CN107828416A - A kind of quantum dot fluorescence composite and its preparation method and application - Google Patents
A kind of quantum dot fluorescence composite and its preparation method and application Download PDFInfo
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- CN107828416A CN107828416A CN201711014175.8A CN201711014175A CN107828416A CN 107828416 A CN107828416 A CN 107828416A CN 201711014175 A CN201711014175 A CN 201711014175A CN 107828416 A CN107828416 A CN 107828416A
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
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- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
Abstract
The present invention relates to a kind of quantum dot fluorescence composite and its preparation method and application, the quantum dot fluorescence composite includes：Graphene, and the polymer microballoon being compound on graphene；The inside of polymer microballoon is embedded with quantum dot；The surface of polymer microballoon is bonded with the surface of graphene by peptide bond.On the one hand improve the compatibility issue of quantum dot and polymeric material, control the pattern of quantum dot polymer composites, avoid the defects of graphene is direct and quantum dot combines easily quenching；On the other hand the excellent barrier water oxygen ability of graphene has been played, has reduced erosion of the water oxygen to quantum dot, while the superior thermal conductivity of graphene can further improve quantum dot composite material stability.The stable quantum dot@PS microballoon@graphene composite materials of composite construction are packaged into quantum dot LED, and the LED oxidative stability that blocks water can be further improved in the case where significantly reducing the optical property of quantum dot.
Description
Technical field
The present invention relates to luminescent material technical field, more particularly to a kind of quantum dot fluorescence composite and preparation method thereof
And application.
Background technology
This year, quantum dot have quickly won the concern of various circles of society as a kind of novel nano fluorescent material.Quantum dot
Possess many beneficial optical properties, such as accurately regulation wavelength of transmitted light, the half-peak breadth of emission peak are very narrow, moreover it is possible to realize very
High fluorescence quantum yield etc., these advantages can be used for realizing the illumination of high quality and the display of super wide colour gamut.
Quantum dot LED is dispersed in polymer substrate generally by by the high quality quantum dot of particular range of wavelengths
In, light conversion layer is formed, then compound foil is covered on LED to realize expected perfect optics performance again, or will
The quantum dot and resin or silica gel of preparation are mixed to get silica-gel mixture, mixture are encapsulated in LED chip, solidification obtains
Quantum dot LED.
But these methods exist it is compatible between many problems, such as the part of quantum dot surface and the long-chain of polymer
The destruction of the infiltration of sex chromosome mosaicism, also oxygen and moisture to quantum dot performance etc..These influence factors ultimately result in low light conversion
Efficiency and fluorescence quantum yield (PLQY), what is more, the LED of these structures possesses bad thermal conductivity, in somewhat high power
Under input (such as operating current is more than 20mA), serious heat problem may result in.
In order to improve the compatibility of quantum dot and silica gel or resinous substrates, we have to before using quantum dot to it
Chemical modification is carried out, but the PLQY of quantum dot may decline, ultimately resulting in quantum dot LED fluorescence efficiency reduces.
And it is to possess many remarkable physicochemical characteristics that single-layer graphene thin slice, which is reported, for example, it is high optical transmittance, good
Good heat conduction and electric conductivity, excellent mechanical performance and water oxygen barrier, heat endurance etc., therefore graphene and quantum dot are combined
The quantum dot LED of preparation can realize more preferable optical property and stability.But quantum dot and graphene are directly mixed into meeting
Quantum dot is caused to be reunited, while quantum dot directly contacts with graphene, and serious fluorescent quenching can also occur.
The research of quantum dot LED stability be promote display with lighting field development key factor, we there is an urgent need to
Some technologies can improve quantum dot LED stability in the case where not influenceing the optical property of quantum dot, promote quantum dot
LED industrialized production.
The content of the invention
In view of problems of the prior art, an object of the present invention is to provide a kind of quantum dot fluorescence composite wood
Material, quantum dot LED stability can be improved in the case where not influenceing the optical property of quantum dot.
For the above-mentioned purpose, the present invention adopts the following technical scheme that：
In a first aspect, the invention provides a kind of quantum dot fluorescence composite, the quantum dot fluorescence composite bag
Include：Graphene, and the polymer microballoon being compound on the graphene；The inside of the polymer microballoon is embedded with quantum
Point；The surface of the polymer microballoon is bonded with the complex method on the surface of the graphene including peptide bond, amido link is bonded, is quiet
Electro Sorb and click react the combination of any one or at least two in bonding.
