CN104449663A - Method for increasing quantum yield of up-conversion nano material - Google Patents

Method for increasing quantum yield of up-conversion nano material Download PDF

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CN104449663A
CN104449663A CN201410783270.4A CN201410783270A CN104449663A CN 104449663 A CN104449663 A CN 104449663A CN 201410783270 A CN201410783270 A CN 201410783270A CN 104449663 A CN104449663 A CN 104449663A
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nayf
naoh
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nayf4
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李志华
王亚南
苗海霞
张然
刘玉香
付颖
杜宇
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Shandong Normal University
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Shandong Normal University
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Abstract

The invention provides a method for increasing quantum yield of an up-conversion nano material. The method for increasing quantum yield of the up-conversion nano material comprises the following steps: (1) by taking YCl3, NH4F and NaOH as main raw materials, and taking oleic acid and 1-octadecene as solvents, reacting at a high temperature for 30-240 minutes, washing, centrifuging and drying to obtain a core NaYF4; (2) by taking the core NaYF4, LnCl3 (Ln represents Y, Yb and Er), NH4F and NaOH as main raw materials, and taking oleic acid and 1-octadecene as solvents, reacting at a high temperature for 10-60 minutes, washing, centrifuging and drying to obtain a core-shell structure NaYF4@NaYF4:Yb, Er; and (3) by taking the core-shell structure NaYF4@NaYF4:Yb, Er, YCl3, NH4F and NaOH as main raw materials, and taking oleic acid and 1-octadecene as solvents, reacting at a high temperature for 10-60 minutes, washing, centrifuging and drying to obtain a core-shell structure NaYF4@NaYF4:Yb, Er@NaYF4 which is delta-doped NaYF4:Yb, Er. By adopting the method, the quantum yield of the NaYF4:Yb, Er is greatly increased; the method has important significance for expanding application of the NaYF4:Yb, Er to biomarkers, analysis and detection, fluorescence imaging and solar cells.

Description

A kind of method improving up-conversion nano material quantum yield
Technical field
The invention belongs to up-conversion nano material preparation field, particularly a kind of method improving up-conversion nano material quantum yield.
Background technology
Be widely used in biomarker with rare earth doped upconverting fluorescent material, analyzing and testing, fluorescence imaging, solar cell, optical information stores and display, the aspects such as optical fiber communication technology.At present, with NaYF 4: Yb, Er are that the research of upconverting fluorescent material in preparation and application of representative becomes international focus, and make great progress in biomarker, fluorescence imaging etc.However, NaYF 4: the quantum yield that Yb, Er are lower limits its deep application, becomes the bottleneck of its widespread use.Therefore, how NaYF is improved 4: the quantum yield of Yb, Er has become the important and difficult issues of current research.At present, NaYF is improved 4: the method for the quantum yield of Yb, Er has: the doping ratio Y:Yb:Er=(78 ~ 80) of (1) rare earth element: (20 ~ 18): 2 (mol ratios); (2) surface passivation-nucleocapsid is modified; (3) surface plasmon resonance effect.But these methods are also not enough to NaYF 4: the quantum yield of Yb, Er increases substantially.
Summary of the invention
For solving the problem, we propose a kind of δ doping of upper conversion nano grain pattern-up-conversion fluorescence body of novelty, that is: the NaYF of nucleocapsid structure 4@NaYF 4: Yb, Er@NaYF 4fluor, to realize NaYF 4: the significantly raising of Yb, Er quantum yield.δ doping is limited in by dopant ion in two dimension (2D) plane, and the concentration gradient of dopant ion is linearly combined with delta-function, so this doping is called δ doping.Step of the invention process is as follows:
Improve a method for up-conversion nano material quantum yield, comprise the steps
1) by YCl 3, oleic acid and the mixing of 1-octadecylene, under vacuum condition, stir, be warming up to 100-105 DEG C, after constant temperature 10-20min, temperature is increased to 150-160 DEG C and constant temperature 30-40min, forms the yellow solution of transparent and homogeneous, be cooled to room temperature; Then NH is added while stirring 4the CH of F and NaOH 3oH solution, after dropwising, continues to be heated to 100-105 DEG C, constant temperature 10-15min, vacuum outgas 10-20min; Finally, under inert gas environment, by above-mentioned solution warms to 280-320 DEG C, reaction 240-300min; Cooling, washing, centrifugal, vacuum-drying, obtain core NaYF 4;
2) by core NaYF 4, LnCl 3, oleic acid and the mixing of 1-octadecylene, under vacuum condition, stir, be warming up to 100-105 DEG C, after constant temperature 10-20min, temperature is increased to 150-160 DEG C and constant temperature 30-40min, is cooled to room temperature; Then NH is added while stirring 4the CH of F and NaOH 3oH solution, after dropwising, continues to be heated to 100-105 DEG C, constant temperature 10-15min, vacuum outgas 10-20min; Finally, under inert gas environment, by above-mentioned solution warms to 280-320 DEG C, reaction 120-160min; Cooling, washing, centrifugal, vacuum-drying, obtain nucleocapsid structure NaYF 4@NaYF 4: Yb, Er;
3) by nucleocapsid structure NaYF 4@NaYF 4: Yb, Er, YCl 3, oleic acid and the mixing of 1-octadecylene, under vacuum condition, stir, be warming up to 100-105 DEG C, after constant temperature 10-20min, temperature is increased to 150-160 DEG C and constant temperature 30-40min, is cooled to room temperature; Then NH is added while stirring 4the CH of F and NaOH 3oH solution, after dropwising, continues to be heated to 100-105 DEG C, constant temperature 10-15min, vacuum outgas 10-20min; Finally, under inert gas environment, by above-mentioned solution warms to 280-320 DEG C, reaction 120-160min, obtains nucleocapsid structure NaYF 4@NaYF 4: Yb, Er@NaYF 4, i.e. the NaYF of δ doping 4: Yb, Er;
Step 1) in, described YCl 3, NH 4the mol ratio of F and NaOH is 1:4-6:2-5, described oleic acid, 1-octadecylene, CH 3the mass ratio of OH solution is 6-8:5-7:10-12, described NaOH and CH 3the mass ratio of OH solution is 0.1-0.3:10-16;
Step 2) in, described LnCl 3, NH 4the mol ratio of F and NaOH is 1:4-6:2-5, described core NaYF 4,oleic acid, 1-octadecylene, CH 3the mass ratio of OH solution is 0.1-0.5:6-8:5-7:10-12, described NaOH and CH 3the mass ratio of OH solution is 0.1-0.3:10-16; Wherein, described LnCl 3the mol ratio of middle Y:Yb:Er is 78 ~ 80:20 ~ 18:2.
Step 3) in, described YCl 3, NH 4the mol ratio of F and NaOH is 1:4-6:2-5, described nucleocapsid structure NaYF 4@NaYF 4: Yb, Er, oleic acid, 1-octadecylene, CH 3the mass ratio of OH solution is 0.1-0.5:6-8:5-7:10-12, described NaOH and CH 3the mass ratio of OH solution is 0.1-0.3:10-16;
Further, step 1) in, described core NaYF 4for near-spherical, polyhedron or six square pieces.
Further, step 2) in, described nucleocapsid structure NaYF 4@NaYF 4: Yb, Er are near-spherical, polyhedron or six square pieces.
Further, step 3) in, described nucleocapsid structure NaYF 4@NaYF 4: Yb, Er@NaYF 4for near-spherical, polyhedron or six square pieces.
Preferably, described wash conditions is be the hexanaphthene of 1:1 and ethanol or ethanol and water washing by volume ratio.
Preferably, described centrifugal condition is centrifugal 2-3 time, rotating speed is 3500-4000r/min, and the time is 3-5min.
Preferably, described vacuum-drying condition is at 100-105 DEG C, dry 10-15min.
Preferably, described rare gas element is nitrogen or argon gas.
Principle of the present invention:
According to NaYF 4: Yb, Er fluor upconversion luminescence mechanism is known, and the transition affecting its fluorescence efficiency mainly contains: (a) Yb 3+→ Yb 3+infrared absorption 2f (7/2)→ 2F (5/2); (b) Yb 3+→ Yb 3+ir radiation 2f (5/2)→ 2f (7/2); (c) Yb 3+the nonradiative transition of → defect; (d) Yb 3+→ Er 3+transmission ofenergy; (e) Er 3+→ Er 3+radiative transition; (f) Er 3+→ Er 3+non-radiative energy transmission; (g) Er 3+the transmission ofenergy of → defect.Wherein b, c, f, g are the raising being unfavorable for quantum yield.
Therefore, NaYF be improved 4: the quantum yield of Yb, Er fluor, needs following condition: (1) increases the concentration of dopant ion; (2) nonradiative relaxation process, i.e. Yb is suppressed 3+→ defect and Er 3+the energy trasfer of → defect; (3) Yb is improved 3+→ Er 3+energy transfer rat; (4) Yb is suppressed 3+→ Yb 3+ir radiation 2f (5/2)→ 2f (7/2).
