CN115125004A - Preparation method of silicon dioxide coated quantum dots - Google Patents
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 129
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 60
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
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- 238000000034 method Methods 0.000 claims abstract description 41
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000077 silane Inorganic materials 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 65
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- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- TYZFMFVWHZKYSE-UHFFFAOYSA-N 3-mercaptohexanol Chemical compound CCCC(S)CCO TYZFMFVWHZKYSE-UHFFFAOYSA-N 0.000 claims description 4
- GBCGIJAYTBMFHI-UHFFFAOYSA-N 3-methyl-3-sulfanylbutan-1-ol Chemical compound CC(C)(S)CCO GBCGIJAYTBMFHI-UHFFFAOYSA-N 0.000 claims description 4
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- DVNPFNZTPMWRAX-UHFFFAOYSA-N 2-triethoxysilylethanethiol Chemical compound CCO[Si](CCS)(OCC)OCC DVNPFNZTPMWRAX-UHFFFAOYSA-N 0.000 claims description 2
- NEJMTSWXTZREOC-UHFFFAOYSA-N 4-sulfanylbutan-1-ol Chemical compound OCCCCS NEJMTSWXTZREOC-UHFFFAOYSA-N 0.000 claims description 2
- UGZAJZLUKVKCBM-UHFFFAOYSA-N 6-sulfanylhexan-1-ol Chemical compound OCCCCCCS UGZAJZLUKVKCBM-UHFFFAOYSA-N 0.000 claims description 2
- XJTWZETUWHTBTG-UHFFFAOYSA-N 8-sulfanyloctan-1-ol Chemical compound OCCCCCCCCS XJTWZETUWHTBTG-UHFFFAOYSA-N 0.000 claims description 2
- FXFJFNVBVKPAPL-UHFFFAOYSA-N 9-sulfanylnonan-1-ol Chemical compound OCCCCCCCCCS FXFJFNVBVKPAPL-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 12
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- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 5
- 238000005253 cladding Methods 0.000 abstract 1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical class [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000004020 luminiscence type Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000004530 micro-emulsion Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
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- 238000001914 filtration Methods 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 230000000740 bleeding effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- URRRJXFWOUCKSG-UHFFFAOYSA-M ethanol;tetramethylazanium;hydroxide Chemical compound [OH-].CCO.C[N+](C)(C)C URRRJXFWOUCKSG-UHFFFAOYSA-M 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
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- 239000002159 nanocrystal Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
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- 238000010791 quenching Methods 0.000 description 1
- 238000010942 self-nucleation Methods 0.000 description 1
- 239000004054 semiconductor nanocrystal Substances 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
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- 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
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- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B82—NANOTECHNOLOGY
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Abstract
The invention discloses a preparation method of silicon dioxide coated quantum dots. The oil phase quantum dots are dispersed in an organic solvent and introduced into a ligand containing sulfydryl for ligand replacement, so that the quantum dots have dispersibility in an alcohol solvent or are beneficial to hydrolytic coating of silane. Carry out the silica cladding with modified St ribbon method with the solution after the replacement, modified St ribbon method prepares quantum dot solution into solution A with the alcohol solvent, prepares oxysilane, alcohol solvent into solution B, prepares solution C with catalyst and water, drips at the uniform velocity simultaneously with solution B, C and adds into solution A and reacts. The method ensures that the silicon dioxide coating a plurality of quantum dots is more uniform, can reduce the generation of blank silicon dioxide, and the prepared quantum dot-silicon dioxide composite material can better keep the fluorescence intensity of the quantum dots and has good dispersibility and light stability.
Description
Technical Field
The invention belongs to the technical field of quantum dots, and particularly relates to a preparation method of silicon dioxide coated quantum dots.
Background
The quantum dot is a zero-dimensional semiconductor nanocrystal material with the size of 2-20nm, has excellent luminescence performance, and has the characteristics of wide excitation wave band, high luminescence efficiency, easily adjustable wavelength, narrow half width and the like. The quantum dots are applied to the display technology, can remarkably improve the color expression capability of a display device, and are key core materials in the novel display technology. However, quantum dots often have high surface activity, and excited electrons and holes easily move to the surfaces of the quantum dots and are captured by surface defects, or react with water and oxygen molecules adsorbed on the surfaces to form hydroxyl radicals and superoxide radicals with high reaction activity, so that the quantum dots are corroded, and the luminescence performance is deteriorated.
