CN113125033B - Fluorescent thermosensitive composite quantum dot material, preparation method thereof and ambient temperature monitoring LED - Google Patents

Fluorescent thermosensitive composite quantum dot material, preparation method thereof and ambient temperature monitoring LED Download PDF

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CN113125033B
CN113125033B CN201911415474.1A CN201911415474A CN113125033B CN 113125033 B CN113125033 B CN 113125033B CN 201911415474 A CN201911415474 A CN 201911415474A CN 113125033 B CN113125033 B CN 113125033B
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CN113125033A (en
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叶炜浩
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TCL Technology Group Co Ltd
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    • 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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Abstract

The invention discloses a fluorescent thermosensitive composite quantum dot material, a preparation method thereof and an environment 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 a red light quantum dot, a green light quantum dot and a blue light quantum dot, the up-conversion fluorescent nano material comprises an inorganic luminescent material matrix, and Yb doped in the inorganic luminescent material matrix 3+ The first rare earth ion and the second rare earth ion. According to the invention, the different energy level change degrees of the first rare earth ion and the second rare earth ion along with the temperature change enable the red light quantum dot, the green light quantum dot and the blue light quantum dot to be excited to different degrees and to display different luminescent colors, so that the purpose of temperature detection is achieved.

Description

Fluorescent thermosensitive composite quantum dot material, preparation method thereof and ambient 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 environment temperature monitoring LED.
Background
The LED is an electroluminescent semiconductor device capable of directly converting electric energy into light energy, is used as 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, so that the LED becomes a main stream product of the illumination industry.
Temperature detection is always an important research area, both in engineering and in the scientific research field. Almost all biological, chemical and physical processes are closely related to temperature, and accurate temperature information is required to be known in industrial production in many fields to ensure reliable operation of the system. In such cases as metallurgy, glass manufacturing, material modeling, food processing, and the like. Under such circumstances, it is very important that the temperature can be accurately and efficiently measured, and the temperature information under the time condition of a specific environment can be mastered only on the premise of accurately measuring the temperature, so that the accurate information between other non-temperature factors and non-temperature factors under the temperature condition, and between the non-temperature factors and the temperature can be accurately judged. However, conventional contact temperature sensing technologies, such as thermocouples, thermal resistors, and radiation thermometers, cannot meet practical requirements due to their own limitations in situations where strong magnetic fields, flow, high voltage, high response rates, and non-contact measurements are required.
Based on the continuous improvement of the temperature measurement requirement, a non-contact type temperature measurement mode is an urgent requirement. The fluorescent thermometer is a temperature sensing device based on LEDs. The fluorescence temperature sensing utilizes temperature to influence fluorescence emission of a material system, so that certain characteristics of fluorescence such as fluorescence intensity, peak spectrum displacement, peak spectrum shape and the like are changed, and the temperature can be calibrated by monitoring the relationship between the change and the temperature. The fluorescent signal is easy to monitor and the reaction is quick, so that the temperature can be displayed in real time. Meanwhile, the fluorescence intensity of the quantum dots presents linear temperature response, and the quantum dots are sensitive to local environments. However, known quantum dot ligands render quantum dot fluorescence insensitive to temperature. For example, when denatured ovalbumin is used as a ligand, and when quantum dots are embedded in polymer particles, the fluorescence intensity of the quantum dots is independent of temperature.
Accordingly, the prior art is still in need of improvement.
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 environmental temperature monitoring LED, and aims to solve the problem that the current quantum dot material is easily influenced by ligands or polymer particles, so that the change of the fluorescence intensity of the quantum dot material is insensitive to temperature.
The technical scheme of the invention is as follows:
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, 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 matrix 3+ The first rare earth ion and the second rare earth ion.
A preparation method of a fluorescent thermosensitive composite quantum dot material comprises the following steps:
an up-conversion fluorescent nanomaterial is provided that includes a phosphor matrix, yb doped in the phosphor matrix 3+ A first rare earth ion, a second rare earth ion;
dispersing the up-conversion fluorescent nanomaterial and a bifunctional organic ligand in an organic solvent, and reacting to generate the bifunctional organic ligand modified up-conversion fluorescent nanomaterial;
and dispersing the up-conversion fluorescent nano material modified by the bifunctional organic ligand, the red light quantum dots, the green light quantum dots and the blue light quantum dots in an organic solvent to prepare the fluorescent thermosensitive composite quantum dot material.
