CN107312520B - LiRE1F4:Yb,RE2,Cd@LiRE1F4Upconversion fluorescence nano material and preparation method thereof - Google Patents
LiRE1F4:Yb,RE2,Cd@LiRE1F4Upconversion fluorescence nano material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of core-shell structure LiRE with synergistic effect1F4:Yb,RE2,Cd@LiRE1F4Upconversion fluorescence nano material and preparation method thereof.The chemical expression of the material is LiRE1 0.78‑xF4: 20%Yb, 2%RE2,xCd@LiRE1F4, wherein RE1For matrix ion (Y3+、Gd3+Or Lu3+), RE2For active ions (Er3+、Tm3+、Ho3+Or Nd3+), the value of x is between 0~78%.The present invention realizes that the synergistic effect of " 1+1 > 2 ", fluorescence intensity have also obtained significant raising by the way that bare nucleus is overmolding to core-shell structure.
Description
Technical field
The invention belongs to up-conversion luminescent material technical fields, and in particular to a kind of core-shell structure with synergistic effect
LiRE1F4:Yb,RE2,Cd@LiRE1F4Upconversion fluorescence nano material and preparation method thereof.
Background technique
The luminous rare earth ion that is mainly based upon of rare earth luminous nano material is sent out by the radiation that high level transits to low-lying level
Light.And as the partial size of nano material is gradually reduced, specific surface area is gradually increased, skin effect enhancing, and skin effect is to luminous
The luminous influence of nano material is significant.Since specific surface area increases, so that the ligancy of the atom in nano particle face is insufficient,
Particle surface generates a large amount of unsaturated bond, vacancy, defect etc., forms luminous quenching centre；Skin effect increases, in receiving
The centre of luminescence (Doped ions) near rice grain surface occurs more Non-radiative relaxation processes and produces under the action of quenching centre
Raw fluorescent quenching, thus reduce nano particle luminous intensity and luminous efficiency (Science, 2010,327,1634-
1638).Skin effect largely reduces the luminescent properties of rare earth luminous nano material, also limits rare earth luminous nanometer
The application prospect of material.Nano material is surface modified, nano-material surface defect and radiationless relaxation can be reduced, mentioned
Its high luminous efficiency (Langmuir, 2008,24,12123-12125).
The better nano material of luminescent properties in order to obtain, carrying out further modification to Illuminant nanometer material surface seems outstanding
It is important.Currently, the surface modification of Illuminant nanometer material mainly carries out shell cladding to nano material, this method is received with one kind
Rice grain is core, coats one layer of uniform nanoshells on surface, forms stable nucleocapsid knot in the case where physically or chemically acting on
Structure nano material (Phys.Rev.B 1996,54,17954-17961).Core-shell Structure Nanoparticles are generally divided into homogeneity nucleocapsid
Structure and heterogeneous core-shell structure, homogeneity core-shell structure refer to that core matrix and shell discrete phase are same, and heterogeneous core-shell structure refers to core
Heart matrix is different with shell matrix.
The shell matrix of heterogeneous core-shell structure has the advantages that core matrix material is not had, and can be good at protecting core
The heart, such as silica shell not only have the characteristics that good translucency, biocompatibility, but also can bear higher temperature
Heat treatment, to promote nano material crystallinity have very great help.However, heterojunction structure shell due to shell host material not
It is same as core matrix material, there are more lattices there is compared with Macrolattice mismatch, further resulting between nucleocapsid between nucleocapsid
Defect, these defects affect core material as new luminescence queenching center and shine.
Homogeneity core-shell structure, relative to heterogeneous core-shell structure, core matrix material is identical as shell, and there is no between nucleocapsid
Lattice mismatch issue, avoid the formation at luminescence queenching center between nucleocapsid；Simultaneously for entire nano particle, identical core
Conchiolin material is equivalent to host material increase, and the energy of shell matrix absorption can also pass to the core centre of luminescence well,
Particle overall luminous efficacy is improved helpful.Under the excitation of 980nm near infrared light, it can be observed that a series of homogeneities
The upper transfer efficiency of nucleocapsid up-conversion nanoparticles can enhance decades of times, including (KYF4:Yb3+/Er3+)@KYF4(AdvFunct
Mater,2008,18: 2913–2918)、(SrF2:Yb3+/Er3+)@SrF2(Cryst Growth Des,2009,9,2013–
2019)、 (YF3:Yb3+/Ln3+)@YF3(Ln=Er, Tm, Er/Tm) (J Mater Chem, 2012,22,20190-20196),
(NaYF4:Yb3+/Ln3+)@NaYF4(Ln=Er, Tm) (Colloid PolymSci, 2013,291,2533-2540),
(NaGdF4:Yb3+/Tm3+)@NaGdF4(Adv Mater,2010,22, 3266–3271).In the identical situation of partial size,
(NaYF4:Yb3+/Er3+)@NaYF4The absolute quantum yield of nanoparticle is no shell NaYF4:Yb3+/Er3+3 times of nanoparticle
(J Opt Soc Am B, 1998,15:996-1008), this result, which directly demonstrates homogeneity shell, to inhibit surface to quench
Effect improves upper transfer efficiency.It is 980nm, laser power density 127W/cm in wavelength2Under conditions of, (LiLuF4: Yb3+/
Tm3+) quantum yield of@LiLuF4 is up to 7.6% (Nano Lett, 2012,12,2852-2858), very close to being even higher by
The upper transfer efficiency (Opt Lett, 2013,38,2101-2103) for the raw material reported before, further demonstrates homogeneity core
Shell structure can effectively inhibit surface quenching effect.
Ion doping and building core-shell structure are two kinds of luminous effective means of enhancing, and the two, which combines, can be achieved collaboration effect
It answers, greatly enhances illumination effect.
Summary of the invention
It is an object of the present invention to propose a kind of core-shell structure LiRE with synergistic effect1F4:Yb,RE2,Cd@
LiRE1F4Upconversion fluorescence nano material, chemical expression LiRE1 0.78-xF4: 20%Yb, 2%RE2,xCd@LiRE1F4,
Wherein RE1For matrix ion, it is selected from Y3+、Gd3+、 Lu3+One of；RE2For active ions, it is selected from Er3+、Tm3+、Ho3+、Nd3+
One of, the value of x is between 0~78%.
Another object of the present invention is to provide a kind of core-shell structure LiRE with synergistic effect1F4:Yb,RE2,Cd@
LiRE1F4The preparation method of upconversion fluorescence nano material, comprising the following steps:
(a) lithium hydroxide (LiOH) is mixed with appropriate amount of deionized water, stirs and heat, trifluoroacetic acid is then added dropwise
(CF3COOH), Li-TFA solution is obtained after solid is completely dissolved；It is prepared and is obtained using same method cadmium oxide (CdO)
Cd-TFA solution is prepared respectively with rare earth oxide and obtains RE1- TFA solution, Yb-TFA solution, RE2- TFA solution；
(b) in proportion by Li-TFA solution, RE made from step (a)1- TFA solution, Yb-TFA solution, RE2- TFA solution,
Cd-TFA solution is uniformly mixed to obtain mixed solution 1；In proportion by Li-TFA solution, RE1- TFA solution is uniformly mixed to mix molten
Liquid 2；
(c) mixed solution 1 obtained by step (b) is evaporated to obtain solid, octadecylene (ODE) and oleic acid (OA), stirring is added
And heating dissolves solid, is removed water respectively, deoxygenation handles to obtain solution A, mixed solution 2 handles to obtain using same method
Solution B；
(d) heated solution A under protective atmosphere, insulation reaction obtain solution C, wash after solution C is cooling through repeated multiple times ethyl alcohol
It washs, hexamethylene disperses, separation of solid and liquid obtains solid；
(e) octadecylene, ultrasonic disperse and agitating and heating are added into step (d) obtained solid, reinjects solution B and carries out instead
It answers；
(f) solid is obtained through repeated multiple times ethanol washing, hexamethylene dispersion, separation of solid and liquid after the reaction was completed, solid is produced
Object is drying to obtain the core-shell structure LiRE with synergistic effect1F4:Yb,RE2,Cd@LiRE1F4Upconversion fluorescence nano material.
According to above scheme, RE is prepared in step (a)1Rare earth oxide used in-TFA solution is selected from yttrium oxide
(Y2O3), gadolinium oxide (Gd2O3), luteium oxide (Lu2O3One of), preparing rare earth oxide used in Yb-TFA solution is oxygen
Change ytterbium, prepares RE2Rare earth oxide used in-TFA solution is selected from erbium oxide (Er2O3), thulium oxide (Tm2O3), holimium oxide
(Ho2O3), neodymia (Nd2O3One of).
According to above scheme, Li, Cd, RE in mixed solution 1 obtained by step (b)1、Yb、RE2The ratio between amount of substance be 2:x:
(0.78-x): 0.2:0.02, wherein the value of x is between 0~78%；Li, RE in mixed solution 21The ratio between amount of substance be 2:
1；1 rare earth ion and Cd in mixed solution2+Total material amount and mixed solution 2 in the ratio between rare earth ion total material amount for 1:(1~
2)。
According to above scheme, step (c) is with rare earth ion and Cd in mixed solution 12+Total material amount 1mmol on the basis of,
The additional amount of octadecylene and oleic acid is 6mL.
