effectively protected; if the mass ratio of the hydrogel material is too high, the mixing uniformity of the hydrogel material and the quantum dot solution can be influenced, and the luminous brightness of the quantum dot composite film can be further influenced.
According to some preferred embodiments of the present application, the coating manner of S1-2 includes any one of spin coating, blade coating, roll coating, spray coating, drop coating, inkjet printing, transfer printing, screen printing, dipping, and casting.
Quantum dot composite films according to some exemplary embodiments of the present application will be described in more detail below with reference to examples; however, the exemplary embodiments of the present application are not limited thereto.
Example 1
Quantum dot composite film 1:
the method comprises the following steps: CH (CH)3NH3PbBr3Perovskite quantum dot-sodium alginate layer; and
coated on CH3NH3PbBr3SiO contained on surface of perovskite quantum dot-sodium alginate layer2The water-resistant layer of (2).
Preparation of quantum dot composite film 1:
s1, adding CH3NH3PbBr3The perovskite quantum dots, chloroform and sodium alginate are evenly mixed and stirred to obtain CH3NH3PbBr3A perovskite quantum dot-sodium alginate mixed system;
wherein the mass of the sodium alginate accounts for CH3NH3PbBr3The mass of the perovskite quantum dot-sodium alginate mixed system is 20 percent.
S2, adding CH3NH3PbBr3Coating the perovskite quantum dot-sodium alginate mixed system on a substrate material, and curing the coated substrate material to obtain the cured CH3NH3PbBr3Perovskite quantum dot-sodium alginate mixture;
s3, curing the CH3NH3PbBr3Separating the perovskite quantum dot-sodium alginate mixture from the substrate material to obtain CH3NH3PbBr3Perovskite quantum dot-sodium alginate layer;
s4, adding CH3NH3PbBr3Perovskite quantum dot-alginic acidAnd soaking the sodium layer in methyl orthosilicate for 5min, taking out the sodium layer, and placing the sodium layer in the air for a period of time to obtain the quantum dot composite film 1.
Characterization of quantum dot composite film 1:
testing the emission spectrum and the luminous efficiency of the fluorescent spectrophotometer with PR670 multiple-diaphragm, and determining the luminous wavelength to be 540 nm; the luminous efficiency was measured to be 62% with 446nm as the excitation wavelength.
The composite film is placed in a test box with the humidity of 85% and the temperature of 85 ℃ for a week, and the luminous wavelength of the composite film is 542nm and the luminous efficiency of the composite film is 60% under the same test conditions.
Example 2
Quantum dot composite film 2:
the method comprises the following steps: an InP quantum dot-sodium alginate layer; and
and the water-blocking layer is coated on the surface of the InP quantum dot-sodium alginate layer and contains polysiloxane.
Preparation of the quantum dot composite film 2:
s1, uniformly mixing and stirring the water-soluble InP quantum dots, deionized water and sodium alginate to obtain an InP quantum dot-sodium alginate mixed system;
wherein the mass of the sodium alginate accounts for 20% of the mass of the InP quantum dot-sodium alginate mixed system.
S2, coating the InP quantum dot-sodium alginate mixed system on a substrate material, and curing the coated substrate material to obtain a cured InP quantum dot-sodium alginate mixture;
s3, separating the solidified InP quantum dot-sodium alginate mixture from the substrate material to obtain an InP quantum dot-sodium alginate layer;
s4, soaking the InP quantum dot-sodium alginate layer in octyl triethoxysilane, taking out after soaking for 5min, and standing in the air for a period of time to obtain the quantum dot composite membrane 2.
Characterization of the quantum dot composite film 2:
testing the emission spectrum and the luminous efficiency of the fluorescent spectrophotometer with PR670 multi-diaphragm, and determining the luminous wavelength to be 628 nm; the luminescence efficiency was measured to be 53% with 446nm as the excitation wavelength.
The composite film is placed in a test box with the humidity of 85% and the temperature of 85 ℃ for a week, and under the same test conditions, the luminous wavelength of the composite film is determined to be 629nm, and the luminous efficiency is determined to be 50%.
Example 3
Quantum dot composite film 3:
the method comprises the following steps: a CdSe quantum dot-polyacrylamide layer; and
SiO coated on the surface of the CdSe quantum dot-polyacrylamide layer2And a water-resistant layer of polysiloxane.
Preparation of the quantum dot composite film 3:
s1, uniformly mixing and stirring the water-soluble CdSe quantum dots, ethanol and the polyacrylamide hydrogel material to obtain a CdSe quantum dot-polyacrylamide mixed system;
wherein the mass of the polyacrylamide hydrogel material accounts for 30% of the mass of the CdSe quantum dot-polyacrylamide mixed system.
S2, coating the CdSe quantum dot-polyacrylamide mixed system on a substrate material, and curing the coated substrate material to obtain a cured CdSe quantum dot-polyacrylamide mixture;
