CN113125033A - 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 PDF

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CN113125033A
CN113125033A CN201911415474.1A CN201911415474A CN113125033A CN 113125033 A CN113125033 A CN 113125033A CN 201911415474 A CN201911415474 A CN 201911415474A CN 113125033 A CN113125033 A CN 113125033A
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CN113125033B (en
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叶炜浩
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TCL Research America Inc
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    • G01K11/14—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 inorganic materials
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    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
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    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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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 an up-conversion fluorescent nano material and a quantum dot material combined on the up-conversion fluorescent nano material, the quantum dot material comprises red light quantum dots, green light quantum dots and blue light quantum dots, the up-conversion fluorescent nano material comprises an inorganic luminescent material matrix, and Yb doped in the inorganic luminescent material matrix3+First rare earth ions, second rare earth ions. In the present invention, the first rare earthThe ions and the second rare earth ions have different corresponding energy level change degrees along with the temperature change, so that the red light quantum dots, the green light quantum dots and the blue light quantum dots are different in excited degree and show different luminescent colors, and the purpose of temperature detection is achieved.

Description

Fluorescent thermosensitive composite quantum dot material, preparation method thereof and environment temperature monitoring LED
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 embedded in 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 an up-conversion fluorescent nano material and a quantum dot material combined on the up-conversion fluorescent nano material, wherein the quantum dot material comprises red light quantum dots, green light quantum dots and blue light quantum dots, the up-conversion fluorescent nano material comprises an inorganic luminescent material matrix, and Yb doped in the inorganic luminescent material matrix3+First rare earth ions, second rare earth ions.
A preparation method of a fluorescent thermosensitive composite quantum dot material comprises the following steps:
an upconversion fluorescent nanomaterial is provided, the upconversion fluorescent nanomaterial comprising a phosphor host, Yb doped in the phosphor host3+First rare earth ions, second rare earth ions;
dispersing the up-conversion fluorescent nano material and bifunctional organic ligand in an organic solvent, and reacting to generate the bifunctional organic ligand modified up-conversion fluorescent nano material;
and dispersing the bifunctional organic ligand modified up-conversion fluorescent nano material, red light quantum dots, green light quantum dots and blue light quantum dots in an organic solvent to prepare 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 an up-conversion fluorescent nano material and a nano material combined on the up-conversion fluorescent nano materialQuantum dot material on rice material, the quantum dot material comprises red light quantum dot, green light quantum dot and blue light quantum dot, the up-conversion fluorescent nano material comprises inorganic luminescent material matrix, Yb doped in the inorganic luminescent material matrix3+First rare earth ions, second rare earth ions. According to the invention, the first rare earth ion and the second rare earth ion have different corresponding energy level change degrees along with the temperature change, so that the red light quantum dot, the green light quantum dot and the blue light quantum dot are excited to different degrees and show different light-emitting colors, and the purpose of temperature detection is achieved, therefore, the fluorescent thermosensitive composite quantum dot material can be used as a light-emitting material of an environment temperature monitoring LED, and the sensitive detection of the environment temperature change is realized.
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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.
The change of fluorescence intensity with temperature is often caused by the fact that a certain energy level or energy level pair of rare earth ions is not good-emitting transition enhanced under the action of temperature, so that the temperature can be calibrated by monitoring the change of fluorescence intensity. But fluctuations in the power of the laser source and loss of optical transmission also affect the fluorescence intensity of the single rare-earth doped material, which can make the temperature monitoring inaccurate. Therefore, the light emitting device is generally realized by adopting a double-doped rare earth material and utilizing the ratio of the intensity of light emitted by energy levels with different temperature light emitting behaviors, and the ratio eliminates the influence of factors except temperature. In this process, the non-radiative transition of the rare-earth doped fluorescent material changes with the temperature, but the fluorescence intensity decreases with the temperature. When two kinds of rare earth with different temperature luminescence behaviors are adopted for doping and the temperature is changed, a fluorescence intensity ratio can be formed due to different non-radiative transition states. However, the fluorescence intensity is greatly reduced, and finally, the weak fluorescence intensity is difficult to monitor the temperature.
In view of the above problems, embodiments of the present invention provide a fluorescent thermosensitive composite quantum dot material, which includes an up-conversion fluorescent nanomaterial and a quantum dot material bonded to the up-conversion fluorescent nanomaterial, where the quantum dot material includes red quantum dots, green quantum dots, and blue quantum dots, the up-conversion fluorescent nanomaterial includes an inorganic luminescent material matrix, and Yb doped in the inorganic luminescent material matrix3+First rare earth ions, second rare earth ions.
