CN102816564A - 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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- CN102816564A CN102816564A CN2012103136428A CN201210313642A CN102816564A CN 102816564 A CN102816564 A CN 102816564A CN 2012103136428 A CN2012103136428 A CN 2012103136428A CN 201210313642 A CN201210313642 A CN 201210313642A CN 102816564 A CN102816564 A CN 102816564A
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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 is the nano material of accurate zero dimension (quasi-zero-dimensional) QD) to quantum dot, is made up of a spot of atom.Usually quantum dot is by the elementary composition nano particle of II-VI family or III-V family; Size less than or near 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, so it can emitting fluorescence after being excited.
Because its distinctive photoelectric property, quantum dot has important use at biological multi-color marking and photoelectric device field.In order to obtain the quantum dot of high monochromaticity and high fluorescence efficiency, common method is through hot injection method synthetic oil dissolubility quantum dot in organic solution.1), the surface of possess hydrophilic property yet quantum dot will be applied to biological field, need satisfy following condition:; 2), has suitable surface functional group; 3) (toxicity is mainly by surface ligand and Cd, not have bio-toxicity
2+Release etc. heavy metal ion causes).
In order to address the above problem, method commonly used at present is for to transfer the oil soluble quantum dot to water-soluble quantum dot through ligand exchange, and the still this phase transition behavior that transfers water-soluble quantum dot to from the oil soluble quantum dot can be accompanied by the significantly decay of fluorescence efficiency usually.In addition, though this method has solved quantum dot in aqueous phase dissolved problem, still do not solve that it possibly have because heavy metal ion discharges the problem of the bio-toxicity that is caused.
In recent years, the surperficial coated Si O that has bibliographical information to pass through at the oil soluble quantum dot
2Shell (surface of its possess hydrophilic property) forms nano combined light-emitting particles, this SiO
2The nano combined luminescent material of coated quantum dots is with the surface of possess hydrophilic property.Document proof SiO is arranged simultaneously
2Shell can significantly reduce the effusion of heavy metal ion, reduces bio-toxicity.But, pass through SiO at present
2The quantum dot that coats, its fluorescence efficiency all can have reduction largely.Therefore, how to keep SiO
2The fluorescence efficiency of the nano combined luminescent material of coated quantum dots has great importance to its application in fields such as biological and opto-electronic conversion.
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 is with the SiO of preparation high fluorescence efficiency
2The nano combined luminescent material of coated quantum dots.
Summary of the invention
Because the above-mentioned defective of prior art, technical problem to be solved by this invention provides a kind of SiO
2The preparation method of the nano combined luminescent material of coated quantum dots is reflected at surface growth one deck SiO of oil soluble quantum dot through conversed phase micro emulsion copolymerization
2Shell carries out aftertreatment then with further raising SiO
2The fluorescence efficiency of the nano combined luminescent material of coated quantum dots.
For realizing above-mentioned purpose, 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 hexanaphthene, perhaps earlier said quantum dot is dissolved in the organic reagent earlier, and then is dissolved in the hexanaphthene;
Step 2, in the solution that step 1 obtains, add TEOS, tensio-active agent and catalyzer to carry out catalytic conversed phase micro emulsion copolymerization reaction;
Step 3, after the time (T1) has been carried out in said reaction, in the solution that carries out said reaction, drip acetone to stop said reaction, the solution that has stopped said reaction is carried out centrifugal treating, obtain SiO
2Coat the Nano composite granules of said quantum dot;
Step 4, clean said Nano composite granules and it is scattered in ethanol or the water, obtain SiO through cleaning through centrifugal treating with ethanol
2After coating the Nano composite granules of said quantum dot and it being dissolved in propyl carbinol, the hydrothermal reaction kettle of putting into inner-wall material and be tetrafluoroethylene carries out anneal; The condition of said anneal is: under the agitation condition, oil bath, oil bath temperature (T), soaking time (T2), reduce to room temperature with water-cooling pattern; Solution to accomplishing said anneal carries out centrifugal treating, obtains the said SiO through said anneal
2Coat the Nano composite granules of said quantum dot;
Step 5, the said Nano composite granules that obtains with ethanol cleaning step four also are scattered in it in ethanol, obtain containing the said SiO through said anneal
2Coat the ethanolic soln of the Nano composite granules of said quantum dot;
Step 6, the said ethanolic soln that step 5 is obtained place and carry out ultraviolet lighting under the uv lamp and handle, and the ultraviolet lighting time (T3), obtain containing through said ultraviolet lighting and handle and the said SiO of said anneal
2Coat the ethanolic soln of the Nano composite granules of said quantum dot.
Further, said 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 among 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 the Tb:ZnS.
Further, the size of said quantum dot is in the scope of 1-10nm.
Further; Said organic reagent in the said step 1 is hydrophobic, and said organic reagent is any one reagent or the mix reagent of any two kinds and above reagent in normal hexane, toluene, YLENE, 4-Chlorotoluene 99.5, methylene dichloride, trichloromethane, tetrachloromethane and the sherwood oil reagent.
Further, the said tensio-active agent in the said step 2 is any one or any two kinds and the above combination among tensio-active agent NP5, NP9 and the TritonX-100.
Further, the said catalyzer in the said step 2 is any one or any two kinds and the above combination in catalyzer methylamine, ammoniacal liquor and the n n dimetylaniline.
Further, the said time T in the said step 31 is 20-80 hour.
Further, the said oil bath temperature T in the said step 4 is 50-90 ℃, and said soaking time T2 is 0.5-2 hour.
Further, the said time T 3 in the said step 6 is not less than 6 hours.。
In preferred embodiments of the present invention, respectively quantum dot CdSe/CdS/ZnS, CdSeS/CdS, Cu:CdS/ZnS, Mn:ZnSe, CdTe/ZnS and CdSe are reflected at the surface growth SiO of quantum dot through conversed phase micro emulsion copolymerization
2Shell also carries out aftertreatment, and aftertreatment comprises anneal and ultraviolet lighting processing.Wherein be reflected at quantum dot surface growth SiO through conversed phase micro emulsion copolymerization
2The step of shell is: quantum dot is dissolved in hexanaphthene, perhaps quantum dot is dissolved in the organic reagent earlier, and then be dissolved in the hexanaphthene; In solution, add TEOS, tensio-active agent and catalyzer and carry out the conversed phase micro emulsion copolymerization reaction; (behind 20h≤T1≤80h), in solution, drip acetone with termination reaction, centrifugal treating obtains SiO to have carried out time T 1 in reaction
2Coat the Nano composite granules of this quantum dot; Clean these Nano composite granules and it is scattered in ethanol or the water SiO of centrifugal treating acquisition with ethanol through cleaning
2Coat the Nano composite granules of this quantum dot.Anneal among the present invention is carried out in hydrothermal reaction kettle, comprises step: with SiO
2After the Nano composite granules that coats this quantum dot is dissolved in propyl carbinol; Put into the hydrothermal reaction kettle that inner-wall material is a tetrafluoroethylene, the condition of processing is: under the agitation condition, oil bath, oil bath temperature T (50 ℃≤T≤90 ℃), soaking time T2 (0.5h≤T1≤2h), reduce to room temperature with water-cooling pattern; This solution of centrifugal treating obtains the SiO of annealed processing
2Coat the Nano composite granules of this quantum dot; Be scattered in the ethanol with ethanol these Nano composite granules of cleaning and with it, obtain containing the SiO of annealed processing
2Coat the ethanolic soln of the Nano composite granules of this quantum dot.Ultraviolet lighting processed steps among the present invention is: this ethanolic soln is placed irradiation under the uv lamp, ultraviolet lighting time T 3 (T3>=6h), obtain containing the SiO through ultraviolet lighting processing and anneal
2Coat the ethanolic soln of the Nano composite granules of this quantum dot.
This shows SiO of the present invention
2The preparation method of the nano combined luminescent material of coated quantum dots is reflected at the surface growth SiO of quantum dot through 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
2The quantum dot that coats can be the quantum dot of single kind, also can be the combination of different types of quantum dot.To the various SiO that prepare
2The test shows of the fluorescence efficiency of the nano combined luminescent material of coated quantum dots is through the SiO that comprises the aftertreatment that anneal and ultraviolet lighting are handled 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 for preparing of the present invention
2The nano combined luminescent material of coated quantum dots can satisfy simultaneously possess hydrophilic property the surface, have suitable surface functional group and do not have these three requirements of bio-toxicity; And has a higher fluorescence efficiency; Therefore can be used for preparing photoelectric devices such as high performance LED, can also be used for biological multi-color marking field.
