CN108070370A - 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
A kind of quantum dot composite material with bi-component substrate of disclosure of the invention and preparation method thereof.The quantum dot composite material includes Mght-transmitting base material, microcapsule layer and quantum dot layer, the microcapsule layer is located on the Mght-transmitting base material, the quantum dot layer is located in the microcapsule layer, the microcapsule layer is formed by microcapsules self assembly, the quantum dot layer is formed by quantum dot self assembly, the microcapsules include shell and kernel, and the shell contains polystyrene and silica, and the kernel is higher fatty acids.The quantum dot composite material of the present invention, the quanta point material of the present invention is not only able to keep the excellent properties such as general quantum dot luminous efficiency height, photochemical stability, and luminous intensity also has specific temperature sensitivity value, is associated or monitors available for specific temperature.The quantum dot composite material of the present invention also has good reusability, and quantum dot will not fall off problem.
Description
The application is application number 2015109955332,24 days December 2015 applying date, denomination of invention " with bi-component
The divisional application of quantum dot composite material of substrate and preparation method thereof ".
Technical field
The present invention relates to a kind of quantum dot composite material, more specifically to a kind of quantum with bi-component substrate
Point composite material and preparation method thereof.
Background technology
When material section size is reduced to nanometer scale, due to its nano effect, material will generate many novel and uniqueness
Better than the various functional characteristics of traditional material, valency is had a wide range of applications in fields such as microelectronics, bioengineering, chemical industry, medicine
Value.
In recent years, using transition metal as the nano luminescent material of active ions, due to its excellent optical characteristics, such as absorb
Wavelength is wide and continuous, and fluorescence emission peak is tunable, fluorescence lifetime length etc., in luminescent device, fluorescence imaging, solar cell, glimmering
Light is detected shows wide application prospect with fields such as biomarkers.However when quantum dot is used for luminescent device or fluoroscopic examination
When, in the range of 25-100 DEG C, the red shift that quantum dot absworption peak wavelength and photoluminescence spectra wavelength occur is generally individually smaller than
10nm.Furthermore although luminous intensity has certain linear relationship with temperature, varying with temperature, luminous intensity is very small,
At a temperature of less than thermal quenching, smaller temperature change will not cause luminous intensity significantly to enhance or weaken.Therefore, the prior art
The very high quantum dot of temperature sensitivity cannot be prepared.
The content of the invention
It is very high with double the present invention provides a kind of temperature sensitivity in order to overcome shortcoming of the prior art
The quantum dot composite material of component substrate.
A kind of quantum dot composite material with bi-component substrate provided by the invention, including Mght-transmitting base material, micro- glue
Cystoblast and quantum dot layer, the microcapsule layer are located on the Mght-transmitting base material, and the quantum dot layer is located at the microcapsule layer
On, the microcapsule layer is formed by microcapsules self assembly, and the quantum dot layer is formed, micro- glue by quantum dot self assembly
Capsule includes shell and kernel, and the shell contains polystyrene and silica, and the kernel is higher fatty acids.
The quantum dot is the quantum dot for dredging yl carboxylic acid modification；Triamido silane and polymerization are passed through in the surface of the microcapsules
Aluminum chloride modified processing, wherein, the chemical formula of triamido silane is H2N-CH2-CH2-NH-CH2-CH2-NH-(CH2)3-Si-
(OCH3)3。
In the quantum dot composite material, the SiO2Weight ratio with the higher fatty acids is (0.2~1.2)
∶1。
Quantum dot commonly used in the art may be employed in the quantum dot.The quantum dot for CdTe, CdSe, InP,
One kind in InAs, CdSe/CdS, CdSe/ZnS, CdSe/ZnSe, CdTe/ZnS, CdHgTe/ZnS, HgTe/HgCdS quantum dot
It is or several.The grain size of quantum dot can be 1-100nm, be preferably 2-20nm, but be not restricted to this.The higher fatty acids is C9
~C18Higher fatty acids, be preferably capric acid, lauric acid, myristic acid, palmitic acid, palmitic acid, pearly-lustre ester acid, stearic acid, oil
One or more in acid, linoleic acid.
The microcapsule layer thickness is 50nm~600nm, is preferably 60nm~500nm, the quantum dot layer thickness for 2~
150nm is preferably 5~100nm；The grain size of the microcapsules is 50nm~600nm, is preferably 60nm~500nm.
Mght-transmitting base material is base material commonly used in the art, is, for example, the ITO electro-conductive glass of light transmission.
The present invention also provides the above-mentioned quantum dot composite material with bi-component substrate preparation method, this method includes
Following steps：
(1) will be (2~6) by weight proportion: (2~10): 1 mixing higher fatty acids, styrene and ethyl orthosilicate, so
Heating makes higher fatty acids melt and stir evenly afterwards, and mixture is made, then aqueous surfactant solution is added in institute
It states in mixture and adds in, be dispersed with stirring and uniformly obtain emulsion, the aqueous solution of ammonium persulfate is then added dropwise in the emulsion,
It after reacting 0.5~6h at 60~95 DEG C, is cooled to room temperature, is then demulsified, stood, vacuum filters, washs and dries, most
It is obtained eventually using higher fatty acids as core, polystyrene and the microcapsules that silica is shell,
(2) microcapsules are added to the water, ultrasonic vibration 30min obtains the dispersion liquid of microcapsules, by Mght-transmitting base material
It is inserted perpendicularly into the dispersion liquid for be used to prepare microcapsules and carries out vertical-growth, take out drying, be made and be covered in Mght-transmitting base material table
The microcapsule layer in face；
(3) Mght-transmitting base material that will be covered with microcapsule layer is disposed vertically and is vertically given birth in the aqueous solution of quantum dot
It is long, drying is taken out, just obtains quantum dot composite material.
In (1) step, quality and higher fatty acids, the benzene of the surfactant in the aqueous surfactant solution
The ratio of the quality sum of ethylene and ethyl orthosilicate is 1: (10~30), the concentration of the aqueous solution of the surfactant are
0.5wt%~5wt%；The quality of ammonium persulfate in the ammonium persulfate solution and higher fatty acids, styrene and positive silicic acid
The ratio of the quality sum of ethyl ester is 1: (10~50), the concentration of the ammonium persulfate solution is 1wt%~10wt%；The table
Face activating agent is polyethylene glycol, sucrose ester, polysorbate, octadecyl benzenesulfonic acid, lauryl sodium sulfate, myristyl sulfate
One or more in sodium, sodium hexadecyl sulfate, neopelex.
In (2) step, the aqueous solution of the quantum dot is the aqueous solution of the quantum dot of mercaptan carboxylic acid's modification.The immersion
Time be 5min~240min.
It is molten with polymeric aluminum chlorides solution and triamido silane before the microcapsules are added to the aqueous solution of quantum dot
Liquid modification microcapsules, are as follows：The Mght-transmitting base material that will be covered with microcapsule layer is positioned over aluminium polychloride
In solution, drying is then taken out, is then then added in triamido solution of silane, then takes out drying.Wherein, aluminium polychloride
Concentration 0.20wt%~0.01wt% of solution.The triamido solution of silane is to contain 0.5wt%~2.0wt% triamido silicon
The ethanol solution of alkane.The dosage of polymeric aluminum chlorides solution and triamido solution of silane submerges microcapsule layer, but is not restricted to
This.
The aqueous solution of the quantum dot is the water-soluble quantum dot of mercaptan carboxylic acid's modification, is repaiied for conventional use of mercaptan carboxylic acid
The water-soluble quantum dot of decorations, the solution of conventional concentration.Its preparation method is as follows：Tellurium powder and sodium borohydride are mixed with water,
Inert ambient environment and constant temperature are reacted, quantum dot precursor liquid is made；Caddy is dissolved in water, then successively
Mercaptan carboxylic acid and sodium hydroxide solution are added in, obtains mixed liquor, entire mixed liquor is moved into autoclave inside liner, letting nitrogen in and deoxidizing,
Then the quantum dot precursor liquid is added in the mixed liquor, carries out hydro-thermal reaction in autoclave, obtain the sulfydryl carboxylic
The water-soluble quantum dot of acid modification.The tellurium powder, sodium borohydride, caddy and the molar ratio of mercaptan carboxylic acid are 1: (20~60)
: (15~45): (6~15).Mercaptan carboxylic acid is preferably thioacetic acid, 2 mercaptopropionic acid and 3- mercaptopropionic acids.
Compared with prior art, it is of the invention to have the following advantages that：
(1) quantum dot composite wood section of the invention, quantum dot of the invention are not only able to that general quantum dot light emitting is kept to imitate
The excellent properties such as rate height, photochemical stability, and luminous intensity also has specific temperature sensitivity value, available for specific
Temperature is associated or monitors.It is embodied in：When the phase transition temperature of environment temperature rise higher fatty acids, quantum dot is compound
Higher fatty acids in material is undergone phase transition, and becomes transparent liquid by lighttight solid-state, the translucency of such microcapsules is big
Width increases, and sequentially passes through the intensity (luminous intensity) of the photoluminescence spectra of microcapsule layer and transparent base material and can occur significantly to increase
Add；When environment temperature is less than the phase transition temperature of higher fatty acids, lighttight solid-state is become by transparent liquid, so micro- glue
The translucency of capsule is greatly reduced, and sequentially passes through the intensity (luminous intensity) of the photoluminescence spectra of microcapsule layer and transparent base material
It can decline to a great extent.Therefore, quantum dot composite material has very strong temperature near higher fatty acids phase transformation temperature points
Sensibility.
It, can be by on-line real time monitoring integral system when the quantum dot composite material of the present invention is applied to fluoroscopic examination
Fluorescence is abnormal the place of variation, can detect the temperature minor variations near temperature sensitivity value.When for quantum dot
It, can be by adjusting temperature value, to regulate and control the significantly change of quantum dot light emitting intensity during device.
The quantum dot composite material of the present invention is suitable for the close sample monitoring with the phase transformation temperature points of higher fatty acids,
It, can be by selecting the higher fatty acids of the different temperatures trade mark, to change since higher fatty acids has the unusual multi-temperature trade mark
The temperature sensitivity value of quantum dot composite material Fatty Acids, so as to realize the real-time monitoring of different samples.
(2) quantum dot composite material of the invention, polystyrene form thicker cladding shell, and polyphenyl with silica
Ethylene has stronger impact strength, is conducive to improve the thermal stability and structural stability of the microcapsules, and can be well
The shortcomings that making up the elasticity of silica and poor compactness, advantageously forms fine and close shell and phase-change material is avoided to leak,
Improve stability.
Silica has the characteristics such as high structural strength, thermostabilization, mechanically stable, chemical stabilization, high heat conduction, can be very
It is good to make up that polystyrene thermostabilization and chemical stability are relatively poor, mechanical property is relatively poor and heat conductivility is relatively poor
The shortcomings that.
Polystyrene and silicon dioxide composite material combine the advantages of polystyrene and silica, and can mutually more
The shortcomings that benefit is individually present has complementary advantages, so as to improve the thermal stability of the microcapsules, chemical stability, mechanically stable
Property and structural stability, so that the high stability of microcapsules.
(3) in the preparation process of quantum dot composite material, ammonium persulfate draws the present invention as the initiator of polymerisation
It sends out polystyrene polymerization and generates poly- polystyrene, while as ester-type hydrolysis catalyst teos hydrolysis generation dioxy
SiClx is so carried out at the same time the interface polymerization reaction of polystyrene and the interface hydrolysis of ethyl orthosilicate, interfacial polymerization
Synergistic effect between reaction and hydrolysis, controls the W-response speed of reaction system, makes preparation well
Microcapsules have good structural homogeneity and stability, so as to realize the microcapsules of even particle size distribution, stable structure
Preparation.
After microcapsule layer is prepared, then aggregated aluminium chloride and diamino silanes solution treatment, so as to modified microcapsule layer
Surface charge, and three-dimensional multidigit point grafting is combined to form with thin yl carboxylic acid in the polyamino of triamido silane, so in table
Under the double action of surface charge and the grafting of multidigit point, quantum dot is very strongly assembled in the surface of microcapsule layer, can be effectively
Prevent coming off for quantum dot surface sulfydryl class ligand, quantum dot sheet have extraordinary time stability and certain acid,
At the same time acid, alkaline stability and antioxidative stabilizer in alkali, oxidation environment also maintain the good biological compatibility of quantum dot
Property, so as to substantially increase the stability of quantum dot in a particular application.
(4) quantum dot composite wood section of the invention, can be used in quantum dot in luminescent device, fluorescence imaging, solar energy
Battery, fluoroscopic examination and biomarker etc..
Specific embodiment
The preparation process of the quantum dot composite material further illustrated the present invention below by embodiment, but it is not considered that
Present invention is limited only by following embodiment, wherein wt% is mass fraction.
The preparation method of the quantum dot solution of mercaptan carboxylic acid's modification uses preparation method commonly used in the art.The present invention
By the metal salt containing quantum dot cation, (cation for example can be Zn2+、Cd2+Or Hg2+) positive with mercaptan carboxylic acid's complexing generation
Ion precursor, then (anion for example can be S with anion precursor2-、Se2-Or Te2-) be heated to reflux so that quantum dot into
Core is simultaneously grown, so as to which the quantum dot solution of mercaptan carboxylic acid's modification be made.The temperature being heated to reflux is 60~90 DEG C, the time for 3~
12h.For example, the cadmium telluride of mercaptan carboxylic acid's modification, the preparation method of CdSe quantum dots solution may be referred to CN102786037A,
The preparation method of the ZnS quantum dots solution of mercaptan carboxylic acid's modification may be referred to CN103242829A.Quantum dot can also be by mercapto
Cadmium sulfide, zinc selenide or the telluride zinc solution self-chambering of yl carboxylic acid modification form.Sulfydryl carboxylic is described in detail in the following each embodiment of the present invention
The preparation method of the cadmium telluride of acid modification.
Embodiment 1
(1) in mass ratio it is myristic acid, styrene and positive silicic acid second that 6: 9: 1 combined phase-change temperature are 52~54 DEG C
Ester obtains mixture；
Said mixture is added in 500mL round-bottomed flasks, is stirred using sheet Stainless Steel, in 1500 turns/min
Mixing speed under heating water bath to 60 DEG C, the neopelex of 1g is added in 100mL water, is uniformly dispersed, and
It is added to after emulsifying 20min in round-bottomed flask, is then warming up to 80 DEG C again, continues to emulsify under the mixing speed of 1500 turns/min
10min obtains uniform microemulsion, wherein, quality and myristic acid, styrene and the positive silicic acid second of neopelex
The ratio of the quality sum of ester is 1: 13；
After the completion of emulsification, the temperature of water-bath is adjusted to 85 DEG C.The ammonium persulfate of 1g is dissolved in the deionized water of 7.5mL
In, and be slowly added dropwise to completely into round-bottomed flask.After the mixing speed stirring 30min of 1500 turns/min, machinery is stirred
The speed mixed is adjusted to 1000 turns/min, and the temperature of water-bath is adjusted to 80 DEG C, after reacting 1.5h, hydrolysis and polymerisation into
Row is complete.Reaction solution is cooled to room temperature, and the NaCl aqueous solutions 10mL that saturation is added into the reaction solution of room temperature is demulsified, and is stood
After 30min, there is lamination, the lotion of layering be washed with distilled water 6 times in a manner that vacuum filters, and with vacuum drying
Case is dried in vacuo 6h under conditions of 45 DEG C, finally obtains using phase-change material as core, and polystyrene and silica are the micro- of shell
Capsule, wherein, the ratio of the quality of ammonium persulfate and the quality sum of myristic acid, styrene and ethyl orthosilicate is 1: 16.
It is characterized by electron scanning micrograph：Microcapsules Size is 160nm~200nm, and particle diameter distribution is uniform,
And the shape of microcapsules is more regular, and surface is smooth.
(2) the ITO electro-conductive glass of light transmission is cut into the fritter of 2*1.5cm, the fritter electro-conductive glass cut is respectively placed in dilute
Hydrochloric acid, absolute ethyl alcohol, deionized water are respectively cleaned by ultrasonic 15min, and drying is for use.The microcapsules for weighing 1g good dispersions are placed in beaker
In, deionized water is added to obtain the dispersion liquid of microcapsules to 10ml, ultrasonic vibration 30min.It measures and moves to two 2*2.5ml's
In measuring cup, for use electro-conductive glass of wash clean is inserted perpendicularly into wherein.Vertical-growth under 55 DEG C of reaction temperatures of air dry oven
12h has the electro-conductive glass of microcapsule layer so as to which self assembly be made.
(3) electro-conductive glass that self assembly has microcapsule layer is put into 100mL polymeric aluminum chlorides solutions, aluminium polychloride
Drying is taken out after the concentration 0.05wt%, 1min of solution, electro-conductive glass is then put into 100mL triamido solution of silane again,
The solvent absolute ethyl alcohol of the solution, the concentration of triamido solution of silane is 0.5wt%, and the chemical formula of triamido silane is H2N-
CH2-CH2-NH-CH2-CH2-NH-(CH2)3-Si-(OCH3)3, drying is taken out after 20min, obtains being assembled with modified microcapsule layer
Electro-conductive glass.
(4) 2mg telluriums powder and 24mg sodium borohydrides are weighed, is moved among the bottle with bottle stopper, leads to nitrogen 5min, covers bottle
Plug.Syringe extracts high purity water 2mL, is injected into bottle, is then then exhausted from the gas that reaction generates in bottle.It will be entire small bottled
It puts in water-bath, reaction temperature is 32 DEG C, is taken out after 2h, is prepared into the fresh precursor liquid of purple.
100mg caddies are added in 100mL water, and glass bar is stirred to caddy particle and is completely dissolved, and add in thioacetic acid
(TGA) entire liquid is moved into autoclave inside liner again, letting nitrogen in and deoxidizing 30min obtains mixed liquor.
Good seal removes the cadmium chloride solution of peroxide, and syringe extracts the fresh precursor liquids prepared of 1mL and is quickly moved to
In cadmium chloride solution (tellurium powder, sodium borohydride, the molar ratio of caddy and thioacetic acid are 1: 41: 33: 9), hydroxide is added in
Sodium solution adjusts PH to 10, covers, assembles autoclave, 80 DEG C of hydro-thermal reaction 12h obtain the quantum of thioacetic acid modification
Point aqueous solution.
(5) electro-conductive glass for being assembled with modified microcapsule layer that step (3) obtains is disposed vertically and is modified in thioacetic acid
Quantum dot aqueous solution 1h, after natural drying, repeat, 5 times repeatedly, complete five layers of quantum dot on photon crystal film
Self assembly, so as to form quantum dot composite material.
(6) using the quantum dot composite material under sepectrophotofluorometer detection different temperatures, the excitation wavelength of quantum dot
400nm under conditions of sepectrophotofluorometer is incident and exit slit spectral band-width is 5nm, measures 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) in mass ratio it is palmitic acid, styrene and positive silicic acid second that 10: 15: 4 combined phase-change temperature are 62~63 DEG C
Ester obtains mixture；
Said mixture is added in 500mL round-bottomed flasks, is stirred using sheet stainless steel, in 1500 turns/min
Mixing speed under heating water bath to 70 DEG C, by the neopelex of 1g be added in the deionized water of 100mL disperse
Uniformly, and it is added in round-bottomed flask after emulsification 10min, 80 DEG C is then warming up to again, under the mixing speed of 1500 turns/min
Continue to emulsify 20min, obtain uniform milky microemulsion, wherein, quality and palmitic acid, the styrene of sodium tetradecyl sulfate
Ratio with the quality sum of ethyl orthosilicate is 1: 25；
After the completion of emulsification, the temperature of water-bath is adjusted to 85 DEG C.The ammonium persulfate of 1g is dissolved in the deionized water of 7.5mL
In, and be slowly added dropwise to completely into round-bottomed flask.After the mixing speed stirring 15min of 1500 turns/min, machinery is stirred
The speed mixed is adjusted to 1000 turns/min, and the temperature of water-bath is adjusted to 85 DEG C, and after reacting 1h, hydrolysis and polymerisation carry out
Completely.Reaction solution is cooled to room temperature, and the NaCl aqueous solutions 10mL that saturation is added into the reaction solution of room temperature is demulsified, and is stood
After 30min, there is lamination, the lotion of layering be washed with distilled water 5 times in a manner that vacuum filters, and with vacuum drying
Case is dried in vacuo 4h under conditions of 50 DEG C, finally obtains using phase-change material as core, and polystyrene and silica are the micro- of shell
Capsule, wherein, the ratio of the quality of ammonium persulfate and the quality sum of palmitic acid, styrene and ethyl orthosilicate is 1: 25.
It is characterized by electron scanning micrograph：Microcapsules Size is 100nm~140nm, and particle diameter distribution is uniform,
And the shape of microcapsules is more regular, and surface is smooth.
(2) the ITO electro-conductive glass of light transmission is cut into the fritter of 2*1.5cm, the fritter electro-conductive glass cut is respectively placed in dilute
Hydrochloric acid, absolute ethyl alcohol, deionized water are respectively cleaned by ultrasonic 15min, and drying is for use.The microcapsules for weighing 1g good dispersions are placed in beaker
In, deionized water is added to obtain the dispersion liquid of microcapsules to 10ml, ultrasonic vibration 30min.It measures and moves to two 2*2.5ml's
In measuring cup, for use electro-conductive glass of wash clean is inserted perpendicularly into wherein.Vertical-growth under 55 DEG C of reaction temperatures of air dry oven
12h has the electro-conductive glass of microcapsule layer so as to which self assembly be made.
(3) 2mg selenium powders and 24mg sodium borohydrides are weighed, is moved among the bottle with bottle stopper, leads to nitrogen 5min, covers bottle
Plug.Syringe extracts high purity water 2mL, is injected into bottle, is then then exhausted from the gas that reaction generates in bottle.It will be entire small bottled
It puts in water-bath, reaction temperature is 32 DEG C, is taken out after 2h, is prepared into the fresh precursor liquid of purple.
100mg caddies are added in 100mL water, and glass bar is stirred to caddy particle and is completely dissolved, and add in thioacetic acid
(TGA) entire liquid is moved into autoclave inside liner again, letting nitrogen in and deoxidizing 30min obtains mixed liquor.
Good seal removes the cadmium chloride solution of peroxide, and syringe extracts the fresh precursor liquids prepared of 1mL and is quickly moved to
In cadmium chloride solution (selenium powder, sodium borohydride, the molar ratio of caddy and thioacetic acid are 1: 41: 33: 9), hydroxide is added in
Sodium solution adjusts PH to 10, covers, assembles autoclave, 80 DEG C of hydro-thermal reaction 12h obtain the quantum of thioacetic acid modification
Point aqueous solution.
(4) electro-conductive glass for being assembled with microcapsule layer that step (2) obtains is disposed vertically in the amount of thioacetic acid modification
Son point aqueous solution 1h, after natural drying, repeats, 6 times repeatedly, completes six layers of quantum dot on photon crystal film from group
Dress, so as to form quantum dot composite material.
(6) using the quantum dot composite material under sepectrophotofluorometer detection different temperatures, the excitation wavelength of quantum dot
For 540nm.Under conditions of sepectrophotofluorometer is incident and exit slit spectral band-width is 5nm, the fluorescence light of system is measured
Spectrum, obtains maximum relative intensity of fluorescence.
Table 2
| 40℃ | 50℃ | 60℃ | 65℃ | 68℃ | 72℃ | |
| Maximum fluorescence intensity (a.u.) | 69 | 68 | 75 | 378 | 383 | 386 |
Embodiment 3
(1) in mass ratio it is lauric acid, styrene and ethyl orthosilicate that 8: 12: 2 combined phase-change temperature are 43~45 DEG C
Obtain mixture；
Said mixture is added in 500mL round-bottomed flasks, is stirred using sheet stainless steel, in 1500 turns/min
Mixing speed under heating water bath to 60 DEG C, the lauryl sodium sulfate of 1g is added in the deionized water of 42.5mL disperse it is equal
It is even, and be added in round-bottomed flask emulsify 15min after, be then warming up to 80 DEG C again, under the mixing speed of 1500 turns/min after
Continuous emulsification 15min, obtains uniform milky microemulsion, wherein, quality and lauric acid, the styrene of neopelex
Ratio with the quality sum of ethyl orthosilicate is 1: 20；
After the completion of emulsification, the temperature of water-bath is adjusted to 85 DEG C.The initiator of 1g and catalyst ammonium persulfate are dissolved in
In the deionized water of 7.5mL, and slowly it is added dropwise to completely into round-bottomed flask.It is stirred with the mixing speed of 1500 turns/min
After 25min, churned mechanically speed is adjusted to 1000 turns/min, and the temperature of water-bath is adjusted to 82 DEG C, after reacting 5h, hydrolysis is anti-
It should be carried out with polymerisation complete.Reaction solution is cooled to room temperature, and the NaCl aqueous solutions of saturation are added into the reaction solution of room temperature
10mL is demulsified, and after standing 30min, there is lamination, and the lotion of layering is washed in a manner that vacuum filters with distillation
It washs 4 times, and 5h is dried in vacuo under conditions of 48 DEG C with vacuum drying chamber, finally obtain using phase-change material as core, polystyrene
With the microcapsules that silica is shell, wherein, the quality of ammonium persulfate and the quality of lauric acid, styrene and ethyl orthosilicate it
The ratio of sum is 1: 20.
It is characterized by electron scanning micrograph：Microcapsules Size is 80nm~110nm, and particle diameter distribution is uniform,
And the shape of microcapsules is more regular, and surface is smooth.
(2) the ITO electro-conductive glass of light transmission is cut into the fritter of 2*1.5cm, the fritter electro-conductive glass cut is respectively placed in dilute
Hydrochloric acid, absolute ethyl alcohol, deionized water are respectively cleaned by ultrasonic 15min, and drying is for use.The microcapsules for weighing 1g good dispersions are placed in beaker
In, deionized water is added to obtain the dispersion liquid of microcapsules to 10ml, ultrasonic vibration 30min.It measures and moves to two 2*2.5ml's
In measuring cup, for use electro-conductive glass of wash clean is inserted perpendicularly into wherein.Vertical-growth under 55 DEG C of reaction temperatures of air dry oven
12h has the electro-conductive glass of microcapsule layer so as to which self assembly be made.
(3) electro-conductive glass that self assembly has microcapsule layer is positioned in 100mL polymeric aluminum chlorides solutions, aluminium polychloride
Drying is taken out after the concentration 0.08wt%, 1min of solution, electro-conductive glass is then put into 100mL triamido solution of silane again,
The solvent absolute ethyl alcohol of the solution, the concentration of triamido solution of silane is 0.6wt%, and the chemical formula of triamido silane is H2N-
CH2-CH2-NH-CH2-CH2-NH-(CH2)3-Si-(OCH3)3, drying is taken out after 20min, obtains being assembled with modified microcapsule layer
Electro-conductive glass.
(4) 2mg selenium powders and 24mg sodium borohydrides are weighed, is moved among the bottle with bottle stopper, leads to nitrogen 5min, covers bottle
Plug.Syringe extracts high purity water 2mL, is injected into bottle, is then then exhausted from the gas that reaction generates in bottle.It will be entire small bottled
It puts in water-bath, reaction temperature is 32 DEG C, is taken out after 2h, is prepared into the fresh precursor liquid of purple.
100mg zinc nitrates are added in 100mL water, and glass bar is stirred to zinc nitrate particle and is completely dissolved, and add in thioacetic acid
(TGA) entire liquid is moved into autoclave inside liner again, letting nitrogen in and deoxidizing 30min obtains mixed liquor.
Good seal removes the zinc nitrate solution of peroxide, and syringe extracts the fresh precursor liquids prepared of 1mL and is quickly moved to
In zinc nitrate solution (selenium powder, sodium borohydride, the molar ratio of zinc nitrate and thioacetic acid are 1: 41: 33: 9), hydroxide is added in
Sodium solution adjusts PH to 10, covers, assembles autoclave, 80 DEG C of hydro-thermal reaction 12h obtain the quantum of thioacetic acid modification
Point aqueous solution.
(5) electro-conductive glass for being assembled with modified microcapsule layer that step (3) obtains is disposed vertically and is modified in thioacetic acid
Quantum dot aqueous solution 1h, after natural drying, repeat, 5 times repeatedly, complete five layers of quantum dot on photon crystal film
Self assembly, so as to form quantum dot composite material.
(6) using the quantum dot composite material under sepectrophotofluorometer detection different temperatures, the excitation wavelength of quantum dot
For 470m.Under conditions of sepectrophotofluorometer is incident and exit slit spectral band-width is 5nm, the fluorescence light of system is measured
Spectrum, obtains maximum relative intensity of fluorescence.
Table 3
| 25℃ | 35℃ | 41℃ | 46℃ | 50℃ | 55℃ | |
| Maximum fluorescence intensity (a.u.) | 75 | 71 | 80 | 408 | 421 | 423 |
Comparative example 1
(1) ethyl orthosilicate is added in 500mL round-bottomed flasks, is stirred using sheet stainless steel, 1500 turns/
The neopelex of 1g is added in 100mL water, is uniformly dispersed to 60 DEG C by heating water bath under the mixing speed of min,
And be added in round-bottomed flask after emulsification 20min, 80 DEG C are then warming up to again, continue breast under the mixing speed of 1500 turns/min
Change 10min, obtain uniform microemulsion, wherein, the quality of neopelex and the ratio of ethyl orthosilicate are 1: 13；
After the completion of emulsification, the temperature of water-bath is adjusted to 85 DEG C.The ammonium persulfate of 1g is dissolved in the deionized water of 7.5mL
In, and be slowly added dropwise to completely into round-bottomed flask.After the mixing speed stirring 30min of 1500 turns/min, machinery is stirred
The speed mixed is adjusted to 1000 turns/min, and the temperature of water-bath is adjusted to 80 DEG C, after reacting 1.5h, hydrolysis and polymerisation into
Row is complete.Reaction solution is cooled to room temperature, and the NaCl aqueous solutions 10mL that saturation is added into the reaction solution of room temperature is demulsified, and is stood
After 30min, there is lamination, the lotion of layering be washed with distilled water 6 times in a manner that vacuum filters, and with vacuum drying
Case is dried in vacuo 6h under conditions of 45 DEG C, obtains silicon dioxide particles, wherein, the quality of ammonium persulfate and silica
Ratio is 1: 16.It is characterized by electron scanning micrograph：Grain size is 110nm~150nm.
(2) the ITO electro-conductive glass of light transmission is cut into the fritter of 2*1.5cm, the fritter electro-conductive glass cut is respectively placed in dilute
Hydrochloric acid, absolute ethyl alcohol, deionized water are respectively cleaned by ultrasonic 15min, and drying is for use.The microcapsules for weighing 1g good dispersions are placed in beaker
In, add deionized water to 10ml,
Ultrasonic vibration 30min obtains the dispersion liquid of microcapsules.Measurement is moved into the measuring cup of two 2*2.5ml, will be washed
Clean for use electro-conductive glass is inserted perpendicularly into wherein.Vertical-growth 12h under 55 DEG C of reaction temperatures of air dry oven, so as to be made certainly
It is assembled with the electro-conductive glass of microcapsule layer.
(3) 2mg telluriums powder and 24mg sodium borohydrides are weighed, is moved among the bottle with bottle stopper, leads to nitrogen 5min, covers bottle
Plug.Syringe extracts high purity water 2mL, is injected into bottle, is then then exhausted from the gas that reaction generates in bottle.It will be entire small bottled
It puts in water-bath, reaction temperature is 32 DEG C, is taken out after 2h, is prepared into the fresh precursor liquid of purple bag.
100mg caddies are added in 100mL water, and glass bar is stirred to caddy particle and is completely dissolved, and add in thioacetic acid
(TGA) entire liquid is moved into autoclave inside liner again, letting nitrogen in and deoxidizing 30min obtains mixed liquor.
Good seal removes the cadmium chloride solution of peroxide, and syringe extracts the fresh precursor liquids prepared of 1mL and is quickly moved to
In cadmium chloride solution (tellurium powder, sodium borohydride, the molar ratio of caddy and thioacetic acid are 1: 41: 33: 9), hydroxide is added in
Sodium solution adjusts PH to 10, covers, assembles autoclave, 80 DEG C of hydro-thermal reaction 12h obtain the quantum of thioacetic acid modification
Point aqueous solution.
(4) electro-conductive glass for being assembled with microcapsule layer that step (2) obtains is disposed vertically in the amount of thioacetic acid modification
Son point aqueous solution 1h, after natural drying, repeats, 5 times repeatedly, completes five layers of quantum dot on photon crystal film from group
Dress, so as to form quantum dot composite material.
(6) using the quantum dot composite material under sepectrophotofluorometer detection different temperatures, using fluorescence spectrophotometry
Mixed solution system under meter detection different temperatures, the excitation wavelength 400nm of quantum dot, sepectrophotofluorometer is incident and is emitted
Under conditions of slit spectral band-width is 5nm, the fluorescence spectrum of system is measured, obtains maximum fluorescence intensity.
Table 4
| 30℃ | 40℃ | 50℃ | 56℃ | 60℃ | 65℃ | |
| Maximum fluorescence intensity (a.u.) | 453 | 457 | 459 | 462 | 464 | 468 |
Pass through the data of table 1-3：The environment temperature of the composite quantum dot microballoon of each embodiment is once slightly above advanced
The phase transition temperature of aliphatic acid, the higher fatty acids in quantum dot composite material have occurred and that phase transformation, are become by lighttight solid-state
Transparent liquid is so significantly increased through the translucency of microcapsule layer and substrate successively, the intensity (hair of photoluminescence spectra
Luminous intensity) it can be significantly increased, such quantum dot is compounded in phase transformation temperature points attachment with very strong temperature sensitivity.And
The environment temperature of the composite quantum dot microballoon of comparative example 1 is in elevation process, and fluorescence intensity change is very small, in the shadow of fluorescent noise
Under sound, it is unfavorable for instrument and is monitored, temperature sensitivity is poor.
Test case 1
It is molten containing 0.5 μ g/L copper ions that embodiment 1-3 and the quantum dot composite material of comparative example 1 are reused into test
Liquid.The result shows that：After the quantum dot composite material of embodiment 1-3 uses 10 times, fluorescence can be restored to original more than 96%,
There is not quantum dot to come off problem；And the quantum dot composite material of comparative example 1, after using 5 times, fluorescence drops to original
90%, drop to less than 80% using fluorescence after 8 times, and there is quantum dot obscission, after using 12 times, occur serious de-
Fall problem, it is impossible to be further continued for using.
Claims (9)
1. a kind of preparation method of the quantum dot composite material with bi-component substrate, which is characterized in that described has double groups
Divide the quantum dot composite material of substrate, including Mght-transmitting base material, microcapsule layer and quantum dot layer, the microcapsule layer is located at described
On Mght-transmitting base material, the quantum dot layer is located in the microcapsule layer, and the microcapsule layer is formed by microcapsules self assembly,
The quantum dot layer is formed by quantum dot self assembly, and the microcapsules include shell and kernel, and the shell contains polyphenyl second
Alkene and silica, the kernel are higher fatty acids, and the higher fatty acids is C9~C18Higher fatty acids；Micro- glue
Cystoblast thickness is 50nm~600nm, and the quantum dot layer thickness is 2~150nm；The grain size of the microcapsules for 50nm~
600nm；The quantum dot for CdTe, CdSe, InP, InAs, CdSe/CdS, CdSe/ZnS, CdSe/ZnSe, CdTe/ZnS,
One kind in CdHgTe/ZnS, HgTe/HgCdS quantum dot；
The preparation method of the quantum dot composite material with bi-component substrate, includes the following steps：
(1) will be (2~6) by weight proportion:(2~10):1 mixing higher fatty acids, styrene and ethyl orthosilicate, Ran Houjia
Heat makes higher fatty acids melt and stir evenly, and mixture is made, and then aqueous surfactant solution is added to described mixed
It closes and is added in object, be dispersed with stirring and uniformly obtain emulsion, the aqueous solution of ammonium persulfate is then added dropwise in the emulsion, 60
It after reacting 0.5~6h at~95 DEG C, is cooled to room temperature, is then demulsified, stood, vacuum filters, washs and dries, final
To using higher fatty acids as core, polystyrene and the microcapsules that silica is shell,
(2) microcapsules are added to the water, ultrasonic vibration, obtain the dispersion liquid of microcapsules, Mght-transmitting base material is inserted perpendicularly into
It is used to prepare in the dispersion liquid of microcapsules and carries out vertical-growth, take out drying, be made and be covered in the Mght-transmitting base material surface
Microcapsule layer；
(3) Mght-transmitting base material that will be covered with microcapsule layer is disposed vertically in the aqueous solution of quantum dot and carries out vertical-growth, takes
Go out drying, just obtain quantum dot composite material.
2. the preparation method of quantum dot composite material described in accordance with the claim 1, it is characterised in that：The table of the microcapsule layer
Triamido silane and aluminium polychloride modification are passed through in face, and the chemical formula of the triamido silane is H2N-CH2-CH2-NH-
CH2-CH2-NH-(CH2)3-Si-(OCH3)3。
3. according to the preparation method of the quantum dot composite material described in claim 1 or 2, it is characterised in that：In the quantum dot
In composite material, the weight ratio of the higher fatty acids, polystyrene and silica is (2~6):(2~10):0.29.
4. the preparation method of quantum dot composite material described in accordance with the claim 1, it is characterised in that：The microcapsule layer thickness
For 60nm~500nm, the quantum dot layer thickness is 5~100nm, and the grain size of the microcapsules is 60nm~500nm.
5. the preparation method of quantum dot composite material described in accordance with the claim 1, it is characterised in that：The higher fatty acids is
One kind in capric acid, lauric acid, myristic acid, palmitic acid, pearly-lustre ester acid, stearic acid, oleic acid, linoleic acid.
6. the preparation method of quantum dot composite material described in accordance with the claim 1, it is characterised in that：In the surfactant
The ratio of the quality of surfactant in aqueous solution and the quality sum of higher fatty acids, styrene and ethyl orthosilicate is 1:
(10~30), the concentration of the aqueous solution of the surfactant is 0.5wt%~5wt%；Mistake in the ammonium persulfate solution
The ratio of the quality of ammonium sulfate and the quality sum of higher fatty acids, styrene and ethyl orthosilicate is 1:(10~50), it is described
The concentration of ammonium persulfate solution is 1wt%~10wt%；The surfactant is polyethylene glycol, sucrose ester, polysorbate, ten
In eight alkyl benzene sulphonates, lauryl sodium sulfate, sodium tetradecyl sulfate, sodium hexadecyl sulfate, neopelex
One or more.
7. according to the preparation method of the quantum dot composite material described in claim 1 or 6, it is characterised in that：The quantum dot
The aqueous solution for the quantum dot that aqueous solution is modified for mercaptan carboxylic acid.
8. according to the preparation method of the quantum dot composite material described in claim 1 or 6, it is characterised in that：Will be covered with it is micro-
The Mght-transmitting base material of capsule layer is disposed vertically before the aqueous solution of quantum dot, molten with polymeric aluminum chlorides solution and triamido silane
Liquid modification microcapsule layer, is as follows：The Mght-transmitting base material that will be covered with microcapsule layer is positioned over aluminium polychloride
Solution in, then take out drying, be then positioned over again in triamido solution of silane, then take out drying.
9. according to the preparation method of the quantum dot composite material described in claim 8, it is characterised in that：The aluminium polychloride is molten
Concentration 0.20wt%~0.01wt% of liquid, the triamido solution of silane are to contain 0.5wt%~2.0wt% triamido silane
Ethanol solution.
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