CN102816563B - Preparation method and application of adjustable-refractivity silicon dioxide coated quantum dot nano composite luminescent material - Google Patents

Preparation method and application of adjustable-refractivity silicon dioxide coated quantum dot nano composite luminescent material Download PDF

Info

Publication number
CN102816563B
CN102816563B CN201210313357.6A CN201210313357A CN102816563B CN 102816563 B CN102816563 B CN 102816563B CN 201210313357 A CN201210313357 A CN 201210313357A CN 102816563 B CN102816563 B CN 102816563B
Authority
CN
China
Prior art keywords
sio
cds
zns
quantum dots
nano
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201210313357.6A
Other languages
Chinese (zh)
Other versions
CN102816563A (en
Inventor
李万万
孙康
赵冰夏
王解兵
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Jiaotong University
Original Assignee
Shanghai Jiaotong University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Jiaotong University filed Critical Shanghai Jiaotong University
Priority to CN201210313357.6A priority Critical patent/CN102816563B/en
Publication of CN102816563A publication Critical patent/CN102816563A/en
Application granted granted Critical
Publication of CN102816563B publication Critical patent/CN102816563B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Luminescent Compositions (AREA)

Abstract

The invention discloses an adjustable-refractivity silicon dioxide coated quantum dot nano composite luminescent material which is composed of SiO2 nanoparticles, wherein each SiO2 particle is a nano composite particle formed by coating SiO2 on a single quantum dot or a nano composite particle formed by coating SiO2 on multiple evenly-dispersed quantum dots. The invention also discloses a method for preparing the nano composite particles (each of which is formed by coating SiO2 on a single quantum dot or coating SiO2 on multiple quantum dots) by inverse microemulsion polymerization reaction. In practical use, the technological parameters, such as consumptions of TEOS (tetraethyl orthosilicate), surfactant, catalyst and quantum dots, reaction time and the like, can be adjusted to adjust the thickness of the SiO2 shell and the proportion of the quantum dot core in the SiO2 coated quantum dot nano composite particles, thereby adjusting the refractivity of the SiO2 coated quantum dot nano composite material. The refractivity of the nano composite luminescent material is adjustable within the range of 1.42-1.98.

Description

The method for making of the nano combined luminescent material of the silicon dioxide-coated quantum dots that a kind of specific refractory power is adjustable and purposes
Technical field
The present invention relates to the preparation method of nano combined luminescent material, relate in particular to the preparation method of the nano combined luminescent material of the adjustable silicon dioxide-coated quantum dots of a kind of specific refractory power.
Background technology
LED is green, environmental protection light source of new generation, the various coloured light LED of widespread use at present send corresponding coloured light with blue-ray LED excitated fluorescent powder, for example white light LEDs is to excite gold-tinted YAG fluorescent material and send white light with blue-ray LED, therefore in the process of packaged LED, fluorescent material and packaged material need to be mixed to form to mixture.But because fluorescent powder grain is larger, in the time of encapsulation, be easy to precipitate, cause fluorescent material skewness in packaged material.Meanwhile, because the specific refractory power difference of fluorescent material and packaged material is larger, on its surface in contact, can form very strong light scattering effect.In addition, fluorescent material is all attached to the surface of LED luminescent wafer conventionally, and the heat that LED when work produces easily causes the junction temperature of fluorescent material, has caused power loss larger.These are all the problems that need to solve while manufacturing various coloured light LED.
A kind of feasible solution is that fluorescent material is distributed to and in outer field packaged material, forms transparent matrix material, but due to traditional fluorescent material particle diameter large (being generally micron order), after mixing with packaged material, very easily reuniting and cause matrix material opaque.
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-Vl 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 the particle diameter little (< 10nm) of quantum dot, its scattering is also less.Although they are still different from the specific refractory power of packaged material, it is feasible obtaining matrix material by certain methods.Meanwhile, the emission wavelength of quantum dot can change with the variation of its size, by selecting the quantum dot of different sorts and different size, can make the luminous covering visible light region of matrix material and adjustable.
Matrix material specific refractory power can be passed through formula
Figure BDA00002072093900011
calculate wherein n compositefor the specific refractory power of matrix material, n iand V irespectively specific refractory power and the volume fraction (content) of the each component of matrix material.Visible, can realize the control to matrix material specific refractory power by the volume fraction that regulates each component.SiO 2be conventional inorganic transparent material, very ripe to its preparation and property research, its specific refractory power is 1.42.Like this, according to the formula of matrix material specific refractory power, by quantum dot (specific refractory power ≈ 2.4) and SiO 2its specific refractory power of the matrix material being mixed to form can be adjusted to identical with the specific refractory power of packaged material, thereby forms the matrix material of whole clearing.
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 adjustable SiO of specific refractory power 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 the adjustable SiO of a kind of specific refractory power 2the nano combined luminescent material of coated quantum dots, reacts preparation SiO by conversed phase micro emulsion copolymerization 2nano composite granules and/or the SiO of coated single quantum dot 2the Nano composite granules of the quantum dot of coated multiple uniformly dispersings has obtained the adjustable SiO of specific refractory power 2the nano combined luminescent material of coated quantum dots, and provide SiO adjustable this specific refractory power 2the nano combined luminescent material of coated quantum dots is applied to the method for photoelectric device.
For achieving the above object, the invention provides the adjustable SiO of a kind of specific refractory power 2the nano combined luminescent material of coated quantum dots, is characterized in that, by SiO 2nano particle composition, described SiO 2particle is SiO 2nano composite granules or the SiO of coated single quantum dot 2the Nano composite granules of the quantum dot of coated multiple uniformly dispersings.
Alternatively, 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, 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, Mn:CdS/ZnS, Cu:CdS, Cu:CdS/ZnS, Cu:ZnS, Mn:ZnS, Mn:ZnSe/ZnS, Mn:ZnSe/ZnO, Cu:ZnSe, Cu:ZnSe/ZnS, Tb:CdS, any one in Tb:CdS/ZnS or Tb:ZnS, the size of described quantum dot is in the scope of 2-10nm.
Further, described SiO 2the Nano composite granules of coated single quantum dot sends monochromatic ray, and its specific refractory power is between 1.42-1.98.
Alternatively, 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, 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, Mn:CdS/ZnS, Cu:CdS, Cu:CdS/ZnS, Cu:ZnS, Mn:ZnS, Mn:ZnSe/ZnS, Mn:ZnSe/ZnO, Cu:ZnSe, Cu:ZnSe/ZnS, Tb:CdS, any multiple combination in Tb:CdS/ZnS or Tb:ZnS, the size of described quantum dot is in the scope of 2-10nm.
Further, described SiO 2the Nano composite granules of coated multiple quantum dots sends polychromatic light, and its specific refractory power is between 1.42-1.98.
Further, described SiO 2the preparation method of the Nano composite granules of coated single quantum dot comprises:
Step 1, described quantum dot is dissolved in to hexanaphthene, or 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 time T 1 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 described SiO 2the Nano composite granules of coated single quantum dot.
Further, described SiO 2the preparation method of the Nano composite granules of coated multiple quantum dots comprises:
Step 1, under agitation condition, in hexanaphthene, add TEOS, tensio-active agent and catalyzer to carry out the conversed phase micro emulsion copolymerization reaction of catalysis;
Step 2, carry out after time T 2 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 2nano particle;
Step 3, clean described SiO with ethanol 2after nano particle, be scattered in and in ethanol, obtained described SiO 2the ethanolic soln of Nano composite granules;
Step 4, in described ethanolic soln, under agitation condition, add silane coupling agent with to described SiO 2nano particle carries out finishing, after elapsed time T3, obtains the SiO through described finishing by centrifugal treating 2nano particle also carries out ethanol cleaning and oven dry to it;
Step 5, described quantum dot is dissolved in to hexanaphthene, or described quantum dot is first dissolved in organic reagent, and then be dissolved in hexanaphthene;
In step 6, the solution that obtains in step 5, under agitation condition, add tensio-active agent to form microemulsion;
Step 7, in described microemulsion, under agitation condition, add the SiO obtaining after completing steps four 2nano particle then adds successively TEOS and catalyzer to carry out the conversed phase micro emulsion copolymerization reaction of catalysis under agitation condition;
Step 8, carry out after time T 4 in the reaction described in step 7, 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 described SiO 2the Nano composite granules of coated multiple quantum dots.
Further, described organic reagent and hexanaphthene 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; Described tensio-active agent is any one tensio-active agent in tensio-active agent NP5, NP9 and Triton X-100 or the mixture of kinds of surface promoting agent arbitrarily; Described catalyzer is any one catalyzer in catalyzer methylamine, ammoniacal liquor and dimethylamine or the mixture of multiple catalysts arbitrarily, and described time T 1 is 20-80 hour.
Further, described time T 2 is 20-80 hour, and described time T 3 is 12-80 hour, and described time T 4 is 20-80 hour.
Further, the present invention also provides a kind of transparent composite for photoelectric device, it is characterized in that by described SiO 2the nano combined luminescent material of coated quantum dots and the composite formation of polymer packaged material, described composite comprising:
Step 1, described polymer packaged material and solidifying agent are mixed with turbine mixer, both are evenly dissolved each other and form the first mixture;
Step 2, in described the first mixture, add described SiO 2the solution of the nano combined luminescent material of coated quantum dots also uses turbine mixer that it is dispersed in described the first mixture to form the second mixture, and described solution is described SiO 2the ethanolic soln of the nano combined luminescent material of coated quantum dots;
Step 3, described the second mixture is placed in to vacuum drying oven to bubble completely dissolve wherein;
Step 4, will drop in the surface of described photoelectric device and heat-treat through the second mixture of step 3 processing;
Described photoelectric device is blue-ray LED or purple LED.
In preferred embodiments of the present invention, respectively Quantum dots CdS e/CdS/ZnS, Cu:CdS/ZnS and ZnSe are reacted to the surface growth SiO at quantum dot by conversed phase micro emulsion copolymerization 2shell, obtains SiO 2the Nano composite granules of coated single quantum dot, concrete steps are: 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.In other preferred embodiments of the present invention, respectively Quantum dots CdS eS/CdS, CdSeTe/CdS/ZnS, Mn:ZnSe and CdSeS/CdS/ZnS and CdSe/CdS/ZnS are reacted to the surface growth SiO at quantum dot by conversed phase micro emulsion copolymerization 2shell, obtains SiO 2the Nano composite granules of coated multiple quantum dots, concrete steps are: in hexanaphthene, add TEOS, tensio-active agent and catalyzer to carry out the conversed phase micro emulsion copolymerization reaction of catalysis; Carry out, after time T 2 (20h≤T2≤80h), in the solution reacting, dripping acetone with termination reaction in reaction, carried out centrifugal treating and obtain SiO 2nano particle; With ethanol cleaning SiO 2after nano particle, be scattered in ethanol, and under agitation condition, add silane coupling agent with to SiO 2nano particle carries out finishing, and after elapsed time T3 (12h≤T3≤80h), centrifugal treating obtains the SiO through finishing 2nano particle also carries out ethanol cleaning and oven dry to it; Quantum dot is dissolved in to hexanaphthene, or quantum dot is first dissolved in organic reagent, and then be dissolved in hexanaphthene; Under agitation condition, add tensio-active agent to form microemulsion, then under agitation condition, add the SiO through finishing 2nano particle then adds TEOS and catalyzer to carry out the conversed phase micro emulsion copolymerization reaction of catalysis under agitation condition; When reaction has been carried out, after time T 4 (20h≤T4≤80h), dripping acetone with termination reaction in the solution reacting, the solution that has stopped reaction is carried out to centrifugal treating, obtain SiO 2the Nano composite granules of coated multiple quantum dots.In an embodiment of the present invention, also by above-mentioned acquisition SiO 2the nano combined luminescent material of coated quantum dots and polymer packaged material are composite to be formed for as the transparent composite of the photoelectric device of LED.Concrete steps are: polymer packaged material and solidifying agent are mixed with turbine mixer, both are evenly dissolved each other and form the first mixture; In the first mixture, add SiO 2the solution of the nano combined luminescent material of coated quantum dots also uses turbine mixer that it is dispersed in the first mixture to form the second mixture; The second mixture is placed in to vacuum drying oven bubble completely dissolve extremely wherein; Treated the second mixture is dropped in to the surface of LED and heat-treats, finally just formed layer of transparent matrix material on the surface of LED.
As can be seen here, the present invention is reacted and has been prepared SiO by conversed phase micro emulsion copolymerization 2nano composite granules and the SiO of coated single quantum dot 2the Nano composite granules of the quantum dot of coated multiple uniformly dispersings.Owing to can, by regulating consumption and the reaction times of TEOS, tensio-active agent, catalyzer and quantum dot, regulating SiO in actual use 2siO in the Nano composite granules of coated quantum dots 2the ratio of shell thickness and quantum dot core, thus SiO can be regulated 2the specific refractory power of the nano composite material of coated quantum dots, the regulation range of specific refractory power is between 1.42-1.98.The present invention has also realized the adjustable SiO of preparation specific refractory power 2the nano combined luminescent material of coated quantum dots, and provide SiO adjustable this specific refractory power 2the nano combined luminescent material of coated quantum dots is applied to the method for photoelectric device.
Below with reference to accompanying drawing, the technique effect of design of the present invention, concrete structure and generation is described further, to understand fully object of the present invention, feature and effect.
Accompanying drawing explanation
Fig. 1 is the adjustable SiO of specific refractory power of the present invention 2the SiO of the nano combined luminescent material of coated quantum dots Cu:CdS/ZnS 2the transmission electron microscope photo of the Nano composite granules of coated single quantum dot Cu:CdS/ZnS.
Fig. 2 is the adjustable SiO of specific refractory power of the present invention 2the SiO of the nano combined luminescent material of coated quantum dots Mn:ZnSe 2the transmission electron microscope photo of the Nano composite granules of the multiple quantum dot Mn:ZnSe of covering amount
Embodiment
Embodiment 1
In the present embodiment, first prepare SiO 2the nano combined luminescent material of coated quantum dots CdSe/CdS/ZnS, it is by SiO 2the Nano composite granules composition of coated quantum dots CdSe/CdS/ZnS, wherein, each Nano composite granules is SiO 2the Nano composite granules of coated single Quantum dots CdS e/CdS/ZnS.Concrete steps are as follows:
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 emission wavelength is 520nm.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 also uses ethanol to clean this Nano composite granules.Wherein, time T 1 is set as 24h.The average particulate diameter that experiment measuring obtains this nano combined luminescent material is 31.2 ± 0.2nm, calculates formula according to matrix material specific refractory power
Figure BDA00002072093900061
calculating its specific refractory power is 1.421, matches with conventional packaged material specific refractory power.
Then by above-mentioned acquisition SiO 2the nano combined luminescent material of coated quantum dots CdSe/CdS/ZnS and polymer packaged material are composite to be formed for as the transparent composite of the photoelectric device of LED.Concrete steps are as follows:
Step 1, polymer packaged material and solidifying agent are mixed with turbine mixer, both are evenly dissolved each other and form the first mixture.In the present embodiment, polymer packaged material is selected bisphenol A type epoxy resin EP-400A, and solidifying agent is selected EP-400B, takes by weight both rear turbine mixers that use they are fully mixed, until they dissolve each other completely, forms the first mixture.
Step 2, in the first mixture, add SiO 2the nano combined luminescent material solution of coated quantum dots CdSe/CdS/ZnS also uses turbine mixer that it is dispersed in the first mixture to form the second mixture.Wherein, SiO 2the nano combined luminescent material solution of coated quantum dots CdSe/CdS/ZnS is SiO 2the ethanolic soln of the Nano composite granules of coated quantum dots CdSe/CdS/ZnS, the second mixture is SiO 2the colloid mixture that the Nano composite granules of coated quantum dots CdSe/CdS/ZnS and epoxy resin form.
Step 3, the second mixture is placed in to vacuum drying oven to bubble completely dissolve wherein.Wherein, the temperature of vacuum drying oven is 30 ℃, and the second mixture rests in vacuum drying oven.
Step 4, will drop in the surface of blue-ray LED and heat-treat through the second mixture of step 3 processing.Heat treated concrete steps are:
The blue-ray LED that surface is had to the second mixture is put into the baking oven of 40 ℃ and is incubated for some time (about 30-60min), oven temperature is elevated to 80 ℃ subsequently and is incubated for some time (about 30-60min) again.Like this, just formed layer of transparent matrix material on the surface of LED, this transparent composite reaches 70% to the transmitance of visible ray.As a comparison, do not wrap up SiO 2quantum dots CdS e/CdS/ZnS and epoxy resin form matrix material be 50% left and right to the transmitance of visible ray.
Embodiment 2
In the present embodiment, first prepare SiO 2the nano combined luminescent material of coated quantum dots Cu:CdS/ZnS, it is by SiO 2the Nano composite granules composition of coated quantum dots Cu:CdS/ZnS, wherein, each Nano composite granules is SiO 2the Nano composite granules of coated single Quantum dots CdS e/CdS/ZnS.Concrete steps are as follows:
Step 1, quantum dot Cu:CdS/ZnS is first dissolved in organic reagent, is then dissolved in hexanaphthene.Wherein, quantum dot Cu:CdS/ZnS is the quantum dot of the two-layer nucleocapsid structure of the CdS/ZnS of Cu doping, and its emission wavelength is 640nm; 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 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 (as shown in Figure 1) of coated quantum dots Cu:CdS/ZnS also uses ethanol to clean this Nano composite granules.Wherein, time T 1 is set as 24h.The average particulate diameter that experiment measuring obtains this nano combined luminescent material is 23.5 ± 0.4nm, calculates formula according to matrix material specific refractory power
Figure BDA00002072093900071
calculating its specific refractory power is 1.44, matches with conventional packaged material specific refractory power.
Then by above-mentioned acquisition SiO 2the nano combined luminescent material of coated quantum dots Cu:CdS/ZnS and polymer packaged material are composite to be formed for as the transparent composite of the photoelectric device of LED.Concrete steps are as follows:
Step 1, polymer packaged material and solidifying agent are mixed with turbine mixer, both are evenly dissolved each other and form the first mixture.In the present embodiment, polymer packaged material is selected silica gel, and solidifying agent is selected EP-400B, takes by weight both rear turbine mixers that use they are fully mixed, until they dissolve each other completely, forms the first mixture.
Step 2, in the first mixture, add SiO 2the nano combined luminescent material solution of coated quantum dots Cu:CdS/ZnS also uses turbine mixer that it is dispersed in the first mixture to form the second mixture.Wherein, SiO 2the nano combined luminescent material solution of coated quantum dots Cu:CdS/ZnS is SiO 2the ethanolic soln of the Nano composite granules of coated quantum dots Cu:CdS/ZnS, the second mixture is SiO 2the colloid mixture that the Nano composite granules of coated quantum dots Cu:CdS/ZnS and silica gel form.
Step 3, the second mixture is placed in to vacuum drying oven to bubble completely dissolve wherein.Wherein, the temperature of vacuum drying oven is 30 ℃, and the second mixture rests in vacuum drying oven.
Step 4, will drop in the surface of blue-ray LED and heat-treat through the second mixture of step 3 processing.Heat treated concrete steps are:
The blue-ray LED that surface is had to the second mixture is put into the baking oven of 40 ℃ and is incubated for some time (about 30-60min), oven temperature is elevated to 80 ℃ subsequently and is incubated for some time (about 30-60min) again.Like this, just formed layer of transparent matrix material on the surface of LED, this transparent composite reaches 60% to the transmitance of visible ray.
Embodiment 3
In the present embodiment, first prepare SiO 2the nano combined luminescent material of coated quantum dots ZnSe, it is by SiO 2the Nano composite granules composition of coated quantum dots ZnSe, wherein, each Nano composite granules is SiO 2the Nano composite granules of coated single quantum dot ZnSe.Concrete steps are as follows:
Step 1, quantum dot ZnSe is first dissolved in organic reagent, is then dissolved in hexanaphthene.Wherein, the emission wavelength of quantum ZnSe is 370nm; Organic reagent is selected toluene, hexanaphthene consumption 9mL.Quantum dot ZnSe 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 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 ZnSe also uses ethanol to clean this Nano composite granules.Wherein, time T 1 is set as 60h.The average particulate diameter that experiment measuring obtains this nano combined luminescent material is 26.3 ± 0.3nm, calculates formula according to matrix material specific refractory power
Figure BDA00002072093900081
calculating its specific refractory power is 1.43, matches with conventional packaged material specific refractory power.
Then by above-mentioned acquisition SiO 2the nano combined luminescent material of coated quantum dots ZnSe and polymer packaged material are composite to be formed for as the transparent composite of the photoelectric device of LED.Concrete steps are as follows:
Step 1, polymer packaged material and solidifying agent are mixed with turbine mixer, both are evenly dissolved each other and form the first mixture.In the present embodiment, polymer packaged material is selected polymethylmethacrylate, and solidifying agent is selected EP-400B, takes by weight both rear turbine mixers that use they are fully mixed, until they dissolve each other completely, forms the first mixture.
Step 2, in the first mixture, add SiO 2the nano combined luminescent material solution of coated quantum dots ZnSe also uses turbine mixer that it is dispersed in the first mixture to form the second mixture.Wherein, SiO 2the nano combined luminescent material solution of coated quantum dots ZnSe is SiO 2the ethanolic soln of the Nano composite granules of coated quantum dots ZnSe, the second mixture is SiO 2the colloid mixture that the Nano composite granules of coated quantum dots ZnSe and polymethylmethacrylate form.
Step 3, the second mixture is placed in to vacuum drying oven to bubble completely dissolve wherein.Wherein, the temperature of vacuum drying oven is 30 ℃, and the second mixture rests in vacuum drying oven.
Step 4, will drop in the surface of blue-ray LED and heat-treat through the second mixture of step 3 processing.Heat treated concrete steps are:
The blue-ray LED that surface is had to the second mixture is put into the baking oven of 40 ℃ and is incubated for some time (about 30-60min), oven temperature is elevated to 80 ℃ subsequently and is incubated for some time (about 30-60min) again.Like this, just formed layer of transparent matrix material on the surface of LED, this transparent composite reaches to 68% the transmitance of visible ray.
Embodiment 4
In the present embodiment, first prepare SiO 2the nano combined luminescent material of coated multiple Quantum dots CdS eS/CdS, it is by SiO 2the Nano composite granules composition of coated multiple Quantum dots CdS eS/CdS, wherein, each Nano composite granules is SiO 2the Nano composite granules of coated multiple Quantum dots CdS eS/CdS.Concrete steps are as follows:
Step 1, under agitation condition, in hexanaphthene, add TEOS, tensio-active agent and catalyzer to carry out the conversed phase micro emulsion copolymerization reaction of catalysis.In the present embodiment, hexanaphthene consumption 10mL, the concrete steps of carrying out the conversed phase micro emulsion copolymerization reaction of catalysis are:
Under agitation condition, add tensio-active agent, add again TEOS after then adding catalyzer, solution to mix.Wherein, tensio-active agent is taken NP5, and consumption 1mL stirs 30min; Catalyzer is selected ammoniacal liquor, consumption 0.4mL; TEOS takes 0.1mL.
Step 2, carry out after time T 2 in the reaction of step 1, 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 2nano particle.Wherein, time T 2 is 20h.
Step 3, the SiO obtaining with ethanol cleaning cleaning step two 2after nano particle, be scattered in and in ethanol, obtained SiO 2the ethanolic soln of Nano composite granules.
In step 4, the ethanolic soln that obtains in step 3, under agitation condition, add silane coupling agent with to SiO 2nano particle carries out finishing, after elapsed time T3, obtains the SiO through finishing by centrifugal treating 2nano particle also carries out ethanol cleaning and oven dry to it.In the present embodiment, silane coupling agent selects APS silane coupling agent, and time T 3 is 24h, the SiO through finishing of acquisition 2nano particle is the SiO that APS silane coupling agent is modified 2nano particle.
Step 5, quantum dot is dissolved in to hexanaphthene.Wherein, the two-layer nucleocapsid structure that Quantum dots CdS eS/CdS is CdSeS/CdS, its emission wavelength is 470nm; Quantum dots CdS eS/CdS is dissolved in the solution that obtains 10mL, 1mM in hexanaphthene.
In step 6, the solution that obtains in step 5, under agitation condition, add tensio-active agent to form microemulsion.Tensio-active agent is selected NP9, consumption 0.1mL, and churning time is 30min.
In step 7, the microemulsion that obtains in step 6, under agitation condition, add the SiO obtaining after completing steps four 2nano particle then adds successively TEOS and catalyzer to carry out the conversed phase micro emulsion copolymerization reaction of catalysis under agitation condition.Wherein, the SiO obtaining after completing steps four 2nano particle is the SiO that APS silane coupling agent is modified 2nano particle, TEOS consumption 0.1mL, stirs 30min; Catalyzer is selected methylamine, and consumption 0.1mL continues to stir under lucifuge condition.
Step 8, carry out, after time T 4, in the solution reacting, dripping acetone with termination reaction in the reaction of step 7, the solution that has stopped reaction has been carried out to centrifugal treating, obtained SiO 2the Nano composite granules of coated multiple Quantum dots CdS eS/CdS also uses ethanol to clean this Nano composite granules.Wherein, time T 4 is 36h.The average particulate diameter that experiment measuring obtains this nano combined luminescent material is 43.6 ± 0.5nm, root
Figure BDA00002072093900101
sub-packaged material is composite to be formed for as the transparent composite of the photoelectric device of LED.Concrete steps are as follows:
Step 1, polymer packaged material and solidifying agent are mixed with turbine mixer, both are evenly dissolved each other and form the first mixture.In the present embodiment, polymer packaged material is selected bisphenol A type epoxy resin EP-400A, and solidifying agent is selected EP-400B, takes by weight both rear turbine mixers that use they are fully mixed, until they dissolve each other completely, forms the first mixture.
Step 2, in the first mixture, add SiO 2the nano combined luminescent material solution of coated multiple Quantum dots CdS eS/CdS also uses turbine mixer that it is dispersed in the first mixture to form the second mixture.Wherein, SiO 2the nano combined luminescent material solution of coated multiple Quantum dots CdS eS/CdS is SiO 2the ethanolic soln of the Nano composite granules of coated multiple Quantum dots CdS eS/CdS, the second mixture is SiO 2the colloid mixture that the Nano composite granules of coated multiple Quantum dots CdS eS/CdS and epoxy resin form.
Step 3, the second mixture is placed in to vacuum drying oven to bubble completely dissolve wherein.Wherein, the temperature of vacuum drying oven is 30 ℃, and the second mixture rests in vacuum drying oven.
Step 4, will drop in the surface of blue-ray LED and heat-treat through the second mixture of step 3 processing.Heat treated concrete steps are:
The blue-ray LED that surface is had to the second mixture is put into the baking oven of 40 ℃ and is incubated for some time (about 30-60min), oven temperature is elevated to 80 ℃ subsequently and is incubated for some time (about 30-60min) again.Like this, just formed layer of transparent matrix material on the surface of LED, this transparent composite reaches 74% to the transmitance of visible ray.
Embodiment 5
In the present embodiment, first prepare SiO 2the nano combined luminescent material of coated multiple Quantum dots CdS eTe/CdS/ZnS, it is by SiO 2the Nano composite granules composition of coated multiple Quantum dots CdS eTe/CdS/ZnS, wherein, each Nano composite granules is SiO 2the Nano composite granules of coated multiple Quantum dots CdS eTe/CdS/ZnS.Concrete steps are as follows:
Step 1, under agitation condition, in hexanaphthene, add TEOS, tensio-active agent and catalyzer to carry out the conversed phase micro emulsion copolymerization reaction of catalysis.In the present embodiment, hexanaphthene consumption 10mL, the concrete steps of carrying out the conversed phase micro emulsion copolymerization reaction of catalysis are:
Under agitation condition, add tensio-active agent, add again TEOS after then adding catalyzer, solution to mix.Wherein, tensio-active agent is taken NP5, and consumption 1mL stirs 30min; Catalyzer is selected ammoniacal liquor, consumption 0.2mL; TEOS takes 0.1mL.
Step 2, carry out after time T 2 in the reaction of step 1, in the solution that carries out described reaction, dripped acetone to stop described reaction, the solution that has stopped reaction has been carried out to centrifugal treating, obtained SiO 2nano particle.Wherein, time T 2 is 20h.
Step 3, the SiO obtaining with ethanol cleaning cleaning step two 2after nano particle, be scattered in and in ethanol, obtained SiO 2the ethanolic soln of Nano composite granules.
In step 4, the ethanolic soln that obtains in step 3, under agitation condition, add silane coupling agent with to SiO 2nano particle carries out finishing, after elapsed time T3, obtains the SiO through finishing by centrifugal treating 2nano particle also carries out ethanol cleaning and oven dry to it.In the present embodiment, silane coupling agent is selected APS silane coupling agent, and time T 3 is 24h, the SiO through finishing of acquisition 2nano particle is the SiO that APS silane coupling agent is modified 2nano particle.
Step 5, Quantum dots CdS eTe/CdS/ZnS is first dissolved in organic reagent, is then dissolved in hexanaphthene.Wherein, the three-layer nuclear shell structure that Quantum dots CdS eTe/CdS/ZnS is CdSeTe/CdS/ZnS, its emission wavelength is 800nm; Organic reagent is selected trichloromethane, hexanaphthene consumption 10mL; Quantum dots CdS eTe/CdS/ZnS is dissolved in the solution that obtains 10mL, 1mM in trichloromethane, and this solution is mixed with hexanaphthene.
In step 6, the solution that obtains in step 5, under agitation condition, add tensio-active agent to form microemulsion.Tensio-active agent is selected NP9, consumption 0.1mL, and churning time is 30min.
In step 7, the microemulsion that obtains in step 6, under agitation condition, add the SiO obtaining after completing steps four 2nano particle then adds successively TEOS and catalyzer to carry out the conversed phase micro emulsion copolymerization reaction of catalysis under agitation condition.Wherein, the SiO obtaining after completing steps four 2nano particle is the SiO that APS silane coupling agent is modified 2nano particle, TEOS consumption 0.1mL, stirs 30min; Catalyzer is selected methylamine, and consumption 0.1mL continues to stir under lucifuge condition.
Step 8, carry out, after time T 4, in the solution reacting, dripping acetone with termination reaction in the reaction of step 7, the solution that has stopped reaction has been carried out to centrifugal treating, obtained SiO 2the Nano composite granules of coated multiple Quantum dots CdS eTe/CdS/ZnS also uses ethanol to clean this Nano composite granules.Wherein, time T 4 is 36h.The average particulate diameter that experiment measuring obtains this nano combined luminescent material is 62.85nm,
Figure BDA00002072093900111
polymer packaged material is composite to be formed for as the transparent composite of the photoelectric device of LED.Concrete steps are as follows:
Step 1, polymer packaged material and solidifying agent are mixed with turbine mixer, both are evenly dissolved each other and form the first mixture.In the present embodiment, polymer packaged material is selected polymethylmethacrylate, and solidifying agent is selected EP-400B, takes by weight both rear turbine mixers that use they are fully mixed, until they dissolve each other completely, forms the first mixture.
Step 2, in the first mixture, add SiO 2the nano combined luminescent material solution of coated multiple Quantum dots CdS eTe/CdS/ZnS also uses turbine mixer that it is dispersed in the first mixture to form the second mixture.Wherein, SiO 2the nano combined luminescent material solution of coated multiple Quantum dots CdS eTe/CdS/ZnS is SiO 2the ethanolic soln of the Nano composite granules of coated multiple Quantum dots CdS eTe/CdS/ZnS, the second mixture is SiO 2the colloid mixture that the Nano composite granules of coated multiple Quantum dots CdS eTe/CdS/ZnS and polymethylmethacrylate form.
Step 3, the second mixture is placed in to vacuum drying oven to bubble completely dissolve wherein.Wherein, the temperature of vacuum drying oven is 30 ℃, and the second mixture rests in vacuum drying oven.
Step 4, will drop in the surface of blue-ray LED and heat-treat through the second mixture of step 3 processing.Heat treated concrete steps are:
The blue-ray LED that surface is had to the second mixture is put into the baking oven of 40 ℃ and is incubated for some time (about 30-60min), oven temperature is elevated to 80 ℃ subsequently and is incubated for some time (about 30-60min) again.Like this, just formed layer of transparent matrix material on the surface of LED, this transparent composite reaches 76% to the transmitance of visible ray.
Embodiment 6
In the present embodiment, first prepare SiO 2the nano combined luminescent material of coated multiple quantum dot Mn:ZnSe, it is by SiO 2the Nano composite granules composition of coated multiple quantum dot Mn:ZnSe, wherein, each Nano composite granules is SiO 2the Nano composite granules of coated multiple quantum dot Mn:ZnSe.Concrete steps are as follows:
Step 1, under agitation condition, in hexanaphthene, add TEOS, tensio-active agent and catalyzer to carry out the conversed phase micro emulsion copolymerization reaction of catalysis.In the present embodiment, hexanaphthene consumption 10mL, 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, and then add catalyzer.Wherein, tensio-active agent is taken NP5, consumption 1mL; TEOS takes 0.1mL, stirs 30min; Catalyzer is selected ammoniacal liquor, consumption 0.3mL; .
Step 2, carry out after time T 2 in the reaction of step 1, in the solution that carries out described reaction, dripped acetone to stop described reaction, the solution that has stopped reaction has been carried out to centrifugal treating, obtained SiO 2nano particle.Wherein, time T 2 is 20h.
Step 3, the SiO obtaining with ethanol cleaning cleaning step two 2after nano particle, be scattered in and in ethanol, obtained SiO 2the ethanolic soln of Nano composite granules.
In step 4, the ethanolic soln that obtains in step 3, under agitation condition, add silane coupling agent with to SiO 2nano particle carries out finishing, after elapsed time T3, obtains the SiO through finishing by centrifugal treating 2nano particle also carries out ethanol cleaning and oven dry to it.In the present embodiment, silane coupling agent is selected APS silane coupling agent, consumption 0.1mL, and time T 3 is 24h, the SiO through finishing of acquisition 2nano particle is the SiO that APS silane coupling agent is modified 2nano particle.
Step 5, quantum dot Mn:ZnSe is first dissolved in organic reagent, is then dissolved in hexanaphthene.Wherein, quantum dot Mn:ZnSe is the quantum dot of the ZnSe of Mn doping, and its emission wavelength is 580nm; 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 6, the solution that obtains in step 5, under agitation condition, add tensio-active agent to form microemulsion.Tensio-active agent is selected NP9, consumption 0.1mL, and churning time is 30min.
In step 7, the microemulsion that obtains in step 6, under agitation condition, add the SiO obtaining after completing steps four 2nano particle then adds successively TEOS and catalyzer to carry out the conversed phase micro emulsion copolymerization reaction of catalysis under agitation condition.Wherein, the SiO obtaining after completing steps four 2nano particle is the SiO that APS silane coupling agent is modified 2nano particle, TEOS consumption 0.1mL, stirs 30min; Catalyzer is selected methylamine, and consumption 0.1mL continues to stir under lucifuge condition.
Step 8, carry out, after time T 4, in the solution reacting, dripping acetone with termination reaction in the reaction of step 7, the solution that has stopped reaction has been carried out to centrifugal treating, obtained SiO 2the Nano composite granules (as shown in Figure 2) of coated multiple quantum dot Mn:ZnSe also uses ethanol to clean this Nano composite granules.Wherein, time T 4 is 36h.The average particulate diameter that experiment measuring obtains this nano combined luminescent material is 62.85nm, calculates formula according to matrix material specific refractory power
Figure BDA00002072093900131
calculating its specific refractory power is 1.52, matches with conventional packaged material specific refractory power.
Then by above-mentioned acquisition SiO 2the nano combined luminescent material of coated multiple quantum dot Mn:ZnSe and polymer packaged material is composite is formed for as the transparent composite of the photoelectric device of LED.Concrete steps are as follows:
Step 1, polymer packaged material and solidifying agent are mixed with turbine mixer, both are evenly dissolved each other and form the first mixture.In the present embodiment, polymer packaged material is selected silica gel, and solidifying agent is selected EP-400B, takes by weight both rear turbine mixers that use they are fully mixed, until they dissolve each other completely, forms the first mixture.
Step 2, in the first mixture, add SiO 2the nano combined luminescent material solution of coated multiple quantum dot Mn:ZnSe also uses turbine mixer that it is dispersed in the first mixture to form the second mixture.Wherein, SiO 2the nano combined luminescent material solution of coated multiple quantum dot Mn:ZnSe is SiO 2the ethanolic soln of the Nano composite granules of coated multiple quantum dot Mn:ZnSe, the second mixture is SiO 2the colloid mixture that the Nano composite granules of coated multiple quantum dot Mn:ZnSe and silica gel form.
Step 3, the second mixture is placed in to vacuum drying oven to bubble completely dissolve wherein.Wherein, the temperature of vacuum drying oven is 30 ℃, and the second mixture rests in vacuum drying oven.
Step 4, will drop in the surface of blue-ray LED and heat-treat through the second mixture of step 3 processing.Heat treated concrete steps are:
The blue-ray LED that surface is had to the second mixture is put into the baking oven of 40 ℃ and is incubated for some time (about 30-60min), oven temperature is elevated to 80 ℃ subsequently and is incubated for some time (about 30-60min) again.Like this, just formed layer of transparent matrix material on the surface of LED, this transparent composite reaches 81% to the transmitance of visible ray.
Embodiment 7
In the present embodiment, first prepare SiO 2the nano combined luminescent material of coated multiple Quantum dots CdS eS/CdS/ZnS and CdSe/CdS/ZnS, it is by SiO 2the Nano composite granules composition of coated multiple Quantum dots CdS eS/CdS/ZnS and CdSe/CdS/ZnS, wherein, each Nano composite granules is SiO 2the Nano composite granules of coated multiple Quantum dots CdS eS/CdS/ZnS and CdSe/CdS/ZnS.Concrete steps are as follows:
Step 1, under agitation condition, in hexanaphthene, add TEOS, tensio-active agent and catalyzer to carry out the conversed phase micro emulsion copolymerization reaction of catalysis.In the present embodiment, hexanaphthene consumption 10mL, 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, and then add catalyzer.Wherein, tensio-active agent is taken NP5, consumption 1mL; TEOS takes 0.1mL, stirs 30min; Catalyzer is selected ammoniacal liquor, consumption 0.3mL; .
Step 2, carry out after time T 2 in the reaction of step 1, in the solution that carries out described reaction, dripped acetone to stop described reaction, the solution that has stopped reaction has been carried out to centrifugal treating, obtained SiO 2nano particle.Wherein, time T 2 is 20h.
Step 3, the SiO obtaining with ethanol cleaning cleaning step two 2after nano particle, be scattered in and in ethanol, obtained SiO 2the ethanolic soln of Nano composite granules.
In step 4, the ethanolic soln that obtains in step 3, under agitation condition, add silane coupling agent with to SiO 2nano particle carries out finishing, after elapsed time T3, obtains the SiO through finishing by centrifugal treating 2nano particle also carries out ethanol cleaning and oven dry to it.In the present embodiment, silane coupling agent is selected APS silane coupling agent, consumption 0.1mL, and time T 3 is 30h, the SiO through finishing of acquisition 2nano particle is the SiO that APS silane coupling agent is modified 2nano particle.
Step 5, Quantum dots CdS eS/CdS/ZnS is first dissolved in the first organic reagent, Quantum dots CdS e/CdS/ZnS is first dissolved in the second organic reagent, be then dissolved in hexanaphthene.Wherein, Quantum dots CdS eS/CdS/ZnS is the quantum dot of the three-layer nuclear shell structure of Quantum dots CdS eS/CdS/ZnS, and its emission wavelength is 510nm; Quantum dots CdS e/CdS/ZnS is the quantum dot of the three-layer nuclear shell structure of CdSe/CdS/ZnS, and its emission wavelength is 580nm.The first organic reagent is selected normal hexane, and the second organic reagent is selected trichloromethane, hexanaphthene consumption 9mL; Quantum dots CdS eS/CdS/ZnS is dissolved in the solution that obtains 0.5mL, 10mM in normal hexane, and Quantum dots CdS e/CdS/ZnS is dissolved in the solution that obtains 0.5mL, 10mM in trichloromethane, and two kinds of solution are mixed with hexanaphthene.
In step 6, the solution that obtains in step 5, under agitation condition, add tensio-active agent to form microemulsion.Tensio-active agent is selected NP9, consumption 0.1mL, and churning time is 30min.
In step 7, the microemulsion that obtains in step 6, under agitation condition, add the SiO obtaining after completing steps four 2nano particle then adds successively TEOS and catalyzer to carry out the conversed phase micro emulsion copolymerization reaction of catalysis under agitation condition.Wherein, the SiO obtaining after completing steps four 2nano particle is the SiO that APS silane coupling agent is modified 2nano particle, TEOS consumption 0.1mL, stirs 30min; Catalyzer is selected methylamine, and consumption 0.1mL continues to stir under lucifuge condition.
Step 8, carry out, after time T 4, in the solution reacting, dripping acetone with termination reaction in the reaction of step 7, the solution that has stopped reaction has been carried out to centrifugal treating, obtained SiO 2the Nano composite granules of coated multiple Quantum dots CdS eS/CdS/ZnSe and CdSe/CdS/ZnS also uses ethanol to clean this Nano composite granules.Wherein, time T 4 is 36h.Calculate formula according to matrix material specific refractory power
Figure BDA00002072093900151
calculating its specific refractory power is 1.48, matches with conventional packaged material specific refractory power.
Then by above-mentioned acquisition SiO 2the nano combined luminescent material of coated multiple Quantum dots CdS eS/CdS/ZnS and CdSe/CdS/ZnS and polymer packaged material is composite is formed for as the transparent composite of the photoelectric device of LED.Concrete steps are as follows:
Step 1, polymer packaged material and solidifying agent are mixed with turbine mixer, both are evenly dissolved each other and form the first mixture.In the present embodiment, polymer packaged material is selected epoxy resin, and solidifying agent is selected EP-400B, takes by weight both rear turbine mixers that use they are fully mixed, until they dissolve each other completely, forms the first mixture.
Step 2, in the first mixture, add SiO 2the nano combined luminescent material solution of coated multiple Quantum dots CdS eS/CdS/ZnS and CdSe/CdS/ZnS also uses turbine mixer that it is dispersed in the first mixture to form the second mixture.Wherein, SiO 2the nano combined luminescent material solution of coated multiple Quantum dots CdS eS/CdS/ZnS and CdSe/CdS/ZnS is SiO 2the ethanolic soln of the Nano composite granules of coated multiple Quantum dots CdS eS/CdS/ZnS and CdSe/CdS/ZnS, the second mixture is SiO 2the colloid mixture that the Nano composite granules of coated multiple Quantum dots CdS eS/CdS/ZnS and CdSe/CdS/ZnS and epoxy resin form.
Step 3, the second mixture is placed in to vacuum drying oven to bubble completely dissolve wherein.Wherein, the temperature of vacuum drying oven is 30 ℃, and the second mixture rests in vacuum drying oven.
Step 4, will drop in the surface of blue-ray LED and heat-treat through the second mixture of step 3 processing.Heat treated concrete steps are:
The blue-ray LED that surface is had to the second mixture is put into the baking oven of 40 ℃ and is incubated for some time (about 30-60min), oven temperature is elevated to 80 ℃ subsequently and is incubated for some time (about 30-60min) again.Like this, just formed layer of transparent matrix material on the surface of LED, this transparent composite reaches 80% to the transmitance of visible ray.
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/Ag2S, CdS/Cd (OH) 2, 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, Mn:CdS/ZnS, Cu:CdS, Cu:CdS/ZnS, Cu:ZnS, Mn:ZnS, Mn:ZnSe/ZnS, Mn:ZnSe/ZnO, Cu:ZnSe, Cu:ZnSe/ZnS, Tb:CdS, any one in Tb:CdS/ZnS or Tb:ZnS, 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 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 (2)

1. the SiO that specific refractory power is adjustable 2the preparation method of the nano combined luminescent material of coated quantum dots, is characterized in that, comprising:
Step 1, under agitation condition, in hexanaphthene, add TEOS, tensio-active agent and catalyzer to carry out the conversed phase micro emulsion copolymerization reaction of catalysis;
Step 2, 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 2nano particle;
Step 3, clean described SiO with ethanol 2after nano particle, be scattered in and in ethanol, obtained described SiO 2the ethanolic soln of Nano composite granules;
Step 4, in described ethanolic soln, under agitation condition, add silane coupling agent with to described SiO 2nano particle carries out finishing, after 12-80 hour, obtains the SiO through described finishing by centrifugal treating 2nano particle also carries out ethanol cleaning and oven dry to it;
Step 5, described quantum dot is dissolved in to hexanaphthene, or described quantum dot is first dissolved in organic reagent, and then be dissolved in hexanaphthene;
In step 6, the solution that obtains in step 5, under agitation condition, add tensio-active agent to form microemulsion;
Step 7, in described microemulsion, under agitation condition, add the SiO obtaining after completing steps four 2nano particle then adds successively TEOS and catalyzer to carry out the conversed phase micro emulsion copolymerization reaction of catalysis under agitation condition;
Step 8, carry out after 20-80 hour in the reaction described in step 7, 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 multiple quantum dots.
2. the adjustable SiO of specific refractory power as claimed in claim 1 2the preparation method of the nano combined luminescent material of coated quantum dots, it is characterized in that, wherein said organic reagent and hexanaphthene 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; Described tensio-active agent is any one tensio-active agent in tensio-active agent NP5, NP9 and Triton X-100 or the mixture of kinds of surface promoting agent arbitrarily; Described catalyzer is any one catalyzer in catalyzer methylamine, ammoniacal liquor and dimethylamine or the mixture of multiple catalysts arbitrarily.
CN201210313357.6A 2012-08-29 2012-08-29 Preparation method and application of adjustable-refractivity silicon dioxide coated quantum dot nano composite luminescent material Active CN102816563B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210313357.6A CN102816563B (en) 2012-08-29 2012-08-29 Preparation method and application of adjustable-refractivity silicon dioxide coated quantum dot nano composite luminescent material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210313357.6A CN102816563B (en) 2012-08-29 2012-08-29 Preparation method and application of adjustable-refractivity silicon dioxide coated quantum dot nano composite luminescent material

Publications (2)

Publication Number Publication Date
CN102816563A CN102816563A (en) 2012-12-12
CN102816563B true CN102816563B (en) 2014-07-09

Family

ID=47301022

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210313357.6A Active CN102816563B (en) 2012-08-29 2012-08-29 Preparation method and application of adjustable-refractivity silicon dioxide coated quantum dot nano composite luminescent material

Country Status (1)

Country Link
CN (1) CN102816563B (en)

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103361067A (en) * 2013-07-16 2013-10-23 天津大学 Water-soluble quantum dot fluorescent nanosphere and preparation method thereof
CN103952136B (en) * 2014-04-29 2016-05-11 吉林大学 Cu doping Type-II type nucleocapsid structure white light quanta point material and preparation method
CN104910918A (en) * 2015-04-30 2015-09-16 中国科学院半导体研究所 Core-shell quantum dot material and preparation method thereof
CN108129811B (en) * 2015-12-30 2020-09-29 浦江县汕淋贸易有限公司 Quantum dot luminescent composite for 3D printing
CN105754603A (en) * 2016-05-11 2016-07-13 青岛海信电器股份有限公司 Quantum dot assembly as well as preparation method and application thereof
CN106147748B (en) * 2016-06-23 2018-08-28 南京大学 A kind of CdSeTe@SiO2Core-shell nano material and preparation method thereof
CN106590624A (en) * 2016-12-05 2017-04-26 河北工业大学 Light-emitting nano-particles and preparation method thereof
CN107142100A (en) * 2017-03-29 2017-09-08 华南理工大学 A kind of graded index parcel quantum dot diaphragm and preparation method thereof
CN108949143A (en) * 2017-05-19 2018-12-07 上海汉邦普净节能科技有限公司 Embedded photoluminescent material
CN108949178A (en) * 2017-05-19 2018-12-07 上海汉邦普净节能科技有限公司 Embedded photoluminescent material
EP4101907A1 (en) * 2017-06-02 2022-12-14 Nexdot Uniformly encapsulated nanoparticles and uses thereof
CN108048093A (en) * 2017-12-05 2018-05-18 湖北大学 A kind of Ag, Mn adulterate the preparation method of ZnSe and ZnS core-shell structured quantum dot
CN110129025A (en) * 2019-05-14 2019-08-16 上海大学 The preparation method of simple Silica-coated quantum dot
CN110452685A (en) * 2019-08-02 2019-11-15 上海交通大学 A kind of encoded signal can careful design quantum dot fluorescence coding microball
CN111303643B (en) * 2020-02-22 2022-02-15 西南石油大学 SiO of core-shell structure2@ paraffin nanoparticle and preparation method thereof
CN112694886A (en) * 2020-12-29 2021-04-23 武双 Oil-soluble tracer for environmental monitoring and preparation method thereof
CN112965295A (en) * 2021-03-08 2021-06-15 合肥福纳科技有限公司 Quantum dot material and preparation method thereof, quantum dot film, backlight module and display device
CN114141961B (en) * 2021-11-18 2023-10-17 深圳市华星光电半导体显示技术有限公司 Regulation layer, preparation method and photoelectric device
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
CN116239823B (en) * 2023-02-15 2024-08-30 广东欧迪明光电科技股份有限公司 Light scattering material, antibacterial master batch and microsphere as well as preparation methods and application thereof
CN116970387B (en) * 2023-07-25 2024-05-10 南京邮电大学 Composite nano material for detecting hydrolyzed milk powder and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101338066A (en) * 2007-07-05 2009-01-07 中国科学院理化技术研究所 Transparent epoxy nano composite material and preparation method and application thereof
CN102382640A (en) * 2011-08-30 2012-03-21 济南大学 High-fluorescent brightness quantum dot composite particle, immunological detection probe and preparation method of the high-fluorescent brightness quantum dot composite particle

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AUPP004497A0 (en) * 1997-10-28 1997-11-20 University Of Melbourne, The Stabilized particles
KR101250859B1 (en) * 2009-05-04 2013-04-04 최경재 Quantum dots and Luminescent devices by using these

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101338066A (en) * 2007-07-05 2009-01-07 中国科学院理化技术研究所 Transparent epoxy nano composite material and preparation method and application thereof
CN102382640A (en) * 2011-08-30 2012-03-21 济南大学 High-fluorescent brightness quantum dot composite particle, immunological detection probe and preparation method of the high-fluorescent brightness quantum dot composite particle

Non-Patent Citations (10)

* Cited by examiner, † Cited by third party
Title
Bright, non-blinking, and less-cytotoxic SiO2 beads with multiple CdSe/ZnS nanocrystals;Ping Yang等;《Chem. Commun.》;20100519;第46卷;4595–4597 *
Coating Aqueous Quantum Dots with Silica via Reverse Microemulsion Method: Toward Size-Controllable and Robust Fluorescent Nanoparticles;Yunhua Yang等;《Chem. Mater. 》;20070731;第19卷;4123-4128 *
Lihong Jing等.Highly Fluorescent CdTe SiO2 Particles Prepared via Reverse Microemulsion Method.《Chem. Mater.》.2009,第22卷420–427. *
Lihong Jing等.Highly Fluorescent CdTe@ SiO2 Particles Prepared via Reverse Microemulsion Method.《Chem. Mater.》.2009,第22卷420–427.
Ping Yang等.Bright, non-blinking, and less-cytotoxic SiO2 beads with multiple CdSe/ZnS nanocrystals.《Chem. Commun.》.2010,第46卷4595–4597.
Preparation of fluorescent SiO2 particles with single CdTe nanocrystal cores by the reverse microemulsion method;yunhua yang等;《ADVANCED MATERIALS》;20050816;第17卷;2354-2357 *
Stable efficient CdSe/CdS/ZnS core/multi-shell nanophosphors fabricated through a phosphine-free route for white light-emitting-diodes with high color rendering properties;Xiebing Wang等;《J. Mater. Chem.》;20110414;第21卷;8558-8565 *
Xiebing Wang等.Stable efficient CdSe/CdS/ZnS core/multi-shell nanophosphors fabricated through a phosphine-free route for white light-emitting-diodes with high color rendering properties.《J. Mater. Chem.》.2011,第21卷8558-8565.
Yunhua Yang等.Coating Aqueous Quantum Dots with Silica via Reverse Microemulsion Method: Toward Size-Controllable and Robust Fluorescent Nanoparticles.《Chem. Mater. 》.2007,第19卷4123-4128.
yunhua yang等.Preparation of fluorescent SiO2 particles with single CdTe nanocrystal cores by the reverse microemulsion method.《ADVANCED MATERIALS》.2005,第17卷2354-2357.

Also Published As

Publication number Publication date
CN102816563A (en) 2012-12-12

Similar Documents

Publication Publication Date Title
CN102816563B (en) Preparation method and application of adjustable-refractivity silicon dioxide coated quantum dot nano composite luminescent material
CN105102580B (en) The quantum dot of encapsulation in porous particle
CN102844403B (en) Phosphorescent substance Nanoparticulate compositions
US9837586B2 (en) Wavelength converters and methods for making the same
CN105957944B (en) White light source containing three bandgap photonic crystals and preparation method thereof
CN108624317B (en) Core-shell quantum dot and preparation method and application thereof
TWI711684B (en) Phosphor with hybrid coating and method of production
CN101238596B (en) Photonic material, its preparation method and uses, lighting device comprising same
CN104781942B (en) LED-based equipment with wide colour gamut
CN107075358A (en) Encapsulated materials in porous particles
KR101362263B1 (en) Phosphor-matrix composite powders for minimizing scattering and LED structure including the same
CN106967412A (en) Containing phosphor particle and using it light-emitting device, containing phosphor plates
CN106414661A (en) Particles with quantum dots and methods of making the same
CN101084112A (en) Optically reliable nanoparticle based nanocomposite hri encapsulant, photonic waveguiding material and high electric breakdown field strength insulator/encapsulant
CN103155179A (en) Quantum dot based lighting
CN105891936A (en) Light guide element, manufacturing method thereof and backlight module set
CN103489996B (en) White-light LED encapsulation technique
CN102906222A (en) Luminescent substances
CN103975041B (en) For the phosphor in LED waterglass
JP6344190B2 (en) Optical semiconductor light emitting device, lighting fixture, display device, and manufacturing method of optical semiconductor light emitting device
CN106715643A (en) Siloxane ligands to be used for dispersing quantum dots in silicone hosts to obtain color converters for led lighting
CN106147749A (en) Fluorescent microsphere be assembled into photonic crystal, and its preparation method and application
CN106497546A (en) White light quanta point composition and preparation method thereof
CN102800794A (en) Optical wavelength conversion device and application thereof in white light emitting device
CN108034420A (en) Inorganic nano-particle embedding terbium complex hybrid luminescent materials and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant