CN109929538A

CN109929538A - A kind of quantum dot composite material and preparation method thereof

Info

Publication number: CN109929538A
Application number: CN201711350474.9A
Authority: CN
Inventors: 叶炜浩
Original assignee: TCL Corp
Current assignee: TCL Corp
Priority date: 2017-12-15
Filing date: 2017-12-15
Publication date: 2019-06-25

Abstract

The present invention discloses a kind of quantum dot composite material and preparation method thereof, and the quantum dot composite material includes: core, and the material of the core is upconversion fluorescence nano material；Wall, the wall coat the core；Quantum dot, the quantum dot are incorporated in the interval layer surface, and the wall is used to reduce the non-radiative decay rate when upconversion fluorescence nano material transmits energy to the quantum dot；The material of the wall is polymer material.It is for reducing the non-radiative decay rate when upconversion fluorescence nano material transmits energy to the quantum dot that the wall, which is added, in the present invention among the upconversion fluorescence nano material and the quantum dot.Infrared light is changed into visible radiation using the upper transformation of upconversion fluorescence nano material by infrared ray excited upconversion fluorescence nano material, excitation quantum dot light emitting is acted on using energy transmission, to achieve the purpose that infrared ray excited quantum dot light emitting.

Description

A kind of quantum dot composite material and preparation method thereof

Technical field

The present invention relates to quantum dot fields more particularly to a kind of quantum dot composite material and preparation method thereof.

Background technique

Quantum dot is widely used in physics, chemistry and biology doctor as a kind of novel nano-material best in quality Etc. fields, the especially research in fields such as illumination, display, laser and biosensors.Since quantum dot size is less than The Exciton Bohr Radius of its body material has strong quantum size effect, as the reduction of size its electronic structure is by body material Quasi-continuous band structure become the discrete energy level structure of similar atom, while energy gap broadens, shine blue shift, passes through and changes quantum The size and component of point can accurately regulate and control the luminescent color of quantum dot.

Quantum dot has continuously distributed excitation spectrum, and being only smaller than 10 nm of emission peak any wavelength below can quilt For exciting fluorescence.The spectral region applied to quantum dot excitation extends to visible light region by UV light region at present.So And the quanta point material that can be effectively excited by infrared light has not been reported.

Furthermore quantum dot belongs to Nonequilibrium Materials, biggish specific surface area, high surface energy and poor environmental stability Oxidation and photo-thermal is caused to be degenerated.Quanta point material investment is in the devices in application, will necessarily be to quantum dot in the case of strong light irradiation Fluorescence property have an impact.Studies have shown that ultraviolet irradiation will increase thermal excitation process, such as photooxidation and curing/sintering, the amount of making Son point luminous intensity reduces, emission peak deviates.This is because chemistry occurs for (1) instead in the electron hole that quantum dot surface generates It answers, forms defect on surface；(2) so that mean temperature is higher than 50 degrees Celsius by photonic absorption, generate part, of short duration high temperature Point, makes quantum dot reunite.

Therefore, the existing technology needs to be improved and developed.

Summary of the invention

In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of quantum dot composite material and its preparations Method, it is intended to existing direct phenomena such as leading to quantum dot surface oxidation, local sintering using ultraviolet excitation quantum dot is solved, and Existing infrared light can not excite the problem of quantum dot light emitting.

Technical scheme is as follows:

A kind of quantum dot composite material, wherein include:

Core, the material of the core are upconversion fluorescence nano material；

Wall, the wall coat the core；

Quantum dot, the quantum dot are incorporated in the interval layer surface, and the wall, which is used to reduce the up-conversion fluorescence, to be received Non-radiative decay rate when rice material transmits from energy to the quantum dot；

The material of the wall is polymer material.

The quantum dot composite material, wherein the wall is made of 2-10 layer material, the total thickness of the wall Degree is denoted as d, and d 5-20nm, preferred d are 5-15nm, and preferred d is 8-12nm.

The quantum dot composite material, wherein the interval layer surface is combined with ligand.Preferably, the ligand choosing In the organic ligand of self-contained sulfydryl, amino-containing organic ligand, carboxylic acid and carboxylic acid derivates organic ligand and parents' polymer It is one or more.

The quantum dot composite material, wherein the up-conversion fluorescence nanometer of the activator doping as nuclear material In material matrix material, the upconversion fluorescence nano material host material is selected from fluoride upconversion fluorescence nano material matrix In material, oxide upconversion fluorescence nano material host material and composite oxides upconversion fluorescence nano material host material One kind；In the upconversion fluorescence nano material host material of activator and the sensitizer doping as nuclear material, institute The upconversion fluorescence nano material host material is stated on fluoride upconversion fluorescence nano material host material, oxide One of fluorescent nano material converted host material and composite oxides upconversion fluorescence nano material host material.Into one Step, the fluoride upconversion fluorescence nano material host material are selected from NaYF₄、NaGaF₄、CaF₂、NaSrF₄、BaY₂F₄、 LiYF₄、ScYF₄、NaLnF₄、SrF₂、BaF₂、MnF₂And Cs₂GeF₆One of.Further, the oxide up-conversion fluorescence is received Rice material matrix material is selected from Y₂O₃、ZrO₂、TiO₂、Gd₂O₃, doping In₂O₃, doping SrY₂O₄, doping TeO₂, doping Al₂O₃, doping ZnO₂, doping Lu₂O₃, doping Er₂O₃, doping Eu₂O₃, doping CeO₂With the La of doping₂O₃In It is a kind of.Further, the composite oxides upconversion fluorescence nano material host material is selected from LiNbO₃、Ln₂BaZnO₂、ALn (MoO₄)₂、GdVO₄、YVo₄、CaZrO₃、CaSc₂O₄、KLu(WO₄)₂、CaCs₂O_4、CaMoO₄、BaTiO₃、Y₂Ti₂O₇、Y₂Si₂O₇、 Y₂SiO₅、Gd₃Ga₅O₁₂、Y₃Al₅O₁₂And Y₂CaGe₄O₁₂One of.

The quantum dot composite material, wherein the quantum dot be selected from CdSe, CdS, ZnSe, ZnS, PbSe, PbS, CdTe、ZnO、MgO、CeO₂、NiO、TiO₂、InP、CaF₂、CdZnS、CdZnSe、CdSeS、PbSeS、ZnCdTe、CdS/ZnS、 CdZnSe/ZnSe、CdSeS/CdSeS/CdS、CdSe/CdZnSe/CdZnSe/ZnSe、CdZnSe/CdZnSe/ZnSe、CdZnS/ ZnS 、CdS/CdZnS/CdZnS/ZnS、CdZnSeS、CdSe/ZnS、CdZnSe/ZnS、CdSe/CdS/ZnS、CdSe/ZnSe/ One of ZnS, CdZnSe/CdZnS/ZnS and InP/ZnS or a variety of.

The quantum dot composite material, wherein the polymer material for being used as interval is selected from polystyrene-Malaysia Acid anhydride, Polyphenylethylene-butyl acrylate, polystyrene-acrylonitrile, nitrocellulose, end hydroxy butadiene, polyacrylic acid-the third Olefin(e) acid butyl ester, polyacrylic acid-styrene, poly- trimethylolpropane trimethacrylate, polymethyl methacrylate or polyamide- Amine.

A kind of preparation method of quantum dot composite material, wherein comprising steps of

A kind of nuclear particle is provided, the material of the nuclear particle is upper conversion fluorescent nano material；

It coats to form the wall on the nuclear particle surface, the material of the wall is polymer material；

The nano-grain is surface modified using coating material, obtains the nano material of coating material Particle；

The solution for being dispersed with the nano-grain of coating material is mixed with quantum dot solution, is incorporated in quantum dot The interval layer surface, obtains the quantum dot composite material；

Non-radiative the declining when wall transmits energy to the quantum dot for reducing the upconversion fluorescence nano material The rate of deceleration.

The utility model has the advantages that the present invention, using upconversion fluorescence nano material as core, core outer cladding wall, wall is combined with outside Quantum dot forms the quantum dot composite material.The present invention is among the upconversion fluorescence nano material and the quantum dot It is non-radiative when the upconversion fluorescence nano material transmits energy to the quantum dot for reducing that the wall, which is added, Rate of decay.The infrared ray excited upconversion fluorescence nano material of the present invention is made using the upper conversion of upconversion fluorescence nano material With, infrared light is changed into visible radiation, using energy transmission act on excitation quantum dot light emitting, effectively excited with reaching infrared light The purpose of quantum dot light emitting.

Detailed description of the invention

Fig. 1 is corresponding NaYF when m is respectively 1,2,3,4,5 in the embodiment of the present invention 1₄:Er³⁺/Yb³⁺@mNaYF₄It is glimmering Light spectrogram.

Fig. 2 is the launching light spectrogram of the corresponding quantum dot composite material of different-thickness wall in the embodiment of the present invention 1.

Fig. 3 is the launching light spectrogram of the corresponding quantum dot composite material of different-thickness wall in the embodiment of the present invention 4.

Fig. 4 is the launching light spectrogram of the corresponding quantum dot composite material of different-thickness wall in the embodiment of the present invention 8.

Fig. 5 is the preparation flow figure of 10 quantum dot composite material of the embodiment of the present invention.

Fig. 6 is the TEM figure for the quantum dot composite material that the embodiment of the present invention 10 is prepared.

Fig. 7 is the launching light spectrogram of the quantum dot composite material of different-thickness wall in the embodiment of the present invention 15, and NaGdF₄:Tm³⁺/Yb³⁺/Nd³⁺Launching light spectrogram.

Specific embodiment

The present invention provides a kind of quantum dot composite material and preparation method thereof, for make the purpose of the present invention, technical solution and Effect is clearer, clear, and the present invention is described in more detail below.It should be appreciated that specific embodiment described herein It is only used to explain the present invention, be not intended to limit the present invention.

The present invention provides a kind of quantum dot composite material preferred embodiment, wherein includes:

Core, the material of the core are upconversion fluorescence nano material；

Wall, the wall coat the core；

Quantum dot, the quantum dot are incorporated in the interval layer surface, and the wall is received for reducing the up-conversion fluorescence Non-radiative decay rate when rice material transmits from energy to the quantum dot.