One aspect of the present invention is avoided graphene and directly combined easily with quantum dot by polymer microballoon coated quantum dots
The defects of quenching, quantum dot stability is improved, on the other hand by the compound of graphene, has played the excellent barrier water of graphene
Oxygen ability, erosion of the water oxygen to quantum dot, while the superior thermal conductivity energy of graphene are reduced, it is steady that composite heat can be improved
It is qualitative, further improve quantum dot composite material stability.The overall construction design that composite is formed in the present invention causes respectively
Cooperateed with mutually between component, further increase stability, achieve 1 plus 1 effect for being more than 2.
Preferably, the material of the quantum dot include cadmium selenide, cadmium telluride, cadmium sulfide, zinc selenide, indium sulphur, indium phosphide,
In selenizing zinc-copper or selenizing MnZn any one or at least two combination, wherein, it is typical but non-limiting to be combined as：Selenium
The combination of the combination of the combination of cadmium and cadmium telluride, cadmium sulfide and zinc selenide, indium sulphur and indium phosphide, selenizing zinc-copper or manganese selenide
The combination of zinc, cadmium sulfide with or selenizing MnZn combination, the combination of zinc selenide, indium sulphur and indium phosphide, preferably cadmium selenide.Selenizing
Cadmium technology of preparing is more ripe, emission peak Wavelength tunable, has narrow half-peak breadth, high quantum yield, Simultaneous Stabilization is relatively
It is high.
Preferably, the quantum dot includes monokaryon quantum dot and/or core-shell quanta dots, preferably nuclear shell structure quantum point, its
Relatively more stable, yield is also relatively higher.
Preferably, the core of the core-shell quanta dots includes cadmium selenide, cadmium telluride, cadmium sulfide, zinc selenide, indium sulphur, phosphatization
In indium, selenizing zinc-copper or selenizing MnZn any one or at least two combination, wherein, typical but non-limiting combination
For：The combination of the combination of cadmium selenide and cadmium telluride, cadmium sulfide and zinc selenide, the combination of indium sulphur, indium phosphide and selenizing zinc-copper, tellurium
Cadmium and the combination of selenizing MnZn, preferably cadmium selenide.
Preferably, the shell of the core-shell quanta dots is included in cadmium sulfide, zinc oxide, zinc sulphide, zinc selenide or zinc telluridse
Any one or at least two combination, wherein, it is typical but non-limiting to be combined as：The combination of cadmium sulfide and zinc oxide, sulphur
Change the combination of zinc and zinc telluridse, the combination of zinc selenide and zinc telluridse, the combination of cadmium sulfide, zinc oxide and zinc sulphide, preferably vulcanize
Cadmium.
Preferably, the composite quality ratio of the graphene and the polymer microballoon is (0.01~10):100, such as
0.01:100、0.02:100、0.05:100、0.08:100、0.1:100、0.2:100、0.3:100、0.4:100、0.5:100、
0.6:100、0.7:100、0.8:100、0.9:100、1:100、1.5:100、2:100、3:100、4:100、5:100、6:100、
7:100、8:100、9:100 or 10:100 etc., preferably (0.1~1):100.
Preferably, the particle diameter of the polymer microballoon is 0.1~50 μm, such as 0.1 μm, 0.2 μm, 0.5 μm, 0.8 μm, 1 μ
M, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm or 50
μm etc., preferably 1~10 μm.
Preferably, the polymer microballoon includes polystyrene, polyacrylic acid, polyethylene, Kynoar or poly- methyl
In methyl acrylate any one or at least two combination, wherein typical but non-limiting be combined as：Polystyrene with
The combination of the combination of the combination of polyacrylic acid, polyethylene and Kynoar, polystyrene and polymethyl methacrylate, poly- third
The combination of olefin(e) acid and polyethylene, the combination of styrene, polyacrylic acid and polyethylene, polyethylene, Kynoar and poly- methyl-prop
The combination of e pioic acid methyl ester, the combination of polystyrene, polyacrylic acid, polyethylene, Kynoar and polymethyl methacrylate；It is excellent
Select polystyrene.
The present invention is not limited the size of graphene, as shown in Figure 1, Figure 2, Figure 3 shows, various sizes of graphene and quantum
The compound of point-polymer microballoon can have a different existing ways, and the relative size of PS microballoons and graphene is different, can make
Difference into graphene to " cladding " effect of PS microballoons, as long as the compound quantity ratio of polymerizing microballoons and graphene is appropriate, with regard to energy
Realize the fluorescence property of the composite of the present invention.