The invention discloses an environment temperature monitoring LED, which comprises a fluorescent thermosensitive composite quantum dot material or a fluorescent thermosensitive composite quantum dot material prepared by the preparation method of the fluorescent thermosensitive composite quantum dot material.
The beneficial effects are that: the invention provides a fluorescent thermosensitive composite quantum dot material, which comprises an up-conversion fluorescent nanomaterial and a quantum dot material combined on the up-conversion fluorescent nanomaterial, wherein the quantum dot material comprises red light quantum dots, green light quantum dots and blue light quantum dots, the up-conversion fluorescent nanomaterial comprises an inorganic luminescent material matrix and Yb doped in the inorganic luminescent material matrix 3+ The first rare earth ion and the second rare earth ion. According to the invention, the red light quantum dots, the green light quantum dots and the blue light quantum dots are excited to different degrees by the different energy levels of the first rare earth ions and the second rare earth ions along with the temperature change, so that different luminescent colors are displayed, and the purpose of temperature detection is achieved.
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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 environment temperature monitoring LED, and the invention is further described in detail below in order to make the purposes, the technical scheme and the effects of the invention clearer and more definite. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The change of fluorescence intensity with temperature is often caused by the enhancement of non-forcible transition of a certain energy level or energy level pair of rare earth ions under the action of temperature, so that the temperature can be calibrated by monitoring the change of fluorescence intensity. Fluctuations in laser source power and loss of light transmission can also affect the fluorescence intensity of single rare earth doped materials, which can make temperature monitoring inaccurate. Therefore, the dual doped rare earth materials are generally adopted, and the ratio of the intensities of the light emitted by the energy levels with different temperature luminescence behaviors is utilized to achieve, and the ratio eliminates the influence of factors other than temperature. In the process, the non-radiative transition of the rare earth doped fluorescent material is changed along with the temperature change, but the fluorescence intensity is reduced along with the temperature increase. When the rare earth with two different temperature luminescence behaviors is 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 weak fluorescence intensity is displayed, so that the temperature is difficult to monitor.
Based on the above problems, an embodiment of the present invention provides a fluorescent thermosensitive composite quantum dot material, which includes an up-conversion fluorescent nanomaterial and a quantum dot material bonded on the up-conversion fluorescent nanomaterial, wherein the quantum dot material includes red light quantum dots, green light quantum dots, and blue light quantum dots, the up-conversion fluorescent nanomaterial includes an inorganic luminescent material matrix, and Yb doped in the inorganic luminescent material matrix 3+ The first rare earth ion and the second rare earth ion.
In this embodiment, since the quantum dot material has better fluorescence intensity and quantum efficiency, it can also exhibit stronger fluorescence at weaker excitation intensity. The embodiment adopts quantum dot material and Yb 3+ First rare earth ionAnd the inorganic luminescent material doped with the second rare earth ions is compounded with the matrix to form the fluorescent thermosensitive composite quantum dot material, when the temperature is increased, the number of excited state particles of the other two rare earth ions in corresponding energy levels is reduced to different degrees, and the fluorescent intensity of the corresponding emitted wavelengths is also reduced to different degrees. For example, in a normal state, the up-conversion fluorescent nanomaterial may emit light with a short wavelength and a long wavelength, and the light emitted by the first rare earth ion and the second rare earth ion may excite three kinds of quantum dots of red, green and blue and all have close fluorescence intensities, so that the fluorescent thermosensitive composite quantum dot material as a whole may exhibit white light or close white light; however, when the temperature is changed, such as the temperature is increased, the light intensity of the short wavelength emitted by one rare earth ion is reduced more than the light of the long wavelength emitted by the other rare earth ion, so that the excitation degree of the blue light quantum dot and the green light quantum dot is reduced, the fluorescence intensity is reduced, and the red light quantum dot can still be excited by the light of the long wavelength, and the fluorescent thermosensitive composite quantum dot material overall shows red light. Therefore, the different energy level change degrees of the first rare earth ion and the second rare earth ion along with the temperature change enable the red, green and blue quantum dots to be excited to different degrees and to display different luminescent colors, so that the purpose of temperature detection is achieved.
In the present 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 numbers on the energy levels of the rare earth ions are changed, and if the particle numbers on the two excited states of the rare earth ions reach a thermal equilibrium state again in a short time, the energy levels are called as thermal coupling energy level pairs; in the same phosphor matrix, the first rare earth ion and the second rare earth ion are in the same excited state, and the energy level difference between the first rare earth ion and the second rare earth ion in the same excited state in this embodiment is 200-2000cm -1 When the thermal coupling energy level pair is formed; due to the existence of such thermally coupled energy level pairs, at elevated temperatures, the firstThe light intensity of one rare earth ion and the light intensity of the second rare earth ion are weakened, and the excited state electrons on the rare earth ion emitting short wavelength light transmit part of energy to the rare earth ion emitting long wavelength light through the coupling effect, so that the excited states of the other two rare earth ions reach balance again, the weakening degree of the light intensity of the short wavelength rare earth ion is larger than that of the long wavelength rare earth ion, the excited degree of the blue-green light quantum dot is reduced, the fluorescence intensity of the blue-green light quantum dot is reduced, and the red light quantum dot can still receive the light excitation of long wavelength, and overall red light is displayed.
In this embodiment, the different energy levels of the first rare earth ion and the second rare earth ion corresponding to the temperature change enable the red light quantum dot, the green light quantum dot and the blue light quantum dot to be excited to different degrees and to display different luminescent colors, so that the purpose of temperature detection is achieved.
In some embodiments, 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 waves of the first rare earth ion and the second rare earth ion are 300-800nm.
In some embodiments, the first rare earth ion and the second rare earth ion are Tb 3+ And Eu 3+ 、Eu 3+ And Sm 3+ 、Er 3+ And Tm 3+ Or Ce 3+ And Eu 3+ But are not limited thereto.
In some embodiments, the surface of the up-conversion fluorescent nanomaterial is bound to a bifunctional organic ligand to which the quantum dot material is bound. In this embodiment, the bifunctional organic ligand may be respectively combined with the rare earth ions doped in the up-conversion fluorescent nanomaterial and the cations on the surface of the quantum dot material through the functional groups of the bifunctional organic ligand, so as to achieve that the quantum dot material is combined on the up-conversion fluorescent nanomaterial through the bifunctional organic ligand.
In some specific embodiments, the difunctional organic ligand is one or more of benzyl mercaptan, thioglycollic acid, mercaptopropionic acid, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, ethylenediamine, octadecyl-p-ethylenebenzyl-dimethyl ammonium 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 a carboxyl group and a mercapto group, and the mercaptopropionic acid can combine with rare earth ions doped in the upconversion fluorescent nanomaterial through its mercapto group and/or carboxyl group to form a mercaptopropionic acid-coated upconversion fluorescent nanomaterial; when the thiol propionic acid-coated up-conversion 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 thiol which are not combined with the thiol propionic acid, so that the quantum dot material is combined with the up-conversion fluorescent nanomaterial through the thiol propionic acid.
In some embodiments, to ensure that the fluorescent thermosensitive composite quantum dot material emits white or near white light when excited, the quantum dot material comprises red, green and blue quantum dots in a mass ratio of (2.5-3.5): (5.5-6.5): (1-1.5).
In some embodiments, the red light quantum dot is CdSe, cdTe, inN, gaAs, cd 1-x Zn x S、Cd 1-x Zn x Se、Zn X Cd 1-X Te、Cd 1-x Zn x S/ZnS)、Cd 1-x Zn x Se/ZnSe、CdSe 1-x S x /CdSe y S 1-y /CdS、CdSe/Cd 1-x Zn x Se/CdyZn 1-y Se/ZnSe、Cd 1-x Zn x Se/CdyZn 1-y Se/ZnSe、CdS/Cd 1-x Zn x S/Cd y Zn 1-y S/ZnS、Cd 1-x ZnxSe y S 1-y And Cd 1-x Zn x One or more of Se/ZnS, but not limited toHere, where x=0.1-0.3, y=0.6-0.8.
In some embodiments, the green quantum dots are GaP, znTe, cd 1-x Zn x S、Cd 1-x Zn x Se、Cd 1-x Zn x S/ZnS、Cd 1-x Zn x Se/ZnSe)、CdSe 1-x S x /CdSe y S 1-y /CdS、CdSe/Cd 1-x Zn x Se/CdyZn 1-y Se/ZnSe、Cd 1-x Zn x Se/CdyZn 1-y Se/ZnSe、CdS/Cd 1-x Zn x S/Cd y Zn 1-y S/ZnS、Cd 1-x ZnxSeyS 1-y And Cd 1- x Zn x One or more of Se/ZnS, but not limited thereto, wherein x=0.4 to 0.8 and y=0.3 to 0.5.
