CN113061435A - Fluorescent thermosensitive composite quantum dot material, preparation method thereof and environment temperature monitoring LED - Google Patents
Fluorescent thermosensitive composite quantum dot material, preparation method thereof and environment temperature monitoring LED Download PDFInfo
- Publication number
- CN113061435A CN113061435A CN201911406744.2A CN201911406744A CN113061435A CN 113061435 A CN113061435 A CN 113061435A CN 201911406744 A CN201911406744 A CN 201911406744A CN 113061435 A CN113061435 A CN 113061435A
- Authority
- CN
- China
- Prior art keywords
- thermosensitive
- quantum dot
- fluorescent
- dot material
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
- C09K11/881—Chalcogenides
- C09K11/883—Chalcogenides with zinc or cadmium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
- G01K11/12—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using changes in colour, translucency or reflectance
- G01K11/16—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using changes in colour, translucency or reflectance of organic materials
- G01K11/165—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using changes in colour, translucency or reflectance of organic materials of organic liquid crystals
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a fluorescent thermosensitive composite quantum dot material, a preparation method thereof and an ambient temperature monitoring LED, wherein the fluorescent thermosensitive composite quantum dot material comprises a polymer core layer, a thermosensitive polymer shell layer coated on the surface of the polymer core layer and quantum dots combined in the thermosensitive polymer shell layer. In the invention, the luminescent wavelength of the fluorescent thermosensitive composite quantum dot material can change along with the change of the environmental temperature, so that the fluorescent thermosensitive composite quantum dot material can be used as a luminescent material of an environmental temperature monitoring LED to realize sensitive detection on the change of the environmental temperature.
Description
Technical Field
The invention relates to the field of fluorescent thermosensitive materials, in particular to a fluorescent thermosensitive composite quantum dot material, a preparation method thereof and an ambient temperature monitoring LED.
Background
The LED is an electroluminescent semiconductor device which can directly convert electric energy into light energy, is used as a modern novel green energy-saving illumination and is expected to replace a traditional light source. The great effect of the LED in the fields of illumination and display is incomparable with other light sources, which makes the LED become the mainstream product in the illumination industry.
Temperature sensing is always an important area of research, both in engineering and in scientific research. Almost all biological, chemical and physical processes are closely related to temperature, and temperature information needs to be accurately mastered in industrial production in many fields to ensure reliable operation of a system. In such cases, such as metallurgy, glass making, material modeling, food processing, and the like. Under the condition, the temperature can be accurately and efficiently measured, the temperature information under a specific environment and time condition can be mastered only on the premise of accurate temperature measurement, and then the accurate information between other non-temperature factors and between the non-temperature factors and the temperature under the temperature condition can be accurately judged. However, the conventional contact temperature sensing technologies, such as thermocouples, thermal resistors, radiation thermometers, etc., cannot meet practical requirements in situations of high magnetic field, flow, high voltage, high response rate, and non-contact measurement due to their limitations.
Based on the continuous improvement of temperature measurement requirements, a non-contact temperature measurement mode becomes an urgent need. A fluorescence thermometer is a temperature sensing device based on an LED. Fluorescence temperature sensing utilizes the fluorescence emission of a temperature-affected material system to change certain characteristics of fluorescence such as fluorescence intensity, peak spectrum displacement, peak spectrum shape and the like, and the temperature can be calibrated by monitoring the relationship between the change and the temperature. Because the fluorescent signal is easy to monitor and the reaction is rapid, the temperature can be displayed in real time. Meanwhile, the fluorescence intensity of the quantum dots is in linear temperature response, and the quantum dots are sensitive to local environments. However, known quantum dot ligands make quantum dot fluorescence insensitive to temperature. For example, when denatured ovalbumin is used as a ligand, and quantum dots are bound to polymer particles, the fluorescence intensity of the quantum dots is independent of temperature.
Therefore, the prior art is still to be improved.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a fluorescent thermosensitive composite quantum dot material, a preparation method thereof and an ambient temperature monitoring LED, and aims to solve the problem that the fluorescence intensity change of the quantum dot material is not sensitive to temperature due to the fact that the conventional quantum dot material is easily affected by ligands or polymer particles.
The technical scheme of the invention is as follows:
a fluorescent thermosensitive composite quantum dot material comprises a polymer core layer, a thermosensitive polymer shell layer coated on the surface of the polymer core layer and quantum dots combined on the thermosensitive polymer shell layer.
A preparation method of a fluorescent thermosensitive composite quantum dot material comprises the following steps:
under inert atmosphere, mixing a surface active monomer, a connecting monomer and a first initiator in deionized water and stirring to react to generate a polymer nuclear layer;
dispersing a thermosensitive polymer monomer and a second initiator in a mixed solvent of water and ethanol to obtain a mixed solution;
adding the polymer core layer into the mixed solution under inert atmosphere, stirring, and reacting to generate a polymer core layer coated by a thermosensitive polymer shell layer;
and dispersing the polymer core layer coated by the thermosensitive polymer shell layer and the quantum dots in an organic solvent, and performing ultrasonic treatment to combine the quantum dots with the thermosensitive polymer shell layer to obtain the fluorescent thermosensitive composite quantum dot material.
An environment temperature monitoring LED comprises the fluorescent thermosensitive composite quantum dot material or the fluorescent thermosensitive composite quantum dot material prepared by the preparation method of the fluorescent thermosensitive composite quantum dot material.
Has the advantages that: the invention provides a fluorescent thermosensitive composite quantum dot material, which comprises a polymer core layer, a thermosensitive polymer shell layer coated on the surface of the polymer core layer and quantum dots combined in the thermosensitive polymer shell layer, wherein the luminous wavelength of the fluorescent thermosensitive composite quantum dot material can change along with the change of environmental temperature, so that the fluorescent thermosensitive composite quantum dot material can be used as a luminous material of an LED (light-emitting diode) for monitoring the environmental temperature, and the sensitive detection of the change of the environmental temperature is realized.
Drawings
Fig. 1 is a flowchart of a method for preparing a fluorescent thermosensitive composite quantum dot material according to an embodiment of the present invention.
Detailed Description
The invention provides a fluorescent thermosensitive composite quantum dot material, a preparation method thereof and an ambient temperature monitoring LED, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In some embodiments, a fluorescent thermosensitive composite quantum dot material is provided, which includes a polymer core layer, a thermosensitive polymer shell layer coated on the surface of the polymer core layer, and a quantum dot bonded to the thermosensitive polymer shell layer.
In this embodiment, in order to enable the distance between the quantum dots determining the fluorescence intensity to be changed, a thermosensitive polymer shell layer sensitive to temperature is covered on the surface of the polymer core layer, and the structure of the thermosensitive polymer shell layer is easy to change when the thermosensitive polymer shell layer is stimulated by external temperature. In this embodiment, the quantum dots may be bonded to the inside or the surface of the thermosensitive polymer shell, and thus, when the temperature is increased, the structure of the thermosensitive polymer shell is shrunk, thereby causing the distance between the quantum dots bonded to the thermosensitive polymer shell to be reduced; conversely, as the temperature decreases, the structure of the thermosensitive polymer shell recovers, causing the distance between the quantum dots incorporated within the thermosensitive polymer shell to increase. Since low density quantum dots have narrower fluorescence spectral bands and stronger fluorescence, increasing the quantum dot density results in a red shift of the emission peak due to interaction of non-radiative excitation transfer between quantum dots and dipole moments associated with quantum dot asymmetry. Therefore, when the temperature is increased to cause the shell structure of the thermosensitive polymer to shrink and the distance of the quantum dots is shortened, the emission wavelength of the quantum dots is red-shifted; and when the temperature is reduced, the shell structure of the thermosensitive polymer is recovered, and when the distance between the quantum dots is increased, the emission wavelength of the quantum dots is blue-shifted.
That is to say, the luminescent wavelength of the fluorescent thermosensitive composite quantum dot material provided by the embodiment can change along with the change of the environmental temperature, so that the fluorescent thermosensitive composite quantum dot material can be used as a luminescent material of an environmental temperature monitoring LED, and the sensitive detection of the environmental temperature change is realized.
In some embodiments, the quantum dots are bound to the thermosensitive polymer shell layer by electrostatic interaction.
In some embodiments, the polymer core layer has a thickness of 100-200 nm.
