CN102816564B - Preparation method and application for nano-composite luminescent material with high fluorescence efficiency and silicon dioxide coated quantum dots - Google Patents
Preparation method and application for nano-composite luminescent material with high fluorescence efficiency and silicon dioxide coated quantum dots Download PDFInfo
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Abstract
The invention discloses a preparation method for nano-composite luminescent material with SiO2 coated quantum dots. The nano-composite luminescent material with the SiO2 coated quantum dots is prepared by growing a SiO2 lamella on the surface of quantum dots by the inversion microemulsion polymerization reaction and subjecting the product to after treatments including annealing treatment and ultraviolet-light treatment. The quantum dots can be a single quantum dot or various quantum dots. The nano-composite luminescent material with the SiO2 coated quantum dots prepared by the method can simultaneously meet requirements on hydrophilic surface, proper surface functional groups and freeness of bio-toxicity and has higher fluorescence efficiency, so that the nano-composite luminescent material with high fluorescence efficiency and SiO2 coated quantum dots can be used for preparation of high-performance photoelectric devices such as LEDs and can be also used for the field of biological multicolor marking.
Description
Technical field
The present invention relates to a kind of preparation method who prepares nano combined luminescent material, relate in particular to a kind of preparation method of nano combined luminescent material of the silicon dioxide-coated quantum dots with high fluorescence efficiency.
Background technology
Quantum dot (quantum dot, QD) is the nano material of accurate zero dimension (quasi-zero-dimensional), is made up of a small amount of atom.Conventionally quantum dot is by the elementary composition nano particle of II-VI family or III-V family, size is less than or approaches exciton Bohr radius (general diameter be no more than 10nm), because its electronics and hole are by quantum confinement, its energy band structure becomes the discrete energy levels structure with molecular characterization, and therefore it can emitting fluorescence after being excited.
Due to its distinctive photoelectric property, quantum dot has important application at biological multi-color marking and field of photoelectric devices.In order to obtain the quantum dot of high monochromaticity and high fluorescence efficiency, common method is by hot injection method synthetic oil dissolubility quantum dot in organic solution.1), there is hydrophilic surface but quantum dot will be applied to biological field, need to meet following condition:; 2), there is suitable surface functional group; 3) (toxicity is mainly by surface ligand and Cd, there is no bio-toxicity
2+release etc. heavy metal ion causes).
In order to address the above problem, at present conventional method is for to transfer oil soluble quantum dot to water-soluble quantum dot by ligand exchange, and still this phase transition behavior that transfers water-soluble quantum dot to from oil soluble quantum dot can be accompanied by the significantly decay of fluorescence efficiency conventionally.In addition, although this method has solved the problem that quantum dot dissolves in water, still do not solve that it may have because heavy metal ion discharges the problem of the bio-toxicity causing.
In recent years, the surperficial coated Si O that has bibliographical information to pass through at oil soluble quantum dot
2shell (it has hydrophilic surface), forms nano combined light-emitting particles, this SiO
2the nano combined luminescent material of coated quantum dots will have hydrophilic surface.There is document to prove SiO simultaneously
2shell can significantly reduce the effusion of heavy metal ion, reduces bio-toxicity.But, pass through at present SiO
2coated quantum dot, its fluorescence efficiency all can have reduction largely.Therefore, how to keep SiO
2to it, the application in fields such as biological and opto-electronic conversion has great importance the fluorescence efficiency of the nano combined luminescent material of coated quantum dots.
Therefore, those skilled in the art is devoted to develop a kind of SiO
2the preparation method of the nano combined luminescent material of coated quantum dots, to prepare the SiO of high fluorescence efficiency
2the nano combined luminescent material of coated quantum dots.
Summary of the invention
Because the above-mentioned defect of prior art, technical problem to be solved by this invention is to provide a kind of SiO
2the preparation method of the nano combined luminescent material of coated quantum dots, reacts the surface growth one deck SiO at oil soluble quantum dot by conversed phase micro emulsion copolymerization
2shell, then carries out aftertreatment further to improve SiO
2the fluorescence efficiency of the nano combined luminescent material of coated quantum dots.
