CN105482822A - Quantum dot composite material with bi-component substrate and preparation method thereof - Google Patents
Quantum dot composite material with bi-component substrate and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a quantum dot composite material with a bi-component substrate and a preparation method thereof. The quantum dot composite material comprises a base material with light transmission, a microcapsule layer and a quantum dot layer, wherein the microcapsule layer is arranged on the base material with light transmission; the quantum dot layer is arranged on the microcapsule layer; the microcapsule layer is formed through self-assembly of microcapsules; the quantum dot layer is formed through self-assembly of quantum dots; each microcapsule comprises a shell and a core; the shell contains polystyrene and silicon dioxide; the core is formed by higher fatty acid. The quantum dot composite material has the advantages that not only can the quantum dot material maintain the excellent properties of common quantum dots, such as high luminous efficiency and photochemical stability, but also the quantum dot material has specific temperature sensitive value related to the luminous intensity, so that the quantum dot composite material can be used for associating or monitoring specific temperatures; the quantum dot composite material also has good reusability; the quantum dots can not fall off.
Description
Technical field
The present invention relates to a kind of quantum dot composite material, more particularly, relate to and a kind of there is quantum dot composite material of two-pack substrate and preparation method thereof.
Background technology
When scantling reduces to nanometer scale, due to its nano effect, material, by producing the various functional performances being better than traditional material of many novelties and uniqueness, is with a wide range of applications in fields such as microelectronics, biotechnology, chemical industry, medical science.
In recent years, take transition metal as the nano luminescent material of active ions, due to the optical characteristics of its excellence, as wide in absorbing wavelength and continuously, fluorescence emission peak is tunable, fluorescence lifetime is long, shows wide application prospect in fields such as luminescent device, fluorescence imaging, solar cell, fluoroscopic examination and biomarkers.But when quantum dot is used for luminescent device or fluoroscopic examination, within the scope of 25-100 DEG C, the red shift that quantum dot absorption peak wavelength and photoluminescence spectra wavelength occur generally all is less than 10nm.Moreover although luminous intensity and temperature have certain linear relationship, vary with temperature, its luminous intensity is very little, lower than at thermal quenching temperature, less temperature variation can not cause luminous intensity significantly strengthen or weaken.Therefore, prior art can not prepare the very high quantum dot of temperature sensitivity.
Summary of the invention
In order to overcome weak point of the prior art, the invention provides the quantum dot composite material with two-pack substrate that a kind of temperature sensitivity is very high.
A kind of quantum dot composite material with two-pack substrate provided by the invention, it comprises Mght-transmitting base material, microcapsule layer and quantum dot layer, described microcapsule layer is positioned on described Mght-transmitting base material, described quantum dot layer is positioned in described microcapsule layer, described microcapsule layer is formed by microcapsule self-assembly, and described quantum dot layer is formed by quantum dot self-assembly, and described microcapsule comprise shell and kernel, described shell contains polystyrene and silicon-dioxide, and described kernel is higher fatty acid.
Described quantum dot is the quantum dot that mercaptan carboxylic acid modifies; The surface of described microcapsule is through triamino silane and polymerize aluminum chloride modification, and wherein, the chemical formula of triamino silane is H
2n-CH
2-CH
2-NH-CH
2-CH
2-NH-(CH
2)
3-Si-(OCH
3)
3.
In described quantum dot composite material, described SiO
2be (0.2 ~ 1.2) with the part by weight of described higher fatty acid: 1.
The quantum dot that described quantum dot can adopt this area routine to use.Described quantum dot is one or more in CdTe, CdSe, InP, InAs, CdSe/CdS, CdSe/ZnS, CdSe/ZnSe, CdTe/ZnS, CdHgTe/ZnS, HgTe/HgCdS quantum dot.The particle diameter of quantum dot can be 1-100nm, is preferably 2-20nm, but is not restricted to this.Described higher fatty acid is C
9~ C
18higher fatty acid, be preferably capric acid, lauric acid, tetradecanoic acid, palmitinic acid, Palmiticacid, the acid of pearly-lustre ester, stearic acid, oleic acid, one or more in linolic acid.
Described microcapsule layer thickness is 50nm ~ 600nm, and be preferably 60nm ~ 500nm, described quantum dot layer thickness is 2 ~ 150nm, is preferably 5 ~ 100nm; The particle diameter of described microcapsule is 50nm ~ 600nm, is preferably 60nm ~ 500nm.
Mght-transmitting base material is the base material that this area routine uses, such as, be the ITO conductive glass of printing opacity.
