CN109810688A - Quantum dot composite particle and its preparation method and application - Google Patents
Quantum dot composite particle and its preparation method and application Download PDFInfo
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- CN109810688A CN109810688A CN201711163221.0A CN201711163221A CN109810688A CN 109810688 A CN109810688 A CN 109810688A CN 201711163221 A CN201711163221 A CN 201711163221A CN 109810688 A CN109810688 A CN 109810688A
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Abstract
The present invention provides a kind of quantum dot composite particles, the quantum dot composite particle includes silicon dioxide-coated quantum dots, and it is incorporated in the metal nanoparticle on the silicon dioxide-coated quantum dots surface, wherein, the silicon dioxide-coated quantum dots include quantum dot and the silicon dioxide layer for being coated on the quantum dot surface, and the metal nanoparticle and the silicon dioxide layer pass through-S-R1‑SCH2CH2R2‑Si(O‑)3Or (O-)3Si‑R1‑SCH2CH2R2‑Si(O‑)3In conjunction with R1、R2It is respectively selected from alkyl or alkyl derivative.
Description
Technical field
The invention belongs to technology of quantum dots field more particularly to a kind of quantum dot composite particle and preparation method thereof and answer
With.
Background technique
In recent years, with the fast development of display technology, colloidal semiconductor nanocrystalline (also known as " quantum dot ") is due to its spy
Some quantum confined effects cause the extensive concern of researcher.In comparison with traditional organic luminescent dyes, quantum dot has
There is exciting light spectrum width, emission spectrum is narrow, and launch wavelength is adjustable, the advantages such as fluorescence efficiency height and photochemical properties stabilization.In addition, amount
Optics, electricity and the transmission performance of son point can be adjusted by synthesis process.These advantages make quantum dot novel aobvious
Show that field has a very important role, becomes great potential by the light emitting diode with quantum dots (QLED) of luminescent layer of quantum dot
Next-generation display and solid-state lighting light source.By the development of many years, QLED technology obtains huge development.However, at present
The luminous efficiency of quantum dot is not still high, and the luminous efficiency of especially blue light quantum point is lower, to limit blue QLED's
Using.
Summary of the invention
The purpose of the present invention is to provide a kind of quantum dot composite particles and preparation method thereof, it is intended to solve existing quantum
The lower problem of the luminous efficiency of point, particularly blue light quantum point.
Another object of the present invention is to provide a kind of QLED devices.
The invention is realized in this way a kind of quantum dot composite particle, the quantum dot composite particle includes silica
Coated quantum dots, and it is incorporated in the metal nanoparticle on the silicon dioxide-coated quantum dots surface, wherein the titanium dioxide
Silicon coated quantum dots include quantum dot and the silicon dioxide layer for being coated on the quantum dot surface, and the metal nanoparticle
Pass through-S-R with the silicon dioxide layer1-SCH2CH2R2-Si(O-)3Or (O-)3Si-R1-SCH2CH2R2-Si(O-)3In conjunction with R1、
R2It is respectively selected from alkyl or alkyl derivative.
Correspondingly, a kind of preparation method of above-mentioned quantum dot composite particle, comprising the following steps:
Silicon dioxide-coated quantum dots are provided, the silicon dioxide-coated quantum dots include quantum dot and are coated on described
The silicon dioxide layer of quantum dot surface, the first dressing agent is contained on the surface of the silicon dioxide layer, and first dressing agent contains
There is (O-)3Si-R2-CH2=CH2, wherein R2Selected from alkyl or alkyl derivative；
Metal nanoparticle is provided, the metal nanoparticle surface contains the second dressing agent, and second dressing agent
Contain-S-R1- SH or (O-)3Si-R1- SH, wherein R1Selected from alkyl or alkyl derivative；
Metal nanoparticle that second dressing agent is contained on surface and surface are contained to the dioxy of first dressing agent
The mixing of SiClx coated quantum dots makes between the silicon dioxide-coated quantum dots and the metal nanoparticle by described first
Dressing agent reacts the-S-R to be formed with second dressing agent1-SCH2CH2R2-Si(O-)3Or (O-)3Si-R1-SCH2CH2R2-Si
(O-)3In conjunction with obtaining quantum dot composite particle.
And a kind of application of quantum dot composite particle, above-mentioned quantum dot composite particle or the above method are prepared
Quantum dot composite particle be used for QLED device luminescent layer.
Quantum dot composite particle provided by the invention, the quantum dot surface coat the silicon dioxide layer, the dioxy
SiClx layer surface is combined with metal nanoparticle metal nanoparticle, wherein the metal nanoparticle and the silica
Layer passes through-S-R1-SCH2CH2R2-Si(O-)3Or (O-)3Si-R1-SCH2CH2R2-Si(O-)3In conjunction with.Amount as characterized above
Son point composite particles, the plasma resonance energy that the metal nanoparticle inside generates can be spread to the quantum dot, draw
The local field strength and the optics density of states for playing the nearby quantum dots dramatically increase, thus enhance the fluorescence intensity of the quantum dot,
And then improve quantum dot light emitting efficiency.Quantum dot composite particle provided by the invention not only improves the luminous efficiency of quantum dot, together
When, the inside and outside quantum efficiency of QLED device is improved, the luminous efficiency of QLED device is increased.
The preparation method of quantum dot composite particle provided by the invention, method is simple, safe, easy to operate, has good
Application prospect.
The application of quantum dot composite particle provided by the invention can be effective due to containing above-mentioned quantum dot composite particle
The inside and outside quantum efficiency of QLED device is improved, the luminous efficiency of QLED device is increased.
Detailed description of the invention
Fig. 1 is the schematic diagram of quantum dot composite particle provided in an embodiment of the present invention；
Fig. 2 is that metal nanoparticle provided in an embodiment of the present invention and silicon dioxide layer pass through-S-R1-SCH2CH2R2-Si
(O-)3In conjunction with quantum dot composite particle general structure schematic diagram；
Fig. 3 is that metal nanoparticle provided in an embodiment of the present invention and silicon dioxide layer pass through (O-)3Si-R1-
SCH2CH2R2-Si(O-)3In conjunction with quantum dot composite particle general structure schematic diagram；
Fig. 4 is the structural schematic diagram of QLED device provided in an embodiment of the present invention.
Specific embodiment
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
In the description of the present invention, it is to be understood that, term " first ", " second " are used for description purposes only, and cannot
It is interpreted as indication or suggestion relative importance or implicitly indicates the quantity of indicated technical characteristic.Define as a result, " the
One ", the feature of " second " can explicitly or implicitly include one or more of the features.In the description of the present invention,
The meaning of " plurality " is two or more, unless otherwise specifically defined.
Such as Fig. 1-3, the embodiment of the invention provides a kind of quantum dot composite particle, the quantum dot composite particle includes two
Silica coated quantum dots, and it is incorporated in the metal nanoparticle on the silicon dioxide-coated quantum dots surface, wherein it is described
Silicon dioxide-coated quantum dots include quantum dot and the silicon dioxide layer for being coated on the quantum dot surface, and the metal is received
Rice grain and the silicon dioxide layer pass through-S-R1-SCH2CH2R2-Si(O-)3Or (O-)3Si-R1-SCH2CH2R2-Si(O-)3Knot
It closes, R1、R2It is respectively selected from alkyl or alkyl derivative.
Quantum dot composite particle provided in an embodiment of the present invention, the quantum dot surface coat the silicon dioxide layer, institute
State silica layer surface and be combined with metal nanoparticle, wherein the metal nanoparticle and the silicon dioxide layer by-
S-R1-SCH2CH2R2-Si(O-)3Or (O-)3Si-R1-SCH2CH2R2-Si(O-)3In conjunction with.The signal of the quantum dot composite particle
Figure as shown in Figure 1, wherein 11 be quantum dot, 22 be silicon dioxide layer, and 33 be metal nanoparticle；The two amounts sub- point of formation is multiple
The general structure schematic diagram difference for closing particle is as shown in Figure 2 and Figure 3.Quantum dot composite particle as characterized above, the metal
The plasma resonance energy generated inside nano particle can be spread to the quantum dot, cause the part of the nearby quantum dots
Field strength and the optics density of states dramatically increase, to enhance the fluorescence intensity of the quantum dot, and then improve quantum dot light emitting efficiency.
Quantum dot composite particle provided by the invention, not only improve quantum dot luminous efficiency, meanwhile, improve QLED device it is interior,
External quantum efficiency increases the luminous efficiency of QLED device.
Specifically, the selection of the quantum dot does not limit strictly in the embodiment of the present invention, preferably oil-soluble quantum
Point.The oil-soluble ligand of the oil-soluble quantum dot surface can assign quantum dot preferable surface property.Specifically, described
Oil-soluble quantum dot include but is not limited to II-VI group quantum dot, iii-v quantum dot, I-III-VI2 race quantum dot at least one
Kind.Specifically, the II-VI group quantum dot includes but is not limited to CdSe, CdS, CdTe, ZnSe, ZnS, CdTe, ZnTe；
CdZnS、CdZnSe、CdZnTe、ZnSeS、ZnSeTe、ZnTeS、CdSeS、CdSeTe、CdTeS、CdZnSeS、CdZnSeTe、
CdZnSTe；The iii-v quantum dot includes but is not limited to InP, InAs, GaP, GaAs, GaSb, AlN, AlP；InAsP；
InNP,InNSb,GaAlNP,InAlNP；I-III-VI2 race quantum dot includes but is not limited to CuInS2、CuInSe2、
AgInS2.The ligand of the oil-soluble quantum dot surface includes but is not limited to fatty acid ligands, amine ligand, in Phosphine ligands at least
It is a kind of.
In the embodiment of the present invention, the metal nanoparticle includes but is not limited to Ag, Au or Pt nano particle.The metal
The partial size of nano particle is preferably 2~10nm.
It is common, it is difficult to be crosslinked between silica and metal nanoparticle.In the embodiment of the present invention, the quantum dot table
Bread covers the silicon dioxide layer, and the silica layer surface is combined with metal nanoparticle, wherein the silicon dioxide layer
In silica and the metal nanoparticle pass through contain-S-R1-SCH2CH2R2-Si(O-)3Or (O-)3Si-R1-
SCH2CH2R2-Si(O-)3Connection.The embodiment of the present invention between the silica and the metal nanoparticle by constructing
Contain-S-R1-SCH2CH2R2-Si(O-)3Or (O-)3Si-R1-SCH2CH2R2-Si(O-)3Crosslinked group realize the titanium dioxide
The connection of silicon and the metal nanoparticle, and then the energy efficient transmitting that the metal nanoparticle plasma resonance is generated
To the quantum dot, and then realize the raising of quantum dot light emitting efficiency.Specifically ,-the S-R1-SCH2CH2R2-Si(O-)3Or
(O-)3Si-R1-SCH2CH2R2-Si(O-)3, can be by the way that the silica containing vinyl-functional and Mercaptofunctional will be contained
The metal nanoparticle of group is prepared, specific method see below by Click (click) chemical action.
Further, the energy transmission between metal nanoparticle described in the embodiment of the present invention and the quantum dot is mainly led to
Both it crosses and controls the thickness of the silicon dioxide layer to adjust, by selecting the thickness of suitable silicon dioxide layer, can make
Between be maintained at suitably apart from upper, so that plasma resonance energy energy of the quantum dot in the metal nanoparticle
In enough effectively transmitting ranges, and then improve the luminous efficiency of quantum dot.Preferably, the silicon dioxide layer with a thickness of 2-
20nm.Within this range, there is suitable transmitting distance, so that metal nanoparticle exists between metal nanoparticle and quantum dot
The resonance energy of generation is excited under the conditions of ultraviolet, can effectively pass to quantum dot, to improve the fluorescence radiation effect of quantum dot
Rate and luminous intensity.It is further preferred that the silicon dioxide layer with a thickness of 3-10nm.Still more preferably, described two
Silicon oxide layer with a thickness of 4-6nm.Within this range, the metal nanoparticle is to the quantum for the thickness of the silica
The plasma enhancement effect of point is most strong.
Quantum dot composite particle described in the embodiment of the present invention can be prepared by following methods.
Correspondingly, the embodiment of the invention provides a kind of preparation method of above-mentioned quantum dot composite particle, including following step
It is rapid:
Step S01. provides silicon dioxide-coated quantum dots, and the silicon dioxide-coated quantum dots include quantum dot and packet
The silicon dioxide layer of the quantum dot surface is overlayed on, the first dressing agent, and described first are contained in the surface of the silicon dioxide layer
Dressing agent contains (O-)3Si-R2-CH2=CH2, wherein R2Selected from alkyl or alkyl derivative；
Step S02. provides metal nanoparticle, and the metal nanoparticle surface contains the second dressing agent, and described the
Two dressing agents contain-S-R1- SH or (O-)3Si-R1- SH, wherein R1Selected from alkyl or alkyl derivative；
The metal nanoparticle that second dressing agent is contained on surface and surface are contained first modification by step S03.
The silicon dioxide-coated quantum dots of agent mix, and make to pass through between the silicon dioxide-coated quantum dots and the metal nanoparticle
First dressing agent reacts the-S-R to be formed with second dressing agent1-SCH2CH2R2-Si(O-)3Or (O-)3Si-R1-
SCH2CH2R2-Si(O-)3In conjunction with obtaining quantum dot composite particle.
The preparation method of quantum dot composite particle provided in an embodiment of the present invention, method is simple, safe, easy to operate, has
Good application prospect.
Specifically, in above-mentioned steps S01, the silicon dioxide-coated quantum dots include quantum dot and are coated on the amount
The first dressing agent is contained on the silicon dioxide layer on son point surface, the surface of the silicon dioxide layer, i.e., the described coated with silica amount
Son point is the silicon dioxide-coated quantum dots that first dressing agent is contained on surface.Preferably, the surface contains described first
The silicon dioxide-coated quantum dots of dressing agent the preparation method comprises the following steps: the quantum dot particle of coated with silica is provided, described in addition
After first dressing agent, it is stirred at room temperature.First dressing agent of end of tape vinyl of the embodiment of the present invention is to being coated with silicon oxide
Quantum dot to carry out alkenyl modified, make vinyl-functional on silica surface band, be to have Mercaptofunctional in step S03
Metal nanoparticle and the vinylation functional group of silica surface of group's modification by Click chemical action in conjunction with provide work
Use site.
First dressing agent contains (O-)3Si-R2-CH2=CH2, wherein R2Selected from alkyl or alkyl derivative, preferably
, the R2The alkyl or alkyl derivative that are amount of carbon atom between 2-20.Specific preferred, the first dressing agent is selected from
Vinyltrimethoxysilane, vinyltriethoxysilane, three tert-butoxy silane of vinyl, vinyl tri-tert peroxide
At least one of silane and vinyltriacetoxy silane.Further, the dosage of first dressing agent is preferred are as follows: institute
The mass ratio for stating the first dressing agent and quantum dot is 0.1~5:1, so that it is enough described to guarantee that the surface of silicon dioxide layer connects
First dressing agent is conducive in step S03, and the first dressing agent reacts to form-S-R with second dressing agent1-SCH2CH2R2-
Si(O-)3Or (O-)3Si-R1-SCH2CH2R2-Si(O-)3。
Room temperature described in the embodiment of the present invention is 10-30 DEG C.Preferably, the mixing time is 6-24 hours.
It is further preferred that the quantum dot particle of the coated with silica is prepared by following methods:
S011., quantum dot primary particles are provided, nonpolar solvent will be dissolved in the quantum dot primary particles, sequentially added
Amphoteric surfactant and polar solvent obtain the first mixed liquor；
S012. alkoxy silane, and the stir process at a temperature of first are added into the first mixed liquor, alkalinity is then added
Catalyst and water, purification process after stirring obtain the quantum dot of coated with silica.
Specifically, the quantum dot of the quantum dot primary particles is as it was noted above, in order to save a piece in above-mentioned steps S011
Width, details are not described herein again.Preferably, the quantum dot primary particles are oil-soluble quantum dot.
The nonpolar solvent can effectively dissolve the oil-soluble quantum dot, including but not limited to chloroform；The polarity
Solvent includes but is not limited to ethyl alcohol.After the oil-soluble quantum dot is completely dissolved, amphoteric surfactant and organic is sequentially added
Alcohol.Wherein, the amphoteric surfactant has water-wet side and hydrophobic end simultaneously, is added after adding the amphoteric surfactant
The polar solvent facilitates the oil-soluble quantum dot and is evenly dispersed in the polar solvent.Preferably, the polarity
Solvent includes but is not limited to ethyl alcohol.Preferably, the amphoteric surfactant is high molecular polymer, is specifically preferably but not limited to
At least one of polyvinylpyrrolidone (PVP), nonylphenol polyoxyethylene ether, alkyl polyglycoside.The preferred polyphosphazene polymer
The oil-soluble ligand layer that object not only remains quantum dot surface is closed, the influence to quantum dot surface performance is reduced；Meanwhile it can be with
It avoids being conducive to the silica that preparation has size uniformity due to the generation for causing " to reunite " after ligand exchange in conventional method
The oil-soluble quantum dot of cladding.It is further preferred that the mass ratio of the high molecular polymer and quantum dot is 10~20:1, from
And can farthest retain the oil-soluble ligand layer of quantum dot surface, avoid as caused by ligand exchange " reuniting " it is same
When, realize the connection of the silica volume of suitable thickness.
In above-mentioned steps S012, the general formula of the silane coupling agent is RSiX1(X2)(X3), wherein X1、X2、X3It is independently chosen from
The alkoxy that can be hydrolyzed, R are the group containing terminal ethylenyl groups.Preferably, the alkoxysilane reagent includes positive silicic acid
At least one of methyl esters, ethyl orthosilicate, positive silicic acid propyl ester or butyl silicate.It is further preferred that the alkoxyl silicone
The mass ratio of alkane and quantum dot is 5~50:1, to obtain silicon dioxide layer of the cladding thickness within the scope of 2-20nm；More preferably
, the mass ratio of the alkoxy silane and quantum dot is 5~30:1, the silicon dioxide layer with a thickness of 3-10nm；It is more excellent
Choosing, the mass ratio of the alkoxy silane and quantum dot is 8~25:1, the silicon dioxide layer with a thickness of 4-6nm.
The stir process at a temperature of first mixes well the alkoxysilane reagent in first mixed liquor.
Preferably, first temperature is 20~70 DEG C, facilitates between quantum dot and the alkoxysilane reagent to crosslink anti-
It answers；The mixing time is preferably 5~20mins.Further, basic catalyst and water is added, promotes between the quantum dot
It is crosslinked by the alkoxysilane reagent.Stirring 4~for 24 hours, it is centrifuged, washs, obtain the quantum of coated with silica
Point.Wherein, the basic catalyst is preferably at least one of ammonium hydroxide, dimethylamine.
In above-mentioned steps S02, as a kind of preferred embodiment, the metal nanoparticle of the second dressing agent is contained on the surface
Preparation method, comprising the following steps:
The metal nanoparticle is mixed with second dressing agent, under an inert atmosphere, stirs 1 at 20~60 DEG C
~for 24 hours, purifying obtains the metal nanoparticle that the second dressing agent is contained on surface.
First dressing agent, which contains, contains-S-R1- SH or (O-)3Si-R1- SH, wherein R1Spread out selected from alkyl or alkyl
Biology, it is preferred that the R1The alkyl or alkyl derivative that are amount of carbon atom between 2-20.It is specific preferred, described the
Two dressing agents are selected from 3- mercaptopropyltriethoxysilane, 3- mercaptopropyl trimethoxysilane, 1,2- dithioglycol, 1,6- oneself two sulphur
At least one of pungent two mercaptan of alcohol, 1,8-, 1,4- succinimide mercaptans, 1,5- pentane disulfide thioalcohol；And/or
Second dressing agent in 3- mercaptopropyltriethoxysilane, 3- mercaptopropyl trimethoxysilane at least one
Kind.
In above-mentioned steps S03, the metal nanoparticle and surface that second dressing agent is contained on surface contain described first
After the silicon dioxide-coated quantum dots mixing of dressing agent, the sulfydryl of the second dressing agent and described first in the metal nanoparticle
The vinyl of dressing agent is combined by Click chemical action, i.e., under initiator effect or ultraviolet irradiation condition, the second dressing agent
In sulfydryl generate free radicals and radical reaction, formation-S-R occur for vinyl in the first dressing agent1-SCH2CH2R2-Si
(O-)3Or (O-)3Si-R1-SCH2CH2R2-Si(O-)3Functional group, by the metal nanoparticle and the coated with silica
Quantum dot crosslinking, obtains quantum dot composite particle.
Preferably, the metal nanoparticle that second dressing agent is contained on surface is contained into first dressing agent with surface
Silicon dioxide-coated quantum dots mixing method are as follows:
Under conditions of ultraviolet lighting or initiator act on, the surface is contained to the metal nano of second dressing agent
The silicon dioxide-coated quantum dots mixing of first dressing agent is contained on particle and surface, makes the vinyl of first dressing agent
Click chemical action occurs with the sulfydryl of second dressing agent, reaction obtains quantum dot composite particle.
In the case where initiator or ultraviolet lighting induce, above-mentioned first dressing agent and described two of the metal nanoparticle surface
Michael addition reaction is occurring for the second dressing agent of the electron deficient of silica coated quantum dots, obtains quantum dot composite particle.
Specifically, surface is had sulfydryl or siloxy under the conditions of existing for the ultraviolet lighting or the initiator
The metal nanoparticle of modified with functional group (the second dressing agent) and the silica of surface vinylated (modification of the second dressing agent)
The quantum dot of cladding combines, and completes the preparation of the quantum dot composite particle of plasma enhancement effect.Wherein, the initiator conduct
Catalyst can accelerate the progress of reaction；The ultraviolet lighting can also be with the generation of Click chemical action.Preferably, described to draw
Sending out agent includes but is not limited at least one of 3,5-dimethylphenyl phosphorus, triethylamine etc..
And a kind of application of quantum dot composite particle, specifically, by above-mentioned quantum dot composite particle or above method system
Standby obtained quantum dot composite particle is used for the luminescent layer of QLED device.
QLED device provided in an embodiment of the present invention can effectively improve due to containing above-mentioned quantum dot composite particle
The inside and outside quantum efficiency of QLED device increases the luminous efficiency of QLED device.
As a specific embodiment, the QLED device, the substrate combined including stacking, hearth electrode, quantum dot light emitting
Layer, top electrode, wherein the quantum dot light emitting layer is compound by quantum dot prepared by above-mentioned quantum dot composite particle or the above method
Particle is made.
Wherein, the hearth electrode is anode, and the top electrode is cathode；Or the hearth electrode is cathode, the top electrode
For anode.