Second aspect, it is described the invention provides the preparation method of quantum dot fluorescence composite as described in relation to the first aspect
Preparation method comprises the following steps：
(1) polymer microballoon is prepared；
(2) step (1) resulting polymers microballoon and quantum dot are added in solvent, add water to be swelled, obtain quantum dot-
Polymer composite microsphere, then, carboxylated obtain carboxylated complex microsphere, or, amination obtains amination complex microsphere；
(3) it is carboxylated complex microsphere obtained by amination graphene and step (2) is compound, or, by carboxylated graphene with
Amination complex microsphere obtained by step (2) is compound, obtains quantum dot fluorescence composite.
The present invention proposes the graphite alkene reaction of the quantum dot polymer microspheres and surface amination using surface carboxyl groups, or
Person is reacted using the graphene of amidized quantum dot polymer microspheres and surface carboxyl groups, forms composite construction stabilization
Quantum dot@PS microballoon@graphene composite materials.
Swelling method can be easy to coat quantum dot in the present invention, it is not necessary to the preparation method of polymer is limited, it is any
Existing method for preparing polymer micro is all applicable, and when preparing polymer microballoon using dispersion copolymerization method, the present invention is molten
The simplicity of swollen method can give full play to the advantage of dispersion copolymerization method, i.e. the polyalcohol microspherulite diameter prepared is uniform, single dispersing
Property is good, improves the fluorescent stability of material, it is easy to accomplish be prepared on a large scale.
Preferably, step (2) described solvent includes：1 mass parts, the mass parts of water 5~20, the mass parts of ethanol 10~30, PVA
5~20 mass parts, the mass parts of PVP 5~20.
Preferably, it is the suitable particle size of guarantee polymer microballoon and homogeneity, step (2) the addition polymer
The amount of microballoon be the solvent 0.01~10wt%, such as 0.01wt%, 0.02wt%, 0.05wt%, 0.08wt%,
0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%,
1wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%,
1.9wt%, 2wt%, 3wt%, 4wt%, 5wt%, 8wt% or 10wt% etc., preferably 0.5~2wt%.
Preferably, step (2) quantum dot and polymer microballoon mass ratio of adding is (0.001~0.3):1, such as
0.001:1、0.005:1、0.008:1、0.01:1、0.02:1、0.05:1、0.08:1、0.09:1、0.1:1、0.15:1、0.2:
1、0.25:1 or 0.3:1 etc., preferably (0.01~0.1):1.
Preferably, step (2) is described plus the speed of water is 0.1~10mL/min, such as 0.1mL/min, 0.2mL/min,
0.5mL/min、0.8mL/min、1mL/min、1.5mL/min、2mL/min、2.5mL/min、3mL/min、4mL/min、5mL/
Min, 6mL/min, 7mL/min, 8mL/min, 9mL/min or 10mL/min etc., preferably 2mL/min.
Preferably, the time of step (2) described swelling is 0.5~6h, for example, 0.5h, 0.8h, 1h, 1.2h, 1.5h,
1.8h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h etc., preferably 1~2h.
Preferably, step (2) described carboxylated specifically includes：Quantum dots-polymer complex microsphere is added into carboxyl solution
In, acted on first by swelling, the swelling of carboxyl precursor solution enters inside complex microsphere, and then 70 DEG C of polymerizations, compound first
The carboxylation reaction of microballoon；Water is added to carry out carboxylation reaction.
Preferably, the carboxyl solution includes the mass parts of styrene 1, the mass parts of olefin(e) acid 0.1~10, divinylbenzene 0.5
~5 mass parts, the mass parts of water 5~20, the mass parts of ethanol 10~30, the mass parts of PVA 5~20, the mass parts of PVP 5~20.Wherein
Styrene, olefin(e) acid and presoma are as presoma, and water, ethanol, PVA and PVP are as solvent.
Preferably, the olefin(e) acid includes any one in acrylic acid, oleic acid, undecenoic acid or hexenoic acid or at least two
Combination, wherein typical but non-limiting be combined as：The combination of the combination of acrylic acid and oleic acid, undecenoic acid and hexenoic acid,
The combination of acrylic acid and hexenoic acid, the combination of acrylic acid, oleic acid and undecenoic acid, acrylic acid, oleic acid, undecenoic acid and hexenoic acid
Combination.
Preferably, the time of the carboxylated is 0.5~24h, for example, 0.5h, 1h, 2h, 5h, 8h, 9h, 10h, 10.2h,
10.5h, 10.8h, 11h, 11.2h, 11.5h, 11.8h, 12h, 15h, 18h, 20h, 22h or 24h etc., preferably 10~12h.
Preferably, step (2) described amination specifically includes：Quantum dots-polymer complex microsphere is added into amino acid solution
In, the carboxyl solution swelling enters the inside of the quantum dots-polymer complex microsphere, and heating carries out polymerisation.
Preferably, the amino acid solution includes the mass parts of styrene 1, the mass parts of olefin(e) acid 0.1~10, divinylbenzene 0.5
~5 mass parts, the mass parts of water 5~20, the mass parts of ethanol 10~30, the mass parts of PVA 5~20, the mass parts of PVP 5~20.Wherein
Styrene, olefin(e) acid and divinylbenzene are presoma, and remaining ingredient is solvent.
Preferably, group of the olefin(e) acid including any one in allyl amine, acrylamide or oleyl amine or at least two
Close, wherein typical but non-limiting be combined as：The combination of the combination of allyl amine and acrylamide, oleyl amine and acrylamide,
The combination of allyl amine, acrylamide and oleyl amine.
Preferably, the amidized time is 0.5~24h, for example, 0.5h, 1h, 2h, 5h, 8h, 9h, 10h, 10.2h,
10.5h, 10.8h, 11h, 11.2h, 11.5h, 11.8h, 12h, 15h, 18h, 20h, 22h or 24h etc., preferably 10~12h.
Preferably, step (3) is described compound specifically includes：Carboxylated complex microsphere obtained by step (2) and EDC/NHS are existed
It is sufficiently mixed in water, EDC and NHS mol ratio is 1 in wherein EDC/NHS:1, with mol ratio 1:1 mixing, is slowly added to amino
Graphite alkene, stirring carry out cross-linking reaction, isolated quantum dot fluorescence composite.
Or, be sufficiently mixed carboxylated graphene and EDC/NHS in ethanol, it is slowly added to carboxylated obtained by step (2)
Graphene, stirring carry out cross-linking reaction, isolated quantum dot fluorescence composite.
Preferably, graphene:EDC/NHS:Complex microsphere mass ratio is (0.1~5):(1~10):100.
Preferably, the time of the stirring is 2~24h, for example, 2h, 5h, 5.5h, 6h, 6.5h, 6.8h, 7h, 7.5h,
7.8h, 8h, 9h, 10h, 12h, 15h, 18h, 20h, 22h or 24h etc., preferably 5~8h.
In addition, present invention also offers another preparation method, it is described unlike preparation method described in second aspect
Step (2) replaces with：
Step (1) resulting polymers microballoon carboxylated is obtained into carboxylated polymers microballoon, by quantum dot and the carboxyl
Fluidized polymer microballoon is added in solvent and is swelled, and obtains carboxylated complex microsphere；
Or, step (1) resulting polymers microballoon amination is obtained into amination polymer microballoon, by quantum dot and the ammonia
Base fluidized polymer microballoon is added in solvent and is swelled, and obtains amination complex microsphere.
The swelling reaction of carboxylated or amination and quantum dot without inevitable sequencing, carboxylated or amination be for
The processing of surface reaction function dough is carried out to polymer microballoon, carboxyl (amino) can be with the graphite of amination (carboxylated)
Amino (carboxyl) in alkene reacts so that polymer microballoon and graphene are more stable with chemical key connection；Therefore can be with
First be swelled and carry out carboxylated processing again, can also first carboxylated be swelled again.Selection two methods in which kind of depend on specific feelings
Condition.Under certain conditions, first it is swelled when carrying out carboxylated processing again, when the acidity of carboxylated presoma is stronger (such as acrylic acid),
Quantum dot may be easily caused and produce fluorescent quenching；In another case, such as the addition of divinylbenzene so that polymer microballoon
Crosslinking is produced, if quantum dot volume is larger, the polymer microballoon of first carboxylated is possible to again can be in swelling reaction
Have influence on quantum dot and enter polymer microballoon.
The third aspect, the invention provides quantum dot fluorescence composite as described in relation to the first aspect biological fluorescent labelling,
Application in display, illumination, solar cell, solar concentrator and laser material.