In some embodiments, the blue light quantum dots are ZnSe, gaN, cd 1-x Zn x S、Cd 1-x Zn x Se、Cd 1-x Zn x S/ZnS、Cd 1-x Zn x Se/ZnSe、CdSe 1-x S x /CdSe y S 1-y /CdS、CdSe/Cd 1-x Zn x Se/CdyZn 1-y Se/ZnSe、Cd 1-x Zn x Se/CdyZn 1-y Se/ZnSe、CdS/Cd 1-x Zn x S/Cd y Zn 1-y S/ZnS、Cd 1-x ZnxSeyS 1-y And Cd 1- x Zn x One or more of Se/ZnS, but not limited thereto, wherein x=0.9-1, y=0.1-0.2.
In some embodiments, the phosphor matrix is NaYF4, ca 5 (PO 4 ) 3 F、CaSiO 3 、SrSiO 3 、BaSiO 3 、LaMgAl 11 O 19 、Y 2 MoO 6 And NaSrPO 4 But are not limited to, one or more of the following.
In some embodiments, a method for preparing a fluorescent thermosensitive composite quantum dot material is also provided, as shown in fig. 1, which includes the steps of:
s10, providing an up-conversion fluorescent nanomaterial, wherein the up-conversion fluorescent nanomaterial comprisesPhosphor matrix, yb doped in said phosphor matrix 3+ And two other rare earth ions, a first rare earth ion, a second rare earth ion;
s20, dispersing the up-conversion fluorescent nanomaterial and the difunctional organic ligand in an organic solvent, and reacting to generate the difunctional organic ligand modified up-conversion fluorescent nanomaterial;
s30, dispersing the up-conversion fluorescent nano material modified by the bifunctional organic ligand, the red light quantum dot, the green light quantum dot and the blue light quantum dot in an organic solvent, and mixing the red light quantum dot, the green light quantum dot and the blue light quantum dot with the bifunctional organic ligand to prepare the fluorescent thermosensitive composite quantum dot material.
Because the quantum dot material has better fluorescence intensity and quantum efficiency, the quantum dot material can also show stronger fluorescence under weaker excitation intensity, and the embodiment adopts the quantum dot material and Yb 3+ And the inorganic luminescent material doped with the first rare earth ions and the second rare earth ions is compounded with the matrix to form the fluorescent thermosensitive composite quantum dot material. 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 dot, the green light quantum dot and the blue light quantum dot have different excitation degrees and different luminescent colors are displayed, the purpose of temperature detection is achieved, and 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 energy level difference between the first rare earth ion and the second rare earth ion is 200-2000cm -1 。
In some embodiments, the up-conversion fluorescent nanomaterial and the bifunctional organic ligand are dispersed in an organic solvent and reacted at 60-75 ℃ for 1-2 hours to produce the bifunctional organic ligand-modified up-conversion fluorescent nanomaterial.
In some embodiments, the up-conversion fluorescent nanomaterial modified by the bifunctional organic ligand and the quantum dot material are mixed in an organic solvent, stirred for 10-20 hours at normal temperature, and then washed with an alcohol solvent to obtain the fluorescent thermosensitive composite quantum dot material.
In some embodiments, an environmental temperature monitoring LED is also provided, which includes the fluorescent thermosensitive composite quantum dot material of the present invention or a fluorescent thermosensitive composite quantum dot material prepared by the preparation method of the fluorescent thermosensitive composite quantum dot material of 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 the temperature change, so that the red light quantum dot, the green light quantum dot and the blue light quantum dot have different excitation degrees and different luminescent colors are displayed, the purpose of temperature detection is achieved, and 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.
