CN113969163A - Quantum dot composite material, preparation method thereof and environment temperature sensor - Google Patents
Quantum dot composite material, preparation method thereof and environment temperature sensor Download PDFInfo
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Abstract
The invention discloses a quantum dot composite material, a preparation method thereof and an environment temperature sensor, wherein the quantum dot composite material comprises a lanthanide metal organic framework and a quantum dot material combined on the lanthanide metal organic framework. The quantum dots have good fluorescence intensity and quantum efficiency, and can show strong fluorescence under the weak excitation light intensity, after the luminous intensity of the quantum dots is reduced, the lost energy can be transmitted to lanthanide metal ions through energy transfer to enhance the luminous intensity, and by utilizing the characteristic, the quantum dot composite material can detect the temperature change of-40 ℃ to 100 ℃, and because the quantum dots and the lanthanide metal ions have high energy transfer efficiency, the signal-to-noise ratio of the composite material is high, and the error value is less than 4%/° C. Therefore, the quantum dot composite material provided by the invention is used as the fluorescent material of the LED in the ambient temperature sensor, and the corresponding ambient temperature can be judged according to the luminous color.
Description
Technical Field
The invention relates to the field of quantum dots, in particular to a quantum dot composite material, a preparation method thereof and an ambient temperature detection LED.
Background
LEDs are electroluminescent semiconductor devices that are encapsulated by epoxy, a means of converting electrical energy directly into light. The LED is used as a modern novel green energy-saving illumination and is expected to replace a traditional light source. The LED light source has great functions in the fields of illumination and display, is incomparable with other light sources, and becomes a mainstream product in the illumination industry.
Quantum dots refer to semiconductor nanocrystalline materials with quantum confinement effect in 3 dimensions of space, and quantum dot light emitting diodes (QLEDs) with low power consumption, low energy consumption, long service time, long illumination time and high intensity have been prepared due to the properties of tunable luminescent color of the size and components, high fluorescence quantum yield, strong absorption of blue light and ultraviolet light, reasonable photochemical stability and the like.
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 accurate control of temperature information is required in industrial production in many fields to ensure reliable operation of systems, such as metallurgy, glass manufacturing, 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 accurate information between other non-temperature factors and between the non-temperature factors and the temperature factors 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.
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-radiation 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 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 quantum dot composite material, a preparation method thereof and an environment temperature sensor, and aims to solve the problem that the existing fluorescence temperature sensor based on a quantum dot material cannot accurately monitor temperature.
The technical scheme of the invention is as follows:
a quantum dot composite comprising a lanthanide metal-organic framework and a quantum dot material bonded to the lanthanide metal-organic framework.
A preparation method of a quantum dot composite material comprises the following steps:
dispersing a lanthanide ion ligand and a lanthanide ion salt in an organic solvent, and reacting to prepare a lanthanide ion precursor solution;
mixing a quantum dot material in the lanthanide ion precursor solution to prepare a quantum dot-lanthanide ion precursor solution;
and adding an organic ligand into the quantum dot-lanthanide ion precursor solution, mixing, and reacting to obtain the quantum dot composite material.
An environment temperature sensor comprises an LED, wherein a fluorescent material in the LED is the quantum dot composite material.
Has the advantages that: the quantum dot composite material provided by the invention comprises a lanthanide metal organic framework and a quantum dot material combined on the lanthanide metal organic framework. The quantum dots have good fluorescence intensity and quantum efficiency, so that strong fluorescence can be shown under the weak excitation light intensity, after the luminous intensity of the quantum dots is reduced, the lost energy is transmitted to lanthanide metal ions in the lanthanide metal organic framework through energy transfer to enhance the luminous intensity of the lanthanide metal ions, and by utilizing the characteristic, the quantum dot composite material can detect the temperature change of-40-100 ℃, and because the quantum dots and the lanthanide metal organic framework have high energy transfer efficiency, the signal-to-noise ratio of the composite material is also high, and the error value is less than 4%/° C. Therefore, the quantum dot composite material provided by the invention is used as the fluorescent material of the LED in the ambient temperature sensor, and the corresponding ambient temperature can be judged according to the luminous color.