The above-mentioned preparation method with the quantum dot composite material of two-pack substrate that the present invention also provides, the method comprises the steps:
(1) will be (2 ~ 6) by weight proportion: (2 ~ 10): 1 mixing higher fatty acid, vinylbenzene and tetraethoxy, then heating makes higher fatty acid melting and stirs, obtained mixture, then water phase surfactant mixture is joined and add in described mixture, dispersed with stirring evenly obtains emulsion, then in described emulsion, drip the aqueous solution of ammonium persulphate, react 0.5 ~ 6h at 60 ~ 95 DEG C after, after being down to room temperature, then breakdown of emulsion is carried out, leave standstill, vacuum filters, washing and drying, finally obtain taking higher fatty acid as core, polystyrene and silicon-dioxide are the microcapsule of shell,
(2) described microcapsule are added to the water, ultrasonic vibration 30min, obtains the dispersion liquid of microcapsule, is vertically inserted by Mght-transmitting base material in the dispersion liquid for the preparation of microcapsule and carries out vertical-growth, take out dry, the obtained microcapsule layer being covered in Mght-transmitting base material surface;
(3) microcapsule will be coated with
The Mght-transmitting base material of layer is vertically positioned in the aqueous solution of quantum dot and carries out vertical-growth, takes out dry, just obtains quantum dot composite material.
In (1) step, the ratio of the quality sum of the quality of the tensio-active agent in described water phase surfactant mixture and higher fatty acid, vinylbenzene and tetraethoxy is 1:(10 ~ 30), the concentration of the aqueous solution of described tensio-active agent is 0.5wt% ~ 5wt%; The ratio of the quality sum of the quality of the ammonium persulphate in described ammonium persulfate solution and higher fatty acid, vinylbenzene and tetraethoxy is 1:(10 ~ 50), the concentration of described ammonium persulfate solution is 1wt% ~ 10wt%; Described tensio-active agent is one or more in polyoxyethylene glycol, sucrose ester, polysorbate, octadecyl benzenesulfonic acid, sodium lauryl sulphate, Trombovar, Sodium palmityl sulfate, Sodium dodecylbenzene sulfonate.
In (2) step, the aqueous solution of described quantum dot is the aqueous solution of the quantum dot that mercaptan carboxylic acid modifies.The time of described immersion is 5min ~ 240min.
Before the aqueous solution described microcapsule being joined quantum dot, with polymeric aluminum chlorides solution and triamino solution of silane modification microcapsule, concrete steps are as follows: be positioned in the solution of polymerize aluminum chloride by the Mght-transmitting base material being coated with microcapsule layer, then drying is taken out, and then join in triamino solution of silane, then take out drying.Wherein, the concentration 0.20wt% ~ 0.01wt% of polymeric aluminum chlorides solution.Described triamino solution of silane is the ethanolic soln containing 0.5wt% ~ 2.0wt% triamino silane.The consumption submergence microcapsule layer of polymeric aluminum chlorides solution and triamino solution of silane, but be not restricted to this.
The aqueous solution of described quantum dot is the water-soluble quantum dot that mercaptan carboxylic acid modifies, and is the water-soluble quantum dot of mercaptan carboxylic acid's modification that routine uses, the solution of conventional working concentration.Its preparation method is as follows: tellurium powder and sodium borohydride are mixed with water, inert ambient environment and constant temperature is reacted, obtained quantum dot precursor liquid; Cadmium chloride fine powder is dissolved in water, then mercaptan carboxylic acid and sodium hydroxide solution is added successively, obtain mixed solution, whole mixed solution is moved to autoclave inside liner, letting nitrogen in and deoxidizing, then described quantum dot precursor liquid is joined in described mixed solution, carry out hydro-thermal reaction at autoclave, obtain the water-soluble quantum dot that described mercaptan carboxylic acid modifies.The molar ratio of described tellurium powder, sodium borohydride, Cadmium chloride fine powder and mercaptan carboxylic acid is 1:(20 ~ 60): (15 ~ 45): (6 ~ 15).Mercaptan carboxylic acid is preferably Thiovanic acid, 2 mercaptopropionic acid and 3-thiohydracrylic acid.
Compared with prior art, tool of the present invention has the following advantages:
(1) quantum dot composite material of the present invention, quantum dot of the present invention not only can keep the excellent properties such as general quantum dot luminous efficiency is high, photochemical stability, and luminous intensity also has specific temperature sensitive value, can be used for associating specific temperature or monitoring.Be embodied in: when envrionment temperature raises the transformation temperature of higher fatty acid, higher fatty acid in quantum dot composite material undergoes phase transition, solid-stately transparent liquid state is become by lighttight, the light transmission of such microcapsule significantly increases, and the intensity (luminous intensity) of passing the photoluminescence spectra of microcapsule layer and transparent base material successively can occur significantly to increase; When the transformation temperature of envrionment temperature lower than higher fatty acid, become lighttight solid-state by transparent liquid state, the light transmission of such microcapsule significantly reduces, and the intensity (luminous intensity) of passing the photoluminescence spectra of microcapsule layer and transparent base material successively can decline to a great extent.Therefore, quantum dot composite material has very strong temperature sensitivity near higher fatty acid phase transformation temperature points.
When quantum dot composite material of the present invention is applied to fluoroscopic examination, by the place of fluorescence generation ANOMALOUS VARIATIONS in on-line real time monitoring integral system, the temperature subtle change near temperature sensitive value can be monitored out.When device for quantum dot, by regulating temperature value, the significantly change of quantum dot light emitting intensity can be regulated and controled.
Quantum dot composite material of the present invention is applicable to the close sample monitoring with the phase transformation temperature points of higher fatty acid, because higher fatty acid has very many temperature trade mark, can by selecting the higher fatty acid of the differing temps trade mark, change the temperature sensitive value of quantum dot composite material Fatty Acids, thus the Real-Time Monitoring of different sample can be realized.
(2) quantum dot composite material of the present invention, polystyrene and silicon-dioxide form thicker coated shell, and polystyrene has stronger shock strength, be conducive to the thermostability and the structural stability that improve these microcapsule, and the elasticity of silicon-dioxide and the poor shortcoming of compactness can be made up well, be conducive to forming fine and close shell and avoiding phase change material to leak, improve stability.
Silicon-dioxide has the characteristic such as high structural strength, thermally-stabilised, mechanically stable, chemically stable, high heat conduction, can be good at making up thermally-stabilised poor, the mechanical characteristics relatively poor and heat conductivility relatively poor shortcoming relative to chemical stability of polystyrene.
Polystyrene and silicon dioxide composite material combine the advantage of polystyrene and silicon-dioxide, and mutually can make up the shortcoming existed separately, have complementary advantages, thus the thermostability of these microcapsule, chemical stability, mechanical stability and structural stability can be improved, thus make the stability of microcapsule higher.
(3) the present invention is in the preparation process of quantum dot composite material, ammonium persulphate causes the poly-polystyrene of polystyrene polymerization generation as the initiator of polyreaction, generate silicon-dioxide as ester-type hydrolysis catalyst teos hydrolysis simultaneously, make the interface polymerization reaction of polystyrene and the interface hydrolysis reaction of tetraethoxy carry out so simultaneously, interface polymerization reaction and hydrolysis reaction synergy each other, well control the W-response speed of reaction system, the microcapsule of preparation are made to have good structural uniformity and stability, thus can even particle size distribution be realized, the preparation of constitutionally stable microcapsule.
After preparation microcapsule layer, again through polymerize aluminum chloride and the process of triamino solution of silane, thus modified microcapsule layer surface charge, and be combined at the polyamino of triamino silane the multidigit point grafting forming three-dimensional with mercaptan carboxylic acid, like this under the dual function of surface charge and the grafting of multidigit point, quantum dot is assembled in the surface of microcapsule layer very securely, can effectively prevent coming off of quantum dot surface sulfydryl class part, quantum dot originally has extraordinary time stability, and in certain acid, alkali, acid in well-oxygenated environment, alkaline stability and antioxidative stabilizer, the good biological meanwhile also maintaining quantum dot is compatible, thus substantially increase quantum dot stability in a particular application.
(4) quantum dot composite material of the present invention, may be used at quantum dot in luminescent device, fluorescence imaging, solar cell, fluoroscopic examination and biomarker etc.
Embodiment
Further illustrate the preparation process of quantum dot composite material of the present invention below by embodiment, but invention should not be deemed limited in following embodiment, wherein wt% is massfraction.
The preparation method of the quantum dot solution that mercaptan carboxylic acid modifies adopts the preparation method of this area routine use.The present invention will (cat ions be as being Zn containing the cationic metal-salt of quantum dot
2+, Cd
2+or Hg
2+) generate positively charged ion precursor with mercaptan carboxylic acid's complexing, then (negatively charged ion can be such as S with negatively charged ion precursor
2-, Se
2-or Te
2-) reflux makes quantum dot nucleation and grows, thus the quantum dot solution that obtained mercaptan carboxylic acid modifies.The temperature of reflux is 60 ~ 90 DEG C, and the time is 3 ~ 12h.Such as, the cadmium telluride that mercaptan carboxylic acid modifies, the preparation method of CdSe quantum dots solution can with reference to CN102786037A, and the preparation method of the ZnS quantum dots solution that mercaptan carboxylic acid modifies can with reference to CN103242829A.Cadmium Sulfide, zinc selenide or the self-chambering of zinc telluridse solution that quantum dot can also be modified by mercaptan carboxylic acid form.The preparation method of the cadmium telluride of each embodiment detailed description mercaptan carboxylic acid modification that the present invention is following.
Embodiment 1
(1) be tetradecanoic acid, vinylbenzene and tetraethoxy that 6:9:1 combined phase-change temperature is 52 ~ 54 DEG C in mass ratio, obtain mixture;
Said mixture is added in 500mL round-bottomed flask, sheet stainless steel is adopted to stir, heating in water bath to 60 DEG C under the stirring velocity of 1500 turns/min, the Sodium dodecylbenzene sulfonate of 1g is joined in 100mL water, be uniformly dispersed, and to add in round-bottomed flask after emulsification 20min, and then be warming up to 80 DEG C, emulsification 10min is continued under the stirring velocity of 1500 turns/min, obtain uniform microemulsion, wherein, the ratio of the quality of Sodium dodecylbenzene sulfonate and the quality sum of tetradecanoic acid, vinylbenzene and tetraethoxy is 1:13;
After emulsification completes, the temperature of water-bath is adjusted to 85 DEG C.The ammonium persulphate of 1g is dissolved in the deionized water of 7.5mL, and drops in round-bottomed flask slowly completely.After stirring 30min with the stirring velocity of 1500 turns/min, churned mechanically speed is adjusted to 1000 turns/min, and the temperature of water-bath is adjusted to 80 DEG C, after reaction 1.5h, hydrolysis reaction and polyreaction are carried out completely.After reaction solution is down to room temperature, in the reaction solution of room temperature, add saturated NaCl aqueous solution 10mL carry out breakdown of emulsion, after leaving standstill 30min, there is demixing phenomenon, the mode distilled water wash that the emulsion of layering is filtered by vacuum 6 times, and with vacuum drying oven vacuum-drying 6h under the condition of 45 DEG C, finally obtain taking phase change material as core, polystyrene and silicon-dioxide are the microcapsule of shell, wherein, the ratio of the quality of ammonium persulphate and the quality sum of tetradecanoic acid, vinylbenzene and tetraethoxy is 1:16.
Characterized known by electron scanning micrograph: Microcapsules Size is 160nm ~ 200nm, even particle size distribution, and the shape matching of microcapsule is regular, smooth surface.
(2) the ITO conductive glass of printing opacity is cut into the fritter of 2*1.5cm, the fritter conductive glass cut is placed in dilute hydrochloric acid, dehydrated alcohol, each ultrasonic cleaning 15min of deionized water respectively, dries up stand-by.The microcapsule taking 1g good dispersity are placed in beaker, add deionized water to 10ml, and ultrasonic vibration 30min obtains the dispersion liquid of microcapsule.Measure in the weighing bottle moving to two 2*2.5ml, conductive glass stand-by for wash clean is vertically inserted wherein.Vertical-growth 12h under air dry oven 55 DEG C of temperature of reaction, thus obtained self-assembly has the conductive glass of microcapsule layer.
(3) conductive glass of microcapsule layer self-assembly is had to put in 100mL polymeric aluminum chlorides solution, the concentration 0.05wt% of polymeric aluminum chlorides solution, take out dry after 1min, and then conductive glass is put into 100mL triamino solution of silane, the solvent dehydrated alcohol of this solution, the concentration of triamino solution of silane is 0.5wt%, and the chemical formula of triamino silane is H
2n-CH
2-CH
2-NH-CH
2-CH
2-NH-(CH
2)
3-Si-(OCH
3)
3, take out dry after 20min, obtain the conductive glass being assembled with modified microcapsule layer.
(4) take 2mg tellurium powder and 24mg sodium borohydride, in the middle of the bottle moving to band bottle stopper, logical nitrogen 5min, builds bottle stopper.Syringe extracts high purity water 2mL, is expelled in bottle, and then discharges the gas that in bottle, reaction produces.Put in water-bath by whole small bottle packing, temperature of reaction is 32 DEG C, takes out after 2h, is prepared into the precursor liquid that purple is fresh.
100mg Cadmium chloride fine powder adds in 100mL water, and glass stick is stirred to Cadmium chloride fine powder particle and dissolves completely, and add Thiovanic acid (TGA) and more whole liquid is moved to autoclave inside liner, letting nitrogen in and deoxidizing 30min, obtains mixed solution.
Good seal is except the cadmium chloride solution of peroxide, syringe extracts the fresh precursor liquid for preparing of 1mL and is quickly moved to (molar ratio of tellurium powder, sodium borohydride, Cadmium chloride fine powder and Thiovanic acid is 1:41:33:9) in cadmium chloride solution, add sodium hydroxide solution and PH is adjusted to 10, build lid, assemble autoclave, 80 DEG C of hydro-thermal reaction 12h, obtain the quantum dot aqueous solution that Thiovanic acid is modified.
(5) conductive glass being assembled with modified microcapsule layer that step (3) obtains vertically is positioned over the quantum dot aqueous solution 1h that Thiovanic acid is modified, after seasoning, repeat, 5 times repeatedly, complete five layers of quantum dot self-assembly on photon crystal film, thus form quantum dot composite material.
(6) quantum dot composite material under adopting spectrophotofluorometer to detect differing temps, the excitation wavelength 400nm of quantum dot, under spectrophotofluorometer incidence and exit slit spectral band-width are the condition of 5nm, measure the fluorescence spectrum of system, obtain maximum fluorescence intensity.
Table 1
| 30℃ | 40℃ | 50℃ | 56℃ | 60℃ | 65℃ | |
| Maximum fluorescence intensity (a.u.) | 74 | 72 | 76 | 388 | 392 | 391 |
Embodiment 2
(1) be palmitinic acid, vinylbenzene and tetraethoxy that 10:15:4 combined phase-change temperature is 62 ~ 63 DEG C in mass ratio, obtain mixture;
Said mixture is added in 500mL round-bottomed flask, sheet stainless steel is adopted to stir, heating in water bath to 70 DEG C under the stirring velocity of 1500 turns/min, the Sodium dodecylbenzene sulfonate of 1g is joined in the deionized water of 100mL and be uniformly dispersed, and to add in round-bottomed flask after emulsification 10min, and then be warming up to 80 DEG C, emulsification 20min is continued under the stirring velocity of 1500 turns/min, obtain uniform oyster white microemulsion, wherein, the ratio of the quality of Trombovar and the quality sum of palmitinic acid, vinylbenzene and tetraethoxy is 1:25;
After emulsification completes, the temperature of water-bath is adjusted to 85 DEG C.The ammonium persulphate of 1g is dissolved in the deionized water of 7.5mL, and drops in round-bottomed flask slowly completely.After stirring 15min with the stirring velocity of 1500 turns/min, churned mechanically speed is adjusted to 1000 turns/min, and the temperature of water-bath is adjusted to 85 DEG C, after reaction 1h, hydrolysis reaction and polyreaction are carried out completely.After reaction solution is down to room temperature, in the reaction solution of room temperature, add saturated NaCl aqueous solution 10mL carry out breakdown of emulsion, after leaving standstill 30min, there is demixing phenomenon, the mode distilled water wash that the emulsion of layering is filtered by vacuum 5 times, and with vacuum drying oven vacuum-drying 4h under the condition of 50 DEG C, finally obtain taking phase change material as core, polystyrene and silicon-dioxide are the microcapsule of shell, and wherein, the ratio of the quality sum of the quality of ammonium persulphate and palmitinic acid, vinylbenzene and tetraethoxy is 1:25.
Characterized known by electron scanning micrograph: Microcapsules Size is 100nm ~ 140nm, even particle size distribution, and the shape matching of microcapsule is regular, smooth surface.
(2) the ITO conductive glass of printing opacity is cut into the fritter of 2*1.5cm, the fritter conductive glass cut is placed in dilute hydrochloric acid, dehydrated alcohol, each ultrasonic cleaning 15min of deionized water respectively, dries up stand-by.The microcapsule taking 1g good dispersity are placed in beaker, add deionized water to 10ml, and ultrasonic vibration 30min obtains the dispersion liquid of microcapsule.Measure in the weighing bottle moving to two 2*2.5ml, conductive glass stand-by for wash clean is vertically inserted wherein.Vertical-growth 12h under air dry oven 55 DEG C of temperature of reaction, thus obtained self-assembly has the conductive glass of microcapsule layer.
(3) take 2mg selenium powder and 24mg sodium borohydride, in the middle of the bottle moving to band bottle stopper, logical nitrogen 5min, builds bottle stopper.Syringe extracts high purity water 2mL, is expelled in bottle, and then discharges the gas that in bottle, reaction produces.Put in water-bath by whole small bottle packing, temperature of reaction is 32 DEG C, takes out after 2h, is prepared into the precursor liquid that purple is fresh.
100mg Cadmium chloride fine powder adds in 100mL water, and glass stick is stirred to Cadmium chloride fine powder particle and dissolves completely, and add Thiovanic acid (TGA) and more whole liquid is moved to autoclave inside liner, letting nitrogen in and deoxidizing 30min, obtains mixed solution.
Good seal is except the cadmium chloride solution of peroxide, syringe extracts the fresh precursor liquid for preparing of 1mL and is quickly moved to (molar ratio of selenium powder, sodium borohydride, Cadmium chloride fine powder and Thiovanic acid is 1:41:33:9) in cadmium chloride solution, add sodium hydroxide solution and PH is adjusted to 10, build lid, assemble autoclave, 80 DEG C of hydro-thermal reaction 12h, obtain the quantum dot aqueous solution that Thiovanic acid is modified.
(4) conductive glass being assembled with microcapsule layer that step (2) obtains vertically is positioned over the quantum dot aqueous solution 1h that Thiovanic acid is modified, after seasoning, repeat, 6 times repeatedly, complete six layers of quantum dot self-assembly on photon crystal film, thus form quantum dot composite material.
(6) quantum dot composite material under adopting spectrophotofluorometer to detect differing temps, the excitation wavelength of quantum dot is 540nm.Under spectrophotofluorometer incidence and exit slit spectral band-width are the condition of 5nm, measure the fluorescence spectrum of system, obtain maximum relative intensity of fluorescence.
Table 2
| 40℃ | 50℃ | 60℃ | 65℃ | 68℃ | 72℃ | |
| Relative intensity of fluorescence (a.u.) | 69 | 68 | 75 | 378 | 383 | 386 |
Embodiment 3
(1) lauric acid, vinylbenzene and the tetraethoxy that are 43 ~ 45 DEG C for 8:12:2 combined phase-change temperature in mass ratio obtain mixture;
Said mixture is added in 500mL round-bottomed flask, sheet stainless steel is adopted to stir, heating in water bath to 60 DEG C under the stirring velocity of 1500 turns/min, the sodium lauryl sulphate of 1g is joined in the deionized water of 42.5mL and be uniformly dispersed, and to add in round-bottomed flask after emulsification 15min, and then be warming up to 80 DEG C, emulsification 15min is continued under the stirring velocity of 1500 turns/min, obtain uniform oyster white microemulsion, wherein, the ratio of the quality of Sodium dodecylbenzene sulfonate and the quality sum of lauric acid, vinylbenzene and tetraethoxy is 1:20;
After emulsification completes, the temperature of water-bath is adjusted to 85 DEG C.The initiator of 1g and catalyzer ammonium persulphate are dissolved in the deionized water of 7.5mL, and drop in round-bottomed flask slowly completely.After stirring 25min with the stirring velocity of 1500 turns/min, churned mechanically speed is adjusted to 1000 turns/min, and the temperature of water-bath is adjusted to 82 DEG C, after reaction 5h, hydrolysis reaction and polyreaction are carried out completely.After reaction solution is down to room temperature, in the reaction solution of room temperature, add saturated NaCl aqueous solution 10mL carry out breakdown of emulsion, after leaving standstill 30min, there is demixing phenomenon, the mode distilled water wash that the emulsion of layering is filtered by vacuum 4 times, and with vacuum drying oven vacuum-drying 5h under the condition of 48 DEG C, finally obtain taking phase change material as core, polystyrene and silicon-dioxide are the microcapsule of shell, and wherein, the ratio of the quality sum of the quality of ammonium persulphate and lauric acid, vinylbenzene and tetraethoxy is 1:20.
Characterized known by electron scanning micrograph: Microcapsules Size is 80nm ~ 110nm, even particle size distribution, and the shape matching of microcapsule is regular, smooth surface.
(2) the ITO conductive glass of printing opacity is cut into the fritter of 2*1.5cm, the fritter conductive glass cut is placed in dilute hydrochloric acid, dehydrated alcohol, each ultrasonic cleaning 15min of deionized water respectively, dries up stand-by.The microcapsule taking 1g good dispersity are placed in beaker, add deionized water to 10ml, and ultrasonic vibration 30min obtains the dispersion liquid of microcapsule.Measure in the weighing bottle moving to two 2*2.5ml, conductive glass stand-by for wash clean is vertically inserted wherein.Vertical-growth 12h under air dry oven 55 DEG C of temperature of reaction, thus obtained self-assembly has the conductive glass of microcapsule layer.
(3) conductive glass of microcapsule layer self-assembly is had to be positioned in 100mL polymeric aluminum chlorides solution, the concentration 0.08wt% of polymeric aluminum chlorides solution, take out dry after 1min, and then conductive glass is put into 100mL triamino solution of silane, the solvent dehydrated alcohol of this solution, the concentration of triamino solution of silane is 0.6wt%, and the chemical formula of triamino silane is H
2n-CH
2-CH
2-NH-CH
2-CH
2-NH-(CH
2)
3-Si-(OCH
3)
3, take out dry after 20min, obtain the conductive glass being assembled with modified microcapsule layer.
(4) take 2mg selenium powder and 24mg sodium borohydride, in the middle of the bottle moving to band bottle stopper, logical nitrogen 5min, builds bottle stopper.Syringe extracts high purity water 2mL, is expelled in bottle, and then discharges the gas that in bottle, reaction produces.Put in water-bath by whole small bottle packing, temperature of reaction is 32 DEG C, takes out after 2h, is prepared into the precursor liquid that purple is fresh.
100mg zinc nitrate adds in 100mL water, and glass stick is stirred to zinc nitrate particle and dissolves completely, and add Thiovanic acid (TGA) and more whole liquid is moved to autoclave inside liner, letting nitrogen in and deoxidizing 30min, obtains mixed solution.
Good seal is except the zinc nitrate solution of peroxide, syringe extracts the fresh precursor liquid for preparing of 1mL and is quickly moved to (molar ratio of selenium powder, sodium borohydride, zinc nitrate and Thiovanic acid is 1:41:33:9) in zinc nitrate solution, add sodium hydroxide solution and PH is adjusted to 10, build lid, assemble autoclave, 80 DEG C of hydro-thermal reaction 12h, obtain the quantum dot aqueous solution that Thiovanic acid is modified.
(5) conductive glass being assembled with modified microcapsule layer that step (3) obtains vertically is positioned over the quantum dot aqueous solution 1h that Thiovanic acid is modified, after seasoning, repeat, 5 times repeatedly, complete five layers of quantum dot self-assembly on photon crystal film, thus form quantum dot composite material.
(6) quantum dot composite material under adopting spectrophotofluorometer to detect differing temps, the excitation wavelength of quantum dot is 470nm.Under spectrophotofluorometer incidence and exit slit spectral band-width are the condition of 5nm, measure the fluorescence spectrum of system, obtain maximum relative intensity of fluorescence.
Table 3
| 25℃ | 35℃ | 41℃ | 46℃ | 50℃ | 55℃ | |
| Relative intensity of fluorescence (a.u.) | 75 | 71 | 80 | 408 | 421 | 423 |
Comparative example 1
(1) tetraethoxy is added in 500mL round-bottomed flask, sheet stainless steel is adopted to stir, heating in water bath to 60 DEG C under the stirring velocity of 1500 turns/min, the Sodium dodecylbenzene sulfonate of 1g is joined in 100mL water, be uniformly dispersed, and to add in round-bottomed flask after emulsification 20min, and then be warming up to 80 DEG C, emulsification 10min is continued under the stirring velocity of 1500 turns/min, obtain uniform microemulsion, wherein, the quality of Sodium dodecylbenzene sulfonate and the ratio of tetraethoxy are 1:13;
After emulsification completes, the temperature of water-bath is adjusted to 85 DEG C.The ammonium persulphate of 1g is dissolved in the deionized water of 7.5mL, and drops in round-bottomed flask slowly completely.After stirring 30min with the stirring velocity of 1500 turns/min, churned mechanically speed is adjusted to 1000 turns/min, and the temperature of water-bath is adjusted to 80 DEG C, after reaction 1.5h, hydrolysis reaction and polyreaction are carried out completely.After reaction solution is down to room temperature, in the reaction solution of room temperature, add saturated NaCl aqueous solution 10mL carry out breakdown of emulsion, after leaving standstill 30min, there is demixing phenomenon, the mode distilled water wash that the emulsion of layering is filtered by vacuum 6 times, and with vacuum drying oven vacuum-drying 6h under the condition of 45 DEG C, obtain silicon dioxide particles, wherein, the quality of ammonium persulphate and the ratio of silicon-dioxide are 1:16.Characterized known by electron scanning micrograph: particle diameter is 110nm ~ 150nm.
(2) the ITO conductive glass of printing opacity is cut into the fritter of 2*1.5cm, the fritter conductive glass cut is placed in dilute hydrochloric acid, dehydrated alcohol, each ultrasonic cleaning 15min of deionized water respectively, dries up stand-by.The microcapsule taking 1g good dispersity are placed in beaker, add deionized water to 10ml,
Ultrasonic vibration 30min, obtains the dispersion liquid of microcapsule.Measure in the weighing bottle moving to two 2*2.5ml, conductive glass stand-by for wash clean is vertically inserted wherein.Vertical-growth 12h under air dry oven 55 DEG C of temperature of reaction, thus obtained self-assembly has the conductive glass of microcapsule layer.
(3) take 2mg tellurium powder and 24mg sodium borohydride, in the middle of the bottle moving to band bottle stopper, logical nitrogen 5min, builds bottle stopper.Syringe extracts high purity water 2mL, is expelled in bottle, and then discharges the gas that in bottle, reaction produces.Put in water-bath by whole small bottle packing, temperature of reaction is 32 DEG C, takes out after 2h, is prepared into the precursor liquid that purple is fresh.
100mg Cadmium chloride fine powder adds in 100mL water, and glass stick is stirred to Cadmium chloride fine powder particle and dissolves completely, and add Thiovanic acid (TGA) and more whole liquid is moved to autoclave inside liner, letting nitrogen in and deoxidizing 30min, obtains mixed solution.
Good seal is except the cadmium chloride solution of peroxide, syringe extracts the fresh precursor liquid for preparing of 1mL and is quickly moved to (molar ratio of tellurium powder, sodium borohydride, Cadmium chloride fine powder and Thiovanic acid is 1:41:33:9) in cadmium chloride solution, add sodium hydroxide solution and PH is adjusted to 10, build lid, assemble autoclave, 80 DEG C of hydro-thermal reaction 12h, obtain the quantum dot aqueous solution that Thiovanic acid is modified.
(4) conductive glass being assembled with microcapsule layer that step (2) obtains vertically is positioned over the quantum dot aqueous solution 1h that Thiovanic acid is modified, after seasoning, repeat, 5 times repeatedly, complete five layers of quantum dot self-assembly on photon crystal film, thus form quantum dot composite material.
(6) quantum dot composite material under adopting spectrophotofluorometer to detect differing temps, mixed solution system under adopting spectrophotofluorometer to detect differing temps, the excitation wavelength 400nm of quantum dot, under spectrophotofluorometer incidence and exit slit spectral band-width are the condition of 5nm, the fluorescence spectrum of mensuration system, obtains maximum fluorescence intensity.
Table 4
| 30℃ | 40℃ | 50℃ | 56℃ | 60℃ | 65℃ | |
| Relative intensity of fluorescence (a.u.) | 453 | 457 | 459 | 462 | 464 | 468 |
Known by showing the data of 1-3: the envrionment temperature of the composite quantum dot microballoon of each embodiment is once a little more than the transformation temperature of higher fatty acid, higher fatty acid in quantum dot composite material undergoes phase transition, solid-stately transparent liquid state is become by lighttight, light transmission so successively through microcapsule layer and substrate significantly increases, the intensity (luminous intensity) of its photoluminescence spectra can occur significantly to increase, and such quantum dot is compounded in phase transformation temperature points annex and has very strong temperature sensitivity.And the envrionment temperature of the composite quantum dot microballoon of comparative example 1 is at elevation process, fluorescence intensity change is very little, and under the impact of fluorescent noise, be unfavorable for that instrument is monitored, temperature sensitivity is poor.
Test case 1
The quantum dot composite material of embodiment 1-3 and comparative example 1 is reused test containing 0.5 μ g/L copper ion solution.Result shows: after the quantum dot composite material of embodiment 1-3 uses 10 times, fluorescence can return to original more than 96%, does not occur that quantum dot comes off problem; And the quantum dot composite material of comparative example 1, after use 5 times, fluorescence drops to original 90%, and after using 8 times, fluorescence drops to less than 80%, and occurs quantum dot obscission, after use 12 times, occurs severe detachment problem, can not continue to use again.
Claims (10)
1. one kind has the quantum dot composite material of two-pack substrate, it is characterized in that, it comprises Mght-transmitting base material, microcapsule layer and quantum dot layer, described microcapsule layer is positioned on described Mght-transmitting base material, and described quantum dot layer is positioned in described microcapsule layer, and described microcapsule layer is formed by microcapsule self-assembly, described quantum dot layer is formed by quantum dot self-assembly, described microcapsule comprise shell and kernel, and described shell contains polystyrene and silicon-dioxide, and described kernel is higher fatty acid.
2. according to quantum dot composite material according to claim 1, it is characterized in that: the surface of described microcapsule layer is through triamino silane and polymerize aluminum chloride modification, and the chemical formula of described triamino silane is H
2n-CH
2-CH
2-NH-CH
2-CH
2-NH-(CH
2)
3-Si-(OCH
3)
3.
3. according to the quantum dot composite material described in claim 1 or 2, it is characterized in that: in described quantum dot composite material, the part by weight of described higher fatty acid, polystyrene and silicon-dioxide is (2 ~ 6): (2 ~ 10): 0.29.
4. according to the quantum dot composite material described in claim 1 or 2, it is characterized in that: described microcapsule layer thickness is 50nm ~ 600nm, be preferably 60nm ~ 500nm, described quantum dot layer thickness is 2 ~ 150nm, is preferably 5 ~ 100nm; The particle diameter of described microcapsule is 50nm ~ 600nm, is preferably 60nm ~ 500nm.
5. according to the quantum dot composite material described in claim 1 or 2, it is characterized in that: described quantum dot is one or more in CdTe, CdSe, InP, InAs, CdSe/CdS, CdSe/ZnS, CdSe/ZnSe, CdTe/ZnS, CdHgTe/ZnS, HgTe/HgCdS quantum dot; Described higher fatty acid is C
9~ C
18higher fatty acid, be preferably capric acid, lauric acid, tetradecanoic acid, palmitinic acid, Palmiticacid, the acid of pearly-lustre ester, stearic acid, oleic acid, one or more in linolic acid.
6., as the preparation method with the quantum dot composite material of two-pack substrate in claim 1-5 as described in any one, it is characterized in that, the method comprises the steps:
(1) will be (2 ~ 6) by weight proportion: (2 ~ 10): 1 mixing higher fatty acid, vinylbenzene and tetraethoxy, then heating makes higher fatty acid melting and stirs, obtained mixture, then water phase surfactant mixture is joined and add in described mixture, dispersed with stirring evenly obtains emulsion, then in described emulsion, drip the aqueous solution of ammonium persulphate, react 0.5 ~ 6h at 60 ~ 95 DEG C after, after being down to room temperature, then breakdown of emulsion is carried out, leave standstill, vacuum filters, washing and drying, finally obtain taking higher fatty acid as core, polystyrene and silicon-dioxide are the microcapsule of shell,
(2) described microcapsule are added to the water, ultrasonic vibration, obtains the dispersion liquid of microcapsule, is vertically inserted by Mght-transmitting base material in the dispersion liquid for the preparation of microcapsule and carries out vertical-growth, take out dry, the obtained microcapsule layer being covered in described Mght-transmitting base material surface;
(3) Mght-transmitting base material being coated with microcapsule layer is vertically positioned in the aqueous solution of quantum dot carries out vertical-growth, take out dry, just obtain quantum dot composite material.
7. in accordance with the method for claim 6, it is characterized in that: the ratio of the quality sum of the quality of the tensio-active agent in described water phase surfactant mixture and higher fatty acid, vinylbenzene and tetraethoxy is 1:(10 ~ 30), the concentration of the aqueous solution of described tensio-active agent is 0.5wt% ~ 5wt%; The ratio of the quality sum of the quality of the ammonium persulphate in described ammonium persulfate solution and higher fatty acid, vinylbenzene and tetraethoxy is 1:(10 ~ 50), the concentration of described ammonium persulfate solution is 1wt% ~ 10wt%; Described tensio-active agent is one or more in polyoxyethylene glycol, sucrose ester, polysorbate, octadecyl benzenesulfonic acid, sodium lauryl sulphate, Trombovar, Sodium palmityl sulfate, Sodium dodecylbenzene sulfonate.
8. according to the method described in claim 6 or 7, it is characterized in that: the aqueous solution of described quantum dot is the aqueous solution of the quantum dot that mercaptan carboxylic acid modifies.
9. according to the method described in claim 6 or 7, it is characterized in that: before the Mght-transmitting base material being coated with microcapsule layer is vertically positioned over the aqueous solution of quantum dot, by polymeric aluminum chlorides solution and triamino solution of silane modification microcapsule layer, concrete steps are as follows: be positioned in the solution of polymerize aluminum chloride by the Mght-transmitting base material being coated with microcapsule layer, then drying is taken out, and then be positioned in triamino solution of silane, then take out drying.
10. in accordance with the method for claim 9, it is characterized in that: the concentration 0.20wt% ~ 0.01wt% of described polymeric aluminum chlorides solution, described triamino solution of silane is the ethanolic soln containing 0.5wt% ~ 2.0wt% triamino silane.
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