Embodiment
Embodiment 1
Step 1, quantum dot CdSe/CdS/ZnS is dissolved in the hexanaphthene.Wherein, quantum dot CdSe/CdS/ZnS is the quantum dot of the three-layer nuclear shell structure of CdSe/CdS/ZnS, and its fluorescence efficiency is 68%.Quantum dot CdSe/CdS/ZnS is dissolved in the solution that obtains 10mL, 1mM in the hexanaphthene.
Step 2, in the solution that step 1 obtains, add TEOS (positive tetraethyl orthosilicate), tensio-active agent and catalyzer to carry out catalytic conversed phase micro emulsion copolymerization reaction.In the present embodiment, the concrete steps of carrying out catalytic conversed phase micro emulsion copolymerization reaction are:
Under agitation condition, add TEOS, add tensio-active agent then and form microemulsion.Wherein, TEOS takes 0.1mL, stirs 10min; Tensio-active agent is taken NP5, and consumption 1mL stirs 30min.Under agitation condition, adding catalyzer reacts with the catalysis conversed phase micro emulsion copolymerization.Wherein, catalyzer is selected methylamine for use, and consumption 0.1mL continues to stir under the lucifuge condition.
Step 3, after time T 1 has been carried out in the reaction of the conversed phase micro emulsion copolymerization of step 2, in the solution that carries out this reaction, drip acetone with termination reaction, the solution that has stopped reaction is carried out centrifugal treating, obtain SiO
2The Nano composite granules of coated quantum dots CdSe/CdS/ZnS.Wherein, time T 1 is set at 24h.
Step 4, the Nano composite granules that obtains with ethanol cleaning step three also are scattered in it in ethanol, obtain the SiO through cleaning through 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 dot CdSe/CdS/ZnS, and its fluorescence efficiency is 26%.
With above-mentioned SiO
2After the Nano composite granules of coated quantum dots CdSe/CdS/ZnS is dissolved in 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 the agitation condition, oil bath, oil bath temperature T, soaking time T2, reduce to room temperature with water-cooling pattern.Adopt induction stirring in the present embodiment, oil bath temperature T is set at 70 ℃, and soaking time T2 is set at 1h.
The solution of accomplishing after the above-mentioned anneal is reduced to room temperature and is carried 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 that obtains with ethanol cleaning step four also are scattered in it in ethanol, obtain containing the SiO of 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 place and carry out ultraviolet lighting under the uv lamp and handle, and ultraviolet lighting time T 3 obtains containing through ultraviolet lighting and handles and the SiO of anneal
2The ethanolic soln of the Nano composite granules of coated quantum dots CdSe/CdS/ZnS.Wherein, adopt portable uv lamp, power is 8W, and its ultraviolet wavelength that sends is 365nm; Time T 3 is set at 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 dot CdSeS/CdS is dissolved in the hexanaphthene.Wherein, quantum dot is the quantum dot of the two-layer nucleocapsid structure of CdSeS/CdS, and its fluorescence efficiency is 54%.Quantum dot CdSeS/CdS is dissolved in the solution that obtains 10mL, 1mM in the hexanaphthene.
Step 2, in the solution that step 1 obtains, add TEOS, tensio-active agent and catalyzer to carry out catalytic conversed phase micro emulsion copolymerization reaction.In the present embodiment, the concrete steps of carrying out catalytic conversed phase micro emulsion copolymerization reaction are:
Under agitation condition, add TEOS, add tensio-active agent then and form microemulsion.Wherein, TEOS takes 0.1mL, stirs 10min; Tensio-active agent is taken NP5, and consumption 1mL stirs 30min.Then under agitation condition, adding catalyzer reacts with the catalysis conversed phase micro emulsion copolymerization.Wherein, catalyzer is selected methylamine for use, and consumption 0.1mL continues to stir under the lucifuge condition.
Step 3, after time T 1 has been carried out in the reaction of the conversed phase micro emulsion copolymerization of step 2, in the solution that carries out this reaction, drip acetone with termination reaction, the solution that has stopped reaction is carried out centrifugal treating, obtain SiO
2The Nano composite granules of coated quantum dots CdSeS/CdS.Wherein, time T 1 is set at 24h.
Step 4, the Nano composite granules that obtains with ethanol cleaning step three also are scattered in it in ethanol, obtain the SiO through cleaning through 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.
With above-mentioned SiO
2After the Nano composite granules of coated quantum dots CdSeS/CdS is dissolved in 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 the agitation condition, oil bath, oil bath temperature T, soaking time T2, reduce to room temperature with water-cooling pattern.Adopt induction stirring in the present embodiment, oil bath temperature T is set at 50 ℃, and soaking time T2 is set at 1h.
The solution of accomplishing after the above-mentioned anneal is reduced to room temperature and is carried 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 that obtains with ethanol cleaning step four also are scattered in it in ethanol, obtain containing the SiO of 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 place and carry out ultraviolet lighting under the uv lamp and handle, and ultraviolet lighting time T 3 obtains containing through ultraviolet lighting and handles and the SiO of anneal
2The ethanolic soln of the Nano composite granules of coated quantum dots CdSeS/CdS.Wherein, adopt portable uv lamp, power is 16W, and its ultraviolet wavelength that sends is 365nm; Time T 3 is set at 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 dissolved in earlier in the organic reagent, is dissolved in the hexanaphthene then.Wherein, quantum dot is that Cu:CdS/ZnS is the quantum dot of the two-layer nucleocapsid structure of the adulterated CdS/ZnS of Cu, and its fluorescence efficiency is 42.6%; Organic reagent is selected normal hexane for use, hexanaphthene consumption 9mL.Quantum dot Cu:CdS/ZnS is dissolved in the solution that obtains 10mL, 1mM in the normal hexane, and this solution is mixed with hexanaphthene.
Step 2, in the solution that step 1 obtains, add TEOS, tensio-active agent and catalyzer to carry out catalytic conversed phase micro emulsion copolymerization reaction.In the present embodiment, the concrete steps of carrying out catalytic conversed phase micro emulsion copolymerization reaction are:
Under agitation condition, add tensio-active agent, add TEOS then and form microemulsion.Wherein, tensio-active agent is taken NP9, and consumption 1mL stirs 30min; TEOS takes 0.1mL, stirs 30min.Then under agitation condition, adding catalyzer reacts with the catalysis conversed phase micro emulsion copolymerization.Wherein, catalyzer is selected n n dimetylaniline for use, and consumption 0.05mL continues to stir under the lucifuge condition.
Step 3, after time T 1 has been carried out in the reaction of the conversed phase micro emulsion copolymerization of step 2, in the solution that carries out this reaction, drip acetone with termination reaction, the solution that has stopped reaction is carried out centrifugal treating, obtain SiO
2The Nano composite granules of coated quantum dots Cu:CdS/ZnS.Wherein, time T 1 is set at 30h.
Step 4, the Nano composite granules that obtains with ethanol cleaning step three also are scattered in it in ethanol, obtain the SiO through cleaning through 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.
With above-mentioned SiO
2After the Nano composite granules of coated quantum dots Cu:CdS/ZnS is dissolved in 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 the agitation condition, oil bath, oil bath temperature T, soaking time T2, reduce to room temperature with water-cooling pattern.Adopt induction stirring in the present embodiment, oil bath temperature T is set at 80 ℃, and soaking time T2 is set at 1h.
The solution of accomplishing after the above-mentioned anneal is reduced to room temperature and is carried 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 that obtains with ethanol cleaning step four also are scattered in it in ethanol, obtain containing the SiO of 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 place and carry out ultraviolet lighting under the uv lamp and handle, and ultraviolet lighting time T 3 obtains containing through ultraviolet lighting and handles and the SiO of anneal
2The ethanolic soln of the Nano composite granules of coated quantum dots Cu:CdS/ZnS.Wherein, adopt portable uv lamp, power is 5W, and its ultraviolet wavelength that sends is 365nm; Time T 3 is set at 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 dissolved in earlier in the organic reagent, is dissolved in the hexanaphthene then.Wherein, quantum dot is that Mn:ZnSe is the quantum dot of the adulterated ZnSe of Mn, and its fluorescence efficiency is 32.1%; Organic reagent is selected trichloromethane for use, hexanaphthene consumption 9mL.Quantum dot Mn:ZnSe is dissolved in the solution that obtains 1mL, 10mM in the trichloromethane, and this solution is mixed with hexanaphthene.