s3, separating the cured CdSe quantum dot-polyacrylamide mixture from the substrate material to obtain a CdSe quantum dot-polyacrylamide layer;
s4, spraying the mixed solution of ethyl orthosilicate and dodecyl trimethoxy silane on the surface of the CdSe quantum dot-polyacrylamide layer, and standing for a period of time in an environment with certain humidity to obtain the quantum dot composite film 3.
Characterization of the quantum dot composite film 3:
testing the emission spectrum and the luminous efficiency of the fluorescent spectrophotometer with PR670 multi-diaphragm, and determining the luminous wavelength to be 528 nm; the luminous efficiency was measured to be 73% with 446nm as the excitation wavelength.
The composite film is placed in a test box with the humidity of 85% and the temperature of 85 ℃ for a week, and under the same test conditions, the luminous wavelength of the composite film is 529nm, and the luminous efficiency is 71%.
Example 4
Quantum dot composite film 4:
the method comprises the following steps: a CdSe quantum dot-polyacrylamide layer; and
SiO coated on the surface of the CdSe quantum dot-polyacrylamide layer2The water-resistant layer of (2).
Preparation of the quantum dot composite film 4:
s1, uniformly mixing and stirring the water-soluble CdSe quantum dots, ethanol and the polyacrylamide hydrogel material to obtain a CdSe quantum dot-polyacrylamide mixed system;
wherein, the mass of the polyacrylamide hydrogel material accounts for 50% of the mass of the CdSe quantum dot-polyacrylamide mixed system.
S2, coating the CdSe quantum dot-polyacrylamide mixed system on a substrate material, and curing the coated substrate material to obtain a cured CdSe quantum dot-polyacrylamide mixture;
s3, separating the cured CdSe quantum dot-polyacrylamide mixture from the substrate material to obtain a CdSe quantum dot-polyacrylamide layer;
s4, soaking the CdSe quantum dot-polyacrylamide layer in ethyl orthosilicate for 5min, taking out the CdSe quantum dot-polyacrylamide layer, and placing the CdSe quantum dot-polyacrylamide layer in air for a period of time to obtain the quantum dot composite film 4.
Characterization of the quantum dot composite film 4:
testing the emission spectrum and the luminous efficiency of the fluorescent spectrophotometer with PR670 multi-diaphragm, and determining the luminous wavelength to be 527 nm; the luminous efficiency was measured to be 76% with 446nm as the excitation wavelength.
The composite film is placed in a test box with the humidity of 85% and the temperature of 85 ℃ for a week, and the luminous wavelength of the composite film is 528nm and the luminous efficiency of the composite film is 75% under the same test conditions.
Comparative example 1
Quantum dot composite film 5:
CH3NH3PbBr3perovskite quantum dot-PVDF composite fluorescent film.
Preparation of the quantum dot composite film 5:
s1, adding CH3NH3PbBr3The polymer components of PVDF, n-octylamine and dimethyl sulfoxide are mixed uniformly and stirred to obtain CH3NH3PbBr3Perovskite quantum dot-PVDF mixed solution;
s2, adding CH3NH3PbBr3Mechanically stirring the perovskite quantum dot-PVDF mixed solution, dispersing at high speed, removing impurities, and removing bubbles in vacuum to obtain CH3NH3PbBr3Perovskite quantum dot-PVDF film forming solution;
s3, adding CH3NH3PbBr3Uniformly coating the perovskite quantum dot-PVDF film-forming solution on a substrate material, and drying to obtain CH3NH3PbBr3Perovskite quantum dot-PVDF complex fluorescent film, namely quantum dot complex film 5.
Characterization of the quantum dot composite film 5:
testing the emission spectrum and the luminous efficiency of the spectrophotometer by using a PR670 multi-diaphragm fluorescence spectrophotometer, and determining that the luminous wavelength is 532 nm; the luminous efficiency was measured to be 37% with 446nm as the excitation wavelength.
The composite film is placed in a test box with the humidity of 85% and the temperature of 85 ℃ for a week, and under the same test conditions, the luminous wavelength of the composite film is determined to be 532nm, and the luminous efficiency is determined to be 13%.
As can be seen from the above examples, the quantum dot composite film of the present application, when placed in a test chamber having a humidity of 85% and a temperature of 85 ℃, had a luminous efficiency decreased by 5% or less, while the quantum dot film of the comparative example had a luminous efficiency decreased by 24%. The quantum dot composite membrane comprises a quantum dot-hydrogel layer and a water-blocking layer coated on the surface of the quantum dot-hydrogel layer, wherein hydrogel in the quantum dot-hydrogel layer has a protective effect on quantum dots dispersed in the hydrogel layer, the adverse effects of water vapor and oxygen in the external environment on the quantum dots are reduced, and the water-blocking layer coated on the surface of the quantum dot-hydrogel layer further blocks the permeation of external water oxygen and the like, so that the quantum dot composite membrane is low in sensitivity to factors such as water oxygen and the like and higher in stability.
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 (8)