According to above scheme, step (c) carries out except water process, water removal mixed solution under the conditions of vacuum, 70~80 DEG C
Time is 10~20min；Deoxygenation processing is carried out under the conditions of argon atmosphere, 100~120 DEG C, the deoxygenation time is 40~60min.
According to above scheme, insulation reaction temperature is 310~320 DEG C in step (d), and the reaction time is 30~40min.
According to above scheme, with rare earth ion and Cd in mixed solution 1 in step (e)2+Total material amount 1mmol be base
The additional amount of standard, octadecylene is 2~4mL, and solution B is injected into mixed solution with the rate of 2~4mL/min at 260 DEG C or less
In, it is then heated to 310~320 DEG C of 30~40min of reaction.
According to above scheme, step (d) and step (f) ethanol washing, hexamethylene dispersion are specifically included: according to 3:7
Volume ratio ethyl alcohol is added in reaction solution, supernatant liquor is discarded after centrifuge separation and obtains solid, solid is distributed to hexamethylene
In, ethyl alcohol is added into dispersion liquid according to same ratio, is centrifugated again and discards supernatant liquor and obtain solid.
According to above scheme, solid product drying temperature is 80 DEG C in step (f), drying time 12h.
Compared with prior art, the invention has the benefit that (1) utilizes common reagent, preparation process is simply easily grasped
Make, bare nucleus is directly scattered in 18 weak solutions, is saved except hexamethylene operates, and avoids hexamethylene and solvent forms vapor of mixture
Object is difficult to the case where removing；(2) its fluorescence is remarkably reinforced in the core-shell structure of upconversion fluorescence nano material.
Detailed description of the invention
Fig. 1 is the LiY that the embodiment of the present invention 1 is prepared0.68Yb0.2Er0.02Cd0.1F4The XRD diagram and LiYF of bare nucleus4's
The comparison diagram of standard card JCPDS 17-0874；
Fig. 2 is LiY prepared by the embodiment of the present invention 10.68Yb0.2Er0.02Cd0.1F4The TEM of bare nucleus schemes；
Fig. 3 is LiY prepared by the embodiment of the present invention 10.68Yb0.2Er0.02Cd0.1F4The grain size distribution of bare nucleus；
Fig. 4 is the core-shell structure LiY with synergistic effect prepared by the embodiment of the present invention 10.68Yb0.2Er0.02Cd0.1F4@
LiYF4The TEM of upper conversion nano crystalline substance material schemes；
Fig. 5 is the core-shell structure LiY with synergistic effect prepared by the embodiment of the present invention 10.68Yb0.2Er0.02Cd0.1F4@
LiYF4The grain size distribution of upper conversion nano crystalline substance material；
Fig. 6 is LiY prepared by the embodiment of the present invention 10.68Yb0.2Er0.02Cd0.1F4Bare nucleus and the nucleocapsid with synergistic effect
Structure LiY0.68Yb0.2Er0.02Cd0.1F4@LiYF4The XPS of up-conversion nano material schemes；
Fig. 7 is LiY prepared by the embodiment of the present invention 10.68Yb0.2Er0.02Cd0.1F4Bare nucleus and the nucleocapsid with synergistic effect
Structure LiY0.68Yb0.2Er0.02Cd0.1F4@LiYF4The fluorescence spectra of up-conversion nano material.
Specific embodiment
To make those of ordinary skill in the art fully understand technical solution of the present invention and beneficial effect, below in conjunction with specific
Embodiment is further described.
Embodiment 1
A kind of preparation method of the upconversion fluorescence nano material of the core-shell structure with synergistic effect, with preparation
LiY0.68Yb0.2Er0.02Cd0.1F4@LiYF4For, specifically comprise the following steps:
(1) lithium hydroxide (LiOH) is mixed with appropriate amount of deionized water, stirs and heat, trifluoroacetic acid is then added dropwise
(CF3COOH), the Li-TFA of clear solution 1mol/L is obtained after solid is completely dissolved；It can be similarly made with cadmium oxide (CdO)
The Y-TFA of 1mol/L, the Yb-TFA of 0.2mol/L, 0.02mol/L can be made with rare earth oxide by the Cd-TFA of 0.2mol/L
ER-TFA.
(2) Y:Yb:Er:Cd=0.68:0.2:0.02:0.01 measures the standard solution that total amount is 1mmol in molar ratio
(Y-TFA+Yb-TFA+Er-TFA+Cd-TFA), it is put into togerther in three-necked flask with 2mmol Li-TFA, is clear solution
1.3mmol Li-TFA and the 1.5mmol Y-TFA measured is put into togerther in three-necked flask using same method, is transparent
Solution 2.