Drawings
Fig. 1 is a flow chart of a preferred embodiment of a method for preparing a quantum dot composite material according to the present invention.
Fig. 2 is a schematic diagram of the preparation of the quantum dot composite material of the present invention.
Detailed Description
The invention provides a quantum dot composite material, a preparation method thereof and an environment temperature sensor, 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.
For the environmental temperature sensor, when the double-doped rare earth material is used for calibrating the temperature instead of the single-rare earth doped material, the non-radiative transition of the rare earth doped fluorescent material changes along with the temperature change, for example, the fluorescence intensity of the rare earth doped fluorescent material and the fluorescence intensity of the rare earth doped fluorescent material both decrease along with the temperature change, and a fluorescence intensity ratio can be formed because the non-radiative transition states of the two rare earth materials are different, and the influence of factors except the temperature can be eliminated through the fluorescence intensity ratio. However, if the fluorescence intensity is greatly reduced, the finally exhibited weak fluorescence intensity is difficult to monitor the ambient temperature.
Based on the problems in the prior art, embodiments of the present invention provide a quantum dot composite material, which includes a lanthanide metal organic framework and a quantum dot material bonded to the lanthanide metal organic framework.
In this embodiment, since the quantum dot material has better fluorescence intensity and quantum efficiency, it can exhibit stronger fluorescence even at a weaker excitation light intensity. In this embodiment, when the temperature is increased, the light emission intensities of the quantum dot material and the lanthanide metal organic framework are both reduced, but the light emission intensity of the lanthanide metal organic framework is reduced to a smaller extent compared with the light emission intensity of the quantum dot material, which is beneficial to the further quantum confinement effect of the nano-micro holes in the lanthanide metal organic framework on the quantum dot material combined inside, so that the light emission centers of the quantum dot material and the lanthanide metal organic framework are overlapped to a larger extent. Therefore, when the luminous intensity of the quantum dot material is reduced, the lost energy can be transmitted to lanthanide metal ions in the lanthanide metal organic framework through energy transfer to enhance the luminous intensity, and by utilizing the characteristic, the quantum dot composite material provided by the embodiment can detect the temperature change of-40 ℃ to 100 ℃, and the signal-to-noise ratio of the composite material is higher due to the higher energy transfer efficiency of the quantum dot composite material and the lanthanide metal ions, and the error value is less than 4%/DEG C.
By adopting the quantum dot composite material provided by the embodiment as the fluorescent material of the LED in the ambient temperature sensor, the corresponding ambient temperature can be judged according to the luminous color of the quantum dot composite material. Specifically, the quantum dot material and the lanthanide metal organic framework in the quantum dot composite material can respectively emit light with different wavelengths after being excited, and the light with the two different wavelengths forms an integral light emitting color to be emitted. By way of example, when the quantum dot material emits green light after being excited and the lanthanide metal-organic framework emits red light after being excited, the quantum dot composite material emits yellow light as a whole at this time; when the temperature changes, the intensity of green light emitted by the quantum dot material and the intensity of red light emitted by the lanthanide metal organic framework change in different degrees, and the proportion of red light to green light forming yellow light changes, so that different yellow lights can be formed, such as lemon yellow, medium chrome yellow, clay yellow and the like, and therefore the corresponding environment temperature can be judged by monitoring the change of the luminescent color of the quantum dot composite material. By way of example, with 0 ℃ as a reference temperature, the light emitted by the quantum dot composite material is chrome yellow; when the light emitted by the quantum dot composite material is monitored to be lemon yellow, the ambient temperature is judged to be reduced to-20 ℃; when the light yellow soil emitted by the quantum dot composite material is monitored, the environmental temperature is judged to be increased to 60 ℃.
In some embodiments, the emission wavelength of the quantum dot material is less than the emission wavelength of the lanthanide metal-organic framework. Since the wavelength of light is inversely proportional to the energy, in this embodiment, the energy of the quantum dot material after being excited is greater than the energy of the lanthanide metal organic frame after being excited, so that when the temperature of the quantum dot composite material is increased, the quantum dot material can transfer part of the energy to the lanthanide metal organic frame, thereby preventing the fluorescence intensity of the quantum dot composite material from being greatly reduced, and facilitating monitoring of the ambient temperature change.
In some embodiments, to increase the resolution of the color change, and thereby make it easier to determine the ambient temperature from the color change, the emission wavelength of the lanthanide metal-organic framework is greater than 600nm and less than 800 nm. In this embodiment, the lanthanide metal organic frame emits red light, and since the wavelength of the emitted light of the quantum dot material is smaller than that of the lanthanide metal organic frame, the quantum dot material can emit green light or blue light, and the red light and the green light or the blue light can form light of multiple colors, so that the ambient temperature can be conveniently determined through color change.
In some embodiments, the lanthanide metal organic framework includes a lanthanide metal ion, and an organic ligand that is coordinately bound to the lanthanide metal ion. The true bookIn the examples, the lanthanide metal ion is Eu3+、Tb3+、Ce3+、Ce4+、Sm3+And Tm3+But are not limited thereto; the organic ligand is benzene tricarboxylic acid, terephthalic acid, 4' -biphenyl dicarboxylic acid and tetracarboxylic acid molecule 5,5- (benzo [ c ]][1,2,5]Thiadiazole-4, 7-substituted) di (isophthalic acid) and 1,3, 5-tri (4-carboxyphenyl) benzene are one or more of, but are not limited to, the organic ligand is soluble in an organic solvent to form a corresponding acid ion, and the acid ion can be bonded with the lanthanide metal ion through a coordination bond. In this example, as shown in fig. 2, the lanthanide metal ions can simultaneously combine with multiple organic ligands to form a lanthanide metal-organic framework monomer, which self-assembles through coordination bonds to form a lanthanide metal-organic framework with intramolecular pores. Further, the surface ligands of the quantum dot material and the organic ligands in the lanthanide metal organic framework are bonded together by covalent bonds. For example, when the surface ligand of the quantum dot material is an amine-based ligand, and the organic ligand in the lanthanide metal organic framework is trimesic acid, in this case, a large number of carboxyl groups are contained in the lanthanide metal organic framework, and the amine-based ligand on the surface of the quantum dot material can undergo a condensation reaction with the carboxyl groups in the trimesic acid and be bonded together through covalent bonds.
In some embodiments, the quantum dot material is a green or blue quantum dot. By way of example, when the quantum dot material is a green quantum dot, the green quantum dot is 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/ZnSWherein x is 0.4-0.8, and y is 0.3-0.5.
When the quantum dot material is a blue light quantum dot, the blue light quantum dot is ZnSe, GaN or 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 present invention also provides a method for preparing a quantum dot composite material, as shown in fig. 1, comprising the steps of:
s10, dispersing the lanthanide ion ligand and the lanthanide ion salt in an organic solvent to prepare a lanthanide ion precursor solution;
s20, mixing a quantum dot material in the lanthanide ion precursor solution to prepare a quantum dot-lanthanide ion precursor solution;
and S30, adding an organic ligand into the quantum dot-lanthanide ion precursor solution, mixing, and reacting to obtain the quantum dot composite material.
In some embodiments, the lanthanide ion ligand and the lanthanide ion salt are dispersed in an organic solvent and reacted at 100-150 ℃ for 1-2h, and the bound water in the lanthanide ion salt is removed, so that the lanthanide ion ligand and the lanthanide ion in the lanthanide ion salt are bound through ionic bonds, thereby obtaining a lanthanide ion precursor solution which is easily dispersed in the organic solvent. In this embodiment, the organic solvent is one or more of octadecene, oleic acid and octadecanoic acid, but is not limited thereto. The lanthanide ion ligand is one or more of sodium acetate, sodium propionate, sodium oleate and sodium stearate, but is not limited thereto. The lanthanide metal ion is Eu3+、Tb3+、Ce3+、Ce4+、Sm3+And Tm3+But is not limited thereto.