The present invention is using upconversion fluorescence nano material as core, core outer cladding wall, and quantum dot, shape are combined with outside wall At the quantum dot composite material.The present invention be added among the upconversion fluorescence nano material and the quantum dot it is described between Interlayer is in order to avoid the quantum dot and the upconversion fluorescence nano material directly contact and generate lossy surface wave. Surface wave is a kind of nonradiative transition, can be as consuming in the form of heat.Mechanism is restricted according to distance, when up-conversion fluorescence is received When rice material and quantum dot interval are too small, non-radiative decay rate is improved rapidly, and attenuation rate reduces, up-conversion fluorescence The energy of nano material radiation is not transferred to quantum dot, but discharges in the form of heat.Therefore, in upper conversion of the invention An interlayer interlayer is provided between fluorescent nano material and quantum dot, the wall is for reducing the up-conversion fluorescence nanometer Non-radiative decay rate when material transmits from energy to the quantum dot, avoids the quantum dot and the up-conversion fluorescence nanometer Material directly contacts and generates lossy surface wave.

Through inventor the study found that space layer d of the invention is arranged in 5 nm≤d≤20nm, non-radiative decay Rate slows down, and attenuation rate improves, and the energy efficient of radiation passes to quantum dot, to excite quantum dot light emitting. Because upconversion fluorescence nano material and quantum dot mutually be intended to contact condition when less than 5 nm, due to the effect of surface wave, Transition is discharged with unirradiated form, and quantum dot does not shine；When being greater than 20 nm, due to upconversion fluorescence nano material and quantum Point distance increases, and energy transfer efficiency is reduced, to reduce its luminous intensity.Preferably, 5 nm≤d≤15nm, it is furthermore preferred that 8 nm≤d≤12nm.By infrared ray excited upconversion fluorescence nano material, the upper conversion of upconversion fluorescence nano material is utilized Effect, is changed into visible radiation for infrared light, and under a certain distance, sends out the quantum dot in ground state by energy transmission Light improves the utilization rate of infrared light to achieve the purpose that infrared ray excited quantum dot light emitting, and effectively prevents so existing Directly lead to quantum dot surface oxidation, local sintering using ultraviolet excitation quantum dot, and has good light steady Qualitative and luminous intensity.The wall can be one layer, it is preferable that for uniform composite particles, the interval is prepared Layer can also be formed by 2-10 straton material layer.

Preferably, the upconversion fluorescence nano material as nuclear material is the up-conversion fluorescence nanometer of activator doping Material matrix material.It is further preferred that the activator is selected from Tm³⁺、Er³⁺、Pr³⁺、Nd³⁺、Sm³⁺、Ho³⁺、Ti²⁺、Cr³⁺、Ni² ⁺、Mo³⁺、Re⁴⁺And Os⁴⁺Deng one of or it is a variety of.Still more preferably, the activator doping as nuclear material Upconversion fluorescence nano material host material in, upconversion fluorescence nano material host material be selected from fluoride up-conversion fluorescence Nano material host material, oxide upconversion fluorescence nano material host material and composite oxides up-conversion fluorescence nanometer material Expect one of host material etc..

Specifically, the fluoride upconversion fluorescence nano material host material as nuclear material is selected from NaYF₄、 NaGaF₄、CaF₂、NaSrF₄、BaY₂F₄、LiYF₄、ScYF₄、NaLnF₄(Ln=Dy, Ho, Er, Tm, Yb, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho or Lu), SrF₂、BaF₂、MnF₂And Cs₂GeF₆One of Deng.With for example, the upconversion fluorescence nano material For NaYF₄:Er³⁺、NaYF₄:Tm³⁺/Nd³⁺、CaF₂:Er³⁺、NaGdF₄:Ho³⁺Deng one of or it is a variety of.

Specifically, the oxide upconversion fluorescence nano material host material as nuclear material is selected from Y₂O₃、ZrO₂、 TiO₂、Gd₂O₃、In₂O₃、SrY₂O₄、TeO₂、Al₂O₃、ZnO₂、Lu₂O₃、Er₂O₃、Eu₂O₃、CeO₂And La₂O₃One of Deng.It is used as Citing, the upconversion fluorescence nano material can be In₂O₃:Er³⁺、Y₂O₃:Er³⁺Deng one of or it is a variety of.

Specifically, the composite oxides upconversion fluorescence nano material host material as nuclear material is selected from LiNbO₃、Ln₂BaZnO₂(Ln=Y、Gd)、ALn(MoO₄)₂(A=Li, Na, K, Ag, Ln=La, Gd, Y), GdVO₄、YVo₄、CaZrO₃、 CaSc₂O₄、KLu(WO₄)₂、CaCs₂O_4、CaMoO₄、BaTiO₃、Y₂Ti₂O₇、Y₂Si₂O₇、Y₂SiO₅、Gd₃Ga₅O₁₂、Y₃Al₅O₁₂With Y₂CaGe₄O₁₂One of Deng.With for example, the upconversion fluorescence nano material is LiGd (MoO₄)₂:Er³⁺。

It is further preferred that the upconversion fluorescence nano material as nuclear material is that activator and sensitizer adulterate Upconversion fluorescence nano material host material.The activator is used cooperatively with sensitizer, and energy can be enhanced in the sensitizer Transmitting, improves the luminous intensity of the activator.Still more preferably, the activator is selected from Tm³⁺、Er³⁺、Pr³⁺、Nd³⁺、 Sm³⁺、Ho³⁺、Ti²⁺、Cr³⁺、Ni²⁺、Mo³⁺、Re⁴⁺And Os⁴⁺Deng one of or it is a variety of；The sensitizer is Yb³⁺.Further Preferably, described in the upconversion fluorescence nano material host material of activator and the sensitizer doping as nuclear material Upconversion fluorescence nano material host material is converted glimmering on fluoride upconversion fluorescence nano material host material, oxide One of light nano material host material and composite oxides upconversion fluorescence nano material host material etc..

Specifically, the fluoride upconversion fluorescence nano material host material as nuclear material is selected from NaYF₄、 NaGaF₄、CaF₂、NaSrF₄、BaY₂F₄、LiYF₄、ScYF₄、NaLnF₄(Ln=Dy, Ho, Er, Tm, Yb, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho or Lu), SrF₂、BaF₂、MnF₂And Cs₂GeF₆One of Deng.With for example, the upconversion fluorescence nano material It can be NaYF₄:Er³⁺/Yb³⁺、NaYF₄:Tm³⁺/Yb³⁺/Nd³⁺、CaF₂:Er³⁺/Yb³⁺、NaGdF₄:Ho³⁺/Yb³⁺One of Deng Or it is a variety of.

Specifically, the oxide upconversion fluorescence nano material host material as nuclear material is selected from Y₂O₃、ZrO₂、 TiO₂、Gd₂O₃、In₂O₃、SrY₂O₄、TeO₂、Al₂O₃、ZnO₂、Lu₂O₃、Er₂O₃、Eu₂O₃、CeO₂And La₂O₃One of Deng.It is used as Citing, the upconversion fluorescence nano material can be In₂O₃:Er³⁺/Yb³⁺、Y₂O₃:Er³⁺/Yb³⁺Deng one of or it is a variety of.

Specifically, the composite oxides upconversion fluorescence nano material host material as nuclear material is selected from LiNbO₃、Ln₂BaZnO₂(Ln=Y、Gd)、ALn(MoO₄)₂(A=Li, Na, K, Ag, Ln=La, Gd, Y), GdVO₄、YVo₄、CaZrO₃、 CaSc₂O₄、KLu(WO₄)₂、CaCs₂O_4、CaMoO₄、BaTiO₃、Y₂Ti₂O₇、Y₂Si₂O₇、Y₂SiO₅、Gd₃Ga₅O₁₂、Y₃Al₅O₁₂With Y₂CaGe₄O₁₂One of Deng.With for example, the upconversion fluorescence nano material is NaYF₄:Er³⁺/Yb³⁺、NaYF₄:Tm³⁺/ Yb³⁺/Nd³⁺、CaF₂:Er³⁺/Yb³⁺、NaGdF₄:Ho³⁺/Yb³⁺Deng one of or it is a variety of.With for example, the up-conversion fluorescence Nano material can be LiGd (MoO₄)₂:Er³⁺/Yb³⁺。

Preferably, the diameter of the core is 7-20nm, and the dissolubility that the size of core will lead to greatly very much composite material reduces, difficult With subsequent applications.

Preferably, the quantum dot is selected from CdSe, CdS, ZnSe, ZnS, PbSe, PbS, CdTe, ZnO, MgO, CeO₂、 NiO、TiO₂、InP、CaF₂、CdZnS、CdZnSe、CdSeS、PbSeS、ZnCdTe、CdS/ZnS、CdZnSe/ZnSe、CdSeS/ CdSeS/CdS、CdSe/CdZnSe/CdZnSe/ZnSe、CdZnSe/CdZnSe/ZnSe、CdZnS/ZnS 、CdS/CdZnS/ CdZnS/ZnS、CdZnSeS、CdSe/ZnS、CdZnSe/ZnS、CdSe/CdS/ZnS、CdSe/ZnSe/ZnS、CdZnSe/ One of CdZnS/ZnS and InP/ZnS etc. or a variety of.

It describes in detail below to the material of wall of the present invention.

It is for dropping that the wall, which is added, among the upconversion fluorescence nano material and the quantum dot in the present invention Non-radiative decay rate when the low upconversion fluorescence nano material transmits from energy to the quantum dot.Infrared light of the present invention swashs It sends out upconversion fluorescence nano material and infrared light is changed into visible spoke using the upper transformation of upconversion fluorescence nano material It penetrates, excitation quantum dot light emitting is acted on using energy transmission, to achieve the purpose that infrared light effectively excites quantum dot light emitting.

Preferably, the interval layer surface is combined with coating material, it is further preferred that the coating material is selected from One in the organic ligand of organic ligand, amino-contained containing sulfydryl, carboxylic acid and carboxylic acid derivates organic ligand and parents' polymer Kind is a variety of.I.e. the present invention is using organic ligand, the organic ligand of amino-contained, carboxylic acid and carboxylic acid derivates are organic matches containing sulfydryl Body or parents' polymer, are surface modified the wall.Using organic ligand to the interval of the nano-grain Layer is surface modified, and the group (such as amido, sulfydryl, carboxyl) in these organic ligands can be with the metallic element of quantum dot surface In conjunction with so that wall is easier with quantum dot ining conjunction with, providing the site of combination for the quantum dot, formation quantum dot is answered Condensation material.

Preferably, the material as wall is upconversion fluorescence nano material host material, is used as wall material The upconversion fluorescence nano material host material of material namely may be used as in the upconversion fluorescence nano material of nuclear material The material of non-impurity-doped substance.It is converted it is further preferred that the upconversion fluorescence nano material host material is selected from fluoride Fluorescent nano material host material, oxide upconversion fluorescence nano material host material and composite oxides up-conversion fluorescence are received One of rice material matrix material etc..

Specifically, the fluoride upconversion fluorescence nano material host material as wall can be selected from NaYF₄、 NaGaF₄、CaF₂、NaSrF₄、BaY₂F₄、LiYF₄、ScYF₄、NaLnF₄(Ln=Dy, Ho, Er, Tm, Yb, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho or Lu), SrF₂、BaF₂、MnF₂And Cs₂GeF₆One of or it is a variety of.

Specifically, the oxide upconversion fluorescence nano material host material as wall can be selected from Y₂O₃、 ZrO₂、TiO₂、Gd₂O₃、In₂O₃、SrY₂O₄、TeO₂、Al₂O₃、ZnO₂、Lu₂O₃、Er₂O₃、Eu₂O₃、CeO₂And La₂O₃One of or It is a variety of.

Specifically, the composite oxides upconversion fluorescence nano material host material as wall can be selected from LiNbO₃、Ln₂BaZnO₂(Ln=Y、Gd)、ALn(MoO₄)₂(A=Li, Na, K, Ag, Ln=La, Gd, Y), GdVO₄、YVo₄、CaZrO₃、 CaSc₂O₄、KLu(WO₄)₂、CaCs₂O_4、CaMoO₄、BaTiO₃、Y₂Ti₂O₇、Y₂Si₂O₇、Y₂SiO₅、Gd₃Ga₅O₁₂、Y₃Al₅O₁₂With Y₂CaGe₄O₁₂One of or it is a variety of.

It is further preferred that the upconversion fluorescence nano material host material for being used as wall is NaYF₄、NaGdF₄、 CaF₂、NaSrF₄One of or it is a variety of.

It should be noted that upconversion fluorescence nano material host material as material spacer layer be used as the upper of nuclear material Upconversion fluorescence nano material host material in fluorescent nano material converted may be the same or different；Between stacking is formed The material of each sub- material layer of interlayer is identical or different.

Upconversion fluorescence nano material host material of the present invention is used as the mechanism of action of wall: restricting machine according to distance Reason, when upconversion fluorescence nano material and quantum dot interval are too small, non-radiative decay rate is improved rapidly, and attenuation is fast Rate reduces, and the energy of upconversion fluorescence nano material radiation is not transferred to quantum dot, but discharges in the form of heat.When From in 5 nm≤d≤20nm, non-radiative decay rate slows down gauge, and attenuation rate improve, radiation it is energy efficient Ground passes to quantum dot, to excite quantum dot light emitting.In addition, the quantum under upconversion fluorescence nano material host material cladding Surface defect of the point composite material due to having repaired core, reduces vacantly building for upconversion fluorescence nano material particle surface, makes Rare earth ion is preferably doped in lattice, to improve the luminous intensity of quantum dot composite material.

Preferably, the material of the wall is polymer material, and stacking forms the material of each sub- material layer of wall It is identical or different.The polymer material can be non-polar polymer (such as polystyrene (PS)) and its copolymer, such as: it is poly- Styrene maleic anhydride (P (St-MAH)), Polyphenylethylene-butyl acrylate (P (ST-BA)), polystyrene-acrylonitrile (P(ST- AN)), nitrocellulose (NC)；May be end hydroxy butadiene (HTPB)；It for polyacrylic acid (PA) and its can also be copolymerized Object, such as: polyacrylic acid-butyl acrylate (P (AA-BA)), polyacrylic acid-styrene, poly- trimethylolpropane tris acrylic acid The polymer such as ester (PTMPTA), polymethyl methacrylate (PMMA), polyamide-amide (PAMAM).

Inventive polymers material is used as the mechanism of action of wall: mechanism is restricted according to distance, when up-conversion fluorescence is received When rice material and quantum dot interval are too small, non-radiative decay rate is improved rapidly, and attenuation rate reduces, up-conversion fluorescence The energy of nano material radiation is not transferred to quantum dot, but discharges in the form of heat.Through inventor test find, when In 5 nm≤d≤20nm, non-radiative decay rate slows down compartment thickness, and attenuation rate improves, and the energy of radiation has Quantum dot is passed to effect, to excite quantum dot light emitting.

Preferably, the material of the wall is oxide material, and stacking forms the material of each sub- material layer of wall It is identical or different.In the oxide material as material spacer layer and the upconversion fluorescence nano material as nuclear material Oxide upconversion fluorescence nano material host material may be the same or different.Preferably, the institute as material spacer layer It states oxide material and is selected from SiO₂、Fe₃O₄、Al₂O₃And TiO₂Deng one of or it is a variety of.

Oxide material of the present invention is used as the mechanism of action of wall: mechanism is restricted according to distance, when up-conversion fluorescence is received When rice material and quantum dot interval are too small, non-radiative decay rate is improved rapidly, and attenuation rate reduces, up-conversion fluorescence The energy of nano material radiation is not transferred to quantum dot, but discharges in the form of heat.Through inventor test find, when In 5 nm≤d≤20nm, non-radiative decay rate slows down compartment thickness, and attenuation rate improves, and the energy of radiation has Quantum dot is passed to effect, to excite quantum dot light emitting.

In a preferred embodiment, the quantum dot includes core, and the material of the core is up-conversion fluorescence nanometer Material；Wall, the wall coat the core, and the material of the wall is formed by 2-10 straton material layer, institute The material of each sub- material layer is stated independently selected from oxide material, upconversion fluorescence nano material host material or polymer material In two or three.It should be noted that the selection of each sub- material layer material, is to be collocated with oxide material, upper conversion In fluorescent nano material host material or polymer material on the basis of two or three, then it is glimmering to oxide material, upper conversion It is that the specific choice of light nano material host material or polymer material is arranged in pairs or groups as a result, i.e. the oxide material of choosing, In upconversion fluorescence nano material host material or polymer material after two or three of collocation, the material of each sub- material layer Material can independently be in oxide material specific in specific one or more, upconversion fluorescence nano material host material It is specific one or more in one or more or polymer material.The oxide material, upconversion fluorescence nano material base The specific choice of material and polymer material is as described above, and this will not be repeated here.

Oxide material of the present invention, upconversion fluorescence nano material host material, polymeric material material for making clothes material layers The mechanism of action: the folded wall formed restricts mechanism according to distance, when between upconversion fluorescence nano material and quantum dot When too small, non-radiative decay rate is improved rapidly, and attenuation rate reduces, the energy of upconversion fluorescence nano material radiation Amount is not transferred to quantum dot, but discharges in the form of heat.Through inventor test find, when space layer 5 nm≤ In d≤20nm, non-radiative decay rate slows down, and attenuation rate improves, and the energy efficient of radiation passes to quantum dot, To excite quantum dot light emitting.

Preferably, the material for coating the first straton material layer of the core is upconversion fluorescence nano material host material, Second straton material layer coats the first straton material layer, and every kind of posterior sub- material layer coats preceding sub- material layer, shape At the wall, the material of the second straton material layer to last straton material layer independently selected from oxide material, Upconversion fluorescence nano material host material or polymer material；Quantum dot, the quantum dot are incorporated in the interval layer surface, Non-radiative decay speed when the wall transmits energy to the quantum dot for reducing the upconversion fluorescence nano material Rate.

The present invention also provides a kind of preparation method preferred embodiments of quantum dot composite material, comprising steps of

It coats to form the wall on the nuclear particle surface；

It is coated in the step of forming the wall on the nuclear particle surface, cladding is formed by 2-10 layers from material layers Folded to form wall, wherein the first straton material layer coats the core, the second straton material layer coats the first straton material Layer, every kind of posterior sub- material layer coat preceding sub- material layer, form the wall.Preferably, the of the core is coated The material of one straton material layer is upconversion fluorescence nano material host material, and the second straton material layer coats first straton Material layer, every kind of posterior sub- material layer coat preceding sub- material layer, form the wall, the second straton material layer To last straton material layer material independently selected from oxide material, upconversion fluorescence nano material host material or polymerization Object material.

In described the step of being surface modified using coating material to the nano-grain, the surface modification Agent can be organic ligand, carboxylic acid and carboxylic acid derivates organic ligand, the parents' polymer of organic ligand, amino-contained containing sulfydryl Deng one of or it is a variety of.The present invention using containing sulfydryl organic ligand, amino-contained organic ligand, carboxylic acid and carboxylic acid derivates Organic ligand or parents' polymer, are surface modified the wall of the nano-grain.Using containing above-mentioned group The reason of coating material is surface modified the wall of the nano-grain is the metallic element of quantum dot surface It is easy to combine with group in these organic ligands (such as amido, carboxyl, sulfydryl), under certain conditions, quantum dot can be tied It closes on separation layer, formation quantum dot composite material, in the quantum dot composite material, interval layer surface is combined with surface modification Agent, the ligand binding of the surface modification and quantum dot surface make quantum dot be incorporated in the interval layer surface.

The size of the nuclear particle is 7-20nm, space layer 2-20nm, preferably 5-15nm, more preferably 8- 12nm.The present invention can be by the size of change variety classes quantum dot, so that quantum dot composite material issues different wave length Light.

In the preparation method, the sub- material of the wall is formed about nuclear particle material, material spacer layer and stacking The selection of the material of layer is as described above, and details are not described herein.

With for example, the organic ligand containing sulfydryl can be in benzyl mercaptan, thioacetic acid (TGA) and mercaptopropionic acid etc. It is one or more.

With for example, the organic ligand of the amino-contained can be ethylenediamine, octadecyl-to ethylene benzyl-dimethyl Ammonium chloride (OVDAC), N, N- dimethyl benzylamine, L-cysteine (L-Cys), reduced glutathione (GSH), bovine serum albumin (BSA) etc. one of or a variety of.

With for example, the carboxylic acid and carboxylic acid derivates organic ligand can be methyl hexahydro phthalic dimethyl acid anhydrides, neighbour One of stupid dicarboxylic acid anhydride, Sodium Polyacrylate, poly- (acrylic acid-maleic acid acid anhydride) etc. are a variety of.

With for example, parents' polymer can be polyvinylpyrrolidone (PVP), dimethyl silicone polymer (PMDS), one of polyethylene glycol, sulfo group polyaniline of polyethyleneimine (BPEI), amido sealing end etc. or a variety of.

Below by several embodiments, the present invention is described in detail.