(3) step (2) acquired solution 1 is placed in draught cupboard, is evaporated to obtain solid under magnetic stirring in 80 DEG C, it is cooling
6mL ODE and 6mL OA is added afterwards, is heated to 60 DEG C of heat preservations until solid is completely dissolved.Then continue to be warming up to 80 DEG C simultaneously
It vacuumizes 15min to be removed water, is then turned off vacuum pump and is passed through Ar gas, be heated to 100 DEG C of heat preservation 40min and carry out deoxygenation, obtain
Solution A.Solution 2 handles to obtain solution B using same method.
(4) solution A is to slowly warm up to 320 DEG C under the conditions of Ar protective atmosphere, it is saturating that insulation reaction 35min obtains yellow
Bright solution C closes protection gas after reaction solution is slowly cooled to room temperature.
(5) by reaction solution: ethyl alcohol is added into solution C for ethyl alcohol=7:3 volume ratio, discards upper layer after 10000rpm centrifugation
Clear liquid obtains white pigmented samples, then uses hexamethylene divided white sample, then presses reaction solution: second is added in ethyl alcohol=7:3 volume ratio
Alcohol is centrifuged with 10000rpm.
(6) liquid is discarded supernatant after being centrifuged, 4mL octadecylene is added thereto, by mixed solution ultrasonic disperse and stirs
Solution B is injected wherein with the rate of 4mL/min at 260 DEG C, is continuously heating to 320 DEG C of insulation reaction 35min by heating.
(7) reaction solution is sucked in centrifuge tube, by reaction solution: ethyl alcohol, 10000rpm is added in ethyl alcohol=7:3 volume ratio
Centrifugation obtains white pigmented samples, with hexamethylene divided white sample, adds ethyl alcohol sedimentation centrifugation, washs at least three repeatedly
It is secondary.Then place the product in, in 80 DEG C of dry 12h, white powdery solids product is obtained under vacuum condition, as upper conversion is glimmering
Luminescent material LiY0.68Yb0.2Er0.02Cd0.1F4@LiYF4。
The LiY that this example is prepared0.68Yb0.2Er0.02Cd0.1F4The XRD diagram of bare nucleus is as shown in Figure 1, bare nucleus
LiY0.68Yb0.2Er0.02Cd0.1F4TEM figure it is as shown in Figure 2.It is rear-earth-doped synthesized by as can be seen from Figure 1
LiY0.68Yb0.2Er0.02Cd0.1F4It can be well matched with standard card, it was demonstrated that the LiYF of pure phase4It is synthesized out.It can from Fig. 3
To find out LiY0.68Yb0.2Er0.02Cd0.1F4Size is uniform, and for dimensions length in 171nm or so, width is naked in 74nm or so
Core assumes diamond in shape.The core-shell structure LiY with synergistic effect of this example preparation0.68Yb0.2Er0.02Cd0.1F4@LiYF4Upper conversion
The TEM of nanocrystalline material as shown in figure 4, the XPS of bare nucleus and core-shell structure as shown in Figure 6 therefrom we can see that
LiY0.68Yb0.2Er0.02Cd0.1F4@LiYF4With core-shell structure.The LiY of this example preparation0.68Yb0.2Er0.02Cd0.1F4Upper conversion
Nanocrystalline material and LiY0.68Yb0.2Er0.02Cd0.1F4@LiYF4The fluorescence spectrum comparison of upper conversion nano-crystal with core-shell structure material
Figure is shown in Fig. 7, this it appears that Er from Fig. 73+Up-conversion fluorescence emission peak is located at 511,527,534,618 and 630nm
Place, when upper conversion nano crystalline substance material has core-shell structure, the intensity at fluorescence spectrum peak is greatly improved.
Embodiment 2
A kind of preparation method of the upconversion fluorescence nano material with core-shell structure, with preparation
LiY0.68Yb0.2Tm0.02Cd0.1F4@LiYF4For, specifically comprise the following steps:
(1) lithium hydroxide (LiOH) is mixed with appropriate amount of deionized water, stirs and heat, trifluoroacetic acid is then added dropwise
(CF3COOH), the Li-TFA of clear solution 1mol/L is obtained after solid is completely dissolved；It can be similarly made with cadmium oxide (CdO)
The Y-TFA of 1mol/L, the Yb-TFA of 0.2mol/L, 0.02mol/L can be made with rare earth oxide by the Cd-TFA of 0.2mol/L
Tm-TFA.