In this embodiment, since the quantum dot material has a good fluorescence intensity and quantum efficiency, it can also exhibit a strong fluorescence under a weak excitation intensity. This example uses quantum dot material and Yb3+And the inorganic luminescent material matrix doped with the first rare earth ions and the second rare earth ions is compounded to form the fluorescent thermosensitive composite quantum dot material, and when the temperature is increased, the fluorescent intensity of the respective wavelengths correspondingly emitted is weakened in different degrees due to the fact that the number of excited state particles of the other two rare earth ions at corresponding energy levels is reduced in different degrees, and the luminescent state of the quantum dot material can be changed by utilizing the characteristic. For example, in a normal state, the upconversion fluorescent nanomaterial can emit light with short wavelength and long wavelength, and the light emitted by the first rare earth ion and the light emitted by the second rare earth ion can excite three quantum dots of red, green and blue and have similar fluorescence intensity, so that the fluorescent thermosensitive composite quantum dot material integrally shows white light or near white light; however, when the temperature changes, such as the temperature rises, the light intensity of the short wavelength emitted by one rare earth ion is weakened to a greater extent than that of the long wavelength emitted by the other rare earth ion, so that the blue quantum dot and the green quantum dot are stimulated to be reduced, the fluorescence intensity is reduced, and the red quantum dot can still be stimulated by the long wavelength light, and then the fluorescence temperature-sensitive composite quantum dot material integrally shows that the red quantum dot can be stimulated by the long wavelength lightLight. Therefore, the first rare earth ion and the second rare earth ion have different corresponding energy level change degrees along with the temperature change, so that the red, green and blue quantum dots have different excited degrees and show different luminescent colors, and the purpose of temperature detection is achieved.
In this embodiment, the energy level difference between the first rare earth ion and the second rare earth ion is 200-2000cm-1. When the rare earth ions are excited, the particle number on the energy level of the rare earth ions can be changed, and if the particle numbers on the excited states of the two rare earth ions can reach a thermal equilibrium state again in a short time, the pair of energy levels is called as a thermal coupling energy level pair; in the same inorganic luminescent material matrix, the first rare earth ion and the second rare earth ion are in the same excited state, and the energy level difference when the first rare earth ion and the second rare earth ion are in the same excited state in this embodiment is 200-2000 cm--1Then a thermally coupled energy level pair may be formed; due to the existence of the thermal coupling energy level pair, when the temperature rises, the light intensity of the first rare earth ion and the second rare earth ion is weakened, and the excited state electrons on the rare earth ions emitting short-wavelength light transfer part of energy to the rare earth ions emitting long-wavelength light through the coupling action, so that the excited states of the other two rare earth ions are balanced again, the weakening degree of the light intensity of the rare earth ions emitting short-wavelength light is larger than that of the rare earth ions emitting long-wavelength light, the stimulated degree of blue-green light quantum dots is reduced, the fluorescence intensity is reduced, the red light quantum dots can still be excited by the long-wavelength light, and the whole red light is shown.
In this embodiment, the first rare earth ion and the second rare earth ion have different corresponding energy level change degrees along with the temperature change, so that the red light quantum dot, the green light quantum dot and the blue light quantum dot are excited differently to show different light emitting colors, thereby achieving the purpose of temperature detection.
In some embodiments, in order to ensure that the fluorescence emitted by the first rare earth ion and the second rare earth ion can excite the quantum dot material to emit light, the emission wavelengths of the first rare earth ion and the second rare earth ion are both 300-800 nm.
In some embodiments, the first and second rare earth ions are Tb3+And Eu3+、Eu3+And Sm3+、Er3+And Tm3+Or Ce3+And Eu3+But is not limited thereto.
In some embodiments, the surface of the upconversion fluorescent nanomaterial is bound with a bifunctional organic ligand, and the quantum dot material is bound on the bifunctional organic ligand. In this embodiment, the bifunctional organic ligand may be respectively bound to the rare earth ions doped in the upconversion fluorescent nanomaterial and the cations on the surface of the quantum dot material through the functional groups of the bifunctional organic ligand, so that the quantum dot material is bound to the upconversion fluorescent nanomaterial through the bifunctional organic ligand.
In some embodiments, the bifunctional organic ligand is one or more of benzyl mercaptan, thioglycolic acid, mercaptopropionic acid, sodium dodecylbenzenesulfonate, sodium dodecylsulfonate, sodium dodecylsulfate, ethylenediamine, octadecyl-p-vinylbenzyl-dimethylammonium chloride, N-dimethylbenzylamine, methylhexahydrophthalic anhydride, phthalic anhydride, sodium polyacrylate, polydimethylsiloxane, polyethyleneimine, and amino-terminated polyethylene glycol, but is not limited thereto. By way of example, when the bifunctional organic ligand is mercaptopropionic acid, the mercaptopropionic acid also has carboxyl and mercapto, and the mercaptopropionic acid can be combined with the rare earth ions doped in the upconversion fluorescent nanomaterial through the mercapto and/or the carboxyl to form a mercaptopropionic acid-coated upconversion fluorescent nanomaterial; when the mercaptopropionic acid-coated upconversion fluorescent nanomaterial is mixed with a quantum dot material, metal ions on the surface of the quantum dot material can be combined with carboxyl or sulfydryl which is not combined with mercaptopropionic acid, so that the quantum dot material is combined on the upconversion fluorescent nanomaterial through the mercaptopropionic acid.
In some embodiments, to ensure that the fluorescent thermosensitive composite quantum dot material can emit white light or near-white light when being excited, the quantum dot material comprises red light quantum dots, green light quantum dots and blue light quantum dots in a mass ratio of (2.5-3.5): (5.5-6.5):(1-1.5).
In some specific embodiments, the red quantum dots are CdSe, CdTe, InN, GaAs, Cd1-xZnxS、Cd1-xZnxSe、ZnXCd1-XTe、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、Cd1-xZnxSeyS1-yAnd Cd1-xZnxOne or more of Se/ZnS, wherein x is 0.1-0.3 and y is 0.6-0.8.
In some specific embodiments, the green quantum dots are GaP, ZnTe, Cd1-xZnxS、Cd1-xZnxSe、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、Cd1-xZnxSeyS1-yAnd Cd1- xZnxOne or more of Se/ZnS, wherein x is 0.4-0.8 and y is 0.3-0.5.
In some specific embodiments, the blue quantum dot is ZnSe, GaN, Cd1-xZnxS、Cd1-xZnxSe、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、Cd1-xZnxSeyS1-yAnd Cd1- xZnxOne or more of Se/ZnS, wherein x is 0.9-1 and y is 0.1-0.2.
In some embodiments, the phosphor matrix is NaYF4, Ca5(PO4)3F、CaSiO3、SrSiO3、BaSiO3、LaMgAl11O19、Y2MoO6And NaSrPO4But is not limited thereto.
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, providing an upconversion fluorescent nanomaterial, wherein the upconversion fluorescent nanomaterial comprises a phosphor host and Yb doped in the phosphor host3+And two other rare earth ions, a first rare earth ion, a second rare earth ion;
s20, dispersing the up-conversion fluorescent nano-material and bifunctional organic ligands in an organic solvent, and reacting to generate the bifunctional organic ligand modified up-conversion fluorescent nano-material;
s30, dispersing the bifunctional organic ligand modified up-conversion fluorescent nano material, red light quantum dots, green light quantum dots and blue light quantum dots in an organic solvent, and mixing to combine the red light quantum dots, the green light quantum dots and the blue light quantum dots with the bifunctional organic ligand to obtain the fluorescent thermosensitive composite quantum dot material.
Since the quantum dot material has better fluorescence intensity and quantum efficiency, and can also show stronger fluorescence under weaker excitation intensity, the quantum dot material and Yb are adopted in the embodiment3+And the first rare earth ion and the inorganic luminescent material matrix doped with the second rare earth ion are compounded to form the fluorescent thermosensitive composite quantum dot materialThe method is simple and easy to realize. In the fluorescent thermosensitive composite quantum dot material prepared by the embodiment, the first rare earth ions and the second rare earth ions have different corresponding energy level change degrees along with the temperature change, so that the red light quantum dots, the green light quantum dots and the blue light quantum dots are different in excited degree and show different luminous colors, and the purpose of temperature detection is achieved.
In some embodiments, the energy level difference between the first rare earth ion and the second rare earth ion is 200-2000cm-1。
In some embodiments, the upconversion fluorescent nanomaterial is dispersed in an organic solvent and reacted for 1 to 2 hours at a temperature of between 60 and 75 ℃ to form the bifunctional organic ligand modified upconversion fluorescent nanomaterial.