Embodiment 1

The preparation method of the quantum dot composite material of the present embodiment comprising steps of

(1) NaYF₄:Er³⁺/Yb³⁺Synthesis:

1), by YCl₃•6H₂O、ErCl₃•6H₂O、YbCl₃•6H₂O, reaction kettle, deoxygenation, 160 DEG C of heat preservations are added in oleic acid and octadecylene 60 minutes；

2) methanol solution and NH of NaOH, is added₄The methanol solution of F, stirring at normal temperature 60 minutes, then 60 DEG C stir 60 minutes, 108 DEG C heat preservation 1 minute, vacuumize 20 minutes, then restore 308 DEG C of normal pressure keep the temperature 20 minutes, be down to room temperature, obtain up-conversion fluorescence and receive Rice material NaYF₄:Er³⁺/Yb³⁺；

(2) NaYF₄:Er³⁺/Yb³⁺@mNaYF₄Synthesis, the m be 1-5 natural number:

1), by YCl₃•6H₂O, reaction kettle is added in oleic acid and octadecylene, and deoxygenation, 150 DEG C keep the temperature 70 minutes；

2) NaYF, is added₄:Er³⁺/Yb³⁺Cyclohexane solution, be cooled to 95 DEG C；

3) methanol solution and NH of NaOH, is added₄The methanol solution of F, stirring at normal temperature 60 minutes, then 70 DEG C stir 50 minutes, 110 DEG C heat preservation 1 minute, vacuumize 30 minutes, then restore 310 DEG C of normal pressure keep the temperature 24 minutes, be down to room temperature, obtain NaYF₄:Er³⁺/Yb³ ⁺@NaYF₄；

4) NaYF, is used₄:Er³⁺/Yb³⁺@NaYF₄Replacement step 2) in NaYF₄:Er³⁺/Yb³⁺, repeat step 1) -3) operation, Obtain NaYF₄:Er³⁺/Yb³⁺@2NaYF₄；

5), be repeated as many times step 1) -3 according to the method for step 4)) operation, obtain nano-grain NaYF₄:Er³⁺/Yb³ ⁺@mNaYF₄, m corresponding NaYF when being respectively 1,2,3,4,5₄:Er³⁺/Yb³⁺@mNaYF₄Fluorescence spectra see Fig. 1, can by Fig. 1 Know, the luminous intensity of core can also be increased substantially by only coating wall, to preferably deliver energy to quantum dot；

(3) NaYF₄:Er³⁺/Yb³⁺@mNaYF₄The synthesis of@QDs:

1), by 1 ml, the NaYF of 10 mM₄:Er³⁺/Yb³⁺@mNaYF₄Ethanol solution add to the ethyl alcohol of 5 mL, 1.5%w/w MPS In, and 20 h are stirred at 25 DEG C；Then mercapto-modified NaYF is cleaned multiple times with ethyl alcohol₄:Er³⁺/Yb³⁺@mNaYF₄；

2), by mercapto-modified NaYF₄:Er³⁺/Yb³⁺@mNaYF₄Ethanol solution add in the solution containing quantum dot, quickly 1 h is stirred, the quantum dot composite material NaYF that will finally obtain₄:Er³⁺/Yb³⁺@mNaYF₄@QDs is cleaned 3 times, between different-thickness The emission spectrum of the corresponding quantum dot composite material of interlayer is shown in Fig. 2.

Embodiment 2

(1) NaYF₄:Er³⁺/Yb³⁺Synthesis:

(2) NaYF₄:Er³⁺/Yb³⁺@mNaGdF₄/NaYF₄Synthesis, the m be 2-10 natural number:

1), by GdCl₃•6H₂O, reaction kettle is added in oleic acid and octadecylene, and deoxygenation, 150 DEG C keep the temperature 80 minutes；

2) NaYF, is added₄:Er³⁺/Yb³⁺Cyclohexane solution, be cooled to 90 DEG C；

3) methanol solution and NH of NaOH, is added₄The methanol solution of F, stirring at normal temperature 50 minutes, then 60 DEG C stir 60 minutes, 110 DEG C heat preservation 2 minutes, vacuumize 20 minutes, then restore 310 DEG C of normal pressure keep the temperature 20 minutes, be down to room temperature, obtain NaYF₄:Er³⁺/Yb³ ⁺@NaGdF₄；

4) NaYF, is used₄:Er³⁺/Yb³⁺@NaGdF₄Replacement step 2) in NaYF₄:Er³⁺/Yb³⁺, use YCl₃•6H₂O replacement step 1) GdCl in₃•6H₂O, repeat step 1) -3) operation, obtain NaYF₄:Er³⁺/Yb³⁺@NaGdF₄/NaYF₄；

5), be repeated as many times step 1) -4) operation, obtain nano-grain NaYF₄:Er³⁺/Yb³⁺@mNaGdF₄/NaYF₄；

(3) NaYF₄:Er³⁺/Yb³⁺@mNaGdF₄/NaYF₄The synthesis of@QDs:

1), by 1 ml, the NaYF of 10 mM₄:Er³⁺/Yb³⁺@mNaGdF₄/NaYF₄Ethanol solution add to the second of 4 mL ethylenediamines In alcohol, and 20 h are stirred at 25 DEG C；Then the NaYF of amido modification is cleaned multiple times with ethyl alcohol₄:Er³⁺/Yb³⁺@mNaGdF₄/ NaYF₄；

2), the NaYF for modifying amido₄:Er³⁺/Yb³⁺@mNaGdF₄/NaYF₄Ethanol solution add to the solution containing quantum dot In, quickly stir 1 h, the quantum dot composite material NaYF that will finally obtain₄:Er³⁺/Yb³⁺@mNaGdF₄/NaYF₄@QDs cleaning 3 Time.

Embodiment 3

The preparation method of the quantum dot composite material of the present embodiment is comprising steps of (1) In₂O₃:Er³⁺/Yb³⁺@mIn₂O₃/Y₂O₃'s Synthesis, the natural number that the m is 2~10:

1), In (NO₃)₃•4.5H₂O、CO(NH₂)₂、Yb(NO₃)₃、Er(NO₃)₃It is dissolved in deionized water, is obtained after oil bath stirring white Color precipitating；Obtained white precipitate is cleaned with dehydrated alcohol and deionized water, dries, obtains presoma In (OH)₃:Er³⁺/ Yb³⁺；

2), by In (OH)₃:Er³⁺/Yb³⁺In deionized water, In (NO is added in dispersion₃)₃•4.5H₂O、CO(NH₂)₂, oil bath stirring After obtain white precipitate, obtained white precipitate is cleaned with dehydrated alcohol and deionized water, dry, obtain presoma In (OH)₃:Er³⁺/Yb³⁺@In(OH)₃；

3), by In (OH)₃:Er³⁺/Yb³⁺@In(OH)₃In deionized water, Y (NO is added in dispersion₃)₃、CO(NH₂)₂, oil bath stirring After obtain white precipitate, obtained white precipitate is cleaned with dehydrated alcohol and deionized water, dry, obtain presoma In (OH)₃:Er³⁺/Yb³⁺@In(OH)₃/Y(OH)₃；

4), be repeated as many times step 2-3) operation, obtain In (OH)₃:Er³⁺/Yb³⁺@mIn(OH)₃/Y(OH)₃；

5), by In (OH)₃:Er³⁺/Yb³⁺@mIn(OH)₃/Y(OH)₃It is placed in Muffle furnace, 3 h is calcined at 500 DEG C, are ground after cooling Mill, obtains In₂O₃:Er³⁺/Yb³⁺@mIn₂O₃/Y₂O₃；

(2) In₂O₃:Er³⁺/Yb³⁺@mIn₂O₃/Y₂O₃The synthesis of@QDs:

1), by 1 ml, the In of 10 mM₂O₃:Er³⁺/Yb³⁺@mIn₂O₃/Y₂O₃Ethanol solution add to 5 mL, 1.5%w/w MPS In ethyl alcohol, and 22 h are stirred at 25 DEG C；Then mercapto-modified In is cleaned multiple times with ethyl alcohol₂O₃:Er³⁺/Yb³⁺@mIn₂O₃/ Y₂O₃；

2), by mercapto-modified In₂O₃:Er³⁺/Yb³⁺@mIn₂O₃/Y₂O₃Ethanol solution add in the solution containing quantum dot, Quickly stirring 1 h, the quantum dot composite material In that will finally obtain₂O₃:Er³⁺/Yb³⁺@mIn₂O₃/Y₂O₃@QDs is cleaned 3 times.

Embodiment 4

(1) NaSrF₄:Tm³⁺/Nd³⁺/Yb³⁺Synthesis:

1), by SrCl₂、TmCl₃•6H₂O、NdCl₃•6H₂O、YbCl₃•6H₂O, oleic acid and octadecylene addition reaction kettle, deoxygenation, 160 DEG C heat preservation 60 minutes；

2) methanol solution and NH of NaOH, is added₄The methanol solution of F, stirring at normal temperature 60 minutes, then 60 DEG C stir 60 minutes, 108 DEG C heat preservation 1 minute, vacuumize 20 minutes, then restore 308 DEG C of normal pressure keep the temperature 20 minutes, be down to room temperature, obtain up-conversion fluorescence and receive Rice material NaSrF₄:Tm³⁺/Nd³⁺/Yb³⁺；

(2) NaSrF₄:Tm³⁺/Nd³⁺/Yb³⁺@mSiO₂/NaSrF₄Synthesis, the m be 2-10 natural number:

1), 0.1 mL CO-520,6 mL hexamethylenes and 4 mL, 10 mM NaSrF₄:Tm³⁺/Nd³⁺/Yb³⁺Cyclohexane solution it is mixed Close 10 min of stirring；

2), 0.3 mL CO-520 and 0.06 mL, 30% ammonium hydroxide are added in step 1) solution, seal 20 min of ultrasound, is formed Transparent emulsion；

3) 0.05 mL TEOS, is added to above-mentioned steps 2) in solution, 600 rpm stir 50 h, obtain NaSrF₄:Tm³⁺/ Nd³⁺/Yb³⁺@SiO₂；

4), by NaSrF₄:Tm³⁺/Nd³⁺/Yb³⁺@SiO₂Disperse in deionized water, by SrCl₂、TmCl₃•6H₂O、NdCl₃• 6H₂O、YbCl₃•6H₂O, reaction kettle is added in oleic acid and octadecylene, and deoxygenation, 160 DEG C keep the temperature 60 minutes；

5) methanol solution and NH of NaOH, is added₄The methanol solution of F, stirring at normal temperature 60 minutes, then 60 DEG C stir 60 minutes, 108 DEG C heat preservation 1 minute, vacuumize 20 minutes, then restore 308 DEG C of normal pressure keep the temperature 20 minutes, be down to room temperature, obtain NaSrF₄:Tm³⁺/ Nd³⁺/Yb³⁺@SiO₂/NaSrF₄；

6), be repeated as many times step 1) -4) operation, obtain nano-grain NaSrF₄:Tm³⁺/Nd³⁺/Yb³⁺@mSiO₂/ NaSrF₄；

(3) NaSrF₄:Tm³⁺/Nd³⁺/Yb³⁺@mSiO₂/NaSrF₄The synthesis of@QDs:

1), by 1 ml, the NaSrF of 10 mM₄:Tm³⁺/Nd³⁺/Yb³⁺@mSiO₂/NaSrF₄Ethanol solution add to 4 mL ethylenediamines Ethyl alcohol in, and 20 h are stirred at 25 DEG C；Then the NaSrF of amido modification is cleaned multiple times with ethyl alcohol₄:Tm³⁺/Nd³⁺/Yb³⁺@ mSiO₂/NaSrF₄；

2), the NaSrF for modifying amido₄:Tm³⁺/Nd³⁺/Yb³⁺@mSiO₂/NaSrF₄Ethanol solution add to containing quantum dot In solution, 1 h, the quantum dot composite material NaSrF that will finally obtain quickly are stirred₄:Tm³⁺/Nd³⁺/Yb³⁺@mSiO₂/NaSrF₄@ QDs is cleaned 3 times, and the emission spectrum of the corresponding quantum dot composite material of different-thickness wall is shown in Fig. 3.

Embodiment 5

(1) NaSrF₄:Tm³⁺/Nd³⁺/Yb³⁺Synthesis:

(2) NaSrF₄:Tm³⁺/Nd³⁺/Yb³⁺@mNaSrF₄The synthesis of/poly- trimethylolpropane trimethacrylate, the m are 2- 10 natural number:

1), by SrCl₂, oleic acid and octadecylene reaction kettle is added, deoxygenation, 150 DEG C keep the temperature 70 minutes；

2) NaSrF, is added₄:Tm³⁺/Nd³⁺/Yb³⁺Cyclohexane solution, be cooled to 95 DEG C；

3) methanol solution and NH of NaOH, is added₄The methanol solution of F, stirring at normal temperature 60 minutes, then 60 DEG C stir 60 minutes, 108 DEG C heat preservation 1 minute, vacuumize 20 minutes, then restore 308 DEG C of normal pressure keep the temperature 20 minutes, be down to room temperature, obtain NaSrF₄:Tm³⁺/ Nd³⁺/Yb³⁺@NaSrF₄；

4), by 4 mL, the NaSrF of 10 mM₄:Tm³⁺/Nd³⁺/Yb³⁺@NaSrF₄Cyclohexane solution, 0.15 mL trihydroxy methyl third After alkane triacrylate closes stirring 30 minutes, initiator is added, 1.5 mg ammonium persulfates (APS) stir 13 under nitrogen protection H obtains dispersion liquid；

5), to above-mentioned steps 4) dispersion liquid in acetone is added, and with after the ethyl alcohol of volume ratio 3:1, water washing, be dispersed in ethyl alcohol In；

6), be repeated several times step 1) -5) operation, obtain nano-grain NaSrF₄:Tm³⁺/Nd³⁺/Yb³⁺@mNaSrF₄/ poly- Trimethylolpropane trimethacrylate；

(3) NaSrF₄:Tm³⁺/Nd³⁺/Yb³⁺@mNaSrF₄The synthesis of/poly- trimethylolpropane trimethacrylate@QDs:

1), by 1 ml, the NaSrF of 10 mM₄:Tm³⁺/Nd³⁺/Yb³⁺@mNaSrF₄The second of/poly- trimethylolpropane trimethacrylate Alcoholic solution adds in the ethyl alcohol of 4 mL ethylenediamines, and 20 h are stirred at 25 DEG C；Then amido modification is cleaned multiple times with ethyl alcohol NaSrF₄:Tm³⁺/Nd³⁺/Yb³⁺@mNaSrF₄/ poly- trimethylolpropane trimethacrylate；

2), the NaSrF for modifying amido₄:Tm³⁺/Nd³⁺/Yb³⁺@mNaSrF₄The ethyl alcohol of/poly- trimethylolpropane trimethacrylate Solution adds in the solution containing quantum dot, quickly stirs 1 h, the quantum dot composite material NaSrF that will finally obtain₄:Tm³⁺/ Nd³⁺/Yb³⁺@mNaSrF₄/ trimethylolpropane trimethacrylate@QDs cleaning 3 times poly-.

Embodiment 6

(1) Y₂O₃:Er³⁺/Yb³⁺Synthesis:

1), Y (NO₃)₃•6H₂O、CO(NH₂)₂、Yb(NO₃)₃、Er(NO₃)₃It is dissolved in deionized water, obtains white after oil bath stirring Precipitating；Obtained white precipitate is cleaned with dehydrated alcohol and deionized water, dries, obtains presoma Y (OH)₃:Er³⁺/Yb³ ⁺；

2), by Y (OH)₃:Er³⁺/Yb³⁺It is placed in Muffle furnace, 1 h is calcined at 600 DEG C, is ground after cooling, obtains Y₂O₃:Er³⁺/ Yb³⁺；

(2) Y₂O₃:Er³⁺/Yb³⁺@mTiO₂The synthesis of/poly- trimethylolpropane trimethacrylate, the m are the nature of 2-10 Number:

1), by 0.003 g octadecyl dimethyl benzyl quaternary ammonium sodium chloride, 6 mL hexamethylenes and 4 mL, 10 mM Y₂O₃:Er³⁺/ Yb³⁺Cyclohexane solution be mixed 10 min；

2) it, takes 0.6 mL diethanol amine and 0.8 mL butyl titanate to be placed in 50 mL beakers, is stirred 30 minutes at 120 DEG C, it is natural It is cooling, obtain clear, yellowish crystalline solid；Then 25 mL deionized waters are added into beaker, stirring and dissolving obtains titanium amine Base alcohol complex solution;

3) 1 mL above-mentioned steps 2, are taken) titanium amido alcohol complex solution is slowly dropped into above-mentioned steps 1 dropwise) in solution, drip Bi Hou is stirred to react 25 h；Then solid is obtained at 100 DEG C after dry 24 h by centrifugation to be placed in Muffle furnace at 450 DEG C 0.5 h is calcined, Y is obtained₂O₃:Er³⁺/Yb³⁺@TiO₂;

4), by 4 mL, the Y of 10 mM₂O₃:Er³⁺/Yb³⁺@TiO₂Cyclohexane solution, 0.08 mL methyl methacrylate mixing After stirring 30 minutes, initiator is added, 2 mg potassium peroxydisulfates (KPS) stir 22 h under nitrogen protection and obtain dispersion liquid;

5), to above-mentioned steps 4) acetone is added in dispersion liquid, and with after the ethyl alcohol of volume ratio 3:1, water washing, it is dispersed in ethyl alcohol In;

6), be repeated several times step 1) -5) operation, obtain Y₂O₃:Er³⁺/Yb³⁺@mTiO₂/ poly- trimethylolpropane tris acrylic acid Ester；

(3) Y₂O₃:Er³⁺/Yb³⁺@mTiO₂The synthesis of/poly- trimethylolpropane trimethacrylate@QDs:

1), by 1 ml, the Y of 10 mM₂O₃:Er³⁺/Yb³⁺@mTiO₂The ethanol solution of/poly- trimethylolpropane trimethacrylate adds Into 2 mL mercaptopropionic acids, and 25 h are stirred at 25 DEG C；Then mercapto-modified Y is cleaned multiple times with ethyl alcohol₂O₃:Er³⁺/Yb³⁺@ mTiO₂/ poly- trimethylolpropane trimethacrylate；

2), by mercapto-modified Y₂O₃:Er³⁺/Yb³⁺@mTiO₂The ethanol solution of/poly- trimethylolpropane trimethacrylate adds to In solution containing quantum dot, 1.5 h, the quantum dot composite material Y that will finally obtain quickly are stirred₂O₃:Er³⁺/Yb³⁺@ mTiO₂/ trimethylolpropane trimethacrylate@QDs cleaning 3 times poly-.

Embodiment 7

(1) NaYF₄:Er³⁺/Yb³⁺Synthesis:

(2) NaYF₄:Er³⁺/Yb³⁺@SiO₂/NaSrF₄The synthesis of/poly- trimethylolpropane trimethacrylate:

1), 0.1 mL CO-520,6 mL hexamethylenes and 4 mL, 10 mM NaYF₄:Er³⁺/Yb³⁺Cyclohexane solution mixing stir Mix 10 min；

2), 0.4 mL CO-520 and 0.08 mL, 30% ammonium hydroxide are added in step 1) solution, seal 20 min of ultrasound, is formed Transparent emulsion；

3) 0.02 mL TEOS, is added to above-mentioned steps 2) in solution, 600 rpm stir 45 h, obtain NaYF₄:Er³⁺/Yb³ ⁺@SiO₂；

4), by NaYF₄:Er³⁺/Yb³⁺@SiO₂Disperse in deionized water, by SrCl₂、TmCl₃•6H₂O、NdCl₃•6H₂O、 YbCl₃•6H₂O, reaction kettle is added in oleic acid and octadecylene, and deoxygenation, 160 DEG C keep the temperature 60 minutes；

5) methanol solution and NH of NaOH, is added₄The methanol solution of F, stirring at normal temperature 60 minutes, then 60 DEG C stir 60 minutes, 108 DEG C heat preservation 1 minute, vacuumize 20 minutes, then restore 308 DEG C of normal pressure keep the temperature 20 minutes, be down to room temperature, obtain NaYF₄:Er³⁺/Yb³ ⁺@SiO₂/NaSrF₄；

6), by 4 mL, the NaYF of 10 mM₄:Er³⁺/Yb³⁺@SiO₂/NaSrF₄Cyclohexane solution, 0.13 mL trihydroxy methyl third After alkane triacrylate closes stirring 28 minutes, initiator is added, 1.5 mg ammonium persulfates (APS) stir 8 h under nitrogen protection Obtain dispersion liquid；

7), to above-mentioned steps 6) dispersion liquid in be added acetone, and with the ethyl alcohol of volume ratio 3:1, water washing, obtain nano material Particle NaYF₄:Er³⁺/Yb³⁺@SiO₂/NaSrF₄/ poly- trimethylolpropane trimethacrylate, is then dispersed in ethyl alcohol, spare；

(3) NaYF₄:Er³⁺/Yb³⁺@SiO₂/NaSrF₄The synthesis of/poly- trimethylolpropane trimethacrylate@QDs:

1), by 1 ml, the NaYF of 10 mM₄:Er³⁺/Yb³⁺@SiO₂/NaSrF₄The ethyl alcohol of/poly- trimethylolpropane trimethacrylate Solution adds in 0.8 mL mercaptopropionic acid, and 20 h are stirred at 25 DEG C；Then it is cleaned multiple times with ethyl alcohol mercapto-modified NaYF₄:Er³⁺/Yb³⁺@SiO₂/NaSrF₄/ poly- trimethylolpropane trimethacrylate；

2), by mercapto-modified NaYF₄:Er³⁺/Yb³⁺@SiO₂/NaSrF₄The ethyl alcohol of/poly- trimethylolpropane trimethacrylate is molten Liquid adds in the solution containing quantum dot, quickly stirs 1 h, the quantum dot composite material NaYF that will finally obtain₄:Er³⁺/Yb³⁺@ SiO₂/NaSrF₄/ trimethylolpropane trimethacrylate@QDs cleaning 3 times poly-.