1. A quantum dot composite film is characterized by comprising the following components:
a quantum dot-hydrogel layer comprising a hydrogel, and quantum dots dispersed in the hydrogel; and
a water-resistant layer coated on the surface of the quantum dot-hydrogel layer, wherein the water-resistant layer contains SiO2And polysiloxane.
2. A method of preparing a quantum dot composite film according to claim 1, comprising the steps of:
s1, providing a quantum dot-hydrogel layer;
s2, coating a silanization reagent on the surface of the quantum dot-hydrogel layer;
s3, after the coated quantum dot-hydrogel layer is placed for a period of time, the silanization reagent performs hydrolysis reaction, and SiO contained in the surface of the quantum dot-hydrogel layer is formed2And/or a water-resistant layer of polysiloxane to obtain the quantum dot composite film.
3. The method for preparing a quantum dot composite film according to claim 2, wherein the coating manner of S2 comprises: and soaking the quantum dot-hydrogel layer in a silanization reagent for a period of time, and taking out.
4. The method for preparing a quantum dot composite film according to claim 2, wherein the coating manner of S2 comprises: spraying and/or sprinkling a silylating agent on the surface of the quantum dot-hydrogel layer.
5. The method of claim 2, wherein the silylation agent comprises at least one of methyl orthosilicate, ethyl orthosilicate, trimethoxysilane, triethoxysilane, dimethyldichlorosilane, 3-aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and vinyltriethoxysilane.
6. The method of claim 2, wherein S1 comprises the steps of:
s1-1, mixing the quantum dots, the hydrogel material and a first solvent to obtain a quantum dot-hydrogel mixed system;
s1-2, coating the quantum dot-hydrogel mixed system on a substrate material;
s1-3, carrying out curing treatment on the coated substrate material to form a cured quantum dot-hydrogel mixture;
s1-4, separating the solidified quantum dot-hydrogel mixture from the substrate material to obtain the quantum dot-hydrogel layer.
7. The method for preparing a quantum dot composite film according to claim 6, wherein the hydrogel material comprises at least one of a natural polymer hydrogel, a synthetic polymer hydrogel, and a hybrid hydrogel of natural and synthetic polymers.
8. The preparation method of the quantum dot composite film according to claim 6, wherein the hydrogel material accounts for 0.1-50 wt% of the quantum dot-hydrogel mixed system.
CN201910471044.5A 2019-05-31 2019-05-31 Quantum dot composite film and preparation method thereof Active CN110129027B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910471044.5A CN110129027B (en) 2019-05-31 2019-05-31 Quantum dot composite film and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910471044.5A CN110129027B (en) 2019-05-31 2019-05-31 Quantum dot composite film and preparation method thereof