For achieving the above object, the invention provides a kind of SiO
2the preparation method of the nano combined luminescent material of coated quantum dots, is characterized in that, comprising:
Step 1, quantum dot is dissolved in to hexanaphthene, or first described quantum dot is first dissolved in organic reagent, and then be dissolved in hexanaphthene;
In step 2, the solution that obtains in step 1, add TEOS, tensio-active agent and catalyzer to carry out the conversed phase micro emulsion copolymerization reaction of catalysis;
Step 3, carry out after the time (T1) in described reaction, in the solution that carries out described reaction, dripped acetone to stop described reaction, the solution that has stopped described reaction has been carried out to centrifugal treating, obtained SiO
2the Nano composite granules of coated described quantum dot;
Step 4, with ethanol clean described Nano composite granules and be scattered in ethanol or water in, by centrifugal treating obtain through cleaning SiO
2the Nano composite granules of coated described quantum dot is also dissolved in after propyl carbinol, and the hydrothermal reaction kettle of putting into inner-wall material and be tetrafluoroethylene carries out anneal; The condition of described anneal is: under agitation condition, oil bath, oil bath temperature (T), soaking time (T2), be down to room temperature with water-cooling pattern; The solution that completes described anneal is carried out to centrifugal treating, obtain the described SiO through described anneal
2the Nano composite granules of coated described quantum dot;
Step 5, the described Nano composite granules obtaining with ethanol cleaning step four are also scattered in ethanol, obtain containing the described SiO through described anneal
2the ethanolic soln of the Nano composite granules of coated described quantum dot;
Step 6, the described ethanolic soln that step 5 is obtained are placed under ultraviolet lamp and carry out ultraviolet lighting processing, the ultraviolet lighting time (T3), obtain containing the described SiO through described ultraviolet lighting processing and described anneal
2the ethanolic soln of the Nano composite granules of coated described quantum dot.
Further, described quantum dot is CdS, HgS, CdSe, CdTe, ZnSe, HgSe, ZnTe, ZnO, PbSe, HgTe, CaAs, InP, InCaAs, CdSe/ZnS, CdSe/ZnSe, CdS/ZnS, Cd/Ag2S, CdS/Cd (OH)
2, any one or multiple combination in CdTe/ZnS, CdTe/CdS, CdSe/ZnSe, CdS/HgS, CdS/HgS/CdS, ZnS/CdS, ZnS/CdS/ZnS, ZnS/HgS/ZnS/CdS, CdSe/CuSe, CdSeTe, CdSeTe/CdS/ZnS, Mn:CdS, Cu:CdS, Cu:ZnS, Mn:ZnS, Mn:ZnSe, Cu:ZnSe, Tb:CdS or Tb:ZnS.
Further, the size of described quantum dot is in the scope of 1-10nm.
Further, described organic reagent in described step 1 is hydrophobic, and described organic reagent is the mix reagent of any one reagent in normal hexane, toluene, dimethylbenzene, parachlorotoluene, methylene dichloride, trichloromethane, tetrachloromethane and sherwood oil reagent or any two kinds and above reagent.
Further, the described tensio-active agent in described step 2 is any one or any two kinds and the above combination in tensio-active agent NP5, NP9 and TritonX-100.
Further, the described catalyzer in described step 2 is any one or any two kinds and the above combination in catalyzer methylamine, ammoniacal liquor and dimethylamine.
Further, the described time T 1 in described step 3 is 20-80 hour.
Further, the described oil bath temperature T in described step 4 is 50-90 ℃, and described soaking time T2 is 0.5-2 hour.
Further, the described time T 3 in described step 6 is not less than 6 hours.。
In preferred embodiments of the present invention, respectively Quantum dots CdS e/CdS/ZnS, CdSeS/CdS, Cu:CdS/ZnS, Mn:ZnSe, CdTe/ZnS and CdSe are reacted to the surface growth SiO at quantum dot by conversed phase micro emulsion copolymerization
2shell also carries out aftertreatment, and aftertreatment comprises anneal and ultraviolet lighting processing.Wherein react at quantum dot surface growth SiO by conversed phase micro emulsion copolymerization
2the step of shell is: quantum dot is dissolved in to hexanaphthene, or quantum dot is first dissolved in organic reagent, and then be dissolved in hexanaphthene; In solution, add TEOS, tensio-active agent and catalyzer to carry out conversed phase micro emulsion copolymerization reaction; Carried out, after time T 1 (20h≤T1≤80h), dripping acetone with termination reaction in solution in reaction, centrifugal treating obtains SiO
2the Nano composite granules of coated this quantum dot; With ethanol clean these Nano composite granules and be scattered in ethanol or water in, centrifugal treating obtain through cleaning SiO
2the Nano composite granules of coated this quantum dot.Anneal in the present invention is carried out in hydrothermal reaction kettle, comprises step: by SiO
2the Nano composite granules of coated this quantum dot is dissolved in after propyl carbinol, put into the hydrothermal reaction kettle that inner-wall material is tetrafluoroethylene, the condition of processing is: under agitation condition, oil bath, oil bath temperature T (50 ℃≤T≤90 ℃), soaking time T2 (0.5h≤T1≤2h), be down to room temperature with water-cooling pattern; This solution of centrifugal treating obtains the SiO of annealed processing
2the Nano composite granules of coated this quantum dot; Clean these Nano composite granules and be scattered in ethanol with ethanol, obtaining the SiO containing annealed processing
2the ethanolic soln of the Nano composite granules of coated this quantum dot.The step of the ultraviolet lighting processing in the present invention is: this ethanolic soln is placed under ultraviolet lamp and is irradiated, and ultraviolet lighting time T 3 (T3>=6h), obtains containing the SiO through ultraviolet lighting processing and anneal
2the ethanolic soln of the Nano composite granules of coated this quantum dot.
As can be seen here, SiO of the present invention
2the preparation method of the nano combined luminescent material of coated quantum dots reacts the surface growth SiO at quantum dot by conversed phase micro emulsion copolymerization
2shell also comprises anneal and the aftertreatment of ultraviolet lighting processing, has successfully prepared SiO
2the nano combined luminescent material of coated quantum dots, wherein SiO
2coated quantum dot can be the quantum dot of single kind, can be also the combination of different types of quantum dot.To the various SiO that prepare
2the test of the fluorescence efficiency of the nano combined luminescent material of coated quantum dots shows, through the SiO of the aftertreatment that comprises anneal and ultraviolet lighting processing of the present invention
2the fluorescence efficiency of the nano combined luminescent material of coated quantum dots is greatly improved, and the highlyest can reach not coated Si O
2quantum dot fluorescence efficiency 82.4%.Like this, the SiO that the present invention prepares
2the nano combined luminescent material of coated quantum dots can meet simultaneously and has hydrophilic surface, has suitable surface functional group and there is no these three requirements of bio-toxicity, and there is higher fluorescence efficiency, therefore can be used for preparing the photoelectric devices such as high performance LED, can also be used for biological multi-color marking field.
Embodiment
Embodiment 1
Step 1, Quantum dots CdS e/CdS/ZnS is dissolved in hexanaphthene.Wherein, the quantum dot of the three-layer nuclear shell structure that Quantum dots CdS e/CdS/ZnS is CdSe/CdS/ZnS, its fluorescence efficiency is 68%.Quantum dots CdS e/CdS/ZnS is dissolved in the solution that obtains 10mL, 1mM in hexanaphthene.
In step 2, the solution that obtains in step 1, add TEOS (tetraethyl orthosilicate), tensio-active agent and catalyzer to carry out the conversed phase micro emulsion copolymerization reaction of catalysis.In the present embodiment, the concrete steps of carrying out the conversed phase micro emulsion copolymerization reaction of catalysis are:
Under agitation condition, add TEOS, then add tensio-active agent to form microemulsion.Wherein, TEOS takes 0.1mL, stirs 10min; Tensio-active agent is taken NP5, and consumption 1mL stirs 30min.Under agitation condition, add catalyzer to react with catalysis conversed phase micro emulsion copolymerization.Wherein, catalyzer is selected methylamine, and consumption 0.1mL continues to stir under lucifuge condition.
Step 3, carry out, after time T 1, in the solution that carries out this reaction, dripping acetone with termination reaction in the conversed phase micro emulsion copolymerization reaction of step 2, the solution that has stopped reaction has been carried out to centrifugal treating, obtained SiO
2the Nano composite granules of coated quantum dots CdSe/CdS/ZnS.Wherein, time T 1 is set as 24h.
Step 4, the Nano composite granules obtaining with ethanol cleaning step three are also scattered in ethanol, obtain the SiO through cleaning by centrifugal treating
2the Nano composite granules of coated quantum dots CdSe/CdS/ZnS.The average particulate diameter that experiment measuring obtains this nano combined luminescent material is 32nm, and its fluorescence intensity is 70.3% of Quantum dots CdS e/CdS/ZnS, and its fluorescence efficiency is 26%.
By above-mentioned SiO
2the Nano composite granules of coated quantum dots CdSe/CdS/ZnS is dissolved in after propyl carbinol, the hydrothermal reaction kettle of putting into inner-wall material and be tetrafluoroethylene carries out anneal, and the condition of anneal is: under agitation condition, oil bath, oil bath temperature T, soaking time T2, be down to room temperature with water-cooling pattern.In the present embodiment, adopt induction stirring, oil bath temperature T is set as 70 ℃, and soaking time T2 is set as 1h.
The solution completing after above-mentioned anneal is down to room temperature and carries out centrifugal treating with water-cooling pattern, obtains the SiO of annealed processing
2the Nano composite granules of coated quantum dots CdSe/CdS/ZnS.
Step 5, the Nano composite granules obtaining with ethanol cleaning step four are also scattered in ethanol, obtain the SiO containing annealed processing
2the ethanolic soln of the Nano composite granules of coated quantum dots CdSe/CdS/ZnS.The SiO of annealed processing
2the median size of the Nano composite granules of coated quantum dots CdSe/CdS/ZnS is constant.
Step 6, the ethanolic soln that step 5 is obtained are placed under ultraviolet lamp and carry out ultraviolet lighting processing, and ultraviolet lighting time T 3 obtains containing the SiO through ultraviolet lighting processing and anneal
2the ethanolic soln of the Nano composite granules of coated quantum dots CdSe/CdS/ZnS.Wherein, adopt Portable ultraviolet lamp, power is 8W, and its ultraviolet wavelength sending is 365nm; Time T 3 is set as 24h.Experiment measuring obtains the SiO of this process ultraviolet lighting processing and anneal
2the fluorescence efficiency of the nano combined luminescent material of coated quantum dots CdSe/CdS/ZnS is 56%.