Compared with prior art, the present invention at least has the advantages that：
1. one aspect of the present invention by polymer microballoon coated quantum dots, can improve the simultaneous of quantum dot and polymeric material
Capacitive problem, the pattern of quantum dot polymer composites is controlled, avoid graphene directly and quantum dot combines easily quenching
The defects of, quantum dot stability is improved, on the other hand by the compound of graphene, has played the excellent barrier water oxygen energy of graphene
Power, spilling for quantum dot is reduced, further improve quantum dot stability.The overall construction design of composite is formed in the present invention
So that being cooperateed with mutually between each component, stability is further increased, achieves 1 plus 1 effect for being more than 2；
2. swelling method of the present invention allows to use dispersion copolymerization method synthetic polymer microballoon, uniform particle sizes, monodispersity are played
Good advantage, it is easy to accomplish be prepared on a large scale；
3. the present invention proposes the graphite alkene reaction of the quantum dot polymer microspheres and surface amination using surface carboxyl groups,
Or reacted using the graphene of amidized quantum dot polymer microspheres and surface carboxyl groups, it is stable to form composite construction
Quantum dot PS microballoon graphene composite materials, be packaged into quantum dot LED, can not seriously reduce quantum dot it is optical
The LED oxidative stability that blocks water further is improved in the case of energy.
Brief description of the drawings
Fig. 1 is that the composite construction for the quantum dot fluorescence microballoon that big size graphene of the present invention is modified hinders the signal that oxygen blocks water
Figure；
Fig. 2 is that the composite construction of the quantum dot fluorescence microballoon that size graphite alkene is modified in the present invention hinders the signal that oxygen blocks water
Figure；
Fig. 3 is that the composite construction for the quantum dot fluorescence microballoon that small size graphene of the present invention is modified hinders the signal that oxygen blocks water
Figure；
Fig. 4 is the scanning electron microscope (SEM) photograph for the quantum dot fluorescence microballoon that big size graphene of the present invention is modified；
Fig. 5 is the scanning electron microscope (SEM) photograph for the quantum dot fluorescence microballoon that small size graphene of the present invention is modified；
Fig. 6 is the scanning electron microscope (SEM) photograph for the PS microballoons that the quantum dot of specific embodiment of the invention comparative example 3 embeds
Mark is illustrated as in Fig. 1~3：11、21、31：Polymer microballoon；12、22、32：Graphene；13、23、33：Oxygen
Son；14、24、34：Hydrone
Embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.But following reality
Example is only the simple example of the present invention, does not represent or limit the scope of the present invention, protection scope of the present invention
It is defined by claims.
Embodiment 1
A kind of quantum dot fluorescence composite, it is made up of graphene and the PS microballoons being compound on graphene；Wherein PS
The inside of microballoon is embedded with CdSe quantum dots；The particle diameter of PS microballoons is 5 μm, and the surface of its surface and graphene passes through peptide bond key
Close.The composite quality ratio of graphene and PS microballoons is 0.5:100.
The preparation process for the quantum dot fluorescence composite that embodiment 1 is provided is as follows：
1) prepared by PS microballoons
PVP is dissolved in the in the mixed solvent being made up of second alcohol and water, input is equipped with thermometer, agitator and condenser
In 250mL four-hole bottles, lead to nitrogen protection, the pre-dispersed 30min at 70 DEG C, then add monomer styrene (St) and initiator
AIBN, 12h is reacted at 70 DEG C, after the completion of reaction, obtain PS microballoons；
2) quantum dot+PS microballoons swelling：
On the basis of the quality of styrene, 10 times of water, 15 times of ethanol, 10%PVA and 10%PVP are added, is sufficiently stirred mixed
Close, add 1%PS microballoons and 0.1% quantum dot, after mixing, water is added with 2mL/min speed, quantum dot PS microballoons is carried out and swells
Swollen 1h, the excellent quantum dot-PS polymer microballoons of luminescent properties are obtained, ethanol washs 3 times, and luminous microballoon is dispersed in ethanol solution
In；
3) quantum dot-PS polymer microballoons surface carboxyl groups
On the basis of the quality of styrene, 1% acrylic acid is added, 1% divinylbenzene, 10 times of water, 15 times of ethanol,
10%PVA and 10%PVP, is thoroughly mixed, and adds 1% quantum dot-PS microballoons.After mixing, quantum dot PS microballoon tables are carried out
Face carboxylated processing.