In practice, the surface of the quantum dot is passivated and coated by dense optical and chemical inert materials to improve the luminescence property and stability of the quantum dot.
The silicon dioxide is an environment-friendly, easy to prepare, stable and compact inorganic material, and is an ideal choice for the surface coating material of the quantum dots.
In the application aspect of quantum dots as display technology, LED and the like, quantum dots are considered as excellent fluorescent materials, at present, a plurality of quantum dot televisions are introduced by Samsung electronics, LG and TCL and have a good display effect, but some basic scientific problems still exist and cannot be solved, wherein the problem of stability of the quantum dots always hinders the development of industrialization of the quantum dots, and the corrosion of water and oxygen to the quantum dots is considered to be one of the most important factors influencing the stability of the quantum dots. Meanwhile, the stability of the quantum dots is also a great challenge in other application fields, such as solar cells, biomarkers, environmental pollution treatment and the like. Silica is introduced into a quantum dot system, and the quantum dots are coated by the silica, so that on one hand, the optical transparency of the silica does not influence the fluorescence performance of the quantum dots, on the other hand, the chemical inertness of the silica protects the quantum dots to reduce the corrosion of water and oxygen to the quantum dots, and the stability of the quantum dots is improved.
At present, there are various methods for coating quantum dots with SiO 2 . The technical characteristics are roughly divided into three categories, for example, patent CN107474821A discloses a preparation method of silica microspheres containing oil phase cadmium selenide quantum dots, in the patent, a silanization reagent is used as a silica raw material, added into an anhydrous organic solvent containing oil phase quantum dots, and slowly hydrolyzed by trace amount of water in the organic solvent to prepare silica-coated quantum dots. The method can show that the condition of the quantum dot surface ligand is limited by the polarity of the solvent, and the quantum dot surface ligand is difficult to form mixed dispersion with other materials, so that the steps and the reaction time length of an experiment are increased, the operation is complicated and difficult to control, and the application prospect of the quantum dot surface ligand is limited.
Due to the limitation OF the oil phase quantum dot surface ligand, methods such as microemulsion, reverse microemulsion and the like are mostly adopted, for example, Blondot et al use a microemulsion method to encapsulate quantum dot ultrafine particles in silicon dioxide (Blondot V, et al. fluoro properties OF self-encapsulated colloidal nanoparticles from CdSe/CdS/ZnS nanocrystals. NEW jour aluminum OF pharmaceuticals. 2020,22, 113026.), and in patent CN106010501A, silicon source, gadolinium source, catalyst and surfactant are used to perform reverse microemulsion reaction under the stirring condition to coat the silicon dioxide layer outside the quantum dots. The two methods require a large amount of organic matters in the preparation process, have complex steps and high cost and cause environmental pollution. In addition, another method is to use silane containing mercapto group to adsorb or modify quantum dots and then coat silica, for example, patent CN110317604B discloses a coating method, in which the surface of silica microsphere is modified by mercaptosilane and then adsorbs quantum dots, and then hydrolysate is used to coat the microsphere with silica, so as to effectively solve the problem of quantum dot agglomeration and improve the stability of quantum dot luminescence. However, the method is complex in experimental process and long in time consumption, and the required modified raw materials are expensive and have small yield. Therefore, how to solve the problem of quantum dot solvent limitation and obtain a preparation method of silica-coated quantum dots with simple operation and more uniform particle size is an urgent problem to be solved.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a silicon dioxide coated quantum dot, which adopts a sulfydryl-containing ligand to modify the surface of the quantum dot, wherein one end of the ligand is sulfydryl which is easy to combine with the surface of the quantum dot, and the other end of the ligand is hydroxyl or oxysilane, so that the limitation of the oil phase quantum dot surface ligand is solved, the quantum dot has alcohol solubility and is easy to coat, a large amount of organic matters are not needed in the replacement process, and the quantum dot can directly participate in coating without purification after replacement. In the coating process, the silicon source solution and the catalyst aqueous solution are respectively prepared, and meanwhile, the silicon dioxide is slowly hydrolyzed and coated on the surface of the quantum dot by a mode of slowly dripping at a constant speed, so that the slow dripping is beneficial to reducing the generation of blank silicon dioxide caused by the rapid hydrolysis and self-nucleation of the silicon source, and the yield is improved. The solvent used in the coating process is cheap and easy to obtain, the steps are simple, and the method is beneficial to the industrialization of the product in terms of cost and process. The silicon dioxide material coating the quantum dots can better keep the fluorescence intensity of the quantum dots, the fluorescence intensity loss is smaller than that of the material obtained by methods such as microemulsion and the like, and under the protection effect of the silicon dioxide layer, the material not only keeps better fluorescence intensity, but also has better stability and long service life.
In order to achieve the purpose, the invention adopts the following scheme:
the preparation method of the silicon dioxide coated quantum dot comprises the following steps:
(1) dispersing the quantum dots in an organic solvent under a reaction atmosphere, and adding a sulfhydryl ligand to perform ligand replacement modification;
(2) dispersing the quantum dot solution modified in the step (1) in an alcohol solvent to prepare a solution A;
(3) preparing an alcohol solvent and oxygen-containing silane into a solution B, and preparing a solution C from an alkaline catalyst and water;
(4) and meanwhile, slowly dripping the solution B and the solution C into the solution A at a constant speed by using injection pumps respectively, uniformly stirring, sealing the reactor, stirring for 1-3 hours in a dark place, centrifuging the reacted mixed solution to obtain a precipitate, washing by using an organic solvent, and drying to obtain the quantum dots coated by the dioxide.
Further, the cation in the quantum dot is Cd 2+ 、Zn 2+ 、Cu 2+ 、Ga 3+ 、In 3+ 、Ag + And Pb 2+ Anion is Se 2- 、S 2- 、Te 2- 、P 3- 、N 3- 、Cl - 、Br - And I - At least one of; the particle size of the quantum dots is 2-20 nm.
Further, the reaction atmosphere is an air atmosphere or an inert gas atmosphere, and preferably, the reaction atmosphere is at least one of a nitrogen atmosphere, an air atmosphere, and an argon atmosphere.
Further, in the step (1), the mercapto ligand is one or more of 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltriethoxysilane, gamma-mercaptopropyltriethoxysilane, 2-mercaptoethanol, 9-mercapto-1-nonanol, 8-mercapto-1-octanol, 6-mercapto-1-hexanol, 4-mercapto-1-butanol, 3-mercapto-1-hexanol, and 3-mercapto-3-methyl-1-butanol. The volume ratio of the organic solvent to the ligand reagent is 5-40: 1, preferably, the volume ratio of the organic solvent to the sulfhydryl ligand is 5-40: 1, and preferably, the ratio of the organic solvent to the sulfhydryl ligand is 10-40: 1.
Further, the organic solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, xylene, toluene, N-butanol, N-octanol, methanol, ethanol, acetone, diethyl ether and chloroform.
Further, the reaction temperature in the ligand replacement modification process is 30-150 ℃, and the reaction time is 2-24 h.
Furthermore, the volume ratio of the modified quantum dots to the alcohol solvent in the solution A is 1: 1-10, preferably 1: 1-3. The volume ratio of the alcohol solvent to the oxygen-containing silane in the solution B is 1: 5-20, preferably 1: 10-15, and the volume ratio of the basic catalyst to water in the solution C is 1: 1-10, preferably 1: 4 to 10.
Further, the alcohol solvent is one or more of n-butanol, n-octanol, methanol and ethanol; the alkaline catalyst is tetramethyl ammonium hydroxide or 2- (dimethylamino) ethyl acrylate; the oxygen-containing silane is one or more of ethyl orthosilicate, methyl orthosilicate and butyl orthosilicate.
Further, the reaction temperature in the step (4) is 15-45 ℃, and the reaction time is 1-3 h.
Further, the dropping speed of the solution B in the step (4) is 0.4-0.7mL/min, and the dropping speed of the solution C is 0.05-0.5 mL/min.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of silicon dioxide coated quantum dots, which has the advantages of simple process, easy operation and mild reaction conditions.
Secondly, the solubility limit of the oil phase quantum dots caused by surface ligands can be improved, and the further controllable surface modification of the quantum dot material is facilitated;
finally, the high fluorescence intensity, short time consumption (about 2-3 hours) and simple operation process are beneficial to the industrialization of the technology, and the silicon dioxide containing quantum dots with uniform particle size can be prepared according to the requirement, so that the silicon dioxide layer protects the quantum dots from being corroded by water and oxygen, and the purpose of improving the stability of the quantum dots is achieved.
In addition, in the aspect of industrial practical application, such as the process of a quantum dot diffusion plate, the composite material can be directly added into a granulation injection molding process, and a finished product with a double-layer water-resisting and oxygen-isolating layer and a manufacturing process of the product are omitted. For example, in the processes of quantum dot photoetching and ink-jet printing, the silicon dioxide can be directly added into photoresist and printing ink, and the process of quantum dot anti-corrosion and the addition of an auxiliary agent can be reduced or avoided due to the protection of the silicon dioxide.
Drawings
FIG. 1 shows green quantum dots (G-QD) under the excitation of blue light of 450nm, and the silica (G-QD-SiO) coated with the green quantum dots prepared by the slow dripping method of the invention 2 -1) and silica coated with green quantum dots prepared by direct rapid mixing method (G-QD-SiO) 2 -2) fluorescence spectra;
FIG. 2 shows red quantum dots (R-QD) under the excitation of 450nm blue light, and the red quantum dots-coated silica (R-QD-SiO) prepared by the slow dropwise adding method of the invention 2 -1) and red quantum dot coated silica (R-QD-SiO) prepared by direct and rapid mixing method 2 -2) fluorescence spectra;
FIG. 3 is G-QD-SiO 2 A TEM image of (B);
fig. 4 is a fluorescence spectrum of a silica material coated with quantum dots by using ammonia water and tetramethylammonium hydroxide as basic catalysts, respectively.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
A preparation method of silicon dioxide coated quantum dots comprises the following steps:
step S1: dispersing quantum dots in an organic solvent under a reaction atmosphere, adding a sulfhydryl ligand at a certain temperature to perform ligand replacement for modification,
step S2: dispersing the modified quantum dot solution in a certain amount of absolute ethyl alcohol to prepare a mixed solution A,
step S3: preparing absolute ethyl alcohol and oxygen-containing silane into a solution B according to a certain proportion, and preparing an alkaline catalyst and water into a solution C according to a certain proportion; and (3) slowly dripping the solution B and the solution C into the solution A at a constant speed by using an injection pump, uniformly stirring, sealing the reactor, and stirring for 1-3 hours in a dark place.
Step S4: and centrifuging the reaction mixed solution to obtain a precipitate, namely a reaction product, washing the reaction product by using an organic solvent such as toluene and ethanol for several times, and drying to obtain the silicon dioxide containing the quantum dots.
Example 1 silica-coated CdSe Green Quantum dots
Under the atmosphere of nitrogen, 0.18g of quantum dots are added into a mixed solution of 16mL of toluene and 8mL of n-butyl alcohol to form a mixed solution, magnetic stirring is carried out to disperse the mixed solution, when the solution is clear, vacuum pumping and air bleeding are carried out for three times when the heating temperature reaches 30 ℃, 0.6mL of 3-mercaptopropyl trimethoxy silane is injected, stirring is carried out for 3 hours under the condition of light shielding to obtain a clear green solution, and the clear green solution is the quantum dot solution after ligand replacement, so that the solution is cooled to 25 ℃ for later use.
Taking 3mL of the modified quantum dot solution, adding the modified quantum dot solution into 7.2mL of absolute ethanol, magnetically stirring for 3-6 minutes to obtain a mixed solution A, preparing a mixed solution B from 2mL of methyl orthosilicate and 16.2mL of absolute ethanol, dropwise adding the solution B into the solution A at a constant speed for 30 minutes by using an injection pump, dropwise adding a solution C prepared from 0.2mL of 25% tetramethylammonium hydroxide ethanol solution, 4mL of absolute ethanol and 1mL of water for 30 minutes by using the injection pump at a constant speed, stirring for 2 hours in a dark place, centrifugally precipitating and filtering a reaction product, repeatedly washing the precipitated product with toluene for 3 times, and drying to obtain the silica-coated CdSe green quantum dot.