In conventional fluorescent body, it is all Uniform Doped in substrate material, transmission ofenergy wherein and radiation effect all carry out in the 3d space of material, and therefore the concentration of sensitized ions, the concentration of excited state ion, the defect concentration of material are the important factors of the quantum yield affecting fluor.Concerning up-conversion fluorescence body, low-energy state (sensitized ions) is the key determining fluor fluorescence efficiency with the rate of energy transfer of high-energy state (excited ion).Defect in conventional fluorescent body is 3D distribution, and the Nonradiative energy transfer of the ion and defect that are in excited state is also statistical distribution in 3D.If it is plane fluor to be designed to 2D, then effectively inhibit carry out of the energy trasfer of excited state ion and defect on vertical plane direction, thus the fluorescence efficiency of fluor is been significantly enhanced.1997, first this technology was applied in ZnS:Mn by Chris J.Summers, and obtains expected result.
According to mentioned above principle, the NaYF of δ doping 4: Yb, Er structure can be designed to the NaYF of nucleocapsid structure 4@NaYF 4: Yb, Er@NaYF 4.
Advantage of the present invention:
The advantage of this phosphor structures is the defect concentration that both can be reduced fluor, also suppresses Yb simultaneously 3+→ Yb 3+ir radiation.
1, the defect concentration of fluor is reduced
The NaYF of δ doping 4: Yb, Er, Yb 3+, Er 3+ion co-doped is in 2D plane, and its energy transfer process will be corrected.Yb 3+transmission ofenergy between → defect is that 3D transmits, and works as Yb 3+when being bound in 2D plane, Yb 3+longitudinal energy transfer process between → defect will be strongly inhibited.W.Park reports, in the fluor of 2D stratiform doping, a point defection for active ions and non-radiative defect causes the non-radiative energy transmission of activator → defect significantly to reduce, because 2D structure greatly can reduce Yb 3+with the recombination probability of defect, estimate Yb 3+→ Er 3+rate of energy transfer will increase with progression.
2, Yb 3+→ Yb 3+the suppression of ir radiation
According to Fermic golden rule, radiative transition speed is described below:
(above-mentioned formula draws from document Henderson, B.; Imbusch, G.F.Optical Spectroscopy of InorganicSolids; Clarendon Press:Oxford, 1989.)
μ e is electric dipole, and g (ω) is Photon state density.The speed of radiative transition is mainly by | <i μ e| f>| matrix element and Photon state density g (ω) determine.On the one hand, from matrix element angle analysis, radiative transition speed can be revised by the symmetry changing lattice in crystal to a certain extent.Yb 3+'s 2f (5/2)→ 2f (7/2)radiative transition be that there is the transition between two like parity energy levels, if parent lattice has inversion symmetry, then 2f (5/2)→ 2f (7/2)radiative transition will become part prohibit, this will greatly suppress this transfer rate.But, theoretical according to Dexter-Foster, Yb while radiative transition rate reduction 3+to the absorption of infrared light ( 2f (7/2)→ 2f (5/2)) also can reduce, the more important thing is that rate of energy transfer also will reduce.Therefore, upper efficiency of conversion can not effectively be improved by reducing radiative transition speed.On the other hand, if revise Photon state density g (ω), only control radiative transition speed and do not affect electronic level can be realized.1973, first Mita etc. put into practice this preliminary idea.They are by BaY 2f 8: Yb, Er fluor is embedded in an annular reflection chamber, because photon is limited in, in cavity, making Yb 3+the radiative lifetime of ion excited state is increased to 3.6ms by 1.9ms.This result means compared with powdery fluor, and the upper efficiency of conversion of this novel structure fluor can improve by 10X multiple.