Embodiment 2
Step 1, Quantum dots CdS eS/CdS is dissolved in hexanaphthene.Wherein, the quantum dot of the two-layer nucleocapsid structure that quantum dot is CdSeS/CdS, its fluorescence efficiency is 54%.Quantum dots CdS eS/CdS is dissolved in the solution that obtains 10mL, 1mM in hexanaphthene.
In step 2, the solution that obtains in step 1, add TEOS, tensio-active agent and catalyzer to carry out the conversed phase micro emulsion copolymerization reaction of catalysis.In the present embodiment, the concrete steps of carrying out the conversed phase micro emulsion copolymerization reaction of catalysis are:
Under agitation condition, add TEOS, then add tensio-active agent to form microemulsion.Wherein, TEOS takes 0.1mL, stirs 10min; Tensio-active agent is taken NP5, and consumption 1mL stirs 30min.Then under agitation condition, add catalyzer to react with catalysis conversed phase micro emulsion copolymerization.Wherein, catalyzer is selected methylamine, and consumption 0.1mL continues to stir under lucifuge condition.
Step 3, carry out, after time T 1, in the solution that carries out this reaction, dripping acetone with termination reaction in the conversed phase micro emulsion copolymerization reaction of step 2, the solution that has stopped reaction has been carried out to centrifugal treating, obtained SiO
2the Nano composite granules of coated quantum dots CdSeS/CdS.Wherein, time T 1 is set as 24h.
Step 4, the Nano composite granules obtaining with ethanol cleaning step three are also scattered in ethanol, obtain the SiO through cleaning by centrifugal treating
2the Nano composite granules of coated quantum dots CdSeS/CdS.The average particulate diameter that experiment measuring obtains this nano combined luminescent material is 38.1nm.
By above-mentioned SiO
2the Nano composite granules of coated quantum dots CdSeS/CdS is dissolved in after propyl carbinol, the hydrothermal reaction kettle of putting into inner-wall material and be tetrafluoroethylene carries out anneal, and the condition of anneal is: under agitation condition, oil bath, oil bath temperature T, soaking time T2, be down to room temperature with water-cooling pattern.In the present embodiment, adopt induction stirring, oil bath temperature T is set as 50 ℃, and soaking time T2 is set as 1h.
The solution completing after above-mentioned anneal is down to room temperature and carries out centrifugal treating with water-cooling pattern, obtains the SiO of annealed processing
2the Nano composite granules of coated quantum dots CdSeS/CdS.
Step 5, the Nano composite granules obtaining with ethanol cleaning step four are also scattered in ethanol, obtain the SiO containing annealed processing
2the ethanolic soln of the Nano composite granules of coated quantum dots CdSeS/CdS.The SiO of annealed processing
2the median size of the Nano composite granules of coated quantum dots CdSeS/CdS is constant.
Step 6, the ethanolic soln that step 5 is obtained are placed under ultraviolet lamp and carry out ultraviolet lighting processing, and ultraviolet lighting time T 3 obtains containing the SiO through ultraviolet lighting processing and anneal
2the ethanolic soln of the Nano composite granules of coated quantum dots CdSeS/CdS.Wherein, adopt Portable ultraviolet lamp, power is 16W, and its ultraviolet wavelength sending is 365nm; Time T 3 is set as 12h.Experiment measuring obtains the SiO of this process ultraviolet lighting processing and anneal
2the fluorescence efficiency of the nano combined luminescent material of coated quantum dots CdSeS/CdS is 43.2%.
Embodiment 3
Step 1, quantum dot Cu:CdS/ZnS is first dissolved in organic reagent, is then dissolved in hexanaphthene.Wherein, quantum dot is that Cu:CdS/ZnS is the quantum dot of the two-layer nucleocapsid structure of the CdS/ZnS of Cu doping, and its fluorescence efficiency is 42.6%; Organic reagent is selected normal hexane, hexanaphthene consumption 9mL.Quantum dot Cu:CdS/ZnS is dissolved in the solution that obtains 10mL, 1mM in normal hexane, and this solution is mixed with hexanaphthene.
In step 2, the solution that obtains in step 1, add TEOS, tensio-active agent and catalyzer to carry out the conversed phase micro emulsion copolymerization reaction of catalysis.In the present embodiment, the concrete steps of carrying out the conversed phase micro emulsion copolymerization reaction of catalysis are:
Under agitation condition, add tensio-active agent, then add TEOS to form microemulsion.Wherein, tensio-active agent is taken NP9, and consumption 1mL stirs 30min; TEOS takes 0.1mL, stirs 30min.Then under agitation condition, add catalyzer to react with catalysis conversed phase micro emulsion copolymerization.Wherein, catalyzer is selected dimethylamine, and consumption 0.05mL continues to stir under lucifuge condition.