Step 2, in the solution that step 1 obtains, add TEOS, tensio-active agent and catalyzer to carry out catalytic conversed phase micro emulsion copolymerization reaction.In the present embodiment, the concrete steps of carrying out catalytic conversed phase micro emulsion copolymerization reaction are:
Under agitation condition, add tensio-active agent, add TEOS then and form microemulsion.Wherein, tensio-active agent is taken NP9, and consumption 1mL stirs 30min; TEOS takes 0.1mL, stirs 30min.Then under agitation condition, adding catalyzer reacts with the catalysis conversed phase micro emulsion copolymerization.Wherein, catalyzer is selected ammoniacal liquor for use, and consumption 0.2mL continues to stir under the lucifuge condition.
Step 3, after time T 1 has been carried out in the reaction of the conversed phase micro emulsion copolymerization of step 2, in the solution that carries out this reaction, drip acetone with termination reaction, the solution that has stopped reaction is carried out centrifugal treating, obtain SiO
2The Nano composite granules of coated quantum dots Mn:ZnSe.Wherein, time T 1 is set at 30h.
Step 4, the Nano composite granules that obtains with ethanol cleaning step three also are scattered in it in ethanol, obtain the SiO through cleaning through 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.
With above-mentioned SiO
2After the Nano composite granules of coated quantum dots Mn:ZnSe is dissolved in 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 the agitation condition, oil bath, oil bath temperature T, soaking time T2, reduce to room temperature with water-cooling pattern.Adopt induction stirring in the present embodiment, oil bath temperature T is set at 60 ℃, and soaking time T2 is set at 1h.
The solution of accomplishing after the above-mentioned anneal is reduced to room temperature and is carried 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 that obtains with ethanol cleaning step four also are scattered in it in ethanol, obtain containing the SiO of 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 place and carry out ultraviolet lighting under the uv lamp and handle, and ultraviolet lighting time T 3 obtains containing through ultraviolet lighting and handles and the SiO of anneal
2The ethanolic soln of the Nano composite granules of coated quantum dots Mn:ZnSe.Wherein, adopt portable uv lamp, power is 6W, and its ultraviolet wavelength that sends is 365nm; Time T 3 is set at 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 dissolved in earlier in the organic reagent, is dissolved in the hexanaphthene then.Wherein, quantum dot is the quantum dot of the two-layer nucleocapsid structure of CdTe/ZnS, and its fluorescence efficiency is 69.3%; Organic reagent is selected toluene for use, hexanaphthene consumption 9mL.Quantum dot CdTe/ZnS is dissolved in the solution that obtains 1mL, 10mM in the toluene, and this solution is mixed with hexanaphthene.
Step 2, in the solution that step 1 obtains, add TEOS, tensio-active agent and catalyzer to carry out catalytic conversed phase micro emulsion copolymerization reaction.In the present embodiment, the concrete steps of carrying out catalytic conversed phase micro emulsion copolymerization reaction are:
Under agitation condition, add catalyzer, the catalyzer of selecting for use is a methylamine, and consumption 0.2mL continues to stir under the lucifuge condition.Under agitation condition, add tensio-active agent then, add TEOS then and form microemulsion.Wherein, tensio-active agent is taken NP5, and consumption 1mL stirs 30min; TEOS takes 0.1mL, stirs 30min.
Step 3, after time T 1 has been carried out in the reaction of the conversed phase micro emulsion copolymerization of step 2, in the solution that carries out this reaction, drip acetone with termination reaction, the solution that has stopped reaction is carried out centrifugal treating, obtain SiO
2The Nano composite granules of coated quantum dots CdTe/ZnS.Wherein, time T 1 is set at 48h.
Step 4, the Nano composite granules that obtains with ethanol cleaning step three also are scattered in it in ethanol, obtain the SiO through cleaning through 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.
With above-mentioned SiO
2After the Nano composite granules of coated quantum dots CdTe/ZnS is dissolved in 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 the agitation condition, oil bath, oil bath temperature T, soaking time T2, reduce to room temperature with water-cooling pattern.Adopt induction stirring in the present embodiment, oil bath temperature T is set at 90 ℃, and soaking time T2 is set at 1h.
The solution of accomplishing after the above-mentioned anneal is reduced to room temperature and is carried 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 that obtains with ethanol cleaning step four also are scattered in it in ethanol, obtain containing the SiO of 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 place and carry out ultraviolet lighting under the uv lamp and handle, and ultraviolet lighting time T 3 obtains containing through ultraviolet lighting and handles and the SiO of anneal
2The ethanolic soln of the Nano composite granules of coated quantum dots CdTe/ZnS.Wherein, adopt portable uv lamp, power is 5W, and its ultraviolet wavelength that sends is 365nm; Time T 3 is set at 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 dot CdSe is dissolved in the hexanaphthene.Wherein, quantum dot is the CdSe quantum dot, and its fluorescence efficiency is 39%; Hexanaphthene consumption 6.5mL.Quantum dot CdSe is dissolved in the solution that obtains 10mL, 1mM in the hexanaphthene.
Step 2, in the solution that step 1 obtains, add TEOS, tensio-active agent and catalyzer to carry out catalytic conversed phase micro emulsion copolymerization reaction.In the present embodiment, the concrete steps of carrying out catalytic conversed phase micro emulsion copolymerization reaction are:
Under agitation condition, add catalyzer, the catalyzer of selecting for use is a n n dimetylaniline, and consumption 0.05mL continues to stir under the lucifuge condition.Under agitation condition, add tensio-active agent then, add TEOS then and 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, after time T 1 has been carried out in the reaction of the conversed phase micro emulsion copolymerization of step 2, in the solution that carries out this reaction, drip acetone with termination reaction, the solution that has stopped reaction is carried out centrifugal treating, obtain SiO
2The Nano composite granules of coated quantum dots CdSe.Wherein, time T 1 is set at 48h.
Step 4, the Nano composite granules that obtains with ethanol cleaning step three also are scattered in it in ethanol, obtain the SiO through cleaning through 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.
With above-mentioned SiO
2After the Nano composite granules of coated quantum dots CdSe is dissolved in 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 the agitation condition, oil bath, oil bath temperature T, soaking time T2, reduce to room temperature with water-cooling pattern.Adopt induction stirring in the present embodiment, the temperature T of oil bath is set at 90 ℃, and time T 2 is set at 1h.
The solution of accomplishing after the above-mentioned anneal is reduced to room temperature and is carried 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 that obtains with ethanol cleaning step four also are scattered in it in ethanol, obtain containing the SiO of 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 place and carry out ultraviolet lighting under the uv lamp and handle, and ultraviolet lighting time T 3 obtains containing through ultraviolet lighting and handles and the SiO of anneal
2The ethanolic soln of the Nano composite granules of coated quantum dots CdSe.Wherein, adopt portable uv lamp, power is 15W, and its ultraviolet wavelength that sends is 365nm; Time T 3 is set at 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%.
Need to prove SiO of the present invention
2The kind of the quantum dot that the quantum dot that the preparation method of the nano combined luminescent material of coated quantum dots is suitable for is not limited to provide in the embodiments herein; 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, among 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 the Tb:ZnS any one, also can be 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 obtaining 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 need not creative work and just can design according to the present invention make many modifications and variation.Therefore, the technician in all present technique field all should be in the determined protection domain by claims under this invention's idea on the basis of existing technology through the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (9)
1. 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 hexanaphthene, perhaps earlier said quantum dot is dissolved in the organic reagent, and then is dissolved in the hexanaphthene;
Step 2, in the solution that step 1 obtains, add TEOS, tensio-active agent and catalyzer to carry out catalytic conversed phase micro emulsion copolymerization reaction;
Step 3, after the time (T1) has been carried out in said reaction, in the solution that carries out said reaction, drip acetone to stop said reaction, the solution that has stopped said reaction is carried out centrifugal treating, obtain SiO
2Coat the Nano composite granules of said quantum dot;
Step 4, clean said Nano composite granules and it is scattered in ethanol or the water, obtain SiO through cleaning through centrifugal treating with ethanol
2After coating the Nano composite granules of said quantum dot and it being dissolved in propyl carbinol, the hydrothermal reaction kettle of putting into inner-wall material and be tetrafluoroethylene carries out anneal; The condition of said anneal is: under the agitation condition, oil bath, oil bath temperature (T) and soaking time (T2), reduce to room temperature with water-cooling pattern; Solution to accomplishing said anneal carries out centrifugal treating, obtains the said SiO through said anneal
2Coat the Nano composite granules of said quantum dot;
Step 5, the said Nano composite granules that obtains with ethanol cleaning step four also are scattered in it in ethanol, obtain containing the said SiO through said anneal
2Coat the ethanolic soln of the Nano composite granules of said quantum dot;
Step 6, the said ethanolic soln that step 5 is obtained place and carry out ultraviolet lighting under the uv lamp and handle, and the ultraviolet lighting time (T3), obtain containing through said ultraviolet lighting and handle and the said SiO of said anneal
2Coat the ethanolic soln of the Nano composite granules of said quantum dot.
2. SiO as claimed in claim 1
2The preparation method of the nano combined luminescent material of coated quantum dots; Wherein said quantum dot is 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 or multiple combination among 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 the Tb:ZnS.
3. 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.
4. SiO as claimed in claim 1
2The preparation method of the nano combined luminescent material of coated quantum dots; Said organic reagent and hexanaphthene in the wherein said step 1 dissolve each other; Said organic reagent is hydrophobic, and said organic reagent is any one reagent or any mixture of plurality of reagents in normal hexane, toluene, YLENE, 4-Chlorotoluene 99.5, methylene dichloride, trichloromethane, tetrachloromethane and the sherwood oil reagent.
5. SiO as claimed in claim 1
2The preparation method of the nano combined luminescent material of coated quantum dots, the said tensio-active agent in the wherein said step 2 is any one tensio-active agent or any mixture of kinds of surface promoting agent among tensio-active agent NP5, NP9 and the Triton X-100.
6. SiO as claimed in claim 1
2The preparation method of the nano combined luminescent material of coated quantum dots, the said catalyzer in the wherein said step 2 is any one catalyzer or any multiple mixture of catalysts in catalyzer methylamine, ammoniacal liquor and the n n dimetylaniline.
7. SiO as claimed in claim 1
2The preparation method of the nano combined luminescent material of coated quantum dots, the said time (T1) in the wherein said step 3 is 20-80 hour.
8. SiO as claimed in claim 1
2The preparation method of the nano combined luminescent material of coated quantum dots, the said oil bath temperature (T) in the wherein said step 4 is 50-90 ℃, said soaking time (T2) is 0.5-2 hour.
9. SiO as claimed in claim 1
2The preparation method of the nano combined luminescent material of coated quantum dots, the said time (T3) in the wherein said step 6 is not less than 6 hours.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106318374A (en) * | 2016-08-17 | 2017-01-11 | 安徽大学 | Method for preparing multi-quantum-dot core-silicon dioxide shell composite structure and application of structure to 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 |
| 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 |
| CN112694886A (en) * | 2020-12-29 | 2021-04-23 | 武双 | Oil-soluble tracer for environmental monitoring and preparation method thereof |
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| 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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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101565621A (en) * | 2009-06-04 | 2009-10-28 | 同济大学 | High fluorescence property nanometer composite microsphere and the production method thereof |
| US20110269297A1 (en) * | 2008-08-21 | 2011-11-03 | Federalnoe Gosudarstvennoe Unitarnoe Predpriatie "Nauchno-Issledovatelskiy | Method for synthesising semiconductor quantum dots |
-
2012
- 2012-08-29 CN CN201210313642.8A patent/CN102816564B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110269297A1 (en) * | 2008-08-21 | 2011-11-03 | Federalnoe Gosudarstvennoe Unitarnoe Predpriatie "Nauchno-Issledovatelskiy | Method for synthesising semiconductor quantum dots |
| CN101565621A (en) * | 2009-06-04 | 2009-10-28 | 同济大学 | High fluorescence property nanometer composite microsphere and the production method thereof |
Non-Patent Citations (3)
| Title |
|---|
| ROLF KOOLE等: "On the Incorporation Mechanism of Hydrophobic Quantum Dots in Silica Spheres by a Reverse Microemulsion Method", 《CHEM. MATER.》 * |
| TIMOTHY V. DUNCAN等: "Improving the Quantum Yields of Semiconductor Quantum Dots through Photoenhancement Assisted by Reducing Agents", 《J. PHYS. CHEM. C》 * |
| XINGPING ZHOU等: "Luminescence Stability of the Silica Encapsulated CdSe Quantum Dots", 《CURRENT NANOSCIENCE》 * |
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