Publications (2)

Publication Number Publication Date
CN110129027A CN110129027A (en) 2019-08-16
CN110129027B true CN110129027B (en) 2022-06-07

Family

ID=67583483

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910471044.5A Active CN110129027B (en) 2019-05-31 2019-05-31 Quantum dot composite film and preparation method thereof

Country Status (1)

Country Link
CN (1) CN110129027B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113046057A (en) * 2021-03-05 2021-06-29 苏州星烁纳米科技有限公司 Quantum dot, core-shell quantum dot prepared from quantum dot and preparation method of core-shell quantum dot

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105085999A (en) * 2015-08-07 2015-11-25 复旦大学 Biocompatible quantum dot light-emitting film and preparation method thereof
CN105870305A (en) * 2016-04-27 2016-08-17 纳晶科技股份有限公司 Quantum dot film and preparation method therefor
CN106505137A (en) * 2016-11-01 2017-03-15 厦门世纳芯科技有限公司 Excellent quantum dot reinforcing membrane of a kind of optical effect and preparation method thereof
CN107650452A (en) * 2017-01-05 2018-02-02 武汉保丽量彩科技有限公司 Antioxidant quantum dot polymer optical film and preparation method and application thereof
CN107817540A (en) * 2014-07-18 2018-03-20 凸版印刷株式会社 Wavelength conversion sheet timber-used diaphragm, wavelength convert sheet material and back light unit
CN108203561A (en) * 2017-12-27 2018-06-26 深圳市华星光电技术有限公司 A kind of leaded light plate coating, preparation method and back light module unit structure

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107817540A (en) * 2014-07-18 2018-03-20 凸版印刷株式会社 Wavelength conversion sheet timber-used diaphragm, wavelength convert sheet material and back light unit
CN105085999A (en) * 2015-08-07 2015-11-25 复旦大学 Biocompatible quantum dot light-emitting film and preparation method thereof
CN105870305A (en) * 2016-04-27 2016-08-17 纳晶科技股份有限公司 Quantum dot film and preparation method therefor
CN106505137A (en) * 2016-11-01 2017-03-15 厦门世纳芯科技有限公司 Excellent quantum dot reinforcing membrane of a kind of optical effect and preparation method thereof
CN107650452A (en) * 2017-01-05 2018-02-02 武汉保丽量彩科技有限公司 Antioxidant quantum dot polymer optical film and preparation method and application thereof
CN108203561A (en) * 2017-12-27 2018-06-26 深圳市华星光电技术有限公司 A kind of leaded light plate coating, preparation method and back light module unit structure

Also Published As

Publication number Publication date
CN110129027A (en) 2019-08-16

Similar Documents

Publication Publication Date Title
EP2669350B1 (en) Composition containing quantum dot fluorescent body, molded body of quantum dot fluorescent body dispersion resin, structure containing quantum dot fluorescent body, light-emitting device, electronic apparatus, mechanical device, and method for producing molded body of quantum dot fluorescent body dispersion resin
RU2648084C2 (en) Ligands based on polydimethylsiloxane for quantum points in organosilicone materials
CN106715643B (en) For dispersing quantum dot in organosilicon main body to obtain the siloxanes ligand of the color converter for LED illumination
EP3147956B1 (en) Led package, backlight unit and illumination device including same, and liquid crystal display device
CN110272660B (en) Quantum dot ink, preparation method of quantum dot color film and quantum dot color film
CN110129027B (en) Quantum dot composite film and preparation method thereof
WO2017166106A1 (en) Composite comprising semiconductor nanocrystals and preparing method therefor
CN110938424B (en) Assembled composite material with quantum dots and nanosheets interconnected and preparation method thereof
CN110275351A (en) The preparation method and quantum dot film of quantum dot film
CN101074368A (en) Light emitting composition, light source device, and display device
CN106813209A (en) Quantum dot film, the manufacture method of quantum dot film and the display containing the quantum dot film
TW201947007A (en) Crosslinked ligands
KR102264799B1 (en) Luminescent material and electronic device having a display function using the same
CN109439067A (en) Quantum dot ink and quantum stippling film
JP7367894B2 (en) Ink compositions, light conversion layers, color filters and light conversion films
KR101841616B1 (en) Semiconductor nanocrystal-siloxane composite resin and preparation method thereof
CN108305928A (en) Wavelength convert component and light-emitting device
KR101878371B1 (en) Preparaion method of semiconductor nanocrystal composite resin composition
KR20160117091A (en) A method of preparing optical film comprising quantum dots
CN110137330A (en) Quantum dot LED light source and preparation method thereof
WO2021246181A1 (en) Method for printing ink composition for formation of light conversion layer, method for forming light conversion layer and cleaning liquid
CN116023929A (en) Surface modified quantum dot, quantum dot compound, preparation method of surface modified quantum dot and quantum dot product
CN110157410A (en) The preparation method of quantum dot compound and product prepared therefrom
KR20220089068A (en) A quantum dot, a quantum dot dispersion, a light converting curable composition, a color filter, a light converting laminating unit and a display device
TW202417395A (en) Quantum dot composite structure and method for forming the same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant