CN109810688B - Quantum dot composite particle and preparation method and application thereof - Google Patents
Quantum dot composite particle and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a quantum dot composite particle, which comprises a silicon dioxide coated quantum dot and a metal nano particle combined on the surface of the silicon dioxide coated quantum dot, wherein the silicon dioxide coated quantum dot comprises a quantum dot and a silicon dioxide layer coated on the surface of the quantum dot, and the metal nano particle and the silicon dioxide layer pass through-S-R1‑SCH2CH2R2‑Si(O‑)3Or (O-)3Si‑R1‑SCH2CH2R2‑Si(O‑)3In combination with, R1、R2Are independently selected from hydrocarbyl or hydrocarbyl derivatives.
Description
Technical Field
The invention belongs to the technical field of quantum dots, and particularly relates to a quantum dot composite particle and a preparation method and application thereof.
Background
In recent years, with the rapid development of display technologies, colloidal semiconductor nanocrystals (also referred to as "quantum dots") have attracted considerable attention from researchers due to their characteristic quantum confinement effects. Compared with the traditional organic luminescent dye, the quantum dot has the advantages of wide excitation spectrum, narrow emission spectrum, adjustable emission wavelength, high fluorescence efficiency, stable photochemical performance and the like. In addition, the optical, electrical and transport properties of the quantum dots can be tuned by the synthesis process. These advantages make quantum dots play an important role in the field of new displays, and quantum dot light emitting diodes (QLEDs) using quantum dots as light emitting layers become potential next generation display and solid state lighting sources. Through years of development, the QLED technology has been greatly developed. However, the current quantum dots still have low luminous efficiency, especially the blue quantum dots have low luminous efficiency, and thus the application of the blue QLED is limited.
Disclosure of Invention
The invention aims to provide a quantum dot composite particle and a preparation method thereof, and aims to solve the problem of low luminous efficiency of the existing quantum dot, particularly a blue light quantum dot.
Another object of the present invention is to provide a QLED device.
The quantum dot composite particle comprises a silicon dioxide coated quantum dot and a metal nanoparticle combined on the surface of the silicon dioxide coated quantum dot, wherein the silicon dioxide coated quantum dot comprises the quantum dot and a silicon dioxide layer coated on the surface of the quantum dot, and the metal nanoparticle and the silicon dioxide layer pass through-S-R1-SCH2CH2R2-Si(O-)3Or (O-)3Si-R1-SCH2CH2R2-Si(O-)3In combination with, R1、R2Are independently selected from hydrocarbyl or hydrocarbyl derivatives.
Correspondingly, the preparation method of the quantum dot composite particle comprises the following steps:
providing a silicon dioxide coated quantum dot, wherein the silicon dioxide coated quantum dot comprises a quantum dot and a silicon dioxide layer coated on the surface of the quantum dot, the surface of the silicon dioxide layer contains a first modifier, and the first modifier contains (O-)3Si-R2-CH2＝CH2Wherein R is2Selected from hydrocarbyl or hydrocarbyl derivatives;
providing metal nano-particles, wherein the surface of the metal nano-particles contains a second modifier, and the second modifier contains-S-R1-SH or (O-)3Si-R1-SH, wherein R1Selected from hydrocarbyl or hydrocarbyl derivatives;
mixing the metal nano-particles with the second modifier on the surface with the silicon dioxide coated quantum dots with the first modifier on the surface, and reacting the silicon dioxide coated quantum dots with the metal nano-particles to form-S-R through the reaction of the first modifier and the second modifier1-SCH2CH2R2-Si(O-)3Or (O-)3Si-R1-SCH2CH2R2-Si(O-)3And combining to obtain the quantum dot composite particles.
The quantum dot composite particle or the quantum dot composite particle prepared by the method is used for a luminous layer of a QLED device.
The surface of the quantum dot is coated with the silicon dioxide layer, and the surface of the silicon dioxide layer is combined with metal nano-particle metal nano-particles, wherein the metal nano-particles and the silicon dioxide layer pass through-S-R1-SCH2CH2R2-Si(O-)3Or (O-)3Si-R1-SCH2CH2R2-Si(O-)3And (4) combining. The quantum dot composite particle with the characteristics has the advantages that the plasma resonance energy generated in the metal nano particle can be diffused to the quantum dot, so that the local field intensity and the optical state density near the quantum dot are obviously increased, the fluorescence intensity of the quantum dot is enhanced, and the light efficiency of the quantum dot is improved. The quantum dot composite particle provided by the invention not only improves the luminous efficiency of the quantum dot, but also improves the internal and external quantum efficiencies of the QLED device and increases the luminous efficiency of the QLED device.
The preparation method of the quantum dot composite particles provided by the invention is simple, safe and easy to operate, and has a good application prospect.
The quantum dot composite particles provided by the invention are used, so that the internal and external quantum efficiency of the QLED device can be effectively improved and the luminous efficiency of the QLED device is increased.
Drawings
Fig. 1 is a schematic view of a quantum dot composite particle provided by an embodiment of the present invention;
FIG. 2 shows a metal nanoparticle and silica layer pass-S-R provided in an embodiment of the present invention1-SCH2CH2R2-Si(O-)3A general structural formula schematic diagram of the combined quantum dot composite particle;
FIG. 3 is a cross-sectional view of a metal nanoparticle and a silicon dioxide layer (O-)3Si-R1-SCH2CH2R2-Si(O-)3A general structural formula schematic diagram of the combined quantum dot composite particle;
fig. 4 is a schematic structural diagram of a QLED device provided in an embodiment of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
As shown in fig. 1 to 3, an embodiment of the present invention provides a quantum dot composite particle, where the quantum dot composite particle includes a silica-coated quantum dot and a metal nanoparticle bonded to a surface of the silica-coated quantum dot, where the silica-coated quantum dot includes a quantum dot and a silica layer coated on a surface of the quantum dot, and the metal nanoparticle and the silica layer pass through-S-R1-SCH2CH2R2-Si(O-)3Or (O-)3Si-R1-SCH2CH2R2-Si(O-)3In combination with, R1、R2Are independently selected from hydrocarbyl or hydrocarbyl derivatives.
In the quantum dot composite particle provided by the embodiment of the invention, the surface of the quantum dot is coated with the silicon dioxide layer, and the surface of the silicon dioxide layer is combined with the metal nano-particles, wherein the quantum dot composite particle is prepared by mixing the silicon dioxide layer and the metal nano-particlesMetal nanoparticles are passed through-S-R with the silica layer1-SCH2CH2R2-Si(O-)3Or (O-)3Si-R1-SCH2CH2R2-Si(O-)3And (4) combining. The schematic diagram of the quantum dot composite particle is shown in fig. 1, wherein 11 is a quantum dot, 22 is a silicon dioxide layer, and 33 is a metal nanoparticle; the general structural formulas of the two kinds of formed quantum dot composite particles are respectively shown in fig. 2 and fig. 3. The quantum dot composite particle with the characteristics has the advantages that the plasma resonance energy generated in the metal nano particle can be diffused to the quantum dot, so that the local field intensity and the optical state density near the quantum dot are obviously increased, the fluorescence intensity of the quantum dot is enhanced, and the light efficiency of the quantum dot is improved. The quantum dot composite particle provided by the invention not only improves the luminous efficiency of the quantum dot, but also improves the internal and external quantum efficiencies of the QLED device and increases the luminous efficiency of the QLED device.
Specifically, in the embodiment of the present invention, the selection of the quantum dot is not strictly limited, and an oil-soluble quantum dot is preferable. The oil-soluble ligand on the surface of the oil-soluble quantum dot can endow the quantum dot with better surface performance. Specifically, the oil-soluble quantum dots include, but are not limited to, at least one of group II-VI quantum dots, group III-V quantum dots, and group I-III-VI2 quantum dots. Specifically, the II-VI group quantum dots include, but are 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 group quantum dots include, but are not limited to, InP, InAs, GaP, GaAs, GaSb, AlN, AlP; InAsP; InNP, InNSb, GaAlNP, InAlNP; the group I-III-VI2 quantum dots include, but are not limited to, CuInS2、CuInSe2、AgInS2. The ligand on the surface of the oil-soluble quantum dot comprises at least one of a fatty acid ligand, an amine ligand and a phosphine ligand.
In embodiments of the present invention, the metal nanoparticles include, but are not limited to, Ag, Au, or Pt nanoparticles. The particle size of the metal nanoparticles is preferably 2-10 nm.
In general, crosslinking between silica and metal nanoparticles is difficult. In the embodiment of the invention, the surface of the quantum dot is coated with the silicon dioxide layer, and metal nano particles are combined on the surface of the silicon dioxide layer, wherein the silicon dioxide and the metal nano particles in the silicon dioxide layer contain-S-R1-SCH2CH2R2-Si(O-)3Or (O-)3Si-R1-SCH2CH2R2-Si(O-)3And (4) connecting. The embodiment of the invention constructs the structure containing-S-R between the silicon dioxide and the metal nano-particles1-SCH2CH2R2-Si(O-)3Or (O-)3Si-R1-SCH2CH2R2-Si(O-)3The cross-linking group realizes the connection of the silicon dioxide and the metal nano-particles, so that the energy generated by the plasma resonance of the metal nano-particles is effectively transferred to the quantum dots, and the luminous efficiency of the quantum dots is improved. In particular, the-S-R1-SCH2CH2R2-Si(O-)3Or (O-)3Si-R1-SCH2CH2R2-Si(O-)3It can be prepared by reacting silica containing vinyl functional groups with metal nanoparticles containing mercapto functional groups by Click chemistry, as described below.
Furthermore, in the embodiment of the present invention, energy transfer between the metal nanoparticle and the quantum dot is mainly adjusted by controlling a thickness of the silicon dioxide layer, and the silicon dioxide layer is properly selected to keep a proper distance therebetween, so that the quantum dot can effectively transfer plasmon resonance energy of the metal nanoparticle within a range, and further the light emitting efficiency of the quantum dot is improved. Preferably, the thickness of the silicon dioxide layer is 2-20 nm. Within the range, the metal nano particles and the quantum dots have proper transmission distance, so that resonance energy generated by the excitation of the metal nano particles under the ultraviolet condition can be effectively transmitted to the quantum dots, and the fluorescence luminous efficiency and luminous intensity of the quantum dots are improved. Further preferably, the thickness of the silicon dioxide layer is 3 to 10 nm. Still more preferably, the thickness of the silicon dioxide layer is 4-6 nm. The thickness of the silicon dioxide is in the range, and the plasma enhancement effect of the metal nanoparticles on the quantum dots is strongest.
The quantum dot composite particle provided by the embodiment of the invention can be prepared by the following method.
Correspondingly, the embodiment of the invention provides a preparation method of the quantum dot composite particle, which comprises the following steps:
step S01, providing a silicon dioxide coated quantum dot, wherein the silicon dioxide coated quantum dot comprises a quantum dot and a silicon dioxide layer coated on the surface of the quantum dot, the surface of the silicon dioxide layer contains a first modifier, and the first modifier contains (O-)3Si-R2-CH2＝CH2Wherein R is2Selected from hydrocarbyl or hydrocarbyl derivatives;
step S02, providing metal nano particles, wherein the surfaces of the metal nano particles contain second modifiers, and the second modifiers contain-S-R1-SH or (O-)3Si-R1-SH, wherein R1Selected from hydrocarbyl or hydrocarbyl derivatives;
step S03, mixing the metal nanoparticles with the second modifier on the surface with the silica-coated quantum dots with the first modifier on the surface, and reacting the silica-coated quantum dots with the metal nanoparticles through the first modifier and the second modifier to form-S-R1-SCH2CH2R2-Si(O-)3Or (O-)3Si-R1-SCH2CH2R2-Si(O-)3And combining to obtain the quantum dot composite particles.
The preparation method of the quantum dot composite particles provided by the embodiment of the invention is simple, safe and easy to operate, and has a good application prospect.
Specifically, in step S01, the silica-coated quantum dot includes a quantum dot and a silica layer coated on the surface of the quantum dot, and the surface of the silica layer contains a first modifier, that is, the silica-coated quantum dot is a silica-coated quantum dot whose surface contains the first modifier. Preferably, the preparation method of the silica-coated quantum dot with the surface containing the first modifier comprises the following steps: providing the quantum dot particles coated with the silicon dioxide, adding the first modifier, and stirring at room temperature. In the embodiment of the invention, the quantum dots coated with the silicon dioxide are subjected to alkenyl modification by using the first modifier with terminal vinyl groups, so that the surface of the silicon dioxide is provided with vinyl functional groups, and action sites are provided for the combination of the metal nanoparticles modified by the mercapto functional groups in the step S03 and the vinyl functional groups on the surface of the silicon dioxide through Click chemical action.
The first modifier contains (O-)3Si-R2-CH2＝CH2Wherein R is2Selected from hydrocarbyl or hydrocarbyl derivatives, preferably, said R2Is a hydrocarbyl or a hydrocarbyl derivative having a carbon number of between 2 and 20. Specifically, the first modifier is preferably at least one selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-t-butoxysilane, and vinyltriacetoxysilane. Still further, the first modifier is preferably used in an amount of: the mass ratio of the first modifier to the quantum dots is 0.1-5: 1, so that the surface of the silicon dioxide layer is connected with enough first modifier, and the step S03 is facilitated when the first modifier reacts with the second modifier to form-S-R1-SCH2CH2R2-Si(O-)3Or (O-)3Si-R1-SCH2CH2R2-Si(O-)3。
The room temperature in the embodiment of the invention is 10-30 ℃. Preferably, the stirring time is 6 to 24 hours.
Further preferably, the silica-coated quantum dot particles are prepared by the following method:
s011, providing quantum dot initial particles, dissolving the quantum dot initial particles in a nonpolar solvent, and sequentially adding an amphoteric surfactant and a polar solvent to obtain a first mixed solution;
and S012, adding alkoxy silane into the first mixed solution, stirring at a first temperature, adding an alkaline catalyst and water, and purifying after stirring to obtain the silicon dioxide coated quantum dot.
Specifically, in the step S011, the quantum dots of the quantum dot initial particles are as described above, and are not repeated herein for brevity. Preferably, the quantum dot primary particles are oil-soluble quantum dots.
The non-polar solvent may be effective to dissolve the oil-soluble quantum dots, including but not limited to chloroform; the polar solvent includes, but is not limited to, ethanol. After the oil-soluble quantum dots are completely dissolved, the amphoteric surfactant and the organic alcohol are sequentially added. The amphoteric surfactant has a hydrophilic end and a lipophilic end, and the polar solvent is added after the amphoteric surfactant is added, so that the oil-soluble quantum dots are uniformly dispersed in the polar solvent. Preferably, the polar solvent includes, but is not limited to, ethanol. Preferably, the amphoteric surfactant is a high molecular polymer, and particularly, but not limited to, at least one of polyvinylpyrrolidone (PVP), nonylphenol polyoxyethylene ether and alkyl polyglycoside is preferred. The preferable high molecular polymer not only keeps the oil-soluble ligand layer on the surface of the quantum dot, but also reduces the influence on the surface performance of the quantum dot; meanwhile, the method can avoid the occurrence of 'agglomeration' caused by ligand exchange in the conventional method, and is beneficial to preparing the silicon dioxide coated oil-soluble quantum dots with uniform size. Further preferably, the mass ratio of the high molecular polymer to the quantum dots is 10-20: 1, so that an oil-soluble ligand layer on the surface of the quantum dots can be retained to the greatest extent, and connection of silica with a proper thickness is realized while 'agglomeration' caused by ligand exchange is avoided.
In the step S012, the general formula of the silane coupling agent is RSiX1(X2)(X3) Wherein X is1、X2、X3Independently selected from hydrolyzable alkoxy radicals, R being a radical containing a terminal vinyl groupA group. Preferably, the alkoxysilane reagent comprises at least one of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, or butyl orthosilicate. Further preferably, the mass ratio of the alkoxy silane to the quantum dots is 5-50: 1, so that a silicon dioxide layer with the coating thickness of 2-20nm is obtained; more preferably, the mass ratio of the alkoxy silane to the quantum dots is 5-30: 1, and the thickness of the silicon dioxide layer is 3-10 nm; more preferably, the mass ratio of the alkoxy silane to the quantum dots is 8-25: 1, and the thickness of the silicon dioxide layer is 4-6 nm.
Stirring at a first temperature, and fully and uniformly mixing the alkoxy silane reagent in the first mixed solution. Preferably, the first temperature is 20-70 ℃, which is beneficial to the crosslinking reaction between the quantum dots and the alkoxy silane reagent; the stirring time is preferably 5-20 mins. Further, a basic catalyst and water are added to promote the crosslinking between the quantum dots through the alkoxy silane reagent. Stirring for 4-24 h, and performing centrifugal separation and washing to obtain the silicon dioxide coated quantum dots. Wherein the basic catalyst is preferably at least one of ammonia water and dimethylamine.
In the above step S02, as a preferred embodiment, the method for preparing metal nanoparticles having a second modifier on the surface includes the following steps:
and mixing the metal nanoparticles with the second modifier, stirring for 1-24 hours at 20-60 ℃ in an inert atmosphere, and purifying to obtain the metal nanoparticles with the second modifier on the surface.
The first modifier contains a compound containing-S-R1-SH or (O-)3Si-R1-SH, wherein R1Selected from hydrocarbyl or hydrocarbyl derivatives, preferably, said R1Is a hydrocarbyl or a hydrocarbyl derivative having a carbon number of between 2 and 20. Particularly preferably, the second modifier is at least one selected from 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 1, 2-ethanedithiol, 1, 6-hexanedithiol, 1, 8-octanedithiol, 1, 4-butanedithiol and 1, 5-pentanedithiol; and/or
The second modifier is at least one selected from 3-mercaptopropyltriethoxysilane and 3-mercaptopropyltrimethoxysilane.
In the step S03, after the metal nanoparticles with the second modifier on the surface are mixed with the silica-coated quantum dots with the first modifier on the surface, the thiol group of the second modifier in the metal nanoparticles is chemically bonded with the vinyl group of the first modifier through Click, that is, under the action of the initiator or the ultraviolet irradiation, the thiol group in the second modifier generates a radical to react with the vinyl group in the first modifier to form-S-R1-SCH2CH2R2-Si(O-)3Or (O-)3Si-R1-SCH2CH2R2-Si(O-)3And (4) a functional group, namely crosslinking the metal nano-particles and the silicon dioxide coated quantum dots to obtain the quantum dot composite particles.
Preferably, the method for mixing the metal nanoparticles having the second modifier on the surface thereof with the silica-coated quantum dots having the first modifier on the surface thereof comprises:
under the action of ultraviolet light or an initiator, mixing the metal nanoparticles with the second modifier on the surface and the silicon dioxide coated quantum dots with the first modifier on the surface, and reacting vinyl of the first modifier and mercapto of the second modifier to obtain the quantum dot composite particles.
Under the induction of an initiator or ultraviolet irradiation, the first modifier on the surface of the metal nano particle and the second modifier which is lack of electrons and is coated with the silicon dioxide on the surface of the quantum dot are subjected to Michael addition reaction to obtain the quantum dot composite particle.
Specifically, under the condition of ultraviolet irradiation or the presence of the initiator, the metal nanoparticles with the surface modified by the mercapto group or the siloxy functional group (second modifier) are combined with the silica-coated quantum dots with the surface modified by the vinylation (modified by the second modifier), so that the preparation of the quantum dot composite particles with the plasma enhancement effect is completed. Wherein, the initiator is used as a catalyst and can accelerate the reaction; the ultraviolet light may also occur with Click chemistry. Preferably, the initiator includes, but is not limited to, at least one of dimethylphenylphosphine, triethylamine, and the like.
The quantum dot composite particle or the quantum dot composite particle prepared by the method is used for a luminous layer of a QLED device.
The QLED device provided by the embodiment of the invention contains the quantum dot composite particles, so that the internal and external quantum efficiency of the QLED device can be effectively improved, and the luminous efficiency of the QLED device is increased.
As a specific embodiment, the QLED device includes a substrate, a bottom electrode, a quantum dot light-emitting layer, and a top electrode, which are stacked and combined, wherein the quantum dot light-emitting layer is made of the quantum dot composite particles or the quantum dot composite particles prepared by the method.
Wherein the bottom electrode is an anode and the top electrode is a cathode; or the bottom electrode is a cathode and the top electrode is an anode.
Preferably, a hole injection layer and/or a hole transport layer is disposed between the anode and the quantum dot light emitting layer. Preferably, an electron injection layer and/or an electron transport layer is disposed between the cathode and the quantum dot light emitting layer.
Wherein, the substrate can be but not limited to an ITO base plate; the anode may be a conductive metal oxide or a conductive polymer; the hole injection layer can be, but is not limited to, at least one of PEDOT, PSS, nickel oxide, molybdenum oxide, vanadium oxide, tungsten oxide, and copper oxide; the hole transport layer can be one or more of TFB, Poly-TPD, PVK and CBP; the electron transport layer can be, but is not limited to, ZnO, ZnMgO, TiO2、WO3、SnO2At least one of AlZnO, ZnSnO, InSnO, TPBI and TAZ; the cathode may be, but is not limited to, at least one of Ag, Al, Au, and an alloy electrode.
As a specific example, as shown in fig. 4, the QLED device includes a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a quantum dot light emitting layer 5, an electron transport layer 6, and a cathode 7, which are sequentially combined, wherein the quantum dot light emitting layer is made of the quantum dot composite particles or the quantum dot composite particles prepared by the above method.
Correspondingly, the embodiment of the invention also provides a preparation method of the QLED device, which comprises the following steps: preparing a substrate, a bottom electrode, a quantum dot light-emitting layer and a top electrode from top to bottom in sequence, wherein the bottom electrode is an anode, and the top electrode is a cathode; or the bottom electrode is a cathode, the top electrode is an anode, and the quantum dot light-emitting layer is made of the quantum dot composite particles or the quantum dot composite particles prepared by the method.
Preferably, a hole injection layer and/or a hole transport layer is/are formed between the anode and the quantum dot light emitting layer. Preferably, an electron injection layer and/or an electron transport layer are prepared between the cathode and the quantum dot light emitting layer.
In the embodiment of the invention, the hole injection layer, the hole transport layer, the quantum dot light-emitting layer, the electron transport layer and the electron injection layer are preferably prepared by a solution processing method, and can be specifically prepared by spin coating, spray coating and transfer printing.
The following description will be given with reference to specific examples.
Example 1
A preparation method of CdSeS/CdZnS blue quantum dot composite particles based on a plasma enhancement effect comprises the following steps:
step S11, coating silicon dioxide on the surface of CdSeS/CdZnS blue quantum dot
And taking 10mg of red quantum dot CdSeS/CdZnS blue quantum dot dry powder, adding 1ml of chloroform, stirring and dissolving completely, and adding 100mg of PVP and 50ml of ethanol to obtain a first mixed solution. To the above first mixed solution, aqueous ammonia having a mass concentration of 6.8% and 0.1ml of tetraethoxysilane were added, and then it was stirred at room temperature for 12 hours. After full reaction, the quantum dots coated by the silicon dioxide can be prepared by centrifugal separation and washing.
Step S12, modifying the surface vinyl of the silicon dioxide
The silica-coated CdSeS/CdZnS blue quantum dot solution obtained in step S11 was poured into a 100ml round bottom flask and stirred vigorously. And adding 0.3ml of vinyl triethoxysilane, and reacting at room temperature for 12h to obtain CdSeS/CdZnS blue quantum dot particles coated with silicon dioxide with vinyl functional groups on the surface.
Step S13, carrying out sulfhydrylation modification on the surface of the metal nano-particle
30ml of an aqueous solution of metal nanoparticles having a concentration of 5mg/ml were poured into a 100ml round bottom flask and stirred vigorously. 0.4ml of 3-mercaptopropyltriethoxysilane was added thereto, and the reaction was carried out at room temperature for 12 hours to obtain metal nanoparticles having mercapto groups on the surface.
Step S14, completing the preparation of the quantum dot composite particles
And (4) mixing the mixed solution prepared in the steps S12 and S13 at room temperature, stirring vigorously, and irradiating for 2 hours by using ultraviolet light to obtain the CdSeS/CdZnS blue quantum dot composite particles based on the plasma enhancement effect.
Example 2
A preparation method of InP/ZnS blue quantum dot composite particles based on a plasma enhancement effect comprises the following steps:
step S21, coating silica on the surface of InP/ZnS blue quantum dot
And (2) adding 1ml of chloroform into 10mg of red quantum dot InP/ZnS blue quantum dot dry powder, and after completely stirring and dissolving, adding 100mg of PVP and 50ml of ethanol to obtain a first mixed solution. To the above first mixed solution, aqueous ammonia having a mass concentration of 6.8% and 0.1ml of tetraethoxysilane were added, and then it was stirred at room temperature for 12 hours. After full reaction, the quantum dots coated by the silicon dioxide can be prepared by centrifugal separation and washing.
Step S22, modifying the surface vinyl of the silicon dioxide
The silica-coated InP/ZnS blue quantum dot solution obtained in step S21 was taken and poured into a 100ml round-bottom flask and stirred vigorously. And adding 0.3ml of vinyl triethoxysilane, and reacting at room temperature for 12 hours to obtain silica coated InP/ZnS blue quantum dot particles with vinyl functional groups on the surfaces.
Step S23, carrying out sulfhydrylation modification on the surface of the metal nano-particle
The preparation of the metal nanoparticles can be carried out by the method in the prior art, and 30ml of aqueous solution of the metal nanoparticles with the concentration of 5mg/ml is poured into a 100ml round-bottom flask and stirred vigorously. 0.4ml of 3-mercaptopropyltriethoxysilane was added thereto, and the reaction was carried out at room temperature for 12 hours to obtain metal nanoparticles having mercapto groups on the surface.
Step S24, completing the preparation of the quantum dot composite particles
And (4) mixing the mixed solution prepared in the step (S22) and the step (S23) at room temperature, stirring vigorously, and irradiating for 2 hours by using ultraviolet light to obtain the InP/ZnS blue quantum dot composite particles based on the plasma enhancement effect.
Example 3
A preparation method of InP/ZnSeS green quantum dot composite particles based on plasma enhancement effect comprises the following steps:
step S31, coating silicon dioxide on the surface of InP/ZnSeS green quantum dot
Taking 10mg of red quantum dot InP/ZnSeS green quantum dot dry powder, adding 1ml of chloroform, stirring and dissolving completely, and adding 100mg of PVP and 50ml of ethanol to obtain a first mixed solution. To the above first mixed solution, aqueous ammonia having a mass concentration of 6.8% and 0.1ml of tetraethoxysilane were added, and then it was stirred at room temperature for 12 hours. After full reaction, the quantum dots coated by the silicon dioxide can be prepared by centrifugal separation and washing.
Step S32, modifying the surface vinyl of the silicon dioxide
The silica-coated InP/ZnSeS green quantum dot solution obtained in step S31 was poured into a 100ml round bottom flask and stirred vigorously. And adding 0.3ml of vinyl triethoxysilane, and reacting at room temperature for 12 hours to obtain the InP/ZnSeS green quantum dot particles coated with silicon dioxide with vinyl functional groups on the surfaces.
Step S33, carrying out sulfhydrylation modification on the surface of the metal nano-particle
The preparation of the metal nanoparticles can be carried out by the method in the prior art, and 30ml of aqueous solution of the metal nanoparticles with the concentration of 5mg/ml is poured into a 100ml round-bottom flask and stirred vigorously. 0.4ml of 3-mercaptopropyltriethoxysilane was added thereto, and the reaction was carried out at room temperature for 12 hours to obtain metal nanoparticles having mercapto groups on the surface.
Step S34, completing the preparation of the quantum dot composite particles
And (3) mixing the mixed solution prepared in the steps S32 and S33 at room temperature, stirring vigorously, and irradiating for 2 hours by using ultraviolet light to obtain the InP/ZnSeS green quantum dot composite particles based on the plasma enhancement effect.
Example 4
A QLED device comprises a substrate, an anode, a hole injection layer, a hole transport layer, a luminescent layer, an electron transport layer and a cathode which are arranged from bottom to top in sequence.
The preparation method of the QLED device comprises the following steps:
s1 preparing a hole injection layer on the substrate containing the anode layer;
s2, preparing a hole transport layer on the surface of the hole injection layer;
s3, preparing a quantum dot light-emitting layer on the surface of the hole transport layer;
s4, preparing an electron transport layer on the quantum dot light-emitting layer;
s5, preparing a cathode layer on the electron injection layer, and then packaging to obtain the QLED device.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
1. The quantum dot composite particle with the plasma enhancement effect is characterized by comprising a silica-coated quantum dot and a metal nanoparticle combined on the surface of the silica-coated quantum dot, wherein the silica-coated quantum dot comprises an oil-soluble quantum dotThe metal nano-particles and the silicon dioxide layer pass through-S-R1-SCH2CH2R2-Si(O-)3Or (O-)3Si-R1-SCH2CH2R2-Si(O-)3In combination with, R1、R2Respectively selected from hydrocarbon radicals with the number of carbon atoms between 2 and 20;
the metal nanoparticles are Ag, Au or Pt nanoparticles, and the particle size of the metal nanoparticles is 2-10 nm;
the thickness of the silicon dioxide layer is 2-20 nm.
2. The plasma-enhanced quantum dot composite particle according to claim 1, wherein the thickness of the silica layer is 3 to 10 nm.
3. A method for preparing a quantum dot composite particle having a plasma enhanced effect according to claim 1 or 2, comprising the steps of:
providing a silicon dioxide coated quantum dot, wherein the silicon dioxide coated quantum dot comprises an oil-soluble quantum dot and a silicon dioxide layer coated on the surface of the oil-soluble quantum dot, the surface of the silicon dioxide layer contains a first modifier, and the first modifier contains (O-)3Si-R2-CH2=CH2Wherein R is2Selected from hydrocarbon groups having a number of carbon atoms between 2 and 20;
providing metal nano-particles, wherein the surface of the metal nano-particles contains a second modifier, and the second modifier contains-S-R1-SH or (O-)3Si-R1-SH, wherein R1Selected from hydrocarbon groups having a number of carbon atoms between 2 and 20;
mixing the metal nano-particles with the second modifier on the surface with the silicon dioxide coated quantum dots with the first modifier on the surface, and reacting the silicon dioxide coated quantum dots with the metal nano-particles to form-S-R through the reaction of the first modifier and the second modifier1-SCH2CH2R2-Si(O-)3Or (O-)3Si-R1-SCH2CH2R2-Si(O-)3And combining to obtain the quantum dot composite particles.
4. The method of preparing quantum dot composite particles with plasma enhanced effect according to claim 3, wherein the method of mixing the metal nanoparticles having the second modifier on the surface thereof with the silica-coated quantum dots having the first modifier on the surface thereof comprises:
under the action of ultraviolet light or an initiator, mixing the metal nanoparticles with the second modifier on the surface and the silicon dioxide coated quantum dots with the first modifier on the surface, and reacting vinyl of the first modifier and mercapto of the second modifier to obtain the quantum dot composite particles.
5. The method of preparing a quantum dot composite particle according to claim 3 or 4, wherein the first modifier is at least one selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-t-butoxysilane, vinyltri-t-butylperoxysilane, and vinyltriacetoxysilane.
6. The method of preparing quantum dot composite particles with plasma enhanced effect according to claim 3 or 4, wherein the second modifier is at least one selected from the group consisting of 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 1, 2-ethanedithiol, 1, 6-hexanedithiol, 1, 8-octanedithiol, 1, 4-butanedithiol, 1, 5-pentanedithiol; and/or
The second modifier is at least one selected from 3-mercaptopropyltriethoxysilane and 3-mercaptopropyltrimethoxysilane.
7. The method of claim 4, wherein the initiator is at least one selected from the group consisting of dimethylphenylphosphine and triethylamine.
8. The method of preparing quantum dot composite particles with plasma enhanced effect according to claim 4, wherein the method of preparing metal nanoparticles with the surface containing the second modifier comprises the following steps:
and mixing the metal nanoparticles with the second modifier, stirring for 1-24 hours at 20-60 ℃ in an inert atmosphere, and purifying to obtain the metal nanoparticles with the second modifier on the surface.
9. The application of the quantum dot composite particles with the plasma enhancement effect is characterized in that the quantum dot composite particles with the plasma enhancement effect, which are prepared by the method of any one of claims 1 to 2 or the method of any one of claims 3 to 8, are used for the light-emitting layer of a QLED device.
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| Thiol-ene Click Reaction as a General Route to Functional Trialkoxysilanes for Surface Coating Applications;Tucker-Schwartz Alexander K.等;《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》;20110727;第133卷(第29期);第11027页 * |
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