Embodiment 8

(1) LiGd (MoO₄)₂:Er³⁺/Yb³⁺Synthesis

1), by Gd (NO₃)₃•6H₂O、Li₂CO₃、(NH₄)₆Mo₇O₂₄•4.5H₂O is dissolved in deionized water, and citric acid is added, and is adjusted PH to 8 is saved, clear solution is stirred to get；

2), above-mentioned clear solution is placed in baking oven, 80 DEG C of 48 h of heat preservation after obtaining xerogel, continue temperature being raised to 120 DEG C heat preservation 24 h, obtain black presoma；

3), black presoma is placed in Muffle furnace, 500 DEG C of 5 h of pre-burning, after cooling grinding, 700 DEG C of 5 h of calcining are finally obtained Upconversion fluorescence nano material LiGd (MoO₄)₂:Er³⁺/Yb³⁺；

(2) LiGd (MoO₄)₂:Er³⁺/Yb³⁺The synthesis of@polymethyl methacrylate

1), by 4 mL, the LiGd (MoO of 10 mM₄)₂: Er³⁺/Yb³⁺Cyclohexane solution, 0.1 mL monomer methacrylic acid first After ester is mixed 30 minutes, initiator is added, 2.5 mg potassium peroxydisulfates (KPS) stir 20 h under nitrogen protection, divided Dispersion liquid；

2), to above-mentioned steps 1) acetone is added in dispersion liquid, and with after the ethyl alcohol of volume ratio 1:1, water washing, it is dispersed in ethyl alcohol In, obtain LiGd (MoO₄)₂:Er³⁺/Yb³⁺The ethanol solution of@polymethyl methacrylate, it is spare；

(3) LiGd (MoO₄)₂:Er³⁺/Yb³⁺The synthesis of@polymethyl methacrylate@QDs

1), by 1 mL LiGd (MoO₄)₂:Er³⁺/Yb³⁺The ethanol solution of@polymethyl methacrylate adds to 2 mL, 1.5%w/w In the ethyl alcohol of MPS, and 18 h are stirred at 25 DEG C；Then mercapto-modified LiGd (MoO is cleaned multiple times with ethyl alcohol₄)₂:Er³⁺/Yb³ ⁺@polymethyl methacrylate；

2), by mercapto-modified LiGd (MoO₄)₂:Er³⁺/Yb³⁺The ethanol solution of@polymethyl methacrylate is added to containing quantum In the solution of point, 1 h, the quantum dot composite material LiGd (MoO that will finally obtain quickly are stirred₄)₂:Er³⁺/Yb³⁺The poly- methyl-prop of@ E pioic acid methyl ester@QDs is cleaned 3 times, and the launching light spectrogram of the quantum dot composite material of different-thickness wall is shown in Fig. 4.

Embodiment 9

(1) In₂O₃:Er³⁺/Yb³⁺Synthesis

1), by In (NO₃)₃•4.5H₂O、CO(NH₂)₂、Yb(NO₃)₃、Er(NO₃)₃It is dissolved in deionized water, is obtained after oil bath stirring White precipitate cleans obtained white precipitate with dehydrated alcohol and deionized water, and drying obtains presoma In (OH)₃:Er³ ⁺/Yb³⁺；

2), by In (OH)₃:Yb³⁺/Er³⁺It is placed in Muffle furnace, 500 DEG C of 2 h of calcining, is ground after cooling, obtain up-conversion fluorescence Nano material In₂O₃:Er³⁺/Yb³⁺；

(2) In₂O₃:Er³⁺/Yb³⁺The synthesis of the poly- trimethylolpropane trimethacrylate of@

1), by 4 mL In₂O₃:Er³⁺/Yb³⁺Cyclohexane solution, 0.15 mL trimethylolpropane trimethacrylate close stirring 30 After minute, initiator is added, 2 mg ammonium persulfates (APS) stir 10 h under nitrogen protection, obtain dispersion liquid；

2), to above-mentioned steps 1) acetone is added in dispersion liquid, and with after the ethyl alcohol of volume ratio 3:1, water washing, it is dispersed in ethyl alcohol In, obtain In₂O₃:Er³⁺/Yb³⁺The ethanol solution of the poly- trimethylolpropane trimethacrylate of@, it is spare；

(3) In₂O₃:Er³⁺/Yb³⁺The synthesis of the poly- trimethylolpropane trimethacrylate@QDs of@

1), by 1 ml In₂O₃:Er³⁺/Yb³⁺The ethanol solution of the poly- trimethylolpropane trimethacrylate of@adds to 0.8 mL sulfydryl In propionic acid, and 20 h are stirred at 25 DEG C；Then mercapto-modified In is cleaned multiple times with ethyl alcohol₂O₃:Er³⁺/Yb³⁺The poly- three hydroxyls first of@ Base propane triacrylate；

2), by mercapto-modified In₂O₃:Er³⁺/Yb³⁺The ethanol solution of the poly- trimethylolpropane trimethacrylate of@adds to amount In the solution of son point, 1 h, the quantum dot composite material In that will finally obtain quickly are stirred₂O₃:Er³⁺/Yb³⁺The poly- trihydroxy methyl third of@ Alkane triacrylate@QDs is cleaned 3 times.

Embodiment 10

As shown in connection with fig. 5, the quantum dot composite material of the present embodiment preparation method comprising steps of

(1) NaYF₄:Er³⁺/Yb³⁺Synthesis:

(2) NaYF₄:Er³⁺/Yb³⁺@SiO₂Synthesis

3) 0.04 mL TEOS, is added to above-mentioned steps 2) in emulsion, 600 rpm stir 48 h, obtain nano material Grain NaYF₄:Er³⁺/Yb³⁺@SiO₂；

4), to above-mentioned steps 3) be added acetone in solution, and with after the ethyl alcohol of volume ratio 1:1, water washing, dispersion in ethanol, Obtain NaYF₄:Er³⁺/Yb³⁺@SiO₂Ethanol solution, it is spare；

(3)、NaYF₄:Er³⁺/Yb³⁺@SiO₂The synthesis of@QDs

1), by 1 ml NaYF₄:Er³⁺/Yb³⁺@SiO₂Ethanol solution add to 4.5 mL, 1.5%w/w 3- sulfydryl -1- propane sulphur In the ethyl alcohol of sour sodium (MPS), and 20 h are stirred at 25 DEG C；Then mercapto-modified NaYF is cleaned multiple times with ethyl alcohol₄:Er³⁺/ Yb³⁺@SiO₂, after cleaning, dispersion is in ethanol；

2), by mercapto-modified NaYF₄:Er³⁺/Yb³⁺@SiO₂Ethanol solution be added into the solution containing quantum dot, quickly 1 h is stirred, the quantum dot composite material NaYF that will finally obtain₄:Er³⁺/Yb³⁺@SiO₂@QDs is cleaned 3 times；To the present embodiment institute State NaYF₄:Er³⁺/Yb³⁺@SiO₂@QDs carries out TEM test, and test result is shown in Fig. 6.

Embodiment 11

(1) NaYF₄:Tm³⁺/Yb³⁺/Nd³⁺Synthesis:

1), by YCl₃•6H₂O、TmCl₃•6H₂O、NdCl₃•6H₂O、YbCl₃•6H₂O, reaction kettle is added in oleic acid and octadecylene, removes Oxygen, 160 DEG C keep the temperature 60 minutes；

2) methanol solution and NH of NaOH, is added₄The methanol solution of F, stirring at normal temperature 60 minutes, then 60 DEG C stir 60 minutes, 108 DEG C heat preservation 1 minute, vacuumize 20 minutes, then restore 308 DEG C of normal pressure keep the temperature 20 minutes, be down to room temperature, obtain conversion fluorescence receive Rice material NaYF₄:Tm³⁺/Yb³⁺/Nd³⁺；

(2) NaYF₄:Tm³⁺/Yb³⁺/Nd³⁺@SiO₂Synthesis

1), 0.05 mL CO-520,6 mL hexamethylenes and 4 mL, 10mM NaYF₄:Tm³⁺/Yb³⁺/Nd³⁺Cyclohexane solution it is mixed Close 10 min of stirring；

2), 0.2 mL CO-520 and 0.05 mL, 30% ammonium hydroxide are added in step 1) solution, seal 20 min of ultrasound, is formed Transparent emulsion；

3) 0.02 mL TEOS, is added to above-mentioned steps 2) in emulsion, 600 rpm stir 45 h；

4), to above-mentioned steps 3) be added acetone in solution, and with after the ethyl alcohol of volume ratio 1:1, water washing, dispersion in ethanol, Obtain NaYF₄:Tm³⁺/Yb³⁺/Nd³⁺@SiO₂Ethanol solution, it is spare；

(3)、NaYF₄:Tm³⁺/Yb³⁺/Nd³⁺@SiO₂The synthesis of@QDs

1), by 1 ml NaYF₄:Tm³⁺/Yb³⁺/Nd³⁺@SiO₂Ethanol solution be added to the ethyl alcohol of 2 mL, 1.5%w/w MPS In, and 18 h are stirred at 25 DEG C；Then mercapto-modified NaYF is cleaned multiple times with ethyl alcohol₄:Tm³⁺/Yb³⁺/Nd³⁺@SiO₂, cleaning Afterwards, disperse in ethanol；

2), by mercapto-modified NaYF₄:Tm³⁺/Yb³⁺/Nd³⁺@SiO₂Ethanol solution be added into the solution containing quantum dot, Quickly stirring 1 h, the quantum dot composite material NaYF that will finally obtain₄:Tm³⁺/Yb³⁺/Nd³⁺@SiO₂@QDs is cleaned 3 times.

