CN116333741A - Rare earth doped sulfur oxide/fluoride heterogeneous core-shell structure nano luminescent material - Google Patents

Rare earth doped sulfur oxide/fluoride heterogeneous core-shell structure nano luminescent material Download PDF

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CN116333741A
CN116333741A CN202310367528.1A CN202310367528A CN116333741A CN 116333741 A CN116333741 A CN 116333741A CN 202310367528 A CN202310367528 A CN 202310367528A CN 116333741 A CN116333741 A CN 116333741A
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宋晓荣
杨登峰
朱家旗
郑伟
黄萍
陈学元
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Fuzhou University
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Abstract

The invention provides a rare earth oxysulfide/fluoride heterogeneous core-shell structure nano luminescent material RE 2 O 2 S:x%Ln 3+ @NaRE’F 4 And a process for producing the same, wherein RE, ln and RE' are each selected from at least one of La, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb, lu or Y, 0<x is less than or equal to 100 mol%; RE is prepared by using RE-containing rare earth salt, ln-containing rare earth salt, alkali metal salt and the like as raw materials 2 O 2 S:x%Ln 3+ A nanocrystalline; then rare earth salt containing RE', sodium source and fluorine source are taken asThe raw material forms NaRE' F on the obtained nanocrystalline 4 The shell layer of the nano luminescent material is prepared. The obtained material has uniform morphology, controllable particle size and good stability, has high-efficiency rare earth up-conversion/down-conversion luminescence performance, and can be used in the fields of fluorescent biological markers, illumination display, optical anti-counterfeiting and the like.

Description

Rare earth doped sulfur oxide/fluoride heterogeneous core-shell structure nano luminescent material
Technical Field
The invention belongs to the field of luminescent materials, and particularly relates to a rare earth oxysulfide/fluoride heterogeneous core-shell structure nano luminescent material, and a preparation method and application thereof.
Background
The rare earth nanometer luminescent material has the unique advantages of large (anti) Stokes displacement, narrow linewidth, long fluorescence lifetime, high stability, low toxicity and the like, and has wide application prospect in biomedical science, optogenetics, nanometer sensing, anti-counterfeiting and the like. The luminous efficiency of rare earth luminescent nanocrystals depends not only on the rare earth ions doped, but also to a large extent on the doped host material. Rare earth oxysulfide (RE) 2 O 2 S) is used as a classical material system, and is a good rare earth doped up-conversion and down-conversion luminescent matrix material. Although rare earth oxysulfide (RE) 2 O 2 S) the bulk material has good luminescence performance, but under the nanoscale, the problems of low luminescence efficiency and poor stability exist due to sulfur/oxygen vacancy defects in crystal lattices and surface fluorescence quenching effect. Fluoride heterogeneous core-shell cladding is an effective means for improving the luminescence of rare earth oxysulfide, and can not only improve the stability of the rare earth oxysulfide, but also effectively protect the inner core, reduce fluorescence quenching, thereby greatly improving the luminescence performance of the material. However, the preparation of such heterogeneous core-shell nanocrystals is still a significant challenge in this field due to the large differences in physicochemical properties and growth kinetics between fluoride and oxysulfide.
Disclosure of Invention
In order to break through the limitations of the prior art, the invention provides a rare earth oxysulfide/fluoride heterogeneous core-shell structure nano luminescent material and a preparation method thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a rare earth oxysulfide/fluoride heterogeneous core-shell structured nano luminescent material is prepared from RE 2 O 2 S:x%Ln 3+ Nanocrystalline as core, naRE' F 4 Is formed by a shell, wherein RE, ln and RE' are respectively selected from at least one of La, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb, lu, Y, 0<x.ltoreq.100 mol%, preferably 0<x≤30 mol％。
The preparation method of the rare earth oxysulfide/fluoride heterogeneous core-shell structure nano luminescent material comprises the following steps:
1) Mixing RE-containing rare earth salt and Ln-containing rare earth salt with alkali metal salt and solvent R, heating to dissolve under the protection of inert gas, and then cooling to room temperature to obtain mixed solution A;
2) Adding a sulfur source into the mixed solution A obtained in the step 1), and heating for dissolution;
3) Heating the solution obtained in the step 2) to obtain RE 2 O 2 S:x%Ln 3+ Nanocrystalline (0)<x is less than or equal to 100 mol percent) and dispersing the same in an organic solvent;
4) Dissolving RE' containing RE salt in solvent R, heating to dissolve under the protection of inert gas, and cooling to room temperature to obtain mixed solution B;
5) Adding a sodium source and a fluorine source into the mixed solution B obtained in the step 4), and heating for dissolution;
6) Adding RE obtained in the step 3) into the reaction liquid obtained in the step 5) 2 O 2 S:x%Ln 3+ The dispersion liquid of the nanocrystalline is heated for reaction to obtain the core-shell RE 2 O 2 S:x%Ln 3+ @NaRE’F 4 A nano luminescent material.
Further, the inert gas in step 1) and step 4) includes any one of nitrogen, helium and argon.
Further, the rare earth salt in step 1) and step 4) is selected from one or more of chloride, oxalate or acetate of Ho, er, tm, tb, eu, ce, sm, dy, nd, pr, gd, yb.
Further, the solvent R in the steps 1) and 4) is a mixture of oleic acid, oleylamine and trioctylamine or octadecene in a volume ratio of (1-10): (1-10): (1-20), preferably (1-3): (2-8): (1-10).
Further, the heating and dissolving in the steps 1) and 4) are to heat to 60-230 ℃ and keep the temperature for 10-180min.
Further, the heating and dissolving in the steps 2) and 5) is to heat to 60-200 ℃ and keep the temperature for 30-180 min.
Further, the molar ratio of RE-containing rare earth salt to Ln-containing rare earth salt used in step 1) is 1 (1-x), wherein x is 0< 100 mol%.
Further, the molar ratio of the total amount of rare earth salt to alkali metal salt used in step 1) is 1 (1-10); the alkali metal salt is selected from LiOH, naOH, KOH, CH 3 COOLi、CH 3 COONa、CH 3 One or more of COOKs.
Further, the amount of the sulfur source in the step 2) is converted according to a molar ratio of 0.5 to 5 of the sulfur contained in the sulfur source to the total amount of the rare earth salt used in the step 1), and preferably the molar ratio is 1 to 3; the sulfur source is selected from thiourea, sulfur powder and Na 2 S, N' N-Diphenylthiourea (DPTU) is preferably any one of thiourea or DPTU.
Further, the heating reaction in step 3) is carried out at a temperature of 240-360 ℃ for 1-180 min, preferably at a temperature of 260-330 ℃ for 30-120min.
Further, the organic solvent in step 3) is cyclohexane, n-hexane, benzene or chloroform, preferably cyclohexane.
Further, the molar ratio of Na and F contained in the sodium source and the fluorine source used in the step 5) to the rare earth salt used in the step 4) is (1-5): 1-10): 1 is converted; the sodium source is selected from NaF, naHF 2 Or NaOH, said fluorine source is selected from NaF, naHF 2 Or NH 4 F, preferably NaHF 2 Or NaOH and NH 4 F。
Further, RE added in step 6) 2 O 2 S:x%Ln 3+ The molar ratio of the nanocrystalline to RE' contained in the rare earth salt in the step 4) is (0.1-1): 0.5-1.
Further, in the step 6), the heating reaction is to heat up to 60-200 ℃ and keep the temperature for 30-180 min, and then heat up to 260-360 ℃ and keep the temperature for 10-180min.