In some embodiments, the bifunctional organic ligand-modified up-conversion fluorescent nanomaterial and a quantum dot material are mixed in an organic solvent, stirred at normal temperature for 10-20h, and then washed with an alcohol solvent to obtain the fluorescent thermosensitive composite quantum dot material.
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 first rare earth ions and the second rare earth ions in the fluorescent thermosensitive composite quantum dot material have different corresponding energy level change degrees along with temperature change, so that the red light quantum dots, the green light quantum dots and the blue light quantum dots are excited to different degrees and show different light-emitting colors, and the purpose of temperature detection is achieved.
The preparation method of the fluorescent thermosensitive composite quantum dot material is described in detail by the following specific examples:
example 1
1. Synthesizing red, green and blue quantum dots, wherein the red quantum dot is CdSe and the green quantum dot is Cd0.6Zn0.4S, the blue quantum dot is Cd0.1Zn0.9S/ZnS；
2. 1mol of YCl3·6H2O、0.05mol ErCl3·6H2O、0.05mol TmCl3·7H2O、0.25mol YbCl3·6H2Adding O, 10mL of oleic acid and 30mL of octadecene into a reaction kettle, deoxidizing, and keeping the temperature at 160 ℃ for 60 minutes; adding NaOH in methanol solution and NH4Stirring the methanol solution of F for 60 minutes at normal temperature, stirring for 60 minutes at 60 ℃, preserving heat for 1 minute at 108 ℃, vacuumizing for 20 minutes, restoring the normal pressure and preserving heat for 20 minutes at 308 ℃, and cooling to room temperature to obtain the upconversion fluorescent nano material NaYF4:Yb3+/Er3+/Tm3+；
3. 4mol of ethylenediamine and 50mg of NaYF4:Yb3+/Er3+/Tm3+Dispersing in 20mL of normal hexane, performing ultrasonic dispersion for 30min, heating to 65 ℃, reacting for 1.5h, and finally cleaning with ethanol; then adding ethylenediamine modified NaYF4:Yb3+/Er3+/Tm3+Adding 4mg of quantum dots (wherein red: green: blue ═ 3:6:1) and 10mL of tetrahydrofuran into a 50mL flask, stirring and reacting for 15h at normal temperature, and then washing with ethanol to obtain the thermosensitive quantum dots/NaYF4:Yb3+/Er3+/Tm3+A composite material.
Example 2
1. And synthesizing red, green and blue quantum dots, wherein the red quantum dot is CdSe and the green quantum dot is Cd0.6Zn0.4S, the blue quantum dot is Cd0.1Zn0.9S/ZnS；
2. Adding 0.25g of CaCl2，0.67g Na2SiO3And 0.3g citric acid in 15ml, 15ml and 10ml deionized water, respectively, and stirred to obtain clear solutions. Then, 0.1mmol of Yb (NO) was added3)3、0.05mmol Eu(NO3)3And 0.05mmol of Sm (NO)3)3Rare earth nitrate is added into 15ml of CaCl2In the solution, 10ml of citric acid was dissolvedThe solution was added dropwise to the previous 15ml of CaCl2Form a 25ml solution and add 15ml Ca2SiO3The solution was added dropwise to the previously formed 25ml solution and magnetically stirred at room temperature for 10min to form a homogeneous solution. The pH of the homogeneous solution was then adjusted to 11 with NaOH solution. While adding NaOH, we can observe NaOH and Ca2+And the rare earth ions react rapidly to form flocculent white precipitates. The mixture was stirred magnetically thoroughly for 1 h. Finally, pouring the mixed solution into a reaction kettle, and preserving the temperature at 180 ℃ for 24 hours. Then calcining the obtained sample in a high temperature furnace at 700 ℃ for 3h, and slowly reducing the temperature to room temperature to obtain CaSiO3:Yb3+/Eu3+/Sm3+Powder;
3. 4mol of thioglycolic acid and 45mg of CaSiO3:Yb3+/Eu3+/Sm3+Dispersing in 20mL of normal hexane, performing ultrasonic dispersion for 30min, heating to 70 ℃, reacting for 2h, and finally cleaning with ethanol; then the CaSiO modified by thioglycollic acid3:Yb3+/Eu3+/Sm3+Adding 6mg of quantum dots (wherein red: green: blue ═ 2.5:6:1.5) and 10mL of tetrahydrofuran into a 50mL flask, stirring and reacting at normal temperature for 12h, and then washing with ethanol to obtain the thermosensitive quantum dots/CaSiO3:Yb3+/Eu3+/Sm3+A composite material.