In some embodiments, a quantum dot material is mixed in the lanthanide ion precursor solution, and stirred for 1-2h such that the quantum dot material and the lanthanide ion ligand in the lanthanide ion precursor solution are bonded together by covalent bonds, forming a quantum dot-lanthanide ion precursor solution.
In some embodiments, an organic ligand is added to the quantum dot-lanthanide ion precursor solution and mixed, and the mixture is reacted for 1 to 3 hours at the temperature of 150-.
In some embodiments, there is also provided an ambient temperature sensor comprising an LED, wherein the fluorescent material in the LED is a quantum dot composite material as described in the above examples. By adopting the quantum dot composite material provided by the embodiment as the fluorescent material of the LED in the ambient temperature sensor, the corresponding ambient temperature can be judged according to the luminous color of the quantum dot composite material. Specifically, the quantum dot material and the lanthanide metal organic framework in the quantum dot composite material can respectively emit light with different wavelengths after being excited, and the light with the two different wavelengths forms an integral light emitting color to be emitted. By way of example, when the quantum dot material emits green light after being excited and the lanthanide metal-organic framework emits red light after being excited, the quantum dot composite material emits yellow light as a whole at this time; when the temperature changes, the intensity of green light emitted by the quantum dot material and the intensity of red light emitted by the lanthanide metal organic framework change in different degrees, and the proportion of red light to green light forming yellow light changes, so that different yellow lights can be formed, such as lemon yellow, medium chrome yellow, clay yellow and the like, and therefore the corresponding environment temperature can be judged by monitoring the change of the luminescent color of the quantum dot composite material.
In some specific embodiments, an ambient temperature sensor is further provided, which includes an LED, and the fluorescent material in the LED is the quantum dot composite material described in the above example, and the composite quantum dot material is composed of the lanthanide metal-organic framework and the quantum dot material bonded to the lanthanide metal-organic framework.
The following is a further explanation of the preparation method of a quantum dot composite material of the present invention by specific examples:
example 1
1.5mmol of sodium acetate and 0.5mmol of Eu (NO)3)3·6H2O is dispersed in 10mL of octadecene and 2mL of oleic acid, and then the mixture is heated to 130 ℃ to react for 1h, so that ionic salt Eu (NO) is removed3)3·6H2Bound water in O;
then 5mg of green light quantum dot Cd synthesized by the prior art is added0.6Zn0.4Se is continuously stirred for 1.5h to enable Eu3+Ions and Cd0.6Zn0.4Se is uniformly mixed (lanthanide ions and quantum dots can be uniformly distributed and are as close as possible when a metal organic framework matrix is generated subsequently), and Cd is obtained0.6Zn0.4Se-Eu3+Precursor solution;
to the above Cd0.6Zn0.4Se-Eu3+Adding 1mmol of benzene tricarboxylic acid (BTC) into the precursor solution, and stirring at room temperature to enable the solution to be mixed with Eu3+Reacting to generate Eu-BTC, reacting for 2h at 150 ℃, and cleaning to obtain Cd0.6Zn0.4Se/Eu-BTC composite material.
Example 2
2mmol of sodium oleate and 0.3mmol of Tb (NO)3)3·6H2O is dispersed in 10mL of octadecene and 2mL of oleic acid, and then the mixture is heated to 150 ℃ to react for 2h, so that the ionic salt Tb (NO) is removed3)3·6H2Bound water in O;
then 3mg of Cd synthesized by the prior art was added0.1Zn0.9Stirring the S/ZnS quantum dots for 2h to ensure that Tb3+And Cd0.1Zn0.9The S/ZnS quantum dots are uniformly mixed (lanthanide ions and the quantum dots can be uniformly distributed and are as close as possible when a metal organic framework matrix is generated in the subsequent process), and Cd is obtained0.1Zn0.9S/ZnS-Tb3+Precursor solution;
to the above Cd0.1Zn0.9S/ZnS-Tb3+Adding 1.5mmol of terephthalic acid (BTB) into the precursor solution, and stirring at room temperature to react with Tb3+Reacting to generate Tb-BTB, reacting for 2h at 200 ℃, and cleaning to obtain Cd0.1Zn0.9S/ZnS/Tb-BTB composite material.