4) carboxylated quantum dot-PS polymer is prepared with graphene composite material
Quantum dot-PS the polymer of carboxylated, EDC/NHS (2%) are fully acted in ethanol solution, are slowly added to 1%
Amination graphene, it is stirred overnight, obtained composite carries out centrifuge washing, is finally scattered in ethanol.
Embodiment 2
A kind of quantum dot fluorescence composite, it is made up of graphene and the PS microballoons being compound on graphene；Wherein PS
The inside of microballoon is embedded with 10% zinc selenide quantum dot；The particle diameter of PS microballoons is 10 μm, and the surface of its surface and graphene passes through
Peptide bond is bonded.The composite quality ratio of graphene and PS microballoons is 1:100.
The preparation process for the quantum dot fluorescence composite that embodiment 2 is provided is as follows：
1) the PS microballoons of carboxylated are prepared
It is similar with the step 1) of embodiment 1, unlike, on the basis of the quality of styrene, 1% is added in styrene
Acrylic acid, the PS microballoons of carboxylated are prepared after 1% divinyl benzene crosslinked；
2) quantum dot+carboxylated PS microballoon swelling：
On the basis of the quality of styrene, 10 times of water are added, 15 times of ethanol, 10%PVA, 10%PVP, are sufficiently stirred mixed
Close, add 1% carboxylated PS microballoons.After mixing, water is added with 2mL/min speed, carries out quantum dot-PS microballoon swelling 1h,
The excellent quantum dot of luminescent properties-carboxylated PS polymer microballoons are obtained, ethanol washs 5 times, and it is molten that luminous microballoon is dispersed in ethanol
In liquid；
3) it is prepared by carboxylated quantum dot-PS polymer, graphene composite material
Quantum dot-PS the polymer of carboxylated, EDC/NHS (5%) are fully acted in ethanol solution, are slowly added to 1%
Amination graphene, it is stirred overnight, obtained composite carries out centrifuge washing, is finally scattered in ethanol.
Embodiment 3
A kind of quantum dot fluorescence composite, it is made up of graphene and the PS microballoons being compound on graphene；Wherein PS
The inside of microballoon is embedded with 10% cadmiumsulfide quantum dot；The particle diameter of PS microballoons is 20 μm, and the surface of its surface and graphene passes through
Peptide bond is bonded.The composite quality ratio of graphene and PS microballoons is 1:100.
The preparation process for the quantum dot fluorescence composite that embodiment 3 is provided is as follows：
1) prepared by PS microballoons
With the step 1) of embodiment 1
2) quantum dot+PS microballoons swelling：
On the basis of the quality of styrene, 10 times of water, 15 times of ethanol, 10%PVA and 10%PVP are added, is sufficiently stirred mixed
Close, add 1%PS microballoons and 0.1% quantum dot, after mixing, water is added with 2mL/min speed, quantum dot PS microballoons is carried out and swells
Swollen 1h, the excellent quantum dot-PS polymer microballoons of luminescent properties are obtained, ethanol washs 3 times, and luminous microballoon is dispersed in ethanol solution
In；
3) quantum dot-PS polymer microballoons surface amination
On the basis of the quality of styrene, 1% acrylamide, 1% divinylbenzene, 10 times of water, 15 times of second are added
Alcohol, 10%PVA and 10%PVP, are thoroughly mixed, and add 1% quantum dot-PS microballoons.After mixing, quantum dot PS microballoons are carried out
Surface amination processing.
4) amination quantum dot-PS polymer is prepared with graphene composite material
Amidized quantum dot-PS polymer, EDC/NHS (5%) are fully acted in ethanol solution, are slowly added to 1%
Carboxylated graphene, is stirred overnight, and obtained composite carries out centrifuge washing, is finally scattered in ethanol.
Comparative example 1
With differing only in for embodiment 1：Save graphene.
Comparative example 2
With differing only in for embodiment 1：Save carboxylated and amination.
Comparative example 3
With differing only in for embodiment 1：Swelling method is substituted with in-situ polymerization, is specially：
In PS microballoon preparation process, directly quantum dot is embedded in polymer microballoon：
PVP is dissolved in the in the mixed solvent being made up of second alcohol and water, input is equipped with thermometer, agitator and condenser
In 250mL four-hole bottles, lead to nitrogen protection, the pre-dispersed 30min at 70 DEG C, then add monomer styrene (St), quantum dot and
Initiator A IBN, 12h is reacted at 70 DEG C, after the completion of reaction, obtain the PS microballoons of quantum dot embedding；
The quenching of quantum dot-PS microballoons quantum dot light emitting is serious obtained by this method, more than 50%, and with swelling method acquired results
Quenching is less than 20%.