Step 3, carry out, after time T 1, in the solution that carries out this reaction, dripping acetone with termination reaction in the conversed phase micro emulsion copolymerization reaction of step 2, the solution that has stopped reaction has been carried out to centrifugal treating, obtained SiO
2the Nano composite granules of coated quantum dots Cu:CdS/ZnS.Wherein, time T 1 is set as 30h.
Step 4, the Nano composite granules obtaining with ethanol cleaning step three are also scattered in ethanol, obtain the SiO through cleaning by centrifugal treating
2the Nano composite granules of coated quantum dots Cu:CdS/ZnS.The average particulate diameter that experiment measuring obtains this nano combined luminescent material is 41.4nm.
By above-mentioned SiO
2the Nano composite granules of coated quantum dots Cu:CdS/ZnS is dissolved in after propyl carbinol, the hydrothermal reaction kettle of putting into inner-wall material and be tetrafluoroethylene carries out anneal, and the condition of anneal is: under agitation condition, oil bath, oil bath temperature T, soaking time T2, be down to room temperature with water-cooling pattern.In the present embodiment, adopt induction stirring, oil bath temperature T is set as 80 ℃, and soaking time T2 is set as 1h.
The solution completing after above-mentioned anneal is down to room temperature and carries out centrifugal treating with water-cooling pattern, obtains the SiO of annealed processing
2the Nano composite granules of coated quantum dots Cu:CdS/ZnS.
Step 5, the Nano composite granules obtaining with ethanol cleaning step four are also scattered in ethanol, obtain the SiO containing annealed processing
2the ethanolic soln of the Nano composite granules of coated quantum dots Cu:CdS/ZnS.The SiO of annealed processing
2the median size of the Nano composite granules of coated quantum dots CdSeS/CdS is constant.
Step 6, the ethanolic soln that step 5 is obtained are placed under ultraviolet lamp and carry out ultraviolet lighting processing, and ultraviolet lighting time T 3 obtains containing the SiO through ultraviolet lighting processing and anneal
2the ethanolic soln of the Nano composite granules of coated quantum dots Cu:CdS/ZnS.Wherein, adopt Portable ultraviolet lamp, power is 5W, and its ultraviolet wavelength sending is 365nm; Time T 3 is set as 40h.Experiment measuring obtains the SiO of this process ultraviolet lighting processing and anneal
2the fluorescence efficiency of the nano combined luminescent material of coated quantum dots Cu:CdS/ZnS is 24.3%.
Embodiment 4
Step 1, quantum dot Mn:ZnSe is first dissolved in organic reagent, is then dissolved in hexanaphthene.Wherein, quantum dot is that Mn:ZnSe is the quantum dot of the ZnSe of Mn doping, and its fluorescence efficiency is 32.1%; Organic reagent is selected trichloromethane, hexanaphthene consumption 9mL.Quantum dot Mn:ZnSe is dissolved in the solution that obtains 1mL, 10mM in trichloromethane, and this solution is mixed with hexanaphthene.
In step 2, the solution that obtains in step 1, add TEOS, tensio-active agent and catalyzer to carry out the conversed phase micro emulsion copolymerization reaction of catalysis.In the present embodiment, the concrete steps of carrying out the conversed phase micro emulsion copolymerization reaction of catalysis are:
Under agitation condition, add tensio-active agent, then add TEOS to form microemulsion.Wherein, tensio-active agent is taken NP9, and consumption 1mL stirs 30min; TEOS takes 0.1mL, stirs 30min.Then under agitation condition, add catalyzer to react with catalysis conversed phase micro emulsion copolymerization.Wherein, catalyzer is selected ammoniacal liquor, and consumption 0.2mL continues to stir under lucifuge condition.
Step 3, carry out, after time T 1, in the solution that carries out this reaction, dripping acetone with termination reaction in the conversed phase micro emulsion copolymerization reaction of step 2, the solution that has stopped reaction has been carried out to centrifugal treating, obtained SiO
2the Nano composite granules of coated quantum dots Mn:ZnSe.Wherein, time T 1 is set as 30h.
Step 4, the Nano composite granules obtaining with ethanol cleaning step three are also scattered in ethanol, obtain the SiO through cleaning by centrifugal treating
2the Nano composite granules of coated quantum dots Mn:ZnSe.The average particulate diameter that experiment measuring obtains this nano combined luminescent material is 28.7nm.
By above-mentioned SiO
2the Nano composite granules of coated quantum dots Mn:ZnSe is dissolved in after propyl carbinol, the hydrothermal reaction kettle of putting into inner-wall material and be tetrafluoroethylene carries out anneal, and the condition of anneal is: under agitation condition, oil bath, oil bath temperature T, soaking time T2, be down to room temperature with water-cooling pattern.In the present embodiment, adopt induction stirring, oil bath temperature T is set as 60 ℃, and soaking time T2 is set as 1h.
The solution completing after above-mentioned anneal is down to room temperature and carries out centrifugal treating with water-cooling pattern, obtains the SiO of annealed processing
2the Nano composite granules of coated quantum dots Mn:ZnSe.