In summary, the quantum dot composite material provided by the present invention includes a lanthanide metal organic framework and a quantum dot material bonded on the lanthanide metal organic framework. The quantum dots have good fluorescence intensity and quantum efficiency, so that strong fluorescence can be shown under the weak excitation light intensity, after the luminous intensity of the quantum dots is reduced, the lost energy is transmitted to lanthanide metal ions in the lanthanide metal organic framework through energy transfer to enhance the luminous intensity of the lanthanide metal ions, and by utilizing the characteristic, the quantum dot composite material can detect the temperature change of-40-100 ℃, and because the quantum dots and the lanthanide metal organic framework have high energy transfer efficiency, the signal-to-noise ratio of the composite material is also high, and the error value is less than 4%/° C. Therefore, the quantum dot composite material provided by the invention is used as the fluorescent material of the LED in the ambient temperature sensor, and the corresponding ambient temperature can be judged according to the luminous color.
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 (11)
1. A quantum dot composite comprising a lanthanide metal-organic framework and a quantum dot material bonded to the lanthanide metal-organic framework.
2. The quantum dot composite of claim 1, wherein the quantum dot material emits light at a wavelength less than a wavelength of light emitted by the lanthanide metal-organic framework.
3. The quantum dot composite of claim 2, wherein the emission wavelength of the lanthanide metal-organic framework is greater than 600nm and less than 800 nm.
4. The quantum dot composite of any of claims 1-3, wherein the lanthanide metal-organic framework comprises a lanthanide metal ion, and an organic ligand that is coordinately bound to the lanthanide metal ion.
5. The quantum dot composite of claim 4, wherein the lanthanide ionic ligand is one or more of sodium acetate, sodium propionate, sodium oleate, and sodium stearate;
and/or, the lanthanide metal ion is Eu3+、Tb3+、Ce3+、Ce4+、Sm3+And Tm3+One or more of;
and/or the organic ligand is one or more of benzene tricarboxylic acid, terephthalic acid, 4' -biphenyl dicarboxylic acid, tetracarboxylic acid molecule 5,5- (benzo [ c ] [1,2,5] thiadiazole-4, 7-substituted) di (isophthalic acid) and 1,3, 5-tri (4-carboxyphenyl) benzene.
6. The quantum dot composite of claim 4, wherein the surface ligands of the quantum dot material are bonded together with the organic ligands in the lanthanide metal organic framework by covalent bonds.
7. The quantum dot composite material of claim 5, wherein the quantum dot material is a green or blue quantum dot.
8. A preparation method of a quantum dot composite material is characterized by comprising the following steps:
dispersing a lanthanide ion ligand and a lanthanide ion salt in an organic solvent to prepare a lanthanide ion precursor solution;
mixing a quantum dot material in the lanthanide ion precursor solution to prepare a quantum dot-lanthanide ion precursor solution;
and adding an organic ligand into the quantum dot-lanthanide ion precursor solution, mixing, and reacting to obtain the quantum dot composite material.
9. The method for preparing the quantum dot composite material according to claim 8, wherein in the step of adding the organic ligand into the quantum dot-lanthanide ion precursor solution and mixing, and reacting to obtain the quantum dot composite material, the reaction temperature is 150-200 ℃, and the reaction time is 1-3 h.
10. An ambient temperature sensor comprising an LED, wherein the fluorescent material in the LED is the quantum dot composite material according to any one of claims 1 to 7.
11. The ambient temperature sensor of claim 10, wherein the composite quantum dot material consists of the lanthanide metal-organic framework and the quantum dot material bonded to the lanthanide metal-organic framework.
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| CN114686208A (en) * | 2020-12-31 | 2022-07-01 | Tcl科技集团股份有限公司 | Composite reagent, anti-counterfeiting combined reagent and anti-counterfeiting method |
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