CN117778008A - Up-conversion rare earth doped nano material capable of emitting white light and preparation method thereof - Google Patents
Up-conversion rare earth doped nano material capable of emitting white light and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a white luminescent up-conversion rare earth doped nano material and a preparation method thereof, which synthesizes a core-shell structure LiYF with the particle size of 28-38nm by a high-temperature coprecipitation method 4 :xHo@LiYbF 4 @LiYF 4 Upconversion nanoparticles (0)<x is less than or equal to 0.02), has good dispersibility and obvious up-conversion luminescence, and shows up-conversion fluorescence of 480nm, 540nm and 650nm under the excitation of 980nm laser, so that the whole color of the fluorescent lamp is shown as white light, and has good application prospect in the fields of biomedicine, solar cells, temperature sensors, photocatalytic degradation and the like.
Description
Technical Field
The invention belongs to the technical field of fluorescent nanomaterial preparation, and particularly relates to a white luminescent up-conversion rare earth doped nanomaterial and a preparation method thereof.
Background
Lanthanide doped upconverting materials are of great interest because of their narrow band emission, low background signal, excellent light stability and rich step levels, being able to emit colors of different wavelengths. These excellent properties make them of great potential in multicolor lighting. Currently, there are two main methods for realizing multicolor light emission. Firstly, in the up-conversion process, the intensity of different red, green and blue lights is controlled by doping rare earth ions between different layers, such as doping Tm under the excitation of 798 nm laser 3+ 、Ho 3+ And Yb 3+ Is doped with Er under 980nm laser excitation 3+ 、Tm 3+ And Yb 3+ NaYF of (F) 4 Tm doping under 980nm laser excitation 3+ 、Ho 3+ And Yb 3+ YF of (2) 3 This is an important technique for achieving multicolor lighting in a single material. Another technique is to control multiple excitation light sources to realize multicolor light emission, but the multi-source white light material has stable optical aberration and low light emitting efficiency. In recent decades, many effective strategies have been tried in order to achieve white light emission, such as: the method is simple and feasible by reasonably selecting host lattices, crystal field effects, doping ion types and concentrations, regulating and controlling a core-shell structure, regulating particle sizes, constructing sub-lattice clusters and the like, wherein the energy absorption process is changed through the regulation and control of the core-shell structure.
Rare earth fluoride matrix materials are of interest due to their low phonon energy, with tetragonal LiYF 4 The hexagonal ring-shaped sub-lattice structure in the structure can effectively inhibit the energy cross relaxation between sensitized ions and improve the sensitization efficiency, and is a material which is matched with NaYF 4 Comparable matrix materials.
Disclosure of Invention
The invention aims to provide a white luminescent up-conversion rare earth doped nano material and a preparation method thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
one of the purposes of the present invention is to provide a white luminescent up-conversion rare earth doped nanomaterial with core-shell junctionA structure sequentially comprising LiY from inside to outside (1-x) F 4 xHo nanocrystal cores, liYbF 4 Sensitization layer and LiYF 4 An inert shell layer, 0 of<x is less than or equal to 0.02. White luminescence can be achieved by changing the structure of the material to cause a change in the energy transfer process.
Further, the particle size of the nanomaterial is 28-38nm.
Further, the nanomaterial exhibits up-conversion fluorescence at 480nm, 540nm, and 650nm with a laser light of wavelength 980 nm.
The second purpose of the invention is to provide a preparation method of the up-conversion rare earth doped nano material for white luminescence, which comprises the following steps of;
（1）Ho 3+ doped LiY (1-x) F 4 Preparation of nanocrystal cores
a) The (1-x) mmolYCl 3 ·6H 2 O、xmmol HoCl 3 ·6H 2 Mixing O, 8ml of oleic acid and 12ml of octadecene, stirring at a rotating speed of 500r/min, vacuumizing to a vacuum degree of 0.08MPa, slowly heating to 150 ℃, preserving heat for half an hour, and naturally cooling to room temperature to obtain a rare earth oleic acid complex;
b) Will contain 4mmol NH 4 Mixing and oscillating the methanol solution of F and the methanol solution containing 1.5mmol of LiOH for 10-30s, then slowly injecting the mixture into the rare earth oleic acid complex obtained in the step a), and preserving the temperature for 30-60min;
c) Vacuumizing to vacuum degree of 0.08MPa, heating to 80deg.C, and maintaining for 15-30min to remove water and methanol;
d) Introducing nitrogen, continuously heating to 300 ℃, preserving heat for 60-90min, and naturally cooling to room temperature;
e) Adding absolute ethanol for precipitation, centrifuging at 7000rpm, centrifuging with mixed solution of cyclohexane and ethanol (1:4, v/v), and washing twice to obtain product, dissolving in cyclohexane to obtain ion doped LiY (1-x) F 4 xHo nanocrystal cores;
（2）LiYbF 4 formation of sensitization layer
f) 1mmol YbCl 3 ·6H 2 After mixing O, 8ml oleic acid and 12ml octadecene,stirring at 500r/min, vacuumizing to 0.08MPa, slowly heating to 150deg.C, maintaining for half an hour, and naturally cooling to room temperature;
g) Adding LiY prepared in the step (1) into the reaction feed liquid in the step f) (1-x) F 4 xHo nanocrystal cores followed by addition of a catalyst containing 4mmol NH 4 F, methanol solution and methanol solution containing 1.5mmol LiOH are kept for 30-60min;
h) Vacuumizing to vacuum degree of 0.08MPa, heating to 80deg.C, and maintaining for 15-30min to remove water and methanol;
i) Introducing nitrogen, continuously heating to 300 ℃, preserving heat for 60-90min, and naturally cooling to room temperature;
j) Adding absolute ethanol for precipitation, centrifuging at 7000rpm, centrifuging with mixed solution of cyclohexane and ethanol (1:4, v/v), and washing twice to obtain product, dissolving in cyclohexane to obtain LiY (1-x) F 4 :xHo@LiYbF 4 A nanocrystal core;
（3）LiYF 4 preparation of inert shell layers
k) 1mmol YCl 3 ·6H 2 Mixing O, 8ml oleic acid and 12ml octadecene, stirring at a rotation speed of 500r/min, vacuumizing to a vacuum degree of 0.08MPa, slowly heating to 150 ℃, preserving heat for half an hour, and naturally cooling to room temperature;
l) adding LiY prepared in the step (2) into the reaction feed liquid in the step j) firstly (1-x) F 4 ：xHo@LiYbF 4 Nanocrystal cores, followed by addition of a solution containing 4mmol NH 4 F, methanol solution and methanol solution containing 1.5mmol LiOH are kept for 30-60min;
m) vacuumizing to 0.08MPa, heating to 80 ℃, and preserving heat for 15-30min to remove water and methanol;
n) introducing nitrogen, continuously heating to 300 ℃, preserving heat for 60-90min, and naturally cooling to room temperature;
o) adding absolute ethanol for precipitation, centrifuging at 7000rpm once, and centrifuging and washing twice with a mixed solution of cyclohexane and ethanol (1:4, v/v), wherein the obtained product is dissolved in cyclohexane to obtain LiY (1-x) F 4 :xHo@LiYbF 4 @LiYF 4 。
The invention has the beneficial effects that:
(1) The invention uses tetragonal phase LiYF with low phonon energy 4 Is taken as a substrate and is doped with Ho and LiYbF 4 The active shell is coated to absorb 980nm infrared photons, and then the surface is coated with an inert shell LiYF 4 The transfer of energy to surface defects is reduced to increase the fluorescence intensity.
(2) The up-conversion nano particles prepared by the invention have good dispersibility, obvious up-conversion luminescence, up-conversion fluorescence of 480nm, 540nm and 650nm under 980nm laser excitation, so that the whole color of the up-conversion nano particles is shown as white light, and the up-conversion nano particles have good application prospects in the fields of biomedicine, solar cells, temperature sensors, photocatalytic degradation and the like.
(3) The method synthesizes the LiY for the first time by a high-temperature coprecipitation method (1-x) F 4 :xHo@LiYbF 4 @LiYF 4 The preparation method has the advantages of low preparation cost, simple process operation, short time consumption and easy preparation.
Drawings
Fig. 1 is an X-ray diffraction pattern of the nanomaterial prepared in examples and comparative examples.
FIG. 2 shows the LiY prepared in the examples 0.995 F 4 :Ho 0.005 @LiYbF 4 @LiYF 4 A transmission electron microscope image (a) and a particle size distribution diagram (b) thereof;
FIG. 3 shows the up-conversion emission patterns (a) and LiY of the nanomaterials prepared in examples and comparative examples under 980nm excitation 0.995 F 4 :Ho 0.005 @LiYbF 4 @LiYF 4 Corresponding color coordinates (b).
Detailed Description
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
EXAMPLES LiY was prepared by high temperature co-precipitation (1-x) F 4 :xHo@LiYbF 4 @LiYF 4 Nanoparticles
The first step: preparation of Ho 3+ Doped LiYF 4 Nanocrystal core:
(a) The (1-x) mmolYCl 3 ·6H 2 O、xmmol HoCl 3 ·H 2 O, 8mL of oleic acid and 12mL of octadecene are mixed in a 250mL three-neck flask, then put into a polytetrafluoroethylene rotor, the rotating speed is set to be 500r/min, a vacuum pump is started to vacuumize to the vacuum degree of 0.08MPa, then the temperature is slowly raised to 150 ℃, the temperature is kept for half an hour, and then the rare earth oleic acid complex is obtained after natural cooling to the room temperature.
(b) Will contain 4mmol NH 4 Mixing and oscillating the methanol solution of F and the methanol solution containing 1.5mmol of LiOH for 10-30s, then slowly injecting the mixture into the obtained rare earth oleic acid complex, and preserving the temperature for 30-60min, wherein the rare earth nano particles begin to nucleate and grow.
(c) Turning on vacuum pump, vacuumizing to vacuum degree of 0.08MPa, heating to 80deg.C, and maintaining for 15-30min to remove water and methanol.
(d) Introducing nitrogen, continuously heating to 300 ℃, preserving heat for 60-90min, and naturally cooling to room temperature after the reaction is finished.
(e) Adding absolute ethanol for precipitation, centrifuging at 7000rpm, centrifuging with mixed solution of cyclohexane and ethanol (1:4, v/v) for washing twice, and dissolving the obtained product in cyclohexane to obtain LiY (1-x) F 4 :xHo（x=0.005、0.01、0.02）。
And a second step of: in the prepared Ho 3+ Doped LiYF 4 LiYbF is coated on the surface of the nanocrystal core 4 Active shell:
(f) 1mmol YbCl 3 ·6H 2 O, 8mL of oleic acid and 12mL of octadecene are mixed in a 250mL three-neck flask, then put into a polytetrafluoroethylene rotor, the rotating speed is set to be 500r/min, a vacuum pump is started to vacuumize to 0.08MPa, then the temperature is slowly raised to 150 ℃, the temperature is kept for half an hour, and then the mixture is naturally cooled to room temperature.
(g) Adding the prepared LiY into the reaction material obtained in the step (f) （1-x） F 4 xHo nanocrystal cores followed by the addition of a catalyst containing 4mmolNH 4 Methanol solution of F and methanol solution containing 1.5mmol LiOHPreserving the temperature of the liquid for 30-60min.
(h) Turning on vacuum pump, vacuumizing to vacuum degree of 0.08MPa, heating to 80deg.C, and maintaining for 15-30min to remove water and methanol.
(i) Introducing nitrogen, continuously heating to 300 ℃, preserving heat for 60-90min, and naturally cooling to room temperature after the reaction is finished.
(j) Adding absolute ethanol for precipitation, centrifuging at 7000rpm, centrifuging with mixed solution of cyclohexane and ethanol (1:4, v/v) for washing twice, and dissolving the obtained product in cyclohexane to obtain LiY (1-x) F 4 :xHo@LiYbF 4 （x=0.005、0.01、0.02）。
And a third step of: in the prepared LiY (1-x) F 4 :xHo@LiYbF 4 LiYF is coated on the surface of the nanocrystal core 4 An inert shell:
(k) 1mmol YCl 3 ·6H 2 O, 8mL of oleic acid and 12mL of octadecene are mixed in a 250mL three-neck flask, then put into a polytetrafluoroethylene rotor, the rotating speed is set to be 500r/min, a vacuum pump is started to vacuumize, the vacuum degree is 0.08MPa, the temperature is slowly raised to 150 ℃, the temperature is kept for half an hour, and then the mixture is naturally cooled to room temperature.