Step 5, the Nano composite granules obtaining with ethanol cleaning step four are also scattered in ethanol, obtain the SiO containing annealed processing
2the ethanolic soln of the Nano composite granules of coated quantum dots Mn:ZnSe.The SiO of annealed processing
2the median size of the Nano composite granules of coated quantum dots Mn:ZnSe is constant.
Step 6, the ethanolic soln that step 5 is obtained are placed under ultraviolet lamp and carry out ultraviolet lighting processing, and ultraviolet lighting time T 3 obtains containing the SiO through ultraviolet lighting processing and anneal
2the ethanolic soln of the Nano composite granules of coated quantum dots Mn:ZnSe.Wherein, adopt Portable ultraviolet lamp, power is 6W, and its ultraviolet wavelength sending is 365nm; Time T 3 is set as 18h.Experiment measuring obtains the SiO of this process ultraviolet lighting processing and anneal
2the fluorescence efficiency of the nano combined luminescent material of coated quantum dots Mn:ZnSe is 19.2%.
Embodiment 5
Step 1, quantum dot CdTe/ZnS is first dissolved in organic reagent, is then dissolved in hexanaphthene.Wherein, the quantum dot of the two-layer nucleocapsid structure that quantum dot is CdTe/ZnS, its fluorescence efficiency is 69.3%; Organic reagent is selected toluene, hexanaphthene consumption 9mL.Quantum dot CdTe/ZnS is dissolved in the solution that obtains 1mL, 10mM in toluene, and this solution is mixed with hexanaphthene.
In step 2, the solution that obtains in step 1, add TEOS, tensio-active agent and catalyzer to carry out the conversed phase micro emulsion copolymerization reaction of catalysis.In the present embodiment, the concrete steps of carrying out the conversed phase micro emulsion copolymerization reaction of catalysis are:
Under agitation condition, add catalyzer, the catalyzer of selecting is methylamine, and consumption 0.2mL continues to stir under lucifuge condition.Then under agitation condition, add tensio-active agent, then add TEOS to form microemulsion.Wherein, tensio-active agent is taken NP5, and consumption 1mL stirs 30min; TEOS takes 0.1mL, stirs 30min.
Step 3, carry out, after time T 1, in the solution that carries out this reaction, dripping acetone with termination reaction in the conversed phase micro emulsion copolymerization reaction of step 2, the solution that has stopped reaction has been carried out to centrifugal treating, obtained SiO
2the Nano composite granules of coated quantum dots CdTe/ZnS.Wherein, time T 1 is set as 48h.
Step 4, the Nano composite granules obtaining with ethanol cleaning step three are also scattered in ethanol, obtain the SiO through cleaning by centrifugal treating
2the Nano composite granules of coated quantum dots CdTe/ZnS.The average particulate diameter that experiment measuring obtains this nano combined luminescent material is 37.2nm.
By above-mentioned SiO
2the Nano composite granules of coated quantum dots CdTe/ZnS is dissolved in after propyl carbinol, the hydrothermal reaction kettle of putting into inner-wall material and be tetrafluoroethylene carries out anneal, and the condition of anneal is: under agitation condition, oil bath, oil bath temperature T, soaking time T2, be down to room temperature with water-cooling pattern.In the present embodiment, adopt induction stirring, oil bath temperature T is set as 90 ℃, and soaking time T2 is set as 1h.
The solution completing after above-mentioned anneal is down to room temperature and carries out centrifugal treating with water-cooling pattern, obtains the SiO of annealed processing
2the Nano composite granules of coated quantum dots CdTe/ZnS.
Step 5, the Nano composite granules obtaining with ethanol cleaning step four are also scattered in ethanol, obtain the SiO containing annealed processing
2the ethanolic soln of the Nano composite granules of coated quantum dots CdTe/ZnS.The SiO of annealed processing
2the median size of the Nano composite granules of coated quantum dots CdTe/ZnS is constant.
Step 6, the ethanolic soln that step 5 is obtained are placed under ultraviolet lamp and carry out ultraviolet lighting processing, and ultraviolet lighting time T 3 obtains containing the SiO through ultraviolet lighting processing and anneal
2the ethanolic soln of the Nano composite granules of coated quantum dots CdTe/ZnS.Wherein, adopt Portable ultraviolet lamp, power is 5W, and its ultraviolet wavelength sending is 365nm; Time T 3 is set as 30h.Experiment measuring obtains the SiO of this process ultraviolet lighting processing and anneal
2the fluorescence efficiency of the nano combined luminescent material of coated quantum dots CdTe/ZnS is 48.2%.
Embodiment 6
Step 1, Quantum dots CdS e is dissolved in hexanaphthene.Wherein, quantum dot is CdSe quantum dot, and its fluorescence efficiency is 39%; Hexanaphthene consumption 6.5mL.Quantum dots CdS e is dissolved in the solution that obtains 10mL, 1mM in hexanaphthene.