Embodiment 12

(1) CaF₂:Er³⁺/Yb³⁺Synthesis

1), by CaCl₂•2H₂O、ErCl₃•6H₂O、YbCl₃•6H₂O, reaction kettle, deoxygenation, 160 DEG C of heat preservations are added in oleic acid and octadecylene 60 minutes；

2) NH, is added₄The methanol solution of F, stirring at normal temperature 60 minutes, then 60 DEG C stirred 60 minutes, 108 DEG C keep the temperature 1 minute, take out true It is 20 minutes empty, then restore 308 DEG C of normal pressure and keep the temperature 20 minutes, it is down to room temperature, obtains upconversion fluorescence nano material CaF₂:Er³⁺/ Yb³⁺；

(2) CaF₂:Er³⁺/Yb³⁺@SiO₂Synthesis

1), 0.15 mL CO-520,6 mL hexamethylenes and 4 mL, 10 mM CaF₂: Er³⁺/Yb³⁺Cyclohexane solution mixing stir Mix 10 min；

2), 0.6 mL CO-520 and 0.15 mL, 30% ammonium hydroxide are added in step 1) solution, seal 20 min of ultrasound, is formed Transparent emulsion；

3) 0.08 mL TEOS, is added to above-mentioned steps 2) in emulsion, 600 rpm stir 50 h；

4), to above-mentioned steps 3) be added acetone in solution, and with after the ethyl alcohol of volume ratio 3:1, water washing, dispersion in ethanol, Obtain CaF₂:Er³⁺/Yb³⁺@SiO₂Ethanol solution, it is spare；

(3) CaF₂:Er³⁺/Yb³⁺@SiO₂The synthesis of@QDs

1), by 1 ml CaF₂:Er³⁺/Yb³⁺@SiO₂Ethanol solution be added to 5 mL, 1.5%w/w MPS ethyl alcohol in, and 22 h are stirred at 25 DEG C；Then mercapto-modified CaF is cleaned multiple times with ethyl alcohol₂:Er³⁺/Yb³⁺@SiO₂, after cleaning, it is dispersed in second In alcohol；

2), by mercapto-modified CaF₂:Er³⁺/Yb³⁺@SiO₂Ethanol solution be added into the solution containing quantum dot, quickly stir 1 h is mixed, the quantum dot composite material CaF that will finally obtain₂:Er³⁺/Yb³⁺@SiO₂@QDs is cleaned 3 times.

Embodiment 13

(1) NaGdF₄:Ho³⁺/Yb³⁺Synthesis

1), by GdCl₃•6H₂O、HoCl₃•6H₂O、YbCl₃•6H₂O, reaction kettle, deoxygenation, 160 DEG C of heat preservations are added in oleic acid and octadecylene 60 minutes；

2) methanol solution and NH of NaOH, is added₄The methanol solution of F, stirring at normal temperature 60 minutes, then 60 DEG C stir 60 minutes, 108 DEG C heat preservation 1 minute, vacuumize 20 minutes, then restore 308 DEG C of normal pressure keep the temperature 20 minutes, be down to room temperature, obtain up-conversion fluorescence and receive Rice material NaGdF₄:Ho³⁺/Yb³⁺；

(2) NaGdF₄:Ho³⁺/Yb³⁺@SiO₂Synthesis

1), 0.12 mL CO-520,6 mL hexamethylenes and 4 mL, 10 mM NaGdF₄: Ho³⁺/Yb³⁺Cyclohexane solution mixing Stir 10 min；

2), 0.5 mL CO-520 and 0.12 mL, 30% ammonium hydroxide are added in step 1) solution, seal 20 min of ultrasound, is formed Transparent emulsion；

3) 0.06 mL TEOS, is added to above-mentioned steps 2) in emulsion, 600 rpm stir 55 h；

4), to above-mentioned steps 3) be added acetone in solution, and with after the ethyl alcohol of volume ratio 2:3, water washing, dispersion in ethanol, Obtain NaGdF₄:Ho³⁺/Yb³⁺@SiO₂Ethanol solution；

(3) NaGdF₄:Ho³⁺/Yb³⁺@SiO₂The synthesis of@QDs

1), by 1 ml NaGdF₄:Ho³⁺/Yb³⁺@SiO₂Ethanol solution be added to 5 mL, 1.5%w/w MPS ethyl alcohol in, and 20 h are stirred at 25 DEG C；Then mercapto-modified NaGdF is cleaned multiple times with ethyl alcohol₄:Ho³⁺/Yb³⁺@SiO₂, after cleaning, dispersion In ethanol；

2), by mercapto-modified NaGdF₄:Ho³⁺/Yb³⁺@SiO₂Ethanol solution be added into the solution containing quantum dot, quickly 1 h is stirred, the quantum dot composite material NaGdF that will finally obtain₄:Ho³⁺/Yb³⁺@SiO₂@QDs is cleaned 3 times.

Embodiment 14

(1) NaYF₄:Tm³⁺/Yb³⁺/Nd³⁺Synthesis:

(2) NaYF₄:Tm³⁺/Yb³⁺/Nd³⁺@TiO₂Synthesis

1), by 0.001 g cetyl trimethyl quaternary ammonium ammonium bromide (CTMAB), 6 mL hexamethylenes and 4 mL, 10 mM NaYF₄: Tm³⁺/Yb³⁺/Nd³⁺Cyclohexane solution be mixed 10 min；

2) it, takes 1 mL diethanol amine and 1.5 mL butyl titanates to be placed in 50 mL beakers, is stirred 30 minutes at 120 DEG C, it is naturally cold But, clear, yellowish crystalline solid is obtained；Then 25 mL deionized waters are added into beaker, stirring and dissolving obtains titanium amido Alcohol complex solution；

3) 1 mL above-mentioned steps 2, are taken) titanium amido alcohol complex solution is slowly dropped into above-mentioned steps 1 dropwise) in solution, drip Bi Hou is stirred to react 30 h；Then solid is obtained at 100 DEG C after dry 24 h by centrifugation to be placed in Muffle furnace at 400 DEG C 1 h is calcined, nano-grain NaYF is obtained₄:Tm³⁺/Yb³⁺/Nd³⁺@TiO₂；

(3)、NaYF₄:Tm³⁺/Yb³⁺/Nd³⁺@TiO₂The synthesis of@QDs

1), by 1 ml NaYF₄:Tm³⁺/Yb³⁺/Nd³⁺@TiO₂Ethanol solution be added to the ethyl alcohol of 4.5 mL, 1.5%w/w MPS In, and 20 h are stirred at 25 DEG C；Then mercapto-modified NaYF is cleaned multiple times with ethyl alcohol₄:Tm³⁺/Yb³⁺/Nd³⁺@TiO₂, cleaning Afterwards, disperse in ethanol；

2), by mercapto-modified NaYF₄:Tm³⁺/Yb³⁺/Nd³⁺@TiO₂Ethanol solution be added into the solution containing quantum dot, Quickly stirring 1 h, the quantum dot composite material NaYF that will finally obtain₄:Tm³⁺/Yb³⁺/Nd³⁺@TiO₂@QDs is cleaned 3 times.

Embodiment 15

(1) NaGdF₄:Tm³⁺/Yb³⁺/Nd³⁺Synthesis:

1), by GdCl₃•6H₂O、TmCl₃•6H₂O、NdCl₃•6H₂O、YbCl₃•6H₂O, reaction kettle is added in oleic acid and octadecylene, removes Oxygen, 160 DEG C keep the temperature 60 minutes；

2) methanol solution and NH of NaOH, is added₄The methanol solution of F, stirring at normal temperature 60 minutes, then 60 DEG C stir 60 minutes, 108 DEG C heat preservation 1 minute, vacuumize 20 minutes, then restore 308 DEG C of normal pressure keep the temperature 20 minutes, be down to room temperature, obtain conversion fluorescence receive Rice material NaGdF₄:Tm³⁺/Yb³⁺/Nd³⁺；

(2) NaGdF₄:Tm³⁺/Yb³⁺/Nd³⁺@SiO₂/Al₂O₃Synthesis

1), 0.1 mL CO-520,6 mL hexamethylenes and 4 mL, 10mM NaGdF₄:Tm³⁺/Yb³⁺/Nd³⁺Cyclohexane solution it is mixed Close 10 min of stirring；

3) 0.02 mL TEOS, is added to above-mentioned steps 2) in emulsion, 600 rpm stir 45 h, obtain NaGdF₄:Tm³⁺/ Yb³⁺/Nd³⁺@SiO₂；

4) 1 mL, 1 mM aluminum sulfate, are added in Xiang Shangshu step 3), and ammonium hydroxide, which is added, maintains pH to 8, reacts 4 h, uses ethyl alcohol It is cleaned with deionized water, 100 DEG C of dryings obtain nano-grain NaGdF₄:Tm³⁺/Yb³⁺/Nd³⁺@SiO₂/Al₂O₃；

(3)、NaGdF₄:Tm³⁺/Yb³⁺/Nd³⁺@SiO₂/Al₂O₃The synthesis of@QDs

1), by 1 ml NaGdF₄:Tm³⁺/Yb³⁺/Nd³⁺@SiO₂/Al₂O₃Ethanol solution be added to 2.5 mL, the amine of 2%w/w In the polyethylene glycol of base sealing end, and 22 h are stirred at 25 DEG C；Then the NaGdF of amido modification is cleaned multiple times with ethyl alcohol₄:Tm³⁺/ Yb³⁺/Nd³⁺@SiO₂/Al₂O₃, after cleaning, dispersion is in ethanol；

2), the NaGdF for modifying amido₄:Tm³⁺/Yb³⁺/Nd³⁺@SiO₂/Al₂O₃Ethanol solution be added to containing quantum dot In solution, 1 h, the quantum dot composite material NaGdF that will finally obtain quickly are stirred₄:Tm³⁺/Yb³⁺/Nd³⁺@SiO₂/Al₂O₃@ QDs is cleaned 3 times, the launching light spectrogram and NaGdF of the quantum dot composite material of different-thickness wall₄:Tm³⁺/Yb³⁺/Nd³⁺'s Launching light spectrogram is shown in Fig. 7.