By taking CdSe quantum dot as an example, quantum dot fluorescence composite of the present invention and the performance difference of prior art are investigated.Table 1
For the quantum dots-polymer microsphere fluorescence spectrum property of embodiment 1 and comparative example.
Table 1
As it can be seen from table 1 larger red shift occurs for the fluorescence emission peak of comparative example 3, while half-peak breadth increases, quantum yield
Substantially reduced compared with embodiment 1, compares figure 6 and Fig. 4~5 are understood, this is due to after substituting swelling method with in-situ polymerization, it is difficult to
Realize the preparation of the PS microballoons of single-size；Thus obtained microsphere is largely reunited simultaneously, and luminescent properties substantially reduce.Comparative examples 1
Understood with comparative example 1~2, graphene and carboxylated, amination modified process are added in the present invention hardly reduces quantum dot
Optical property.
Table 2 is embodiment 1 and (2835 blue-light LED chips are the quantum dots-polymer microballoon stability contrast table of comparative example
Light source, 10000mW/cm2Irradiated under light intensity, determine holding of the material emission intensity after different irradiation times compared with initial strength
Rate, arrange in table 2).
Table 2
| Irradiation time | 0h | 1h | 4h | 20h | 90h |
| CdSe quantum dot | 100% | 47.4% | 38.5% | 28.4% | 23.8% |
| Embodiment 1 | 100% | 92.3% | 87.5% | 78.2% | 65.4% |
| Comparative example 1 | 100% | 87.1% | 81.3% | 60.5% | 44.6% |
| Comparative example 2 | 100% | 86.0% | 80.4% | 61.2% | 42.8% |
| Comparative example 3 | 100% | 82.9% | 78.2% | 54.2% | 33.3% |
From table 2 it can be seen that addition graphene and carboxylated, amination modified process, the swelling method exist in the present invention
On the premise of the optical property for hardly reducing quantum dot, quantum dot stability in material is greatly improved.Embodiment 2, embodiment 3
It is similar with the effect of embodiment 1, repeat no more.
Applicant states that the present invention illustrates the detailed process equipment of the present invention and technological process by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, selection of concrete mode etc., all fall within the present invention's
Within the scope of protection domain and disclosure.
Claims (10)
1. a kind of quantum dot fluorescence composite, it is characterised in that the quantum dot fluorescence composite includes：Graphene, with
And it is compound in the polymer microballoon on the graphene；
The inside of the polymer microballoon is embedded with quantum dot；
The surface of the polymer microballoon is bonded with the complex method on the surface of the graphene including peptide bond, amido link is bonded,
Electrostatic Absorption and click react the combination of any one or at least two in bonding.
2. quantum dot fluorescence composite as claimed in claim 1, it is characterised in that the material of the quantum dot includes selenizing
Any one in cadmium, cadmium telluride, cadmium sulfide, zinc selenide, indium sulphur, indium phosphide, selenizing zinc-copper or selenizing MnZn or at least two
The combination of kind, preferably cadmium selenide；
Preferably, the quantum dot includes monokaryon quantum dot and/or core-shell quanta dots, preferably core-shell quanta dots；
Preferably, the core of the core-shell quanta dots includes cadmium selenide, cadmium telluride, cadmium sulfide, zinc selenide, indium sulphur, indium phosphide, selenium
Change in zinc-copper or selenizing MnZn any one or at least two combination, preferred cadmium selenide；
Preferably, the shell of the core-shell quanta dots includes any in cadmium sulfide, zinc oxide, zinc sulphide, zinc selenide or zinc telluridse
It is a kind of or at least two combination, preferred cadmium sulfide.
3. quantum dot fluorescence composite as claimed in claim 1 or 2, it is characterised in that the graphene polymerize with described
The composite quality ratio of thing microballoon is (0.01~10):100, preferably (0.1~1):100.
4. the quantum dot fluorescence composite as described in any one of claims 1 to 3, it is characterised in that the polymer microballoon
Particle diameter be 0.1~50 μm, preferably 1~10 μm；
Preferably, the polymer microballoon includes polystyrene, polyacrylic acid, polyethylene, Kynoar or polymethyl
In sour methyl esters any one or at least two combination, preferred polystyrene.