In step 2, the solution that obtains in step 1, add TEOS, tensio-active agent and catalyzer to carry out the conversed phase micro emulsion copolymerization reaction of catalysis.In the present embodiment, the concrete steps of carrying out the conversed phase micro emulsion copolymerization reaction of catalysis are:
Under agitation condition, add catalyzer, the catalyzer of selecting is dimethylamine, and consumption 0.05mL continues to stir under lucifuge condition.Then under agitation condition, add tensio-active agent, then add TEOS to form microemulsion.Wherein, tensio-active agent is taken Triton X-100, and consumption 1.77mL stirs 30min; TEOS takes 0.1mL, stirs 30min.
Step 3, carry out, after time T 1, in the solution that carries out this reaction, dripping acetone with termination reaction in the conversed phase micro emulsion copolymerization reaction of step 2, the solution that has stopped reaction has been carried out to centrifugal treating, obtained SiO
2the Nano composite granules of coated quantum dots CdSe.Wherein, time T 1 is set as 48h.
Step 4, the Nano composite granules obtaining with ethanol cleaning step three are also scattered in ethanol, obtain the SiO through cleaning by centrifugal treating
2the Nano composite granules of coated quantum dots CdSe.The average particulate diameter that experiment measuring obtains this nano combined luminescent material is 34.5nm.
By above-mentioned SiO
2the Nano composite granules of coated quantum dots CdSe is dissolved in after propyl carbinol, the hydrothermal reaction kettle of putting into inner-wall material and be tetrafluoroethylene carries out anneal, and the condition of anneal is: under agitation condition, oil bath, oil bath temperature T, soaking time T2, be down to room temperature with water-cooling pattern.In the present embodiment, adopt induction stirring, the temperature T of oil bath is set as 90 ℃, and time T 2 is set as 1h.
The solution completing after above-mentioned anneal is down to room temperature and carries out centrifugal treating with water-cooling pattern, obtains the SiO of annealed processing
2the Nano composite granules of coated quantum dots CdSe.
Step 5, the Nano composite granules obtaining with ethanol cleaning step four are also scattered in ethanol, obtain the SiO containing annealed processing
2the ethanolic soln of the Nano composite granules of coated quantum dots CdSe.The SiO of annealed processing
2the median size of the Nano composite granules of coated quantum dots CdSe is constant.
Step 6, the ethanolic soln that step 5 is obtained are placed under ultraviolet lamp and carry out ultraviolet lighting processing, and ultraviolet lighting time T 3 obtains containing the SiO through ultraviolet lighting processing and anneal
2the ethanolic soln of the Nano composite granules of coated quantum dots CdSe.Wherein, adopt Portable ultraviolet lamp, power is 15W, and its ultraviolet wavelength sending is 365nm; Time T 3 is set as 15h.Experiment measuring obtains the SiO of this process ultraviolet lighting processing and anneal
2the fluorescence efficiency of the nano combined luminescent material of coated quantum dots CdSe is 26.8%.
It should be noted that SiO of the present invention
2the kind of the quantum dot providing in embodiment is herein provided the applicable quantum dot of preparation method of the nano combined luminescent material of coated quantum dots, and can be CdS, HgS, CdSe, CdTe, ZnSe, HgSe, ZnTe, ZnO, PbSe, HgTe, CaAs, InP, InCaAs, CdSe/ZnS, CdSe/ZnSe, CdS/ZnS, Cd/Ag
2s, CdS/Cd (OH)
2, any one in CdTe/ZnS, CdTe/CdS, CdSe/ZnSe, CdS/HgS, CdS/HgS/CdS, ZnS/CdS, ZnS/CdS/ZnS, ZnS/HgS/ZnS/CdS, CdSe/CuSe, CdSeTe, CdSeTe/CdS/ZnS, Mn:CdS, Cu:CdS, Cu:ZnS, Mn:ZnS, Mn:ZnSe, Cu:ZnSe, Tb:CdS or Tb:ZnS, can be also any two kinds or above combination in these quantum dots.For latter event, can be select arbitrarily in these quantum dots two kinds or more than, they are mixed to get with the ratio of needs.