The preparation method of the fluorescent thermosensitive composite quantum dot material is described in detail by a specific embodiment:
example 1
1. Synthesizing red-green-blue quantum dots, wherein the red quantum dots are CdSe, and the green quantum dots are Cd 0.6 Zn 0.4 S, blue quantum dots are Cd 0.1 Zn 0.9 S/ZnS；
2. 1mol YCl 3 ·6H 2 O、0.05mol ErCl 3 ·6H 2 O、0.05mol TmCl 3 ·7H 2 O、0.25mol YbCl 3 ·6H 2 Adding O, 10mL of oleic acid and 30mL of octadecene into a reaction kettle, deoxidizing, and preserving heat for 60 minutes at 160 ℃; methanol solution of NaOH and NH 4 F, stirring the methanol solution at normal temperature for 60 minutes, stirring the mixture for 60 minutes at the temperature of 60 ℃ again, preserving the heat for 1 minute at the temperature of 108 ℃, vacuumizing for 20 minutes, recovering the normal pressure, preserving the heat for 20 minutes at the temperature of 308 ℃, and cooling to the room temperature to obtain the up-conversion fluorescent nano material NaYF 4 :Yb 3+ /Er 3+ /Tm 3+ ；
3. 4mol of ethylenediamine and 50mg of NaYF 4 :Yb 3+ /Er 3+ /Tm 3+ In 20mL of n-hexane, the mixture was dispersed,ultrasonic dispersing for 30min, heating to 65deg.C for 1.5 hr, and washing with ethanol; then ethylenediamine-modified NaYF 4 :Yb 3+ /Er 3+ /Tm 3+ Adding the mixture with 4mg of quantum dots (red: green: blue=3:6:1) and 10mL of tetrahydrofuran into a 50mL flask, stirring at normal temperature for reaction for 15h, and then washing with ethanol to obtain the thermosensitive quantum dots/NaYF 4 :Yb 3+ /Er 3+ /Tm 3+ A composite material.
Example 2
1. Synthesizing red, green and blue quantum dots, wherein the red quantum dots are CdSe, and the green quantum dots are Cd 0.6 Zn 0.4 S, blue quantum dots are Cd 0.1 Zn 0.9 S/ZnS；
2. 0.25g CaCl 2 ，0.67g Na 2 SiO 3 And 0.3g of citric acid were dissolved in 15ml,15ml and 10ml deionized water, respectively, and stirred to give clear solutions. Then, 0.1mmol Yb (NO) 3 ) 3 、0.05mmol Eu(NO 3 ) 3 And 0.05mmol Sm (NO) 3 ) 3 Adding rare earth nitrate into 15ml CaCl 2 10ml of citric acid solution was added drop wise to the previous 15ml CaCl solution 2 25ml of solution was formed and 15ml of Ca was added 2 SiO 3 The solution was added dropwise to 25ml of the solution formed above and magnetically stirred at room temperature for 10min to form a homogeneous solution. Then, the pH of the homogeneous solution was adjusted to 11 with NaOH solution. While NaOH was added, we can observe NaOH and Ca 2+ The rare earth ions react rapidly to form flocculent white precipitate. The mixture was stirred magnetically well for 1h. Finally, the mixed solution is poured into a reaction kettle, and the temperature is kept at 180 ℃ for 24 hours. Calcining the obtained sample in a high temperature furnace at 700 ℃ for 3 hours, and then slowly reducing the temperature to room temperature to obtain CaSiO 3 :Yb 3+ /Eu 3+ /Sm 3+ A powder;
3. 4mol of thioglycollic acid are reacted with 45mg of CaSiO 3 :Yb 3+ /Eu 3+ /Sm 3+ Dispersing in 20mL of n-hexane, performing ultrasonic dispersion for 30min, heating to 70 ℃ for reaction for 2h, and finally cleaning with ethanol; then, thioglycollic acid modified CaSiO 3 :Yb 3+ /Eu 3+ /Sm 3+ Adding the mixture with 6mg of quantum dots (red: green: blue=2.5:6:1.5) and 10mL of tetrahydrofuran into a 50mL flask, stirring and reacting for 12h at normal temperature, and then washing with ethanol to obtain the thermosensitive quantum dots/CaSiO 3 :Yb 3+ /Eu 3+ /Sm 3+ A composite material.
In summary, the fluorescent thermosensitive composite quantum dot material provided by the invention comprises an up-conversion fluorescent nanomaterial and a quantum dot material combined on the up-conversion fluorescent nanomaterial, wherein the quantum dot material comprises red light quantum dots, green light quantum dots and blue light quantum dots, the up-conversion fluorescent nanomaterial comprises an inorganic luminescent material matrix, and Yb doped in the inorganic luminescent material matrix 3+ The first rare earth ion and the second rare earth ion. According to the invention, the red light quantum dots, the green light quantum dots and the blue light quantum dots are excited to different degrees by the different energy levels of the first rare earth ions and the second rare earth ions along with the temperature change, so that different luminescent colors are displayed, and the purpose of temperature detection is achieved.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.