In summary, the present invention provides a fluorescent thermosensitive composite quantum dot material, which includes an up-conversion fluorescent nano material and a quantum dot material combined on the up-conversion fluorescent nano material, wherein the quantum dot material includes a red light quantum dot, a green light quantum dot and a blue light quantum dot, the up-conversion fluorescent nano material includes an inorganic luminescent material matrix, and Yb doped in the inorganic luminescent material matrix3+First rare earth ions, second rare earth ions. According to the invention, the first rare earth ion and the second rare earth ion have different corresponding energy level change degrees along with the temperature change, so that the red light quantum dot, the green light quantum dot and the blue light quantum dot are excited to different degrees and show different luminescent colors, thereby achieving the purpose of temperature detection, and therefore, the fluorescent thermosensitive composite quantum dot material can be used as the luminescent of an ambient temperature monitoring LEDThe material realizes sensitive detection on environmental temperature change.
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 (10)

1. The fluorescent thermosensitive composite quantum dot material is characterized by comprising an up-conversion fluorescent nano material and a quantum dot material combined on the up-conversion fluorescent nano material, wherein the quantum dot material comprises red light quantum dots, green light quantum dots and blue light quantum dots, the up-conversion fluorescent nano material comprises an inorganic luminescent material matrix, and Yb doped in the inorganic luminescent material matrix3+First rare earth ions, second rare earth ions.
2. The fluorescence thermosensitive composite quantum dot material according to claim 1, wherein the energy level difference between the first rare earth ion and the second rare earth ion is 200-2000cm-1(ii) a And/or
The emission wave of the first rare earth ions is 300-800 nm; and/or
The emission wave of the second rare earth ions is 300-800 nm.
3. The fluorescent thermosensitive composite quantum dot material according to claim 1, wherein the first rare earth ion and the second rare earth ion are Tb3+And Eu3+、Eu3+And Sm3+、Er3+And Tm3+Or Ce3+And Eu3+One group of (1).
4. The fluorescent thermosensitive composite quantum dot material according to claim 1, wherein a bifunctional organic ligand is bound to the surface of the up-conversion fluorescent nanomaterial, and the quantum dot material is bound to the bifunctional organic ligand.
5. The fluorescent thermosensitive composite quantum dot material according to claim 4, wherein the bifunctional organic ligand is one or more of benzyl mercaptan, thioglycolic acid, mercaptopropionic acid, sodium dodecylbenzenesulfonate, sodium dodecylsulfonate, sodium dodecylsulfate, ethylenediamine, octadecyl-p-vinylbenzyl-dimethylammonium chloride, N-dimethylbenzylamine, methylhexahydrophthalic anhydride, phthalic anhydride, sodium polyacrylate, polydimethylsiloxane, polyethyleneimine, and amino-terminated polyethylene glycol.
6. The fluorescent thermosensitive composite quantum dot material according to claim 1, wherein the mass ratio of the red, green and blue quantum dots is (2.5-3.5): (5.5-6.5):(1-1.5).
7. The fluorescence thermosensitive composite quantum dot material according to claim 1, wherein the inorganic luminescent material matrix is NaYF4, Ca5(PO4)3F、CaSiO3、SrSiO3、BaSiO3、LaMgAl11O19、Y2MoO6And NaSrPO4One or more of (a).
8. A preparation method of a fluorescent thermosensitive composite quantum dot material is characterized by comprising the following steps:
an upconversion fluorescent nanomaterial is provided, the upconversion fluorescent nanomaterial comprising a phosphor host, Yb doped in the phosphor host3+First rare earth ions, second rare earth ions;
dispersing the up-conversion fluorescent nano material and bifunctional organic ligand in an organic solvent, and reacting to generate the bifunctional organic ligand modified up-conversion fluorescent nano material;
and dispersing the bifunctional organic ligand modified up-conversion fluorescent nano material, red light quantum dots, green light quantum dots and blue light quantum dots in an organic solvent to prepare the fluorescent thermosensitive composite quantum dot material.
9. The method for preparing the fluorescence thermal sensitive composite quantum dot material as claimed in claim 8, wherein the energy level difference between the first rare earth ion and the second rare earth ion is 200-2000cm-1(ii) a And in the step of dispersing the upconversion fluorescent nanomaterial and bifunctional organic ligand in an organic solvent to react to generate the bifunctional organic ligand modified upconversion fluorescent nanomaterial, the reaction temperature is 60-75 ℃, and/or the reaction time is 1-2 hours.
10. 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 7 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 8 to 9.
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