(l) Adding the prepared LiY into the reaction material obtained in the step (k) (1-x) F 4 :xHo@LiYbF 4 Nanocrystal cores, followed by addition of a solution containing 4mmol NH 4 F in methanol and 1.5mmol LiOH in methanol, and keeping the temperature for 30-60min.
(m) turning on a vacuum pump, vacuumizing to a vacuum degree of 0.08MPa, raising the temperature to 80 ℃, and preserving the temperature for 15-30min to remove water and methanol.
(n) introducing nitrogen, continuously heating to 300 ℃, preserving heat for 60-90min, and naturally cooling to room temperature after the reaction is finished.
(o) adding absolute ethanol to precipitate and centrifuging at 7000rpm, centrifuging and washing twice with a mixed solution of cyclohexane and ethanol (1:4, v/v), and finally dissolving the obtained product in cyclohexane to obtain LiY (1-x) F 4 :xHo@LiYbF 4 @LiYF 4 （x=0.005、0.01、0.02）。
Comparative example LiYb was prepared by high temperature co-precipitation 0.995 F 4 :Ho 0.005 @LiYF 4 Nanoparticles
Will be 0.995mmolYbCl 3 ·6H 2 O、0.005mmol HoCl 3 ·6H 2 O, 8mL of oleic acid and 12mL of octadecene are mixed in a 250mL three-neck flask, then put into a polytetrafluoroethylene rotor, the rotating speed is set to be 500r/min, a vacuum pump is started to vacuumize to the vacuum degree of 0.08MPa, then the temperature is slowly raised to 150 ℃, the temperature is kept for half an hour, and then the rare earth oleic acid complex is obtained after natural cooling to the room temperature.
(b) Will contain 4mmol NH 4 Mixing and oscillating the methanol solution of F and the methanol solution containing 1.5mmol of LiOH for 10-30s, then slowly injecting the mixture into the obtained rare earth oleic acid complex, and preserving the temperature for 30-60min, wherein the rare earth nano particles begin to nucleate and grow.
(c) Turning on vacuum pump, vacuumizing to vacuum degree of 0.08MPa, heating to 80deg.C, and maintaining for 15-30min to remove water and methanol.
(d) Introducing nitrogen, continuously heating to 300 ℃, preserving heat for 60-90min, and naturally cooling to room temperature after the reaction is finished.
(e) Precipitating with anhydrous ethanol, centrifuging at 7000rpm, centrifuging with mixed solution of cyclohexane and ethanol (1:4, v/v), washing twice, and dissolving the obtained product in cyclohexane to obtain LiYb 0.995 F 4 :Ho 0.005 A nanocrystal core.
And a second step of: in the prepared Ho 3+ Doped LibYF 4 LiYF is coated on the surface of the nanocrystal core 4 An inert shell:
(f) 1mmol YCl 3 ·6H 2 O, 8mL of oleic acid and 12mL of octadecene are mixed in a 250mL three-neck flask, then put into a polytetrafluoroethylene rotor, the rotating speed is set to be 500r/min, a vacuum pump is started to vacuumize to 0.08MPa, then the temperature is slowly raised to 150 ℃, the temperature is kept for half an hour, and then the mixture is naturally cooled to room temperature.
(g) Adding the prepared LiYb into the reaction material obtained in the step (f) 0.995 F 4 :Ho 0.005 Nanocrystal cores, followed by addition of a solution containing 4mmolNH 4 F in methanol and 1.5mmol LiOH in methanol, and keeping the temperature for 30-60min.
(h) Turning on vacuum pump, vacuumizing to vacuum degree of 0.08MPa, heating to 80deg.C, and maintaining for 15-30min to remove water and methanol.
(i) Introducing nitrogen, continuously heating to 300 ℃, preserving heat for 60-90min, and naturally cooling to room temperature after the reaction is finished.