In some embodiments, the thermosensitive polymer shell layer has a thickness of 50-70 nm.
In some embodiments, there is also provided a method for preparing a fluorescent thermosensitive composite quantum dot material, as shown in fig. 1, which includes the steps of:
s10, under an inert atmosphere, mixing a surface active monomer, a connecting monomer and a first initiator in deionized water and stirring to react to generate a polymer core layer;
s20, dispersing the thermosensitive polymer monomer and the second initiator in a mixed solvent of water and ethanol to obtain a mixed solution;
s30, adding the polymer core layer into the mixed solution under inert atmosphere, stirring, and reacting to generate a polymer core layer coated by a thermosensitive polymer shell layer;
s40, dispersing the polymer core layer and the quantum dots coated by the thermosensitive polymer shell layer in an organic solvent, and performing ultrasonic treatment to combine the quantum dots with the thermosensitive polymer shell layer to obtain the fluorescent thermosensitive composite quantum dot material.
The preparation method of the fluorescent thermosensitive composite quantum dot material provided by the embodiment is simple and easy to operate, the luminescent wavelength of the prepared fluorescent thermosensitive composite quantum dot material can change along with the change of the environmental temperature, and the fluorescent thermosensitive composite quantum dot material has better light transmittance after being dispersed in resin, so that the fluorescent thermosensitive composite quantum dot material can be used as a luminescent material of an environmental temperature monitoring LED, and the sensitive detection of the change of the environmental temperature is realized.
In some embodiments, the surface active monomer is a hydrophilic monomer containing a double bond and the linking monomer is a hydrophobic monomer containing a double bond. In this embodiment, the colloidal polymer may be prepared by a soap-free emulsion polymerization method, the hydrophilic monomer may be copolymerized with the hydrophobic monomer dissolved in the water phase to form an amphoteric oligomer radical, and the amphoteric oligomer radical gradually polymerizes and forms microspheres from the water phase; because water is a continuous phase, hydrophilic groups of the hydrophilic monomers preferentially form polymerization to form microspheres, and hydrophobic groups of the hydrophobic monomers are distributed on the surfaces of the microspheres to obtain the core-shell type microspheres with the hydrophilic-hydrophobic structures, namely the colloidal polymer is prepared. In the embodiment, the microspheres can exist stably even without an emulsifier, and because no emulsifier (i.e., surfactant) is added in the reaction process, adverse effects of the emulsifier on the experiment in the subsequent reaction can be avoided.
In some specific embodiments, the surface active monomer is one or more of acrylic acid, hydroxyethyl methacrylate, epoxyethyl methacrylate, sodium methylpropylsulfonate, 2-sulfonylethyl methacrylate, and dimethylvinylpyridine methanesulfonate, but is not limited thereto.
In some specific embodiments, the linking monomer is one or more of styrene, phenylpropene, and 4-phenyl-1-butene, but is not limited thereto. In this embodiment, the connecting monomers each have a double bond with a strong activity, which makes it easy to react with a double bond in a subsequent thermosensitive polymer, so that the thermosensitive polymer can be connected to the surface of the colloidal polymer.
In some specific embodiments, the first initiator is one or both of potassium persulfate and azoisobutyronitrile, but is not limited thereto.
In some embodiments, a connecting monomer is dissolved in deionized water, the mixture is stirred uniformly and then gradually added with the surface active monomer, and nitrogen is introduced, wherein the molar ratio of the surface active monomer to the connecting monomer is 1: 8-15; and then adding an initiator, setting the reaction temperature to be 65-80 ℃, and carrying out free radical copolymerization reaction in deionized water for 8-15h to obtain the polymer core layer.
In some embodiments, a thermosensitive polymer monomer and an initiator are dispersed in a mixed solvent of water and ethanol to obtain a mixed solution; and adding the polymer core layer into the mixed solution under inert atmosphere, stirring, and reacting for 1-5h at 60-80 ℃ to generate the polymer core layer coated by the thermosensitive polymer shell layer. In this embodiment, the surface of the polymer core layer contains double bonds with strong activity, which makes it easy to react with double bonds and/or amino groups in the thermosensitive polymer, so that the thermosensitive polymer can be connected to the surface of the colloidal polymer, thereby forming a polymer core layer coated by a thermosensitive polymer shell layer.
In some embodiments, the thermosensitive polymer monomer is one or more of, but is not limited to, N-vinyl caprolactam, N-isopropyl acrylamide, N-vinyl isobutyramide, and N-propyl acrylamide; the second initiator is one or two of potassium persulfate and azoisobutyronitrile, but is not limited thereto. In this embodiment, the thermosensitive polymer monomer may undergo a polymerization reaction under the water bath condition and the action of the initiator to generate a thermosensitive polymer, the surface of the thermosensitive polymer has a large number of amino groups and double bonds, and the amino groups and the double bonds may also react with the double bonds on the surface of the polymer core layer under the water bath condition, so that the thermosensitive polymer is connected to the surface of the polymer core layer to form a thermosensitive polymer shell layer.
In some embodiments, the volume ratio of water to ethanol in the mixed solvent of water and ethanol is 10-20: 1. In this embodiment, the mixed solvent may have different polarities by adjusting the volume ratio of water to ethanol, so as to adjust the thickness of the shell layer formed on the surface of the polymer core layer by the thermosensitive polymer. Because the thermosensitive polymer is a hydrophobic material and is mainly dispersed in an organic phase (namely ethanol or the surface of a polymer core layer), when the water alcohol is relatively large, namely the polarity of a solvent is relatively large, the thermosensitive polymer is driven to be distributed on the surface of the polymer core layer in a biased manner, because the surface of the polymer core layer contains the double bonds of the hydrophobic connecting monomers, the double bonds and/or amino groups on the thermosensitive polymer can be driven to react with the double bonds of the connecting monomers, and the thickness of the shell layer of the obtained thermosensitive polymer is thicker; on the contrary, when the ratio of the water to the alcohol is lower, the thickness of the shell layer of the prepared thermosensitive polymer is thinner.
In some embodiments, the polymer core layer coated by the thermosensitive polymer shell layer and the quantum dots are dispersed in an organic solvent and subjected to ultrasonic treatment, so that the quantum dots are combined in the thermosensitive polymer shell layer to obtain the fluorescent thermosensitive composite quantum dot material. In this embodiment, in the ultrasonic treatment process, the quantum dot may be bonded inside or on the surface of the thermosensitive polymer shell, and since the thermosensitive polymer shell contains a large number of amino groups and double bonds, the negatively charged amino groups may have an electrostatic interaction with the positively charged metal ions on the surface of the quantum dot, so that the quantum dot is bonded inside or on the surface of the thermosensitive polymer shell.
In some embodiments, the quantum dot is CdSe, ZnSe, PbSe, CdTe, ZnO, InP, GaN, GaP, AlP, InN, ZnTe, InAs, GaAs, CaF2、Cd1-xZnxS、Cd1-xZnxSe、CdSeyS1-y、PbSeyS1-y、ZnXCd1-XTe、CdS/ZnS、Cd1-xZnxS/ZnS、Cd1-xZnxSe/ZnSe、CdSe1-xSx/CdSeyS1-y/CdS、CdSe/Cd1-xZnxSe/CdyZn1-ySe/ZnSe、Cd1-xZnxSe/CdyZn1-ySe/ZnSe、CdS/Cd1-xZnxS/CdyZn1-yS/ZnS、NaYF4、NaCdF4、Cd1- xZnxSeyS1-y、CdSe/ZnS、Cd1-xZnxOne or more of Se/ZnS, CdSe/CdS/ZnS, CdSe/ZnSe/ZnS, but not limited thereto.
In some embodiments, an ambient temperature monitoring LED is further provided, which includes the fluorescent thermosensitive composite quantum dot material according to the present invention or the fluorescent thermosensitive composite quantum dot material prepared by the preparation method of the fluorescent thermosensitive composite quantum dot material according to the present invention. The fluorescent thermosensitive composite quantum dot material comprises a polymer core layer, a thermosensitive polymer shell layer coated on the surface of the polymer core layer and quantum dots combined on the thermosensitive polymer shell layer, and the luminous wavelength of the fluorescent thermosensitive composite quantum dot material can change along with the change of the environmental temperature, so that the fluorescent thermosensitive composite quantum dot material can be used as a luminous material of an LED for monitoring the environmental temperature, and the sensitive detection of the change of the environmental temperature is realized.
The preparation method of the fluorescent thermosensitive composite quantum dot material is described in detail by the following specific examples:
example 1
1. Carrying out emulsifier-free radical copolymerization reaction in distilled water, wherein the molar ratio of a connecting monomer to a surface active monomer is 10: 1; firstly, dissolving styrene in 45mL of deionized water, stirring uniformly, gradually adding 1mmol of acrylic acid, and introducing nitrogen for 30min to remove oxygen; then, 0.06mmol of potassium persulfate is added, the temperature of the polymerization mixture is adjusted to 70 ℃, the polymerization reaction is carried out under nitrogen, and the mixture is stirred for 10 hours to obtain poly (acrylic acid-co-styrene) microspheres;
2. taking the poly (acrylic acid-co-styrene) microspheres as seeds for reaction, dispersing 0.5mmol of N-vinyl caprolactam monomer and 0.5mmol of potassium persulfate in a mixed solvent of water and ethanol with a ratio of 20:1, and adding 1mmol of poly (acrylic acid-co-styrene) microspheres seeds under stirring; introducing nitrogen for 30min to remove oxygen, and stirring for 4h in a water bath at 70 ℃ to obtain poly (acrylic acid-co-styrene) microspheres coated with poly (N-vinyl caprolactam);
3. dispersing 0.5mg of CdSe quantum dots in 1mL of isopropanol, adding 1mL of isopropanol solution of poly (acrylic acid-co-styrene) microspheres coated with 3 wt% of poly (N-vinyl caprolactam), ultrasonically stirring for 20min at room temperature, and cleaning with deionized water and isopropanol to obtain the CdSe quantum dot fluorescent thermosensitive polymer.
Example 2
1. Carrying out emulsifier-free radical copolymerization reaction in distilled water, wherein the molar ratio of a connecting monomer to a surface active monomer is 15: 1; firstly, dissolving phenyl propene in 40mL of deionized water, stirring uniformly, gradually adding 1mmol of hydroxyethyl methacrylate, and introducing nitrogen for 30min to remove oxygen; then, adding 0.08mmol of azoisobutyronitrile, adjusting the temperature of the polymerization mixture to 80 ℃, carrying out polymerization reaction under nitrogen, and stirring for 10 hours to obtain poly (hydroxyethyl methacrylate-co-phenylpropylene) microspheres;
2. taking the poly (hydroxyethyl methacrylate-co-phenylpropylene) microspheres as seeds for reaction, dispersing 1mmol of N-vinyl isobutyramide monomer and 0.5mmol of azoisobutyronitrile in a mixed solvent of water and ethanol with a ratio of 15:1, and adding 1mmol of the poly (hydroxyethyl methacrylate-co-phenylpropylene) microspheres seeds under stirring; introducing nitrogen for 30min to remove oxygen, and stirring for 5h in water bath at 65 ℃ to obtain N-vinyl isobutyramide coated poly (hydroxyethyl methacrylate-co-phenylpropylene) microspheres;
3. adding 0.5mg of Cd1-xZnxDispersing Se quantum dots in 1mL of isopropanol, adding 1mL of 4 wt% isopropanol solution of the N-vinyl isobutyramide coated poly (hydroxyethyl methacrylate-co-phenylpropylene) microspheres, ultrasonically stirring at room temperature for 30min, washing with deionized water and isopropanol to obtain Cd1-xZnxSe quantum dot fluorescent thermosensitive polymer.
Example 3
1. Carrying out emulsifier-free radical copolymerization reaction in distilled water, wherein the molar ratio of a connecting monomer to a surface active monomer is 8: 1; dissolving the connected 4-phenyl-1-butene in 30mL of deionized water, stirring uniformly, gradually adding 1mmol of methacrylic acid-2-sulfonyl ethyl ester, and introducing nitrogen for 30min to remove oxygen; then, 0.08mmol of azoisobutyronitrile is added, the temperature of the polymerization mixture is adjusted to 75 ℃, the polymerization reaction is carried out under nitrogen, and the mixture is stirred for 15 hours to obtain poly (2-sulfonyl ethyl methacrylate-co-4-phenyl-1-butylene) microspheres;
2. taking the poly (2-sulfonylethyl methacrylate-co-4-phenyl-1-butene) microspheres as seeds for reaction, dispersing 2mmol of N-propyl acrylamide monomer and 0.5mmol of azoisobutyronitrile into a mixed solvent of water and ethanol with the ratio of 10:1, and adding 1mmol of the poly (2-sulfonylethyl methacrylate-co-4-phenyl-1-butene) microspheres seeds under stirring; introducing nitrogen for 30min to remove oxygen, and stirring for 5h in a water bath at 65 ℃ to obtain N-propyl acrylamide coated poly (2-sulfoethyl methacrylate-co-4-phenyl-1-butylene) microspheres;
3. 0.3mg of CdSe/ZnS quantum dots are dispersed in 1mL of isopropanol, 1mL of 2 wt% isopropanol solution of the N-propyl acrylamide-coated poly (2-sulfoethyl methacrylate-co-4-phenyl-1-butene) is added, ultrasonic stirring is carried out for 26min at room temperature, and the CdSe/ZnS quantum dot fluorescent thermosensitive polymer is obtained after the mixture is washed by deionized water and isopropanol.
In summary, the invention provides a fluorescent thermosensitive composite quantum dot material, which comprises a polymer core layer, a thermosensitive polymer shell layer coated on the surface of the polymer core layer, and quantum dots combined on the thermosensitive polymer shell layer; the luminescent wavelength of the fluorescent thermosensitive composite quantum dot material can change along with the change of the environmental temperature, so that the fluorescent thermosensitive composite quantum dot material can be used as a luminescent material of an environmental temperature monitoring LED, and the sensitive detection of the environmental temperature change is realized.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (12)
1. The fluorescent thermosensitive composite quantum dot material is characterized by comprising a polymer core layer, a thermosensitive polymer shell layer coated on the surface of the polymer core layer and quantum dots combined on the thermosensitive polymer shell layer.
2. The fluorescent thermosensitive composite quantum dot material according to claim 1, wherein the quantum dot is bonded inside or on the surface of the thermosensitive polymer shell layer by electrostatic interaction.
3. The fluorescence thermosensitive composite quantum dot material according to claim 1, wherein the thickness of the polymer core layer is 100-200 nm; and/or the thickness of the shell layer of the thermosensitive polymer is 50-70 nm.
4. A preparation method of a fluorescent thermosensitive composite quantum dot material is characterized by comprising the following steps:
under inert atmosphere, mixing a surface active monomer, a connecting monomer and a first initiator in deionized water and stirring to react to generate a polymer nuclear layer;
dispersing a thermosensitive polymer monomer and a second initiator in a mixed solvent of water and ethanol to obtain a mixed solution;
adding the polymer core layer into the mixed solution under inert atmosphere, stirring, and reacting to generate a polymer core layer coated by a thermosensitive polymer shell layer;
and dispersing the polymer core layer coated by the thermosensitive polymer shell layer and the quantum dots in an organic solvent and carrying out ultrasonic treatment to obtain the fluorescent thermosensitive composite quantum dot material.
5. The method for preparing the fluorescent thermosensitive composite quantum dot material according to claim 4, wherein the molar ratio of the surface active monomer to the connecting monomer is 1: 8-15.
6. The preparation method of the fluorescent thermosensitive composite quantum dot material according to claim 4, wherein in the step of mixing and stirring the surface active monomer, the connecting monomer and the first initiator in deionized water under an inert atmosphere to react to generate the polymer core layer, the reaction temperature is 65-80 ℃; and/or the reaction time is 8-15 h.
7. The method for preparing the fluorescent thermosensitive composite quantum dot material according to any one of claims 4 to 6, wherein the surface active monomer is a hydrophilic monomer containing a double bond, and/or the connecting monomer is a hydrophobic monomer containing a double bond.
8. The method for preparing the fluorescent thermosensitive composite quantum dot material according to any one of claims 4 to 6, wherein the surface active monomer is one or more of acrylic acid, hydroxyethyl methacrylate, epoxyethyl methacrylate, sodium methylpropylsulfonate, 2-sulfonylethyl methacrylate and dimethylvinylpyridine methylsulfonate; and/or the connecting monomer is one or more of styrene, phenyl propylene and 4-phenyl-1-butene; and/or the first initiator is one or two of potassium persulfate and azoisobutyronitrile; and/or the second initiator is one or two of potassium persulfate and azoisobutyronitrile.
9. The method for preparing the fluorescent thermosensitive composite quantum dot material according to claim 4, wherein the volume ratio of water to ethanol in the mixed solvent of water and ethanol is 10-20: 1.
10. The method for preparing the fluorescent thermosensitive composite quantum dot material according to claim 4, wherein the thermosensitive polymer monomer is one or more of N-vinyl caprolactam, N-isopropyl acrylamide, N-vinyl isobutyramide and N-propyl acrylamide; and/or the second initiator is one or two of potassium persulfate and azoisobutyronitrile.
11. The method for preparing the fluorescent thermosensitive composite quantum dot material according to claim 4, wherein in the step of adding the polymer core layer into the mixed solution and stirring the mixture under an inert atmosphere to react to generate the polymer core layer coated by the thermosensitive polymer shell layer, the reaction temperature is 60-80 ℃; and/or the reaction time is 1-5 h.
12. An environment temperature monitoring LED, characterized in that the LED comprises the fluorescent thermosensitive composite quantum dot material according to any one of claims 1 to 3 or the fluorescent thermosensitive composite quantum dot material prepared by the preparation method of the fluorescent thermosensitive composite quantum dot material according to any one of claims 4 to 11.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911406744.2A CN113061435A (en) | 2019-12-31 | 2019-12-31 | Fluorescent thermosensitive composite quantum dot material, preparation method thereof and environment temperature monitoring LED |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911406744.2A CN113061435A (en) | 2019-12-31 | 2019-12-31 | Fluorescent thermosensitive composite quantum dot material, preparation method thereof and environment temperature monitoring LED |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113061435A true CN113061435A (en) | 2021-07-02 |
Family
ID=76558485
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911406744.2A Pending CN113061435A (en) | 2019-12-31 | 2019-12-31 | Fluorescent thermosensitive composite quantum dot material, preparation method thereof and environment temperature monitoring LED |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113061435A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115200739A (en) * | 2022-06-16 | 2022-10-18 | 哈尔滨工业大学（威海） | Calibration-free optical fiber temperature sensor and sensing device based on fluorescence wavelength demodulation |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103386135A (en) * | 2013-07-24 | 2013-11-13 | 上海交通大学 | Preparation method of multifunctional medicine carrier integrating magnetism, fluorescence and thermosensitivity |
| CN105131947A (en) * | 2015-07-29 | 2015-12-09 | 辽宁大学 | Composite shell carbon dots for fluorescent nanometer thermometer and their preparation method and use |
| CN105524288A (en) * | 2015-12-16 | 2016-04-27 | 浙江大学 | Quantum dot-doped polyion liquid-polyacrylamide interpenetrating network hydrogel and preparation method thereof |
| CN107255532A (en) * | 2017-05-08 | 2017-10-17 | 东南大学 | A kind of SMD luminance temperature of metal phasmon and infrared ray sensor |
| CN108641706A (en) * | 2018-06-01 | 2018-10-12 | 南京邮电大学 | A kind of quantum dot fluorescence polymer microballoon and preparation method thereof |
| CN109010274A (en) * | 2018-10-24 | 2018-12-18 | 宁夏医科大学 | A kind of Ci Re Lazer type fluorescent glue bundle of particle and preparation method thereof |
| CN109652061A (en) * | 2019-01-28 | 2019-04-19 | 广东普加福光电科技有限公司 | A kind of quantum dot/polymer microballoon composite material, preparation method and application |
-
2019
- 2019-12-31 CN CN201911406744.2A patent/CN113061435A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103386135A (en) * | 2013-07-24 | 2013-11-13 | 上海交通大学 | Preparation method of multifunctional medicine carrier integrating magnetism, fluorescence and thermosensitivity |