Claims (5)

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 a red light quantum dot, a green light quantum dot and a blue light quantum dot, and the mass ratio of the red light quantum dot to the green light quantum dot to the blue light quantum dot is (2.5-3.5) (5.5-6.5) (1-1.5); the up-conversion fluorescent nanomaterial comprises a phosphor matrix and Yb doped in the phosphor matrix 3+ A first rare earth ion, a second rare earth ion; wherein the first diluteThe emission wave of the soil ions is 300-800nm; and/or the emission wave of the second rare earth ion is 300-800nm; the first rare earth ion and the second rare earth ion are Tb 3+ And Eu 3+ 、Eu 3+ And Sm 3+ 、Er 3+ And Tm 3+ Or Ce 3+ And Eu 3+ A group of (a) in (b); the energy level difference between the first rare earth ion and the second rare earth ion is 200 cm to 2000cm -1 The surface of the up-conversion fluorescent nanomaterial is combined with a bifunctional organic ligand, the quantum dot material is combined with the bifunctional organic ligand, and the bifunctional organic ligand is one or more of benzyl mercaptan, thioglycollic acid, mercaptopropionic acid, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, ethylenediamine, octadecyl-p-vinylbenzyl-dimethyl ammonium chloride, N-dimethylbenzylamine, methyl hexahydro-o-phthalyl anhydride, phthalic anhydride, sodium polyacrylate, polydimethylsiloxane, polyethyleneimine and amino-terminated polyethylene glycol.
2. The fluorescent thermosensitive composite quantum dot material according to claim 1, wherein the phosphor matrix is NaYF4, ca 5 (PO 4 ) 3 F、CaSiO 3 、SrSiO 3 、BaSiO 3 、LaMgAl 11 O 19 、Y 2 MoO 6 And NaSrPO 4 One or more of the following.
3. The preparation method of the fluorescent thermosensitive composite quantum dot material is characterized by comprising the following steps:
an up-conversion fluorescent nanomaterial is provided that includes a phosphor matrix, yb doped in the phosphor matrix 3+ A first rare earth ion, a second rare earth ion; wherein the energy level difference between the first rare earth ion and the second rare earth ion is 200 cm to 2000cm -1 The method comprises the steps of carrying out a first treatment on the surface of the The emission wave of the first rare earth ion is 300-800nm; and/or the emission wave of the second rare earth ion is 300-800nm; the first rare earth ion and the second rare earth ionFor Tb 3+ And Eu 3+ 、Eu 3+ And Sm 3+ 、Er 3+ And Tm 3+ Or Ce 3+ And Eu 3+ A group of (a) in (b);
dispersing the up-conversion fluorescent nanomaterial and a bifunctional organic ligand in an organic solvent, and reacting to generate the bifunctional organic ligand modified up-conversion fluorescent nanomaterial, wherein the bifunctional organic ligand is one or more of benzyl mercaptan, thioglycollic acid, mercaptopropionic acid, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, ethylenediamine, octadecyl-p-vinylbenzyl-dimethyl ammonium chloride, N-dimethylbenzylamine, methyl hexahydro-phthalic anhydride, sodium polyacrylate, polydimethylsiloxane, polyethyleneimine and amino-terminated polyethylene glycol;
and dispersing the up-conversion fluorescent nano material modified by the bifunctional organic ligand, red light quantum dots, green light quantum dots and blue light quantum dots in an organic solvent, wherein the mass ratio of the red light quantum dots to the green light quantum dots to the blue light quantum dots is (2.5-3.5) (5.5-6.5) (1-1.5), and the fluorescent thermosensitive composite quantum dot material is prepared.
4. The method of preparing fluorescent thermosensitive composite quantum dot material according to claim 3, wherein in the step of dispersing the up-conversion fluorescent nanomaterial and the bifunctional organic ligand in an organic solvent, the reaction temperature is 60-75 ℃ and/or the reaction time is 1-2h.
5. An environmental temperature monitoring LED, comprising the fluorescent thermosensitive composite quantum dot material according to any one of claims 1 to 2 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 3 to 4.
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