The invention adopts a high-temperature coprecipitation method, and inhibits RE by regulating and controlling the surface ligand 2 O 2 S nanocrystalline inside S 2- Vacancy defect, RE is successfully prepared for the first time 2 O 2 S@NaREF 4 A heterogeneous core-shell structure nano luminescent material. The novel heterogeneous core-shell structure is hopeful to combine respective luminescence advantages of rare earth fluoride and oxysulfide, obtain a new luminescence characteristic different from a single matrix material, realize efficient up-conversion and down-transfer luminescence of rare earth ions, and can be applied to the fields of fluorescent biomarkers, illumination display, X-ray scintillators, optical anti-counterfeiting, optical coding and the like.
Advantageous effects
1. The invention provides a rare earth oxysulfide/fluoride heterogeneous core-shell structured nano luminescent material which has the advantages of monodispersion, uniform appearance, controllable particle size, adjustable shell thickness, good stability and efficient rare earth up-conversion/down-transfer luminescence, wherein the fluoride heterogeneous core-shell cladding can not only improve the stability of the rare earth oxysulfide, but also effectively protect the inner core, reduce fluorescence quenching, thereby greatly improving the luminescence performance of the material.
2. The invention provides a preparation method of a rare earth oxysulfide/fluoride heterogeneous core-shell structure nano luminescent material, which has the advantages of easy control of conditions, direct purchase of raw materials, short reaction period, simple process, good repeatability, uniform size and morphology of synthesized nano particles and good dispersibility.
Drawings
FIG. 1 shows Gd synthesized in example 1 2 O 2 S:10%Eu 3+ Nanocrystalline and Gd 2 O 2 S:10%Eu 3+ @NaYF 4 Powder diffraction pattern of core shell nanocrystals.
FIG. 2 shows Gd synthesized in example 1 2 O 2 S:10%Eu 3+ Nanocrystalline (a) and Gd 2 O 2 S: 10%Eu 3+ @NaYF 4 And (3) a transmission electron microscope image of the core-shell nanocrystal (b).
FIG. 3 shows Gd synthesized in example 1 2 O 2 S:10%Eu 3+ Nanocrystalline and Gd 2 O 2 S:10%Eu 3+ @NaYF 4 Excitation and emission spectrum of core-shell nanocrystalline.
FIG. 4 shows Gd synthesized in example 2 2 O 2 S:2%Sm 3+ @NaYF 4 And (3) a transmission electron microscope image of the core-shell nanocrystal.
FIG. 5 shows Gd synthesized in example 2 2 O 2 S:10%Tb 3+ Nanocrystalline and Gd 2 O 2 S: 10%Tb 3+ @NaYF 4 Excitation and emission spectrum of core-shell nanocrystalline.
FIG. 6 shows Gd synthesized in example 2 2 O 2 S:2%Sm 3+ Nanocrystalline and Gd 2 O 2 S: 2%Sm 3+ @NaYF 4 Excitation and emission spectrum of core-shell nanocrystalline.
FIG. 7 shows Gd synthesized in example 2 2 O 2 S:2%Dy 3+ Nanocrystalline and Gd 2 O 2 S: 2%Dy 3+ @NaYF 4 Excitation and emission spectrum of core-shell nanocrystalline.
FIG. 8 shows Gd synthesized in example 3 2 O 2 S:20%Yb 3+ ,0.5%Tm 3+ Nanocrystalline and Gd 2 O 2 S:20%Yb 3+ ,0.5%Tm 3 + @NaYF 4 Powder diffraction pattern of core shell nanocrystals.
FIG. 9 shows Gd synthesized in example 3 2 O 2 S:20%Yb 3+ ,0.5%Tm 3+ @NaYF 4 And (3) a transmission electron microscope image of the core-shell nanocrystal.
FIG. 10 shows Gd synthesized in example 3 2 O 2 S:20%Yb 3+ ,0.5%Tm 3+ Nanocrystalline and Gd 2 O 2 S:20%Yb 3+ ,0.5%Tm 3+ @NaYF 4 Up-conversion spectrogram of core-shell nanocrystalline under 980 nm excitation.