Accompanying drawing explanation
Fig. 1 is NaYF 4: Yb, Er fluor upconversion luminescence mechanism figure;
Fig. 2 is the NaYF that structural representation and high-resolution electron microscopy figure (a) are annular-δ doping 4: Yb, Er schematic diagram; B (): I is core NaYF 4, II is nucleocapsid structure NaYF 4@NaYF 4: Yb, Er, III are nucleocapsid structure NaYF 4@NaYF 4: Yb, Er@NaYF 4;
Fig. 3 is low power Electronic Speculum figure (A) core NaYF 4; (B) nucleocapsid structure NaYF 4@NaYF 4: Yb, Er; (C) nucleocapsid structure NaYF 4@NaYF 4: Yb, Er@NaYF 4, i.e. the NaYF of δ doping 4: Yb, Er;
Fig. 4 is grain size distribution (A) core NaYF 4; (B) nucleocapsid structure NaYF 4@NaYF 4: Yb, Er; (C) nucleocapsid structure NaYF 4@NaYF 4: Yb, Er@NaYF 4, i.e. the NaYF of δ doping 4: Yb, Er;
Fig. 5 is X-ray energy spectrum figure;
Fig. 6 is fluorescence spectrum figure.(C/S: nucleocapsid structure NaYF 4@NaYF 4: Yb, Er; C/S/S: nucleocapsid structure NaYF 4@NaYF 4: Yb, Er@NaYF 4, i.e. the NaYF of δ doping 4: Yb, Er)
Embodiment
Following examples will be further described the present invention, but not thereby limiting the invention.
Embodiment 1:
(1) 0.195g YCl is taken 3(1mmol) solid, joins in the there-necked flask of 100mL, then adds 6mL oleic acid (OA) and 15mL 1-octadecylene (ODE), and vacuum lower magnetic force stirs and is warming up to 100 DEG C gradually, keeps 10min, removes the O in solvent 2and water.Then temperature be increased to 150 DEG C and keep 30min, forming the yellow solution of transparent and homogeneous.Stop after naturally cooling to room temperature vacuumizing, dropwise add 10mL while stirring and be dissolved with 0.1482g (4mmol) NH 4the CH of F and 0.1g (2.5mmol) NaOH 3oH solution, is heated to 100 DEG C in atmosphere and keeps 10min to remove the methyl alcohol in solvent.Then 10min is vacuumized at such a temperature, with the O in removing system 2and water.Afterwards at N 2be rapidly heated to 290 DEG C under protective atmosphere, keep sustained reaction 240min at this temperature.Naturally cool to after room temperature until system, stop logical N 2.By gained sample hexanaphthene: ethanol (v:v=1:1) solution washing, centrifugal 2-3 time, vacuum-drying, obtains core NaYF 4, pattern is class ball, and particle diameter is uneven, productive rate about 8%.
(2) 0.1g core NaYF is taken 4solid and 0.212g (1mmol) LnCl 3(Y:Yb:Er=80:18:2) solid, joins in the there-necked flask of 100mL, then adds 6mL oleic acid (OA) and 15mL 1-octadecylene (ODE), and vacuum lower magnetic force stirs and is warming up to 100 DEG C gradually, keeps 10min.Then temperature be increased to 150 DEG C and keep 30min.Stop after naturally cooling to room temperature vacuumizing, dropwise add 10mL while stirring and be dissolved with 0.1482g (4mmol) NH 4the CH of F and 0.1g (2.5mmol) NaOH 3oH solution, is heated to 100 DEG C in atmosphere and keeps 10min.Then 10min is vacuumized at such a temperature, afterwards at N 2be rapidly heated to 290 DEG C under protective atmosphere, keep sustained reaction 120min at this temperature.Naturally cool to after room temperature until system, stop logical N 2.By gained sample hexanaphthene: ethanol (v:v=1:1) solution washing, centrifugal 2-3 time, vacuum-drying, obtains nucleocapsid structure NaYF 4@NaYF 4: Yb, Er, pattern is class ball, and particle diameter is uneven, productive rate about 5%.
(3) 0.1g nucleocapsid structure NaYF) is taken 4@NaYF 4: Yb, Er solid and 0.195g YCl 3(1mmol) solid, joins in the there-necked flask of 100mL, then adds 6mL oleic acid (OA) and 15mL 1-octadecylene (ODE), and vacuum lower magnetic force stirs and is warming up to 100 DEG C gradually, keeps 10min.Then temperature be increased to 150 DEG C and keep 30min, stopping after naturally cooling to room temperature vacuumizing, dropwise add 10mL while stirring and be dissolved with 0.1482g (4mmol) NH 4the CH of F and 0.1g (2.5mmol) NaOH 3oH solution, is heated to 100 DEG C in atmosphere and keeps 10min, then vacuumizing 10min at such a temperature, afterwards at N 2be rapidly heated to 290 DEG C under protective atmosphere, keep sustained reaction 120min at this temperature.Naturally cool to after room temperature until system, stop logical N 2.By gained sample hexanaphthene: ethanol (v:v=1:1) solution washing, centrifugal 2-3 time, vacuum-drying, obtains nucleocapsid structure NaYF 4@NaYF 4: Yb, Er@NaYF 4, i.e. the NaYF of δ doping 4: Yb, Er, pattern is class ball, and particle diameter is uneven, productive rate <5%.
Embodiment 2:
(1) core NaYF 4preparation with embodiment 1, difference is temperature of reaction is 300 DEG C, keeps sustained reaction 120min at this temperature, obtains NaYF 4, pattern is polyhedron, and particle diameter is about 20nm, productive rate about 27%.
(2) nucleocapsid structure NaYF 4@NaYF 4: the preparation of Yb, Er is with embodiment 1, and difference is temperature of reaction is 300 DEG C, keeps sustained reaction 60min at this temperature, obtains NaYF 4@NaYF 4: Yb, Er, pattern is polyhedron, and particle diameter is about 22nm, productive rate about 8%.
(3) NaYF of δ doping 4: the preparation of Yb, Er is with embodiment 1, and difference is temperature of reaction is 300 DEG C, keeps sustained reaction 60min at this temperature, obtains NaYF 4@NaYF 4: Yb, Er@NaYF 4, pattern is polyhedron, and particle diameter is about 25nm, productive rate <5%.
Embodiment 3:
(1) core NaYF 4preparation with embodiment 1, difference is temperature of reaction is 310 DEG C, keeps sustained reaction 60min at this temperature, obtains NaYF 4, pattern is six square pieces, and particle diameter is about 20nm, productive rate about 32%.
(2) nucleocapsid structure NaYF 4@NaYF 4: the preparation of Yb, Er is with embodiment 1, and difference is temperature of reaction is 310 DEG C, keeps sustained reaction 30min at this temperature, obtains NaYF 4@NaYF 4: Yb, Er, pattern is six square pieces, and particle diameter is about 22nm, productive rate about 24%.
(3) NaYF of δ doping 4: the preparation of Yb, Er is with embodiment 1, and difference is temperature of reaction is 310 DEG C, keeps sustained reaction 30min at this temperature, obtains NaYF 4@NaYF 4: Yb, Er@NaYF 4, pattern is six square pieces, and particle diameter is about 25nm, productive rate about 17%.
Embodiment 4:
(1) core NaYF 4preparation with embodiment 1, difference is temperature of reaction is 320 DEG C, keeps sustained reaction 60min at this temperature, obtains NaYF 4, pattern is six square pieces, and particle diameter is about 20nm, productive rate about 55%.
(2) nucleocapsid structure NaYF 4@NaYF 4: the preparation of Yb, Er is with embodiment 1, and difference is temperature of reaction is 320 DEG C, keeps sustained reaction 20min at this temperature, obtains NaYF 4@NaYF 4: Yb, Er, pattern is six square pieces, and particle diameter is about 27nm, productive rate about 53%.
(3) NaYF of δ doping 4: the preparation of Yb, Er is with embodiment 1, and difference is temperature of reaction is 320 DEG C, keeps sustained reaction 20min at this temperature, obtains NaYF 4@NaYF 4: Yb, Er@NaYF 4, pattern is six square pieces, and particle diameter is about 46nm, productive rate about 50%.
Embodiment 5:
(1) core NaYF 4preparation with embodiment 1, difference is temperature of reaction is 330 DEG C, keeps sustained reaction 60min at this temperature, obtains NaYF 4, pattern is six square pieces.When temperature of reaction being increased to 330 DEG C, particle size is between 35-50nm, and productive rate is increased to about 64%.Due to the rising of temperature of reaction, cause speed of response suddenly to be accelerated, make the size of particle be difficult to control, but particle shape can not change.
(2) nucleocapsid structure NaYF 4@NaYF 4: the preparation of Yb, Er is with embodiment 1, and difference is temperature of reaction is 330 DEG C, keeps sustained reaction 20min at this temperature, obtains NaYF 4@NaYF 4: Yb, Er, pattern is six square pieces, and particle diameter is uneven, productive rate about 56%.
(3) NaYF of δ doping 4: the preparation of Yb, Er is with embodiment 1, and difference is temperature of reaction is 330 DEG C, keeps sustained reaction 20min at this temperature, obtains NaYF 4@NaYF 4: Yb, Er@NaYF 4, pattern is six square pieces, and particle diameter is uneven, productive rate about 41%.
By reference to the accompanying drawings the specific embodiment of the present invention is described although above-mentioned; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still within protection scope of the present invention.

Claims (8)

1. improve a method for up-conversion nano material quantum yield, it is characterized in that, comprise the steps
1) by YCl 3, oleic acid and the mixing of 1-octadecylene, under vacuum condition, stir, be warming up to 100-105 DEG C, after constant temperature 10-20min, temperature is increased to 150-160 DEG C and constant temperature 30-40min, forms the yellow solution of transparent and homogeneous, be cooled to room temperature; Then NH is added while stirring 4the CH of F and NaOH 3oH solution, after dropwising, continues to be heated to 100-105 DEG C, constant temperature 10-15min, vacuum outgas 10-20min; Finally, under inert gas environment, by above-mentioned solution warms to 280-320 DEG C, reaction 240-300min; Cooling, washing, centrifugal, vacuum-drying, obtain core NaYF 4;
2) by core NaYF 4, LnCl 3, oleic acid and the mixing of 1-octadecylene, under vacuum condition, stir, be warming up to 100-105 DEG C, after constant temperature 10-20min, temperature is increased to 150-160 DEG C and constant temperature 30-40min, is cooled to room temperature; Then NH is added while stirring 4the CH of F and NaOH 3oH solution, after dropwising, continues to be heated to 100-105 DEG C, constant temperature 10-15min, vacuum outgas 10-20min; Finally, under inert gas environment, by above-mentioned solution warms to 280-320 DEG C, reaction 120-160min; Cooling, washing, centrifugal, vacuum-drying, obtain nucleocapsid structure NaYF 4@NaYF 4: Yb, Er;
3) by nucleocapsid structure NaYF 4@NaYF 4: Yb, Er, YCl 3, oleic acid and the mixing of 1-octadecylene, under vacuum condition, stir, be warming up to 100-105 DEG C, after constant temperature 10-20min, temperature is increased to 150-160 DEG C and constant temperature 30-40min, is cooled to room temperature; Then NH is added while stirring 4the CH of F and NaOH 3oH solution, after dropwising, continues to be heated to 100-105 DEG C, constant temperature 10-15min, vacuum outgas 10-20min; Finally, under inert gas environment, by above-mentioned solution warms to 280-320 DEG C, reaction 120-160min, obtains nucleocapsid structure NaYF 4@NaYF 4: Yb, Er@NaYF 4, i.e. the NaYF of δ doping 4: Yb, Er;
Step 1) in, described YCl 3, NH 4the mol ratio of F and NaOH is 1:4-6:2-5, described oleic acid, 1-octadecylene, CH 3the mass ratio of OH solution is 6-8:5-7:10-12, described NaOH and CH 3the mass ratio of OH solution is 0.1-0.3:10-16;
Step 2) in, described LnCl 3, NH 4the mol ratio of F and NaOH is 1:4-6:2-5, described core NaYF 4, oleic acid, 1-octadecylene, CH 3the mass ratio of OH solution is 0.1-0.5:6-8:5-7:10-12, described NaOH and CH 3the mass ratio of OH solution is 0.1-0.3:10-16; Wherein, described LnCl 3the mol ratio of middle Y:Yb:Er is 78 ~ 80:20 ~ 18:2;
Step 3) in, described YCl 3, NH 4the mol ratio of F and NaOH is 1:4-6:2-5, described nucleocapsid structure NaYF 4@NaYF 4: Yb, Er, oleic acid, 1-octadecylene, CH 3the mass ratio of OH solution is 0.1-0.5:6-8:5-7:10-12, described NaOH and CH 3the mass ratio of OH solution is 0.1-0.3:10-16.
2. the method for claim 1, is characterized in that, step 1) in, described core NaYF 4for near-spherical, polyhedron or six square pieces.
3. the method for claim 1, is characterized in that, step 2) in, described nucleocapsid structure NaYF 4@NaYF 4: Yb, Er are near-spherical, polyhedron or six square pieces.
4. the method for claim 1, is characterized in that, step 3) in, described nucleocapsid structure NaYF 4@NaYF 4: Yb, Er@NaYF 4for near-spherical, polyhedron or six square pieces.
5. the method for claim 1, is characterized in that, described wash conditions is be the hexanaphthene of 1:1 and ethanol or ethanol and water washing by volume ratio.
6. the method for claim 1, is characterized in that, described centrifugal condition is centrifugal 2-3 time, rotating speed is 3500-4000r/min, and the time is 3-5min.
7. the method for claim 1, is characterized in that, described vacuum-drying condition is at 100-105 DEG C, dry 10-15min.
8. the method for claim 1, is characterized in that, described rare gas element is nitrogen or argon gas.
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