More than describe preferred embodiment of the present invention in detail.Should be appreciated that those of ordinary skill in the art just can design according to the present invention make many modifications and variations without creative work.Therefore, all those skilled in the art, all should be in by the determined protection domain of claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (5)
1. a SiO
2the preparation method of the nano combined luminescent material of coated quantum dots, is characterized in that, comprising:
Step 1, quantum dot is dissolved in to hexanaphthene, or first described quantum dot is dissolved in organic reagent, and then be dissolved in hexanaphthene;
In step 2, the solution that obtains in step 1, add TEOS, tensio-active agent and catalyzer to carry out the conversed phase micro emulsion copolymerization reaction of catalysis;
Step 3, carry out after 20-80 hour in described reaction, in the solution that carries out described reaction, dripped acetone to stop described reaction, the solution that has stopped described reaction has been carried out to centrifugal treating, obtained SiO
2the Nano composite granules of coated described quantum dot;
Step 4, with ethanol clean described Nano composite granules and be scattered in ethanol or water in, by centrifugal treating obtain through cleaning SiO
2the Nano composite granules of coated described quantum dot is also dissolved in after propyl carbinol, and the hydrothermal reaction kettle of putting into inner-wall material and be tetrafluoroethylene carries out anneal; The condition of described anneal is: under agitation condition, oil bath, oil bath temperature be that 50-90 ℃, soaking time are 0.5-2 hour, are down to room temperature with water-cooling pattern; The solution that completes described anneal is carried out to centrifugal treating, obtain the described SiO through described anneal
2the Nano composite granules of coated described quantum dot;
Step 5, the described Nano composite granules obtaining with ethanol cleaning step four are also scattered in ethanol, obtain containing the described SiO through described anneal
2the ethanolic soln of the Nano composite granules of coated described quantum dot;
Step 6, the described ethanolic soln that step 5 is obtained are placed under ultraviolet lamp and carry out ultraviolet lighting processing, and the ultraviolet lighting time is not less than 6 hours, obtain containing the described SiO through described ultraviolet lighting processing and described anneal
2the ethanolic soln of the Nano composite granules of coated described quantum dot;
Described quantum dot is CdS, HgS, CdSe, CdTe, ZnSe, HgSe, ZnTe, PbSe, HgTe, CaAs, InP, InCaAs, CdSe/ZnS, CdSe/ZnSe, CdS/ZnS, Cd/Ag
2s, CdS/Cd (OH)
2, any one or multiple combination in CdTe/ZnS, CdTe/CdS, CdSe/ZnSe, CdS/HgS, CdS/HgS/CdS, ZnS/CdS, ZnS/CdS/ZnS, ZnS/HgS/ZnS/CdS, CdSe/CuSe, CdSeTe, CdSeTe/CdS/ZnS, Mn:CdS, Cu:CdS, Cu:ZnS, Mn:ZnS, Mn:ZnSe, Cu:ZnSe, Tb:CdS or Tb:ZnS.
2. SiO as claimed in claim 1
2the preparation method of the nano combined luminescent material of coated quantum dots, the size of wherein said quantum dot is in the scope of 1-10nm.
3. SiO as claimed in claim 1
2the preparation method of the nano combined luminescent material of coated quantum dots, described organic reagent and hexanaphthene in wherein said step 1 dissolve each other, described organic reagent is hydrophobic, and described organic reagent is any one reagent in normal hexane, toluene, dimethylbenzene, parachlorotoluene, methylene dichloride, trichloromethane, tetrachloromethane and sherwood oil reagent or the mixture of plurality of reagents arbitrarily.
4. SiO as claimed in claim 1
2the preparation method of the nano combined luminescent material of coated quantum dots, the described tensio-active agent in wherein said step 2 is any one tensio-active agent in tensio-active agent NP5, NP9 and Triton X-I00 or the mixture of kinds of surface promoting agent arbitrarily.
5. SiO as claimed in claim 1
2the preparation method of the nano combined luminescent material of coated quantum dots, the described catalyzer in wherein said step 2 is any one catalyzer in catalyzer methylamine, ammoniacal liquor and dimethylamine or the mixture of multiple catalysts arbitrarily.
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| CN103805173A (en) * | 2014-02-18 | 2014-05-21 | 东南大学 | Gram-scale preparation of core-shell structure quantum dot and method for coating silicon dioxide on surface of core-shell structure quantum dot |
| CN107474821A (en) * | 2016-06-07 | 2017-12-15 | 上海交通大学 | A kind of Silica-coated quantum dot and preparation method thereof |
| CN106318374B (en) * | 2016-08-17 | 2019-03-05 | 安徽大学 | A kind of preparation method of multi layered quantum dots core-silica shell composite structure and its application in the led |
| CN107219574A (en) * | 2017-05-25 | 2017-09-29 | 深圳市华星光电技术有限公司 | Quantum-dot structure, guide-lighting solution and preparation method, light guide structure and backlight module |
| CN112694886A (en) * | 2020-12-29 | 2021-04-23 | 武双 | Oil-soluble tracer for environmental monitoring and preparation method thereof |
| CN113061437B (en) * | 2021-03-04 | 2023-03-31 | 苏州星烁纳米科技有限公司 | Cadmium-free quantum dot with core-shell structure and preparation method thereof, water-soluble quantum dot and fluorescence labeling reagent |
| CN114275805A (en) * | 2021-12-30 | 2022-04-05 | 杭州电子科技大学 | Wrapping SiO outside ZnO2Method for synthesizing composite nano-particles |
| CN116534807A (en) * | 2023-05-05 | 2023-08-04 | 济南德亨医学科技有限公司 | Modification method of CdSe nano particles and obtained product |
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