| CN105131947A (en) * | 2015-07-29 | 2015-12-09 | 辽宁大学 | Composite shell carbon dots for fluorescent nanometer thermometer and their preparation method and use |
| CN105524288A (en) * | 2015-12-16 | 2016-04-27 | 浙江大学 | Quantum dot-doped polyion liquid-polyacrylamide interpenetrating network hydrogel and preparation method thereof |
| CN107255532A (en) * | 2017-05-08 | 2017-10-17 | 东南大学 | A kind of SMD luminance temperature of metal phasmon and infrared ray sensor |
| CN108641706A (en) * | 2018-06-01 | 2018-10-12 | 南京邮电大学 | A kind of quantum dot fluorescence polymer microballoon and preparation method thereof |
| CN109010274A (en) * | 2018-10-24 | 2018-12-18 | 宁夏医科大学 | A kind of Ci Re Lazer type fluorescent glue bundle of particle and preparation method thereof |
| CN109652061A (en) * | 2019-01-28 | 2019-04-19 | 广东普加福光电科技有限公司 | A kind of quantum dot/polymer microballoon composite material, preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| JIANHUA LÜ等: "Coordination-induced assemblies of quantum dots in amphiphilic thermo-responsive block copolymer micelles: morphologies, optical properties and applications", 《POLYMER CHEMISTRY》 * |
| LI ZHOU等: "Thermo-sensitive and photoluminescent hydrogels: Synthesis, characterization, and their drug-release property", 《MATERIALS SCIENCE AND ENGINEERING C》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115200739A (en) * | 2022-06-16 | 2022-10-18 | 哈尔滨工业大学（威海） | Calibration-free optical fiber temperature sensor and sensing device based on fluorescence wavelength demodulation |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10553750B2 (en) | Semiconductor nanocrystals, methods for making same, compositions, and products | |
| Sheng et al. | In-situ encapsulation of quantum dots into polymer microspheres | |
| Bae et al. | Single-step synthesis of quantum dots with chemical composition gradients | |
| Li et al. | Large-scale synthesis of nearly monodisperse CdSe/CdS core/shell nanocrystals using air-stable reagents via successive ion layer adsorption and reaction | |
| JP4073323B2 (en) | Functional beads, reading method and reading apparatus thereof | |
| US11060022B2 (en) | Quantum dot-containing materials and products including same cross reference to related applications | |
| Dworak et al. | Acceptor Concentration Dependence of Förster Resonance Energy Transfer Dynamics in Dye–Quantum Dot Complexes | |
| Firth et al. | Production and luminescent properties of CdSe and CdS nanoparticle–polymer composites | |
| TWI608076B (en) | Quantum dots stabilized with a metal thiol polymer | |
| CN103094488B (en) | Electroluminescence device and manufacturing method thereof | |
| CN107221833B (en) | A kind of tunable Random Laser array device based on phasmon nanostructure | |
| US10126485B2 (en) | Optical film and lighting and display products including same | |
| TW201947006A (en) | Quantum dot material and manufacturing method thereof | |
| CN107828416A (en) | Quantum dot fluorescent composite material and preparation method and application thereof | |
| CN113061435A (en) | Fluorescent thermosensitive composite quantum dot material, preparation method thereof and environment temperature monitoring LED | |
| JP2022541422A (en) | Core-shell nanostructures containing surface-bound zinc halides and zinc carboxylates | |
| JP2017512237A (en) | Method for producing quantum dot polymer film | |
| CN106206965A (en) | A kind of quantum dot packaging body and preparation method thereof | |
| CN104250329A (en) | Polymer nanocomposite optical material and preparation method thereof | |
| KR20220141230A (en) | Resin molded article containing quantum dot and fabrication method thereof | |
| CN110658169B (en) | Hyperspectrum-based transmission-type testing device and method for luminescent characteristics of fluorescent powder | |
| TWI632220B (en) | Combination solution of colloidal quantum dots and method for making the same | |
| Kulkarni et al. | Quantum Dot–Polymer Composites in Light-Emitting Diode Applications | |
| CN113969163A (en) | Quantum dot composite material, preparation method thereof and environment temperature sensor | |
| US20190115212A1 (en) | Core-shell nanoplatelets and uses thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210702 |
|
| RJ01 | Rejection of invention patent application after publication |