FIG. 11 shows Gd synthesized in example 4 2 O 2 S: 20%Yb 3+ ,1%Ho 3+ Nanocrystalline and Gd 2 O 2 S: 20%Yb 3+ ,1%Ho 3 + @NaYF 4 Up-conversion spectrogram of core-shell nanocrystalline under 980 nm excitation.
FIG. 12 shows Gd synthesized in example 4 2 O 2 S:49%Yb 3+ ,1%Er 3+ Nanocrystalline and Gd 2 O 2 S: 49%Yb 3+ ,1%Er 3+ @NaYF 4 Up-conversion spectrogram of core-shell nanocrystalline under 980 nm excitation.
FIG. 13 shows the La synthesized in example 5 2 O 2 S:20%Yb 3+ ,0.5%Tm 3+ And (3) a transmission electron microscope image of the nanocrystalline.
FIG. 14 is a Y synthesized in example 6 2 O 2 S:20%Yb 3+ ,0.5%Tm 3+ @NaYF 4 Core-shell nanocrystals and Y 2 O 2 S: 20%Yb 3+ ,0.5%Tm 3+ Upconversion spectrum of nanocrystals under 980 nm excitation.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is understood that these examples are provided only for illustrating the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications of the present invention may be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents are intended to fall within the scope of the present invention as defined by the appended claims.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the reagents, materials, etc. used in the examples described below are commercially available unless otherwise specified.
The product of the embodiment of the invention adopts the model of MiniFlex2, rigaku as manufacturer and the radiation wavelength of copper target as the instrument for powder diffraction characterizationλ= 0.154187 nm。
The product of the embodiment of the invention is used for transmission electron microscope detection, and the model of the instrument is TECNAI G2F 20, and the manufacturer is FEI.
The model of an instrument used for up-conversion emission spectrum characterization of the product is FLS980, the manufacturer is Edinburgh, and the excitation light source is a xenon lamp and a 980 nm semiconductor laser.
Example 1: gd (Gd) 2 O 2 S:10%Eu 3+ @NaYF 4 Preparation of heterogeneous core-shell nanocrystals
0.90 mmol Gd (CH) was weighed out 3 COO) 3 、0.10 mmol Eu(CH 3 COO) 3 1 mmol LiOH, then 4 mL oleic acid, 6 mL oleylamine and 10 mL trioctylamine are added, heated to 120 ℃ under nitrogen atmosphere and incubated for 30 min to form a clear transparent solution, then cooled to room temperature; weighing 3 mmol of DPTU, dissolving in 20 mL ethanol, dropwise adding into the solution, stirring for 10 min to fully mix, heating to 80deg.C, maintaining the temperature for 30 min to form pale yellow transparent solution, heating to 320 deg.C, reacting 1 h, cooling to room temperature, adding 20 mL acetone, precipitating, separating, and washing for several times to obtain Gd 2 O 2 S:10%Eu 3+ The nanocrystals were dispersed in 5mL cyclohexane for use.
1 mmol Y (CH) was weighed out 3 COO) 3 Then adding 2 mL oleic acid, 4 mL oleylamine and 14 mL trioctylamine, heating to 160 ℃ under nitrogen atmosphere, preserving heat for 30 min to form a transparent solution, and then cooling to room temperature; 10 mL containing 2.5 mmol NaOH and 4 mmol NH were added 4 F, heating the methanol solution to 60 ℃ and preserving the temperature for 30 min; next, add Gd containing 1 mmol 2 O 2 S:10%Eu 3+ Heating the cyclohexane solution of the nanocrystalline to 80 ℃, and preserving heat for 30 min to form a yellowish transparent solution; heating to 300 ℃, reacting 1 h, cooling to room temperature, adding 20 mL ethanol, centrifuging, washing for several times to obtain Gd 2 O 2 S:10%Eu 3+ @NaYF 4 Heterogeneous core-shell nanocrystals.