(j) Precipitating with anhydrous ethanol, centrifuging at 7000rpm, centrifuging with mixed solution of cyclohexane and ethanol (1:4, v/v), washing twice, and dissolving the obtained product in cyclohexane to obtain LiYb 0.995 F 4 :Ho 0.005 @LiYF 4 And (3) nanoparticles.
Performance test:
1. characterization of Crystal form
The samples synthesized in the examples and comparative examples were dried and ground into powder for X-ray diffraction characterization, and the results are shown in FIG. 1. From FIG. 1, it can be confirmed that the synthesized nanomaterial is tetragonal LiYF 4 And adjust Ho 3+ The molar concentration of doping causes the lattice to expand or contract.
2. Morphology characterization:
LiY synthesized in example 1 0.995 F 4 :Ho 0.005 @LiYbF 4 @LiYF 4 Dispersing in cyclohexane, dripping on silicon wafer, drying, and performing transmission electron microscope to test its morphology and size, and the result is shown in figure 2. From FIG. 2, it can be seen that the prepared sample has a uniform morphology and a size of about 35nm.
3. Up-conversion spectral test:
the samples synthesized in the example and the comparative example 1 are respectively placed in a four-way cuvette, a 980nm laser is externally connected as a light source, and the laser power is 1500-2000mW/cm 2 Fluorescence spectrum test was performed, and the results are shown in fig. 3. From FIG. 3, it can be seen that the sample exhibits up-conversion fluorescence at 480nm, 540nm and 655nm, and Ho 3+ When the doping concentration is 0.5% mmol, the fluorescence emission intensity of the up-converted blue light is maximum, and the doping concentration is 0.5% mmol Ho according to the color coordinates 3+ The sample of (2) is white luminescence, the doping concentration is optimalAnd (5) selecting concentration.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (6)
1. A white luminescent up-conversion rare earth doped nano material is characterized in that: the nano material has a core-shell structure, which sequentially comprises LiY from inside to outside (1-x) F 4 xHo nanocrystal cores, liYbF 4 Sensitization layer and LiYF 4 An inert shell layer, 0 of<x≤0.02。
2. The white luminescent up-conversion rare earth doped nanomaterial of claim 1, characterized in that: the grain size of the nanometer material is 28-38nm.
3. The white luminescent up-conversion rare earth doped nanomaterial of claim 1, characterized in that: the nanomaterial exhibits up-conversion fluorescence at 480nm, 540nm, and 650nm with a laser of wavelength 980 nm.
4. A method for preparing the white luminescent up-conversion rare earth doped nanomaterial according to any of claims 1 to 3, characterized in that: comprises the following steps of;
(1) By stoichiometric ratio YCl 3 ·6H 2 O、HoCl 3 ·6H 2 O、LiOH、NH 4 F, mixing with oleic acid and octadecene, performing high-temperature treatment in an inert gas atmosphere, cooling to room temperature, and performing centrifugal washing to obtain the ion doped LiY (1-x) F 4 xHo nanocrystal cores;
(2) Stoichiometric YbCl ratio 3 ·6H 2 O、LiOH、NH 4 F, mixing with oleic acid and octadecene, and adding the LiY prepared in the step (1) (1-x) F 4 xHo nanometer crystal nucleus, introducing inert gas for high temperature treatment, and naturally cooling to room temperature to coat the active shell layer to form LiYbF 4 Sensitization layer, and thenCentrifugal washing to obtain LiY (1-x) F 4 :xHo@LiYbF 4 A nanocrystal core;
(3) By stoichiometric ratio YCl 3 ·6H 2 O、LiOH、NH 4 F, mixing with oleic acid and octadecene, and adding the LiY prepared in the step (2) (1-x) F 4 :xHo@LiYbF 4 Nanocrystal core, introducing inert gas for high temperature treatment, and naturally cooling to room temperature after reaction to enable epitaxial growth of LiYF 4 The inert shell layer is coated on the nanocrystal core, and the up-conversion rare earth doped nanomaterial is obtained through centrifugal washing.
5. The method of manufacturing according to claim 4, wherein: the volume ratio of oleic acid to octadecene used in each step was 8:12.
6. The method of manufacturing according to claim 4, wherein: the high temperature treatment in each step is to keep the temperature at 300 ℃ for 60-90min.
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