Embodiment 16

(1) In₂O₃:Er³⁺/Yb³⁺Synthesis:

2), by In (OH)₃:Er³⁺/Yb³⁺It is placed in Muffle furnace, 2 h is calcined at 500 DEG C, is ground after cooling, obtains In₂O₃:Er³⁺/ Yb³⁺；

(2) In₂O₃:Er³⁺/Yb³⁺@TiO₂/Al₂O₃Synthesis

1), by 0.005 g neopelex (SDBS), 6 mL hexamethylenes and 4 mL, 10 mM In₂O₃:Er³⁺/Yb³⁺'s 10 min are mixed in cyclohexane solution；

2) it, takes 0.7 mL diethanol amine and 1 mL butyl titanate to be placed in 50 mL beakers, is stirred 30 minutes at 120 DEG C, it is naturally cold But, clear, yellowish crystalline solid is obtained；Then 25 mL deionized waters are added into beaker, stirring and dissolving obtains titanium amido Alcohol complex solution；

3) 1 mL above-mentioned steps 2, are taken) titanium amido alcohol complex solution is slowly dropped into above-mentioned steps 1 dropwise) in solution, drip Bi Hou is stirred to react 25 h；Then solid is obtained at 100 DEG C after dry 24 h by centrifugation to be placed in Muffle furnace at 450 DEG C 0.5 h is calcined, nano-grain In is obtained₂O₃:Er³⁺/Yb³⁺@TiO₂；

4) 0.5 mL, 1 mM aluminum sulfate, are added in Xiang Shangshu step 3), and ammonium hydroxide, which is added, maintains pH to 7, reacts 5 h, uses second Pure and mild deionized water cleaning, 100 DEG C of dryings obtain nano-grain In₂O₃:Er³⁺/Yb³⁺@TiO₂/Al₂O₃；

(3)、In₂O₃:Er³⁺/Yb³⁺@TiO₂/Al₂O₃The synthesis of@QDs

1), by 1 ml In₂O₃:Er³⁺/Yb³⁺@TiO₂/Al₂O₃Ethanol solution be added to 3 mL, the polyethyleneimine of 5%w/w In, and 25 h are stirred at 25 DEG C；Then the In of amido modification is cleaned multiple times with ethyl alcohol₂O₃:Er³⁺/Yb³⁺@TiO₂/Al₂O₃, clearly After washing, dispersion is in ethanol；

2), the In for modifying amido₂O₃:Er³⁺/Yb³⁺@TiO₂/Al₂O₃Ethanol solution be added into the solution containing quantum dot, Quickly stirring 1.5 h, the quantum dot composite material In that will finally obtain₂O₃:Er³⁺/Yb³⁺@TiO₂/Al₂O₃@QDs is cleaned 3 times.

In conclusion a kind of quantum dot composite material provided by the invention and preparation method thereof.It more than the present invention converts glimmering Light nano material is core, and upconversion fluorescence nano material outer cladding separation layer is combined with quantum dot outside separation layer, forms quantum dot Composite material.It is to make the amount that the separation layer is added among the upconversion fluorescence nano material and the quantum dot Son point and the upconversion fluorescence nano material separate, and the quantum dot and the upconversion fluorescence nano material is avoided directly to connect It touches and generates lossy surface wave.By infrared ray excited upconversion fluorescence nano material, up-conversion fluorescence nanometer material is utilized The upper transformation of material, is changed into visible radiation for infrared light, excitation quantum dot light emitting is acted on using energy transmission, to reach red The purpose of outer light excitation quantum dot light emitting, improves the utilization rate of infrared light, and avoids and existing direct utilize ultraviolet excitation Quantum dot leads to quantum dot surface oxidation, local sintering.

It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention Protect range.

Claims

1. a kind of quantum dot composite material characterized by comprising

Core, the material of the core are upconversion fluorescence nano material；

Wall, the wall coat the core；

Quantum dot, the quantum dot are incorporated in the interval layer surface, and the wall is received for reducing the up-conversion fluorescence Non-radiative decay rate when rice material transmits from energy to the quantum dot；

The material of the wall is polymer material.

2. quantum dot composite material according to claim 1, which is characterized in that the material spacer layer is selected from polyphenyl second Alkene-maleic anhydride, Polyphenylethylene-butyl acrylate, polystyrene-acrylonitrile, nitrocellulose, end hydroxy butadiene, poly- third Olefin(e) acid-butyl acrylate, polyacrylic acid-styrene, poly- trimethylolpropane trimethacrylate, polymethyl methacrylate and poly- One of amide-amine.

3. quantum dot composite material according to claim 1, which is characterized in that the wall is by 2-10 straton material layer Stacking is formed.

4. quantum dot composite material according to claim 3, which is characterized in that each sub- material layer material independently selects Self-polystyrene-maleic anhydride, Polyphenylethylene-butyl acrylate, polystyrene-acrylonitrile, nitrocellulose, terminal hydroxy group polybutadiene Alkene, polyacrylic acid-butyl acrylate, polyacrylic acid-styrene, poly- trimethylolpropane trimethacrylate, polymethylacrylic acid One of methyl esters and polyamide-amide.

5. quantum dot composite material according to any one of claims 1 to 4, which is characterized in that the total thickness of the wall Degree is denoted as d, d 5-20nm.

6. quantum dot composite material according to claim 5, which is characterized in that d 5-15nm.

7. quantum dot composite material according to claim 6, which is characterized in that d 8-12nm.

8. quantum dot composite material according to any one of claims 1 to 4, which is characterized in that the wall with it is described The surface that quantum dot combines is combined with surfactant body.

9. quantum dot composite material according to claim 8, which is characterized in that the surfactant is selected from containing sulfydryl Organic ligand, amino-containing organic ligand, carboxyl and one of carboxylic acid derivates organic ligand and parents' polymer or a variety of.

10. quantum dot composite material according to any one of claims 1 to 4, which is characterized in that as described in the core Upconversion fluorescence nano material is the upconversion fluorescence nano material host material of activator doping；Or the institute as the core Stating upconversion fluorescence nano material is the upconversion fluorescence nano material host material that activator and sensitizer adulterate.

11. quantum dot composite material according to claim 10, which is characterized in that the upconversion fluorescence nano material is The upconversion fluorescence nano material host material of activator doping, the activator are selected from Tm³⁺、Er³⁺、Pr³⁺、Nd³⁺、Sm³⁺、Ho³ ⁺、Ti²⁺、Cr³⁺、Ni²⁺、Mo³⁺、Re⁴⁺And Os⁴⁺One of or it is a variety of；Or the upconversion fluorescence nano material is activator With the upconversion fluorescence nano material host material of sensitizer doping, the activator is selected from Tm³⁺、Er³⁺、Pr³⁺、Nd³⁺、Sm³⁺、 Ho³⁺、Ti²⁺、Cr³⁺、Ni²⁺、Mo³⁺、Re⁴⁺And Os⁴⁺One of or it is a variety of；The sensitizer is Yb³⁺。

12. quantum dot composite material according to claim 10, which is characterized in that the material as the core is activator The upconversion fluorescence nano material host material of doping, wherein the upconversion fluorescence nano material host material is selected from fluorination Turn on object upconversion fluorescence nano material host material, oxide upconversion fluorescence nano material host material and composite oxides Change one of fluorescent nano material host material；Or the material as the core be activator and sensitizer adulterate upper turn Change fluorescent nano material host material, wherein the upconversion fluorescence nano material host material is converted glimmering on fluoride Light nano material host material, oxide upconversion fluorescence nano material host material and composite oxides up-conversion fluorescence nanometer One of material matrix material.

13. quantum dot composite material according to claim 12, which is characterized in that the fluoride up-conversion fluorescence nanometer Material matrix material is selected from NaYF₄、NaGaF₄、CaF₂、NaSrF₄、BaY₂F₄、LiYF₄、ScYF₄、NaLnF₄、SrF₂、BaF₂、MnF₂ And Cs₂GeF₆One of；

Or the oxide upconversion fluorescence nano material host material is selected from Y₂O₃、ZrO₂、TiO₂、Gd₂O₃、In₂O₃、SrY₂O₄、 TeO₂、Al₂O₃、ZnO₂、Lu₂O₃、Er₂O₃、Eu₂O₃、CeO₂And La₂O₃One of；

Or the composite oxides upconversion fluorescence nano material host material is selected from LiNbO₃、Ln₂BaZnO₂、ALn(MoO₄)₂、 GdVO₄、YVo₄、CaZrO₃、CaSc₂O₄、KLu(WO₄)₂、CaCs₂O_4、CaMoO₄、BaTiO₃、Y₂Ti₂O₇、Y₂Si₂O₇、Y₂SiO₅、 Gd₃Ga₅O₁₂、Y₃Al₅O₁₂And Y₂CaGe₄O₁₂One of.

14. a kind of preparation method of quantum dot composite material, which is characterized in that comprising steps of

It coats to form the wall on the nuclear particle surface, the material of the wall is polymer material, is spaced The nano-grain of layer cladding；

The nano-grain is surface modified using coating material, obtains the nano material of surface modification Particle；

The solution for being dispersed with the nano-grain of surface modification is mixed with quantum dot solution, is incorporated in quantum dot The interval layer surface, obtains the quantum dot composite material；

15. preparation method according to claim 14, which is characterized in that the diameter of the nuclear particle is 7-20nm.

16. preparation method according to claim 14, which is characterized in that the material of the wall is selected from polystyrene- Maleic anhydride, Polyphenylethylene-butyl acrylate, polystyrene-acrylonitrile, nitrocellulose, end hydroxy butadiene, polypropylene Acid-butyl acrylate, polyacrylic acid-styrene, poly- trimethylolpropane trimethacrylate, polymethyl methacrylate and polyamides One of amine-amine.

17. preparation method according to claim 14, which is characterized in that between described in coating and to be formed on the nuclear particle surface In the step of interlayer, cladding, which is formed, forms wall from material layer by 2-10 layers, wherein the first straton material layer coats institute Core is stated, the second straton material layer coats the first straton material layer, and every kind of posterior sub- material layer coats preceding sub- material Layer, forms the wall.

18. preparation method according to claim 17, which is characterized in that each sub- material layer material is independently selected from poly- Styrene maleic anhydride, Polyphenylethylene-butyl acrylate, polystyrene-acrylonitrile, nitrocellulose, end hydroxy butadiene, Polyacrylic acid-butyl acrylate, polyacrylic acid-styrene, poly- trimethylolpropane trimethacrylate, polymethyl methacrylate One of with polyamide-amide.

19. the preparation method of quantum dot composite material according to claim 14, which is characterized in that the coating material In organic ligand, carboxylic acid and carboxylic acid derivates organic ligand and parents' polymer selected from organic ligand, amino-contained containing sulfydryl It is one or more.

20. the preparation method of quantum dot composite material according to claim 19, which is characterized in that the having containing sulfydryl Machine ligand is selected from one of benzyl mercaptan, thioacetic acid and mercaptopropionic acid or a variety of；

The organic ligand of the amino-contained is selected from ethylenediamine, octadecyl-to ethylene benzyl-alkyl dimethyl ammonium chloride, N, N- diformazan One of base benzylamine, L-cysteine, reduced glutathione and bovine serum albumin are a variety of；

The carboxylic acid and carboxylic acid derivates organic ligand are selected from methyl hexahydro phthalic dimethyl acid anhydrides, phthalic dicarboxylic acid anhydride, poly- third One of olefin(e) acid sodium and poly- (acrylic acid-maleic acid acid anhydride) are a variety of；

Parents' polymer can block poly- for polyvinylpyrrolidone, dimethyl silicone polymer, polyethyleneimine, amido One of ethylene glycol, sulfo group polyaniline are a variety of.