Example 2 silica-coated CdSe Red Quantum dots
Under the atmosphere of nitrogen, 0.12g of quantum dots are added into 12mL of DMF to form a mixed solution, magnetic stirring is carried out to disperse the mixed solution, the mixed solution is heated to 100 ℃, the solution is vacuumized and deflated for three times, 7mL of 3-mercaptopropyltrimethoxysilane is injected at 100 ℃, the mixed solution is stirred for 3 hours at 100 ℃, the temperature is increased to 130 ℃ for reaction for 20 minutes, then increased to 140 ℃ for reaction for 20 minutes, and then increased to 150 ℃ for reaction for 30 minutes, so that a clear orange-red solution is obtained, and the clear orange-red solution is the quantum dot solution after ligand replacement, and the solution is reduced to 25 ℃. Taking 3mL of the modified quantum dot solution, adding the modified quantum dot solution into 7.2mL of absolute ethanol, magnetically stirring for 3-6 minutes to obtain a mixed solution A, preparing a mixed solution B from 2mL of tetraethoxysilane and 16.2mL of absolute ethanol, dropwise adding the solution B into the solution A at a constant speed for 30 minutes by using an injection pump, dropwise adding a solution C prepared from 0.2mL of 25% tetramethylammonium hydroxide ethanol solution, 4mL of absolute ethanol and 1mL of water for 30 minutes by using the injection pump at a constant speed, stirring for 2 hours in a dark place, centrifugally precipitating and filtering a reaction product, repeatedly washing the precipitated product with toluene for 3 times, and drying to obtain the silica-coated CdSe red quantum dot.
Example 3 silica-coated InP Green Quantum dots
Under the atmosphere of nitrogen, 0.2g of quantum dots are added into a mixed solution of 18mL of toluene and 9mL of n-butyl alcohol to form a mixed solution, magnetic stirring is carried out to disperse the mixed solution, when the solution is clear, vacuum pumping and air bleeding are carried out for three times when the heating temperature reaches 30 ℃, 1.2mL of 3-mercaptopropyl trimethoxy silane is injected, stirring is carried out for 3 hours under the condition of light shielding to obtain a clear green solution, and the clear green solution is the quantum dot solution after ligand replacement, so that the solution is reduced to 25 ℃ for later use.
Adding 3mL of the modified quantum dot solution into 8mL of absolute ethyl alcohol, magnetically stirring for 3-6 minutes to obtain a mixed solution A, preparing a mixed solution B from 2.5mL of tetraethoxysilane and 20mL of absolute ethyl alcohol, slowly and dropwise adding the solution B into the solution A at a constant speed, stirring for 3 minutes, simultaneously slowly and dropwise adding a solution C consisting of 0.25 mL of ammonia water solution at a constant speed, quickly stirring and sealing, stirring for 2 hours in a dark place, centrifugally precipitating and filtering a reaction product, repeatedly washing the precipitated product with ethanol for 3 times, and drying to obtain the silica-coated InP green quantum dot.
TABLE 1
Table 1 shows the green quantum dot-coated silicon dioxide powder (G-QD-SiO) prepared by the slow dropping method of the present invention 2 -1 powder) and green quantum dot coated silica powder (G-QD-SiO) prepared by direct rapid mixing method 2 -2 powder), wherein the direct and rapid mixing method comprises the steps of mixing an alcohol solvent with the displaced quantum dot solution, rapidly pouring the oxygen-containing silane, the alkaline catalyst and the water, rapidly stirring uniformly, and then sealing for reaction, wherein the types, the amounts and the reaction time of the reagents are the same as those of the method.
As can be seen from table 1, PLQY of the product prepared by the present invention is greatly improved compared with PLQY of the product prepared by the direct rapid addition method, because the slow dropping of the present invention enables the surface of the quantum dot to be more completely coated, and the surface defect is passivated during the coating process, the PLQY is higher, while the rapid mixing method generates more blank silica on the one hand, so that more quantum dots are exposed outside; on the other hand, the fast coating process may cause the silicon dioxide on the surface of the quantum dot to have larger defects, so that the quantum dot is corroded.