5. the preparation method of quantum dot fluorescence composite as described in any one of Claims 1 to 4, it is characterised in that the system
Preparation Method comprises the following steps：
(1) polymer microballoon is prepared；
(2) step (1) resulting polymers microballoon and quantum dot are added in solvent, adds water to be swelled, obtain quantum dot-polymerization
Thing complex microsphere, then, carboxylated obtain carboxylated complex microsphere, or, amination obtains amination complex microsphere；
(3) it is carboxylated complex microsphere obtained by amination graphene and step (2) is compound, or, by carboxylated graphene and step
(2) gained amination complex microsphere is compound, obtains quantum dot fluorescence composite.
6. preparation method as claimed in claim 5, it is characterised in that step (2) described solvent includes：The mass parts of styrene 1,
The mass parts of water 5~20, the mass parts of ethanol 10~30, the mass parts of PVA 5~20, the mass parts of PVP 5~20；
Preferably, step (2) it is described add polymer microballoon amount be the solvent 0.01~10wt%, preferably 0.5~
2wt%；
Preferably, step (2) quantum dot and polymer microballoon mass ratio of adding is (0.001~0.3):1, preferably (0.01
~0.1):1；
Preferably, step (2) is described plus the speed of water is 0.1~10mL/min, preferably 2mL/min；
Preferably, the time of step (2) described swelling is 0.5~6h, preferably 1~2h.
7. the preparation method as described in claim 5 or 6, it is characterised in that step (2) described carboxylated specifically includes：Will amount
Sub- point-polymer composite microsphere is added in carboxyl solution, and it is compound micro- that the carboxyl solution swelling enters the quantum dots-polymer
The inside of ball, heating carry out polymerisation；
Preferably, the carboxyl solution includes the mass parts of styrene 1, the mass parts of olefin(e) acid 0.1~10, the matter of divinylbenzene 0.5~5
Measure part, the mass parts of water 5~20, the mass parts of ethanol 10~30, the mass parts of PVA 5~20, the mass parts of PVP 5~20；
Preferably, group of the olefin(e) acid including any one in acrylic acid, oleic acid, undecenoic acid or hexenoic acid or at least two
Close；
Preferably, the time of the carboxylated is 0.5~24h, preferably 10~12h；
Preferably, step (2) described amination specifically includes：Quantum dots-polymer complex microsphere is added in amino acid solution, institute
The inside that amino acid solution swelling enters the quantum dots-polymer complex microsphere is stated, heating carries out polymerisation；
Preferably, the amino acid solution includes：The mass parts of styrene 1, the mass parts of olefin(e) acid 0.1~10, divinylbenzene 0.5~5
Mass parts, the mass parts of water 5~20, the mass parts of ethanol 10~30, the mass parts of PVA 5~20, the mass parts of PVP 5~20；
Preferably, combination of the olefin(e) acid including any one in allyl amine, acrylamide or oleyl amine or at least two；
Preferably, the amidized time is 0.5~24h, preferably 10~12h.
8. the preparation method as described in any one of claim 5~7, it is characterised in that step (3) is described compound to be specifically included：
Carboxylated complex microsphere obtained by step (2) and EDC/NHS are sufficiently mixed in water, EDC's and NHS rubs in wherein EDC/NHS
You are than being 1:1, amination graphene is slowly added to, stirring carries out cross-linking reaction, isolated quantum dot fluorescence composite；
Or, be sufficiently mixed carboxylated graphene and EDC/NHS in ethanol, it is slowly added to carboxyl graphite obtained by step (2)
Alkene, stirring carry out cross-linking reaction, isolated quantum dot fluorescence composite；
Preferably, graphene:EDC/NHS:Complex microsphere mass ratio is (0.1~5):(1~10):100；
Preferably, the time of the stirring is 2~24h, preferably 5~8h.
9. the preparation method as described in any one of claim 5~8, it is characterised in that the step (2) replaces with：
Step (1) resulting polymers microballoon carboxylated is obtained into carboxylated polymers microballoon, quantum dot and the carboxylated are gathered
Compound microballoon is added in solvent and is swelled, and obtains carboxylated complex microsphere；
Or, step (1) resulting polymers microballoon amination is obtained into amination polymer microballoon, by quantum dot and the amination
Polymer microballoon is added in solvent and is swelled, and obtains amination complex microsphere.
10. quantum dot fluorescence composite is in biological fluorescent labelling, display, illumination, too as described in any one of Claims 1 to 4
Application in positive energy battery, solar concentrator and laser material.
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