FIGS. 1-3 are each synthesized Gd 2 O 2 S:10%Eu 3+ Nanocrystalline and Gd 2 O 2 S:10%Eu 3+ @NaYF 4 Powder diffraction pattern, transmission electron microscope pattern, excitation and emission of core-shell nanocrystallineA spectrogram. As shown in the figure, gd 2 O 2 S:10%Eu 3+ The nanocrystalline is Gd 2 O 2 S hexagonal pure phase, while the diffraction peak of the core-shell structure nanocrystalline contains Gd 2 O 2 S and alpha-NaYF 4 Two different diffraction peaks (fig. 1); gd (Gd) 2 O 2 S:10%Eu 3+ The core-shell structure nanocrystalline has good dispersibility in cyclohexane and uniform morphology, and the average grain diameters of the core-shell structure nanocrystalline are 5.4 nm and 7.6 nm (figure 2); and the excitation emission intensity of the core-shell structure nanocrystalline is compared with Gd 2 O 2 S:10%Eu 3+ The nanocrystals were enhanced without significant changes in the characteristic peak positions and spectral peak cleavage (fig. 3).
Example 2
0.10 mmol Eu (CH) dosed in example 1, with the other reaction conditions unchanged 3 COO) 3 Respectively replaced by 0.10 mmol of Tb (CH) 3 COO) 3 、0.02 mmol Sm(CH 3 COO) 3 And 0.02 mmol Dy (CH) 3 COO) 3 The method comprises the steps of carrying out a first treatment on the surface of the And the solvent is changed into 1 mL oleic acid, 5mL oleylamine and 14 mL trioctylamine to synthesize the corresponding Gd 2 O 2 S:10%Tb 3+ @NaYF 4 、Gd 2 O 2 S:2%Sm 3 + @NaYF 4 、Gd 2 O 2 S:2%Dy 3+ @NaYF 4 Heterogeneous core-shell nanocrystals.
FIG. 4 is a synthesized Gd 2 O 2 S: 2%Sm 3+ @NaYF 4 And (3) a transmission electron microscope image of the core-shell nanocrystal. As shown in the figure, the core-shell structure nanocrystalline is monodisperse and uniform in morphology and size, and the average grain diameter is 9.9 nm.
FIGS. 5-7 are each synthesized Gd 2 O 2 S:10%Tb 3+ Nanocrystalline, gd 2 O 2 S:2%Sm 3+ Nanocrystalline, gd 2 O 2 S:2%Dy 3+ And (3) exciting and emitting spectrograms of the nanocrystalline and the nanocrystalline with the core-shell structure. It is further seen from the graph that the excitation emission intensity of the core-shell structure nanocrystalline is higher than that of rare earth doped Gd 2 O 2 S nano-crystals are enhanced, and the characteristic peak position and the spectrum peak splitting are not changed obviously.
Example 3: gd (Gd) 2 O 2 S: 20%Yb 3+ ,0.5%Tm 3+ @NaYF 4 Preparation of heterogeneous core-shell nanocrystals
0.795 mmol Gd (CH) 3 COO) 3 、0.200 mmol Yb(CH 3 COO) 3 、0.005 mmol Tm(CH 3 COO) 3 1 mmol LiOH, then 4 mL oleic acid, 6 mL oleylamine and 10 mL trioctylamine are added, heated to 120 ℃ under nitrogen atmosphere and incubated for 30 min to form a clear transparent solution, then cooled to room temperature; weighing 3 mmol of DPTU, dissolving in 20 mL ethanol, dropwise adding into the solution, stirring for 10 min to fully mix, heating to 80deg.C, maintaining the temperature for 30 min to form pale yellow transparent solution, heating to 320 deg.C, reacting 1 h, cooling to room temperature, adding 20 mL acetone, precipitating, separating, and washing for several times to obtain Gd 2 O 2 S: 20%Yb 3+ ,0.5%Tm 3+ The nanocrystals were dispersed in 5mL cyclohexane for use.
1 mmol Y (CH) was weighed out 3 COO) 3 Then adding 2 mL oleic acid, 5mL oleylamine and 13 mL trioctylamine, heating to 160 ℃ under nitrogen atmosphere, preserving heat for 30 min to form a transparent solution, and then cooling to room temperature; 10 mL containing 2.5 mmol NaOH and 4 mmol NH were added 4 F, heating the methanol solution to 60 ℃ and preserving the temperature for 30 min; next, add Gd containing 1 mmol 2 O 2 S: 20%Yb 3+ ,0.5%Tm 3+ Heating the cyclohexane solution of the nanocrystalline to 80 ℃, and preserving heat for 30 min to form a yellowish transparent solution; heating to 310 ℃, reacting 1.5 and h, cooling to room temperature, adding 20 and mL ethanol, centrifuging, washing for several times to obtain Gd 2 O 2 S: 20%Yb 3+ ,0.5%Tm 3+ @NaYF 4 Heterogeneous core-shell nanocrystals.
FIGS. 8-10 are respectively synthesized Gd 2 O 2 S:20%Yb 3+ ,0.5%Tm 3+ Nanocrystalline and Gd 2 O 2 S:20%Yb 3+ ,0.5%Tm 3 + @NaYF 4 Powder diffraction pattern of core-shell nanocrystalline, transmission electron microscope pattern, and up-conversion spectrum under 980 nm excitation. From the figure, gd 2 O 2 S: 20%Yb 3+ ,0.5%Tm 3+ The nanocrystalline is Gd 2 O 2 S pure phase, diffraction peak of core-shell structure nanocrystalline containing Gd 2 O 2 S and alpha-NaYF 4 Two different diffraction peaks (fig. 8); the core-shell structure nanocrystalline has good dispersibility in cyclohexane and uniform morphology, and the average grain diameter is 9.9 nm (figure 9); gd (Gd) 2 O 2 S:20%Yb 3+ ,0.5%Tm 3+ @NaYF 4 The heterogeneous core-shell nanocrystal greatly improves the up-conversion luminescence performance of the core nanocrystal, and does not change Tm 3+ Is characterized by peak position and spectral peak cleavage.
Example 4:
under otherwise unchanged reaction conditions, 0.005 mmol Tm (CH) of the charge in example 3 was used 3 COO) 3 Respectively replaced by 0.01 mmol Er (CH) 3 COO) 3 、0.01 mmol Ho(CH 3 COO) 3 Can synthesize corresponding Gd 2 O 2 S:20%Yb 3+ ,1%Ho 3+ @NaYF 4 And Gd 2 O 2 S:49%Yb 3+ ,1%Er 3+ @NaYF 4 Heterogeneous core-shell nanocrystals.
FIGS. 11 and 12 show synthesized Gd 2 O 2 S: 20%Yb 3+ ,1%Ho 3+ Nanocrystalline, gd 2 O 2 S: 49%Yb 3+ ,1%Er 3+ Upconversion spectrogram of nanocrystalline and nanocrystalline with core-shell structure under 980 nm excitation. The figure further shows that the rare earth doped heterogeneous core-shell structure nanocrystalline greatly improves the up-conversion luminescence performance of the core nanocrystalline, and the characteristic peak position and spectrum peak splitting of the core nanocrystalline are not changed.
Example 5: la (La) 2 O 2 S:20%Yb 3+ ,0.5%Tm 3+ Preparation of nanocrystals
0.795 mmol of La (CH) 3 COO) 3 、0.200 mmol Yb(CH 3 COO) 3 、0.005 mmol Tm(CH 3 COO) 3 1 mmol LiOH, then 2 mL oleic acid, 8 mL oleylamine and 10 mL trioctylamine are added, heated to 120 ℃ under nitrogen atmosphere and incubated for 30 min to form a clear transparent solution, then cooled to room temperature; weighing 3 mmol of DPTU, dissolving in 20 mL ethanol, dropwise adding into the above solution, stirring for 10 min to fillMixing, heating to 80deg.C, maintaining for 30 min to form pale yellow transparent solution, heating to 320 deg.C, reacting 1. 1 h, cooling to room temperature, adding 20. 20 mL acetone, precipitating, separating, and washing for several times to obtain La 2 O 2 S: 20%Yb 3+ ,0.5%Tm 3+ And (3) nanocrystalline.
FIG. 13 shows the synthesized La 2 O 2 S:20%Yb 3+ ,0.5%Tm 3+ And (3) a transmission electron microscope image of the nanocrystalline. As shown in the figure, la 2 O 2 S:20%Yb 3+ ,0.5%Tm 3+ The nanocrystalline has good dispersibility in cyclohexane and uniform morphology, and the average grain diameter is 5.1 nm.
Example 6: y is Y 2 O 2 S:20%Yb 3+ ,0.5%Tm 3+ @NaYF 4 Preparation of heterogeneous core-shell nanocrystals
Weigh 0.795 mmol Y (CH) 3 COO) 3 、0.200 mmol Yb(CH 3 COO) 3 、0.005 mmol Tm(CH 3 COO) 3 1 mmol LiOH, then 3 mL oleic acid and 6 mL oleylamine and 11 mL trioctylamine are added, heated to 120 ℃ under nitrogen atmosphere and incubated for 30 min to form a clear transparent solution, then cooled to room temperature; weighing 3 mmol of DPTU, dissolving in 20 mL ethanol, dropwise adding into the solution, stirring for 10 min to fully mix, heating to 80deg.C, maintaining the temperature for 30 min to form yellowish transparent solution, heating to 320 deg.C, reacting 1 h, cooling to room temperature, adding 20 mL acetone, precipitating, separating, and washing for several times to obtain Y 2 O 2 S: 20%Yb 3+ ,0.5%Tm 3+ And (3) nanocrystalline.
The Y obtained 2 O 2 S: 20%Yb 3+ ,0.5%Tm 3+ The nanocrystals were dispersed in 5mL cyclohexane for use. 1 mmol Y (CH) was weighed out 3 COO) 3 Then adding 2 mL oleic acid, 5mL oleylamine and 13 mL trioctylamine, heating to 160 ℃ under nitrogen atmosphere, preserving heat for 30 min to form a transparent solution, and then cooling to room temperature; 10 mL containing 2.5 mmol NaOH and 4 mmol NH were added 4 F, heating the methanol solution to 60 ℃ and preserving the temperature for 30 min; then adding a solution containing 1 mmol of Y 2 O 2 S: 20%Yb 3+ ,0.5%Tm 3+ Heating the cyclohexane solution of the nanocrystalline to 80 ℃ and preserving heat for 30 percentmin, forming a pale yellow transparent solution; heating to 310 deg.C, reacting 1.5. 1.5 h, cooling to room temperature, adding 20 mL ethanol, centrifuging, washing for several times to obtain Y 2 O 2 S:20%Yb 3+ ,0.5%Tm 3+ @NaYF 4 Heterogeneous core-shell nanocrystals.
FIG. 14 is a synthesized Y 2 O 2 S:20%Yb 3+ ,0.5%Tm 3+ @NaYF 4 Core-shell nanocrystals and Y 2 O 2 S: 20%Yb 3+ ,0.5%Tm 3+ Upconversion spectrum of nanocrystals under 980 nm excitation. The figure also shows that the rare earth doped heterogeneous core-shell structure nanocrystalline greatly improves the up-conversion luminescence performance of the core nanocrystalline, and the characteristic peak position and spectrum peak splitting of the core nanocrystalline are not changed.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A rare earth oxysulfide/fluoride heterogeneous core-shell structured nano luminescent material is characterized in that RE is adopted as the nano luminescent material 2 O 2 S:x%Ln 3+ Nanocrystalline as core, naRE' F 4 Is formed by a shell, wherein RE, ln and RE' are respectively selected from at least one of La, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb, lu, Y, 0<x≤100 mol％。
2. A method for preparing the rare earth oxysulfide/fluoride heterogeneous core-shell structured nano luminescent material as set forth in claim 1, comprising the steps of:
1) Mixing RE-containing rare earth salt and Ln-containing rare earth salt with alkali metal salt and solvent R, heating to dissolve under the protection of inert gas, and then cooling to room temperature to obtain mixed solution A;
2) Adding a sulfur source into the mixed solution A obtained in the step 1), and heating for dissolution;
3) Subjecting the solution obtained in step 2) toHeating for reaction to obtain RE 2 O 2 S: x%Ln 3+ Nanocrystalline and dispersing it in organic solvent;
4) Dissolving RE' containing RE salt in solvent R, heating to dissolve under the protection of inert gas, and cooling to room temperature to obtain mixed solution B;
5) Adding a sodium source and a fluorine source into the mixed solution B obtained in the step 4), and heating for dissolution;
6) Adding RE obtained in the step 3) into the reaction liquid obtained in the step 5) 2 O 2 S:x%Ln 3+ The dispersion liquid of the nanocrystalline is heated for reaction to obtain the core-shell RE 2 O 2 S: x%Ln 3+ @NaRE’F 4 A nano luminescent material.
3. The method of claim 2, wherein in operation, the rare earth salt is selected from one or more of the group consisting of chloride, oxalate, and acetate of Ho, er, tm, tb, eu, ce, sm, dy, nd, pr, gd, yb;
the solvent R is a mixture composed of oleic acid, oleylamine and trioctylamine or octadecene according to the volume ratio of (1-10): (1-10): (1-20).
4. The method according to claim 2, wherein in operation, the heating to dissolve is performed by heating to 60-230 ℃ and maintaining for 10-180 min;
the heating and dissolving are heating to 60-200deg.C and maintaining for 30-180 min.
5. The preparation method according to claim 2, wherein the molar ratio of RE-containing rare earth salt to Ln-containing rare earth salt used in step 1) is 1 (1-x) in terms of 0< x.ltoreq.100 mol%;
the molar ratio of the total rare earth salt to the alkali metal salt is 1 (1-10);
the alkali metal salt is selected from LiOH, naOH, KOH, CH 3 COOLi、CH 3 COONa、CH 3 One or more of COOKs.
6. The preparation method according to claim 2, wherein the amount of the sulfur source in the step 2) is converted to a molar ratio of 0.5 to 5 of the sulfur contained therein to the total amount of the rare earth salt used in the step 1);
the sulfur source is selected from thiourea, sulfur powder and Na 2 S, N' N-diphenylthiourea.
7. The method according to claim 2, wherein the heating reaction in step 3) is carried out at a temperature of 240-360 ℃ for a period of 1-180 min;
the organic solvent is cyclohexane, normal hexane, benzene or chloroform.
8. The process according to claim 2, wherein the sodium source and the fluorine source used in step 5) are converted in such a manner that the molar ratio of Na and F contained therein to the rare earth salt used in step 4) is (1-5): 1-10): 1;
the sodium source is selected from NaF, naHF 2 Or NaOH, said fluorine source being selected from NaF, naHF 2 Or NH 4 F。
9. The process according to claim 2, wherein RE added in step 6) 2 O 2 S:x%Ln 3+ The molar ratio of the nanocrystalline to RE' contained in the rare earth salt in the step 4) is (0.1-1): 0.5-1.
10. The preparation method according to claim 2, wherein the heating reaction in step 6) is performed by heating to 60-200 ℃ and maintaining the temperature for 30-180 min, heating to 260-360 ℃ and maintaining the temperature for 10-180min.
CN202310367528.1A 2023-04-07 2023-04-07 Rare earth doped sulfur oxide/fluoride heterogeneous core-shell structure nano luminescent material Pending CN116333741A (en)

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