As can be seen from fig. 1 and fig. 2, the quantum dot-silica composite material prepared by the present invention has less loss of fluorescence intensity after coating and can better maintain the fluorescence intensity of the quantum dot compared with the unmodified quantum dot; compared with the composite material prepared by a direct and rapid mixing method, the composite material has higher fluorescence intensity, which shows that the preparation method of the invention has advantages in maintaining the fluorescence intensity of the quantum dots.
Ammonia water as a common basic catalyst in the St nanober method helps to form silica microspheres, but ammonia water can quench quantum dots to a certain degree in the preparation process of silica-coated quantum dots, and tetramethyl ammonium hydroxide as a common catalyst in the synthesis of silicon products can better maintain the fluorescence intensity of the quantum dots in the preparation process, as can be seen from fig. 4, the quantum dot silica coated with tetramethyl ammonium hydroxide as a catalyst has higher fluorescence intensity, and the product of ammonia water as a catalyst is obviously reduced.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (10)
1. A preparation method of silicon dioxide coated quantum dots is characterized by comprising the following steps: the method comprises the following steps:
(1) under the reaction atmosphere, dispersing the quantum dots in an organic solvent, and adding a sulfydryl ligand to perform ligand replacement modification;
(2) dispersing the quantum dot solution modified in the step (1) in an alcohol solvent to prepare a solution A;
(3) preparing an alcohol solvent and oxygen-containing silane into a solution B, and then preparing a basic catalyst and water into a solution C;
(4) and simultaneously, slowly dropwise adding the solution B and the solution C to the solution A at a constant speed by using an injection pump respectively, uniformly stirring, sealing the reactor, stirring for 1-3 hours in a dark place, centrifuging the reacted mixed solution to obtain a precipitate, washing by using an organic solvent, and drying to obtain the quantum dots coated with the dioxide.
2. The method for preparing the silicon dioxide coated quantum dot as claimed in claim 1, wherein the cation in the quantum dot is Cd 2+ 、Zn 2+ 、Cu 2+ 、Ga 3+ 、In 3+ 、Ag + And Pb 2+ Anion is Se 2- 、S 2- 、Te 2- 、P 3- 、N 3- 、Cl - 、Br - And I - At least one of; the particle size of the quantum dots is 2-20 nm.
3. The method according to claim 1, wherein the reaction atmosphere is an air atmosphere or an inert gas atmosphere.
4. The method for preparing the silica-coated quantum dot according to claim 1, wherein the mercapto ligand is one or more selected from the group consisting of 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltriethoxysilane, γ -mercaptopropyltriethoxysilane, 2-mercaptoethanol, 9-mercapto-1-nonanol, 8-mercapto-1-octanol, 6-mercapto-1-hexanol, 4-mercapto-1-butanol, 3-mercapto-1-hexanol, and 3-mercapto-3-methyl-1-butanol.
5. The method for preparing the silica-coated quantum dot according to claim 1, wherein the organic solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, xylene, toluene, N-butanol, N-octanol, methanol, ethanol, acetone, diethyl ether, and chloroform.
6. The preparation method of the silicon dioxide coated quantum dot according to claim 1, wherein the reaction temperature in the ligand replacement modification process is 30-150 ℃, and the reaction time is 2-24 h.
7. The method for preparing the silicon dioxide coated quantum dot according to claim 1, wherein the volume ratio of the modified quantum dot to the alcohol solvent in the solution A is 1: 1-3, the volume ratio of the alcohol solvent to the oxysilane in the solution B is 1: 10-15, and the volume ratio of the basic catalyst to water in the solution C is 1: 4 to 10.
8. The method for preparing the silicon dioxide coated quantum dot according to claim 1, wherein the alcohol solvent is one or more of n-butanol, n-octanol, methanol and ethanol; the alkaline catalyst is tetramethyl ammonium hydroxide; the oxygen-containing silane is one or more of ethyl orthosilicate, methyl orthosilicate and butyl orthosilicate.
9. The preparation method of the silicon dioxide coated quantum dot according to claim 1, wherein the reaction temperature in the step (4) is 15-45 ℃ and the reaction time is 1-3 h.
10. The method for preparing the silicon dioxide coated quantum dot according to claim 1, wherein the dropping speed of the solution B in the step (4) is 0.4-0.7mL/min, and the dropping speed of the solution C is 0.05-0.5 mL/min.
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