Preferably, hole injection layer and/or hole transport are provided between the anode and the quantum dot light emitting layer
Layer.Preferably, electron injecting layer and/or electron transfer layer are provided between the cathode and the quantum dot light emitting layer.
Wherein, the substrate can be, but not limited to ito substrate；The anode can be conductive metal oxide or conduction
Polymer；The hole injection layer can be but be not limited to PEDOT:PSS, nickel oxide, molybdenum oxide, vanadium oxide, tungsten oxide, oxidation
At least one of copper；The hole transmission layer one of can be but be not limited to TFB, Poly-TPD, PVK, CBP or more
Kind；The electron transfer layer can be but be not limited to ZnO, ZnMgO, TiO2、WO3、SnO2、AlZnO、ZnSnO、InSnO、TPBI、
At least one of TAZ；The cathode can be, but not limited at least one of Ag, Al, Au and alloy electrode.
As a specific embodiment, as shown in figure 4, the QLED device includes the substrate 1 successively combined, anode 2, sky
Cave implanted layer 3, hole transmission layer 4, quantum dot light emitting layer 5, electron transfer layer 6 and cathode 7, wherein the quantum dot light emitting layer
It is made of quantum dot composite particle prepared by above-mentioned quantum dot composite particle or the above method.
Correspondingly, the embodiment of the invention also provides a kind of preparation methods of QLED device, comprising the following steps: from upper and
Under be sequentially prepared substrate, hearth electrode, quantum dot light emitting layer, top electrode, wherein the hearth electrode is anode, and the top electrode is
Cathode；Or the hearth electrode is cathode, the top electrode is anode, wherein the quantum dot light emitting layer uses above-mentioned quantum dot
Composite particles or the quantum dot composite particle of above method preparation are made.
Preferably, hole injection layer and/or hole transport are prepared between the anode and the quantum dot light emitting layer
Layer.Preferably, electron injecting layer and/or electron transfer layer are prepared between the cathode and the quantum dot light emitting layer.
In the embodiment of the present invention, the hole injection layer, hole transmission layer, quantum dot light emitting layer, electron transfer layer, electronics
Implanted layer preferably uses solution processing method to prepare, and can specifically use spin coating, spraying, prepared by the mode of transfer.
It is illustrated combined with specific embodiments below.
Embodiment 1
A kind of preparation method of the CdSeS/CdZnS blue quantum dot composite particle based on plasma enhancement effect, including
Following steps:
Step S11, by coated with silica in CdSeS/CdZnS blue quantum dot surface
10mg red quantum dot CdSeS/CdZnS blue quantum dot dry powder is taken, 1ml chloroform is added, it is to be mixed to have dissolved
Quan Hou is added 100mg PVP and 50ml ethyl alcohol, has obtained the first mixed solution.Quality is added into above-mentioned first mixed solution
Concentration is 6.8% ammonium hydroxide and 0.1ml ethyl orthosilicate, then places it in and stirs 12h at room temperature.After sufficiently reacting, through from
Heart separation, after washing, can prepare the quantum dot of coated with silica.
Step S12, silica surface vinyl modified
The CdSeS/CdZnS blue quantum dot solution for the coated with silica for taking step S11 to obtain, pours into the circle of 100ml
Bottom flask, is vigorously stirred.0.3ml vinyltriethoxysilane is added thereto, reacts 12h at room temperature, obtains surface and have
The coated with silica of vinyl-functional is in CdSeS/CdZnS blue quantum dot particle.
Step S13, sulfhydrylation modification is carried out to metal nanoparticle surface
Taking 30ml concentration is the aqueous solution of the metal nanoparticle of 5mg/ml, pours into the round-bottomed flask of 100ml, acutely stirs
It mixes.0.4ml 3- mercaptopropyltriethoxysilane is added thereto, reacts 12h at room temperature, obtains the metal that surface has sulfydryl
Nano particle.
Step S14, the preparation of quantum dot composite particle is completed
Mixed solution prepared in step S12 and step S13 is mixed at room temperature, is vigorously stirred, and in purple
Outer light irradiates 2h, and a kind of CdSeS/CdZnS blue quantum dot composite particle based on plasma enhancement effect can be obtained.
Embodiment 2
A kind of preparation method of the InP/ZnS blue quantum dot composite particle based on plasma enhancement effect, including it is following
Step:
Step S21, by coated with silica in InP/ZnS blue quantum dot surface
10mg red quantum dot InP/ZnS blue quantum dot dry powder is taken, 1ml chloroform is added, after dissolution completely to be mixed,
100mg PVP and 50ml ethyl alcohol is added, has obtained the first mixed solution.Mass concentration is added into above-mentioned first mixed solution is
6.8% ammonium hydroxide and 0.1ml ethyl orthosilicate, then place it in and stir 12h at room temperature.After sufficiently reacting, it is centrifuged,
After washing, the quantum dot of coated with silica can be prepared.
Step S22, silica surface vinyl modified
The InP/ZnS blue quantum dot solution for taking the coated with silica obtained in step S21, pours into the round bottom of 100ml
Flask is vigorously stirred.0.3ml vinyltriethoxysilane is added thereto, reacts 12h at room temperature, obtains surface with second
The coated with silica of alkenyl-functional groups is in InP/ZnS blue quantum dot particle.
Step S23, sulfhydrylation modification is carried out to metal nanoparticle surface
The preparation of metal nanoparticle can be using the method preparation in technology today, and taking 30ml concentration is the gold of 5mg/ml
The aqueous solution of metal nano-particle pours into the round-bottomed flask of 100ml, is vigorously stirred.Three second of 0.4ml 3- mercapto propyl is added thereto
Oxysilane reacts 12h at room temperature, obtains the metal nanoparticle that surface has sulfydryl.
Step S24, the preparation of quantum dot composite particle is completed
Mixed solution prepared in step S22 and step S23 is mixed at room temperature, is vigorously stirred, and in purple
Outer light irradiates 2h, and a kind of InP/ZnS blue quantum dot composite particle based on plasma enhancement effect can be obtained.
Embodiment 3
A kind of preparation method of the InP/ZnSeS green quantum dot composite particle based on plasma enhancement effect, including with
Lower step:
Step S31, by coated with silica in InP/ZnSeS green quantum dot surface
10mg red quantum dot InP/ZnSeS green quantum dot dry powder is taken, 1ml chloroform is added, dissolution to be mixed is complete
Afterwards, 100mg PVP and 50ml ethyl alcohol is added, has obtained the first mixed solution.It is dense that quality is added into above-mentioned first mixed solution
Degree is 6.8% ammonium hydroxide and 0.1ml ethyl orthosilicate, then places it in and stirs 12h at room temperature.After sufficiently reacting, through being centrifuged
Separation, after washing, can prepare the quantum dot of coated with silica.
Step S32, silica surface vinyl modified
The InP/ZnSeS green quantum dot point solution for taking the coated with silica obtained in step S31, pours into 100ml's
Round-bottomed flask is vigorously stirred.0.3ml vinyltriethoxysilane is added thereto, reacts 12h at room temperature, obtains surface band
There is the coated with silica of vinyl-functional in InP/ZnSeS green quantum dot particle.
Step S33, sulfhydrylation modification is carried out to metal nanoparticle surface
The preparation of metal nanoparticle can be using the method preparation in technology today, and taking 30ml concentration is the gold of 5mg/ml
The aqueous solution of metal nano-particle pours into the round-bottomed flask of 100ml, is vigorously stirred.Three second of 0.4ml 3- mercapto propyl is added thereto
Oxysilane reacts 12h at room temperature, obtains the metal nanoparticle that surface has sulfydryl.
Step S34, the preparation of quantum dot composite particle is completed
Mixed solution prepared in step S32 and step S33 is mixed at room temperature, is vigorously stirred, and in purple
Outer light irradiates 2h, and a kind of InP/ZnSeS green quantum dot composite particle based on plasma enhancement effect can be obtained.
Embodiment 4
A kind of QLED device, including substrate, anode, hole injection layer, hole transmission layer, the hair set gradually from bottom to top
Photosphere, electron transfer layer and cathode.
The preparation method of the QLED device the following steps are included:
S1 prepares hole injection layer on the substrate containing anode layer；
S2 prepares hole transmission layer on the surface of hole injection layer；
S3 prepares quantum dot light emitting layer on the surface of hole transmission layer；
S4 prepares electron transfer layer on quantum dot light emitting layer；
S5 prepares cathode layer on electron injecting layer, is then packaged, and obtains QLED device.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of quantum dot composite particle, which is characterized in that the quantum dot composite particle includes silicon dioxide-coated quantum dots,
And it is incorporated in the metal nanoparticle on the silicon dioxide-coated quantum dots surface, wherein the coated with silica quantum
Put including quantum dot and be coated on the silicon dioxide layer of the quantum dot surface, and the metal nanoparticle and the dioxy
SiClx layer passes through-S-R1-SCH2CH2R2-Si(O-)3Or (O-)3Si-R1-SCH2CH2R2-Si(O-)3In conjunction with R1、R2It is respectively selected from
Alkyl or alkyl derivative.
2. quantum dot composite particle as described in claim 1, which is characterized in that the silicon dioxide layer with a thickness of 2-
20nm。
3. quantum dot composite particle as claimed in claim 2, which is characterized in that the silicon dioxide layer with a thickness of 3-
10nm。
4. a kind of preparation method of the quantum dot composite particle as described in claim any one of 1-3, which is characterized in that including following
Step:
Silicon dioxide-coated quantum dots are provided, the silicon dioxide-coated quantum dots include quantum dot and are coated on the quantum
The silicon dioxide layer on point surface, the first dressing agent is contained on the surface of the silicon dioxide layer, and first dressing agent contains
(O-)3Si-R2-CH2=CH2, wherein R2Selected from alkyl or alkyl derivative；
Metal nanoparticle is provided, the metal nanoparticle surface contains the second dressing agent, and second dressing agent contain-
S-R1- SH or (O-)3Si-R1- SH, wherein R1Selected from alkyl or alkyl derivative；
Metal nanoparticle that second dressing agent is contained on surface and surface are contained to the silica of first dressing agent
Coated quantum dots mixing makes to modify between the silicon dioxide-coated quantum dots and the metal nanoparticle by described first
Agent reacts the-S-R to be formed with second dressing agent1-SCH2CH2R2-Si(O-)3Or (O-)3Si-R1-SCH2CH2R2-Si(O-)3
In conjunction with obtaining quantum dot composite particle.
5. the preparation method of quantum dot composite particle as claimed in claim 4, which is characterized in that surface is contained described second
The method that the metal nanoparticle of dressing agent is mixed with the silicon dioxide-coated quantum dots that first dressing agent is contained on surface are as follows:
Under conditions of ultraviolet lighting or initiator act on, the surface is contained to the metal nanoparticle of second dressing agent
The silicon dioxide-coated quantum dots mixing for containing first dressing agent with surface, makes vinyl and the institute of first dressing agent
Click chemical action occurs for the sulfydryl for stating the second dressing agent, and reaction obtains quantum dot composite particle.
6. the preparation method of quantum dot composite particle as described in claim 4 or 5, which is characterized in that first dressing agent
Selected from vinyltrimethoxysilane, vinyltriethoxysilane, three tert-butoxy silane of vinyl, vinyl tri-tert
At least one of peroxy-silane and vinyltriacetoxy silane.
7. the preparation method of quantum dot composite particle as described in claim 4 or 5, which is characterized in that second dressing agent
Selected from 3- mercaptopropyltriethoxysilane, 3- mercaptopropyl trimethoxysilane, 1,2- dithioglycol, 1,6- ethanthiol, 1,8-
At least one of pungent two mercaptan, 1,4- succinimide mercaptans, 1,5- pentane disulfide thioalcohol；And/or
Second dressing agent is selected from least one of 3- mercaptopropyltriethoxysilane, 3- mercaptopropyl trimethoxysilane.
8. the preparation method of quantum dot composite particle as claimed in claim 5, which is characterized in that the initiator is selected from diformazan
At least one of base phenyl phosphorus, triethylamine.
9. the preparation method of quantum dot composite particle as claimed in claim 5, which is characterized in that the surface is contained second and repaired
Adorn the preparation method of the metal nanoparticle of agent, comprising the following steps:
The metal nanoparticle is mixed with second dressing agent, under an inert atmosphere, at 20~60 DEG C stir 1~
For 24 hours, purifying obtains the metal nanoparticle that the second dressing agent is contained on surface.
10. a kind of application of quantum dot composite particle, which is characterized in that any one of the claim 1-3 quantum dot is compound
The quantum dot composite particle that any one of particle or claim 4-9 the method are prepared is used for the luminescent layer of QLED device.
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|---|---|---|---|---|
| CN103525398A (en) * | 2013-10-21 | 2014-01-22 | 京东方科技集团股份有限公司 | Quantum dot composite particle and preparation method thereof, photoelectric element and photoelectric equipment |
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| CN103525398A (en) * | 2013-10-21 | 2014-01-22 | 京东方科技集团股份有限公司 | Quantum dot composite particle and preparation method thereof, photoelectric element and photoelectric equipment |
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| KOBAYASHI YOSHIO等: "Fabrication of quantum dot/silica core-shell particles immobilizing Au nanoparticles and their dual imaging functions", 《APPLIED NANOSCIENCE》 * |
| TUCKER-SCHWARTZ ALEXANDER K.等: "Thiol-ene Click Reaction as a General Route to Functional Trialkoxysilanes for Surface Coating Applications", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
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| CN112768537A (en) * | 2019-10-21 | 2021-05-07 | Tcl集团股份有限公司 | Composite material and preparation method thereof |
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