CN107955599A - 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 " have 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 scantling is reduced to nanometer scale, due to its nano effect, material will produce 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, the nano luminescent material using transition metal as active ions, due to its excellent optical characteristics, such as absorbs
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.But 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, its luminous intensity is very small,
At a temperature of less than thermal quenching, less temperature change will not cause luminous intensity significantly to strengthen 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, it includes 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 SiO2Part by weight with the higher fatty acids is (0.2~1.2)
∶1。
The quantum dot can use quantum dot commonly used in the art.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 particle diameter 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, laurate, 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 particle diameter 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 printing opacity.
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
State in mixture and add, be dispersed with stirring and uniformly obtain emulsion, the aqueous solution of ammonium persulfate is then added dropwise in the emulsion,
After reacting 0.5~6h at 60~95 DEG C, it is cooled to room temperature, is then demulsified, stood, vacuum filters, washs and dries, most
Obtain 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, is made and is 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 ethene 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, comprise the following steps that：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 diamino silanes solution 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, obtains mixed liquor, whole 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 material of the invention, quantum dot of the invention are not only able to keep general quantum dot light emitting 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 increase, sequentially passing through the intensity (luminous intensity) of the photoluminescence spectra of microcapsule layer and transparent base material 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
Sensitiveness.
, 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 change, can detect the temperature minor variations near temperature sensitivity value.When for quantum dot
, 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,
, 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 that the real-time monitoring of different samples can be realized.
(2) quantum dot composite material of the invention, polystyrene form thicker cladding shell, and polyphenyl with silica
Ethene has stronger impact strength, is conducive to improve the heat endurance and structural stability of the microcapsules, and can be well
The shortcomings that making up the elasticity and poor compactness of silica, advantageously forms the shell of densification and avoids phase-change material from leaking,
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 heat endurance 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
Send out polystyrene polymerization and generate 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 even particle size distribution, constitutionally stable microcapsules
Preparation.
After microcapsule layer is prepared, then aggregated aluminium chloride and the processing of triamido solution of silane, so that modified microcapsule layer
Surface charge, and three-dimensional more sites 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 more sites, 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 has an extraordinary time stability, and certain acid,
Acid, alkaline stability and antioxidative stabilizer in alkali, oxidation environment, the good biological at the same time also maintaining quantum dot are compatible
Property, so as to substantially increase the stability of quantum dot in a particular application.
(4) quantum dot composite material of the invention, can be used in quantum dot in luminescent device, fluorescence imaging, solar energy
Battery, fluoroscopic examination and biomarker etc..
Embodiment
Below by embodiment come further illustrate the present invention quantum dot composite material preparation process, 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 that 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, by the temperature adjustment of water-bath 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 by way of 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.
Characterized by electron scanning micrograph：Microcapsules Size is 160nm~200nm, and particle diameter distribution is uniform,
And the shape of microcapsules is more regular, surface is smooth.
(2) the ITO electro-conductive glass of printing opacity 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 stand-by.The microcapsules for weighing 1g good dispersions are placed in beaker
In, adding deionized water, ultrasonic vibration 30min, obtains the dispersion liquid of microcapsules to 10ml.Measure and move to two 2*2.5ml's
In measuring cup, the stand-by 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, so that self assembly, which is made, the electro-conductive glass of microcapsule layer.
(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 expelled in bottle, is then then exhausted from the gas that reaction produces in bottle.Will be whole small bottled
Put 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 thioacetic acid
(TGA) whole 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
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, by the temperature adjustment of water-bath 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 by way of 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.
Characterized by electron scanning micrograph：Microcapsules Size is 100nm~140nm, and particle diameter distribution is uniform,
And the shape of microcapsules is more regular, surface is smooth.
(2) the ITO electro-conductive glass of printing opacity 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 stand-by.The microcapsules for weighing 1g good dispersions are placed in beaker
In, adding deionized water, ultrasonic vibration 30min, obtains the dispersion liquid of microcapsules to 10ml.Measure and move to two 2*2.5ml's
In measuring cup, the stand-by 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, so that self assembly, which is made, the electro-conductive glass of microcapsule layer.
(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 expelled in bottle, is then then exhausted from the gas that reaction produces in bottle.Will be whole small bottled
Put 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 thioacetic acid
(TGA) whole 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
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 laurate, 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 laurate, the styrene of neopelex
Ratio with the quality sum of ethyl orthosilicate is 1: 20；
After the completion of emulsification, by the temperature adjustment of water-bath 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.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 by way of vacuum filters with distillation
Wash 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 laurate, styrene and ethyl orthosilicate it
The ratio of sum is 1: 20.
Characterized by electron scanning micrograph：Microcapsules Size is 80nm~110nm, and particle diameter distribution is uniform,
And the shape of microcapsules is more regular, surface is smooth.
(2) the ITO electro-conductive glass of printing opacity 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 stand-by.The microcapsules for weighing 1g good dispersions are placed in beaker
In, adding deionized water, ultrasonic vibration 30min, obtains the dispersion liquid of microcapsules to 10ml.Measure and move to two 2*2.5ml's
In measuring cup, the stand-by 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, so that self assembly, which is made, the electro-conductive glass of microcapsule layer.
(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 expelled in bottle, is then then exhausted from the gas that reaction produces in bottle.Will be whole small bottled
Put 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 thioacetic acid
(TGA) whole 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
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 470nm.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, by the temperature adjustment of water-bath 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 by way of 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.Characterized by electron scanning micrograph：Particle diameter is 110nm~150nm.
(2) the ITO electro-conductive glass of printing opacity 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 stand-by.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 stand-by 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 expelled in bottle, is then then exhausted from the gas that reaction produces in bottle.Will be whole small bottled
Put 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 thioacetic acid
(TGA) whole 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
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 its photoluminescence spectra
Luminous intensity) it can be significantly increased, such quantum dot, which is compounded in phase transformation temperature points annex, has 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 return 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 quantum dot composite material with bi-component substrate, it is characterised in that it includes Mght-transmitting base material, microcapsule layer
And quantum dot layer, the microcapsule layer are located on the Mght-transmitting base material, the quantum dot layer is located in the microcapsule layer, institute
State microcapsule layer to be formed by microcapsules self assembly, the quantum dot layer is formed, the microcapsules bag by quantum dot self assembly
Include shell and kernel, the shell contains polystyrene and silica, and the kernel is higher fatty acids, the higher aliphatic
Acid is C9~C18Higher fatty acids；In the quantum dot composite material, the higher fatty acids, polystyrene and titanium dioxide
The part by weight of silicon is (2~6):(2~10):0.29；The microcapsule layer thickness is 50nm~600nm, the quantum dot layer
Thickness is 2~150nm；The particle diameter of the microcapsules is 50nm~600nm；The quantum dot for CdTe, CdSe, InP, InAs,
One kind in CdSe/CdS, CdSe/ZnS, CdSe/ZnSe, CdTe/ZnS, CdHgTe/ZnS, HgTe/HgCdS quantum dot.
2. quantum dot composite material described in accordance with the claim 1, it is characterised in that：Three ammonia are passed through on the surface of the microcapsule layer
Base silane and aluminium polychloride modification, the chemical formula of the triamido silane is H2N-CH2-CH2-NH-CH2-CH2-NH-
(CH2)3-Si-(OCH3)3。
3. 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 are 5~100nm, and the particle diameter of the microcapsules is 60nm~500nm.
4. quantum dot composite material described in accordance with the claim 1, it is characterised in that：The higher fatty acids is capric acid, bay
One kind in acid, myristic acid, palmitic acid, pearly-lustre ester acid, stearic acid, oleic acid, linoleic acid.
A kind of 5. preparation side of the quantum dot composite material with bi-component substrate in 1-4 such as claim as described in any one
Method, it is characterised in that this method comprises 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
Added in compound, be dispersed with stirring and uniformly obtain emulsion, the aqueous solution of ammonium persulfate is then added dropwise in the emulsion, 60
After reacting 0.5~6h at~95 DEG C, be cooled to room temperature, be then demulsified, stood, vacuum filters, washs and dry, it is final must
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, is made and is 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.
6. in accordance with the method for claim 5, it is characterised in that：Surfactant in the aqueous surfactant solution
The ratio of quality sum of quality and higher fatty acids, styrene and ethyl orthosilicate be 1:(10~30), the surface are lived
The concentration of the aqueous solution of property agent is 0.5wt%~5wt%；The quality of ammonium persulfate in the ammonium persulfate solution and advanced fat
The ratio of the quality sum of fat acid, styrene and ethyl orthosilicate is 1:(10~50), the concentration of the ammonium persulfate solution are
1wt%~10wt%；The surfactant is polyethylene glycol, sucrose ester, polysorbate, octadecyl benzenesulfonic acid, dodecane
One or more in base sodium sulphate, sodium tetradecyl sulfate, sodium hexadecyl sulfate, neopelex.
7. according to the method described in claim 5 or 6, it is characterised in that：The aqueous solution of the quantum dot is modified for mercaptan carboxylic acid
Quantum dot aqueous solution.
8. according to the method described in claim 5 or 6, it is characterised in that：Hang down in the Mght-transmitting base material that will be covered with microcapsule layer
Directly it is positioned over before the aqueous solution of quantum dot, with polymeric aluminum chlorides solution and triamido solution of silane modification microcapsule layer,
Comprise the following steps that：The Mght-transmitting base material that will be covered with microcapsule layer is positioned in the solution of aluminium polychloride, is then taken out dry
It is dry, then it is positioned over again in triamido solution of silane, then takes out drying.
9. in accordance with the method for claim 8, it is characterised in that：The concentration 0.20wt% of the polymeric aluminum chlorides solution~
0.01wt%, the triamido solution of silane are the ethanol solution containing 0.5wt%~2.0wt% triamido silane.
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