(2) Y:Yb:Tm:Cd=0.68:0.2:0.02:0.01 measures the standard solution that total amount is 1mmol in molar ratio
(Y-TFA+Yb-TFA+Tm-TFA+Cd-TFA), it is put into togerther in three-necked flask with 2mmol Li-TFA, is clear solution
1.3mmol Li-TFA and the 1.5mmol Y-TFA measured is put into togerther in three-necked flask using same method, is transparent
Solution 2.
(3) step (b) acquired solution is placed in draught cupboard, is evaporated to obtain solid under magnetic stirring in 80 DEG C, it is cooling
6mLODE and 6mLOA is added afterwards, is heated to 60 DEG C of heat preservations until solid is completely dissolved.It then continues to be warming up to 80 DEG C and take out
Vacuum 15min is removed water, and is then turned off vacuum pump and is passed through Ar gas, is heated to 100 DEG C of heat preservation 40min and is carried out deoxygenation, obtains molten
Liquid A.Solution 2 handles to obtain solution B using same method.
(4) solution A is to slowly warm up to 320 DEG C under the conditions of Ar protective atmosphere, it is saturating that insulation reaction 35min obtains yellow
Bright solution C closes protection gas after reaction solution is slowly cooled to room temperature.
(5) by reaction solution: ethyl alcohol is added into solution C for ethyl alcohol=7:3 volume ratio, discards upper layer after 10000rpm centrifugation
Clear liquid obtains white pigmented samples, then uses hexamethylene divided white sample, then presses reaction solution: second is added in ethyl alcohol=7:3 volume ratio
Alcohol is centrifuged with 10000rpm.
(6) liquid is discarded supernatant after being centrifuged, 4mL octadecylene is added thereto, by mixed solution ultrasonic disperse and stirs
Solution B is injected wherein with the rate of 4mL/min at 260 DEG C, is continuously heating to 320 DEG C of insulation reaction 35min by heating.
(7) reaction solution is sucked in centrifuge tube, by reaction solution: ethyl alcohol, 10000rpm is added in ethyl alcohol=7:3 volume ratio
Centrifugation obtains white pigmented samples, with hexamethylene divided white sample, adds ethyl alcohol sedimentation centrifugation, washs at least three repeatedly
It is secondary.Then place the product in, in 80 DEG C of dry 12h, white powdery solids product is obtained under vacuum condition, as upper conversion is glimmering
Luminescent material LiY0.68Yb0.2Tm0.02Cd0.1F4。
Claims (10)
1. a kind of core-shell structure LiRE with synergistic effect1F4:Yb,RE2,Cd@LiRE1F4Upconversion fluorescence nano material,
It is characterized in that, chemical expression LiRE1 0.78-xF4: 20%Yb, 2%RE2,xCd@LiRE1F4, wherein RE1For matrix ion,
Selected from Y3+、Gd3+、Lu3+One of；RE2For active ions, it is selected from Er3+、Tm3+、Ho3+、Nd3+One of, 0 < x≤
78%.
2. a kind of core-shell structure LiRE with synergistic effect1F4:Yb,RE2,Cd@LiRE1F4The system of upconversion fluorescence nano material
Preparation Method, which comprises the following steps:
(a) lithium hydroxide is mixed with appropriate amount of deionized water, stirred and heated, trifluoroacetic acid is then added dropwise, it is completely molten to solid
Li-TFA solution is obtained after solution；It is prepared to obtain Cd-TFA solution with cadmium oxide using same method, be distinguished with rare earth oxide
Preparation obtains RE1- TFA solution, Yb-TFA solution, RE2- TFA solution；
(b) in proportion by Li-TFA solution, RE made from step (a)1- TFA solution, Yb-TFA solution, RE2- TFA solution, Cd-
TFA solution is uniformly mixed to obtain mixed solution 1；In proportion by Li-TFA solution, RE1- TFA solution is uniformly mixed to obtain mixed solution 2；
(c) mixed solution 1 obtained by step (b) is evaporated to obtain solid, octadecylene and oleic acid is added, stirring and heating keeps solid molten
Solution, is removed water, deoxygenation handles to obtain solution A respectively, and mixed solution 2 handles to obtain solution B using same method；
(d) heated solution A under protective atmosphere, insulation reaction obtains solution C, through repeated multiple times ethanol washing, ring after solution C is cooling
Hexane dispersion, separation of solid and liquid obtain solid；
(e) octadecylene, ultrasonic disperse and agitating and heating are added into step (d) obtained solid, reinjects solution B and is reacted；
(f) solid is obtained through repeated multiple times ethanol washing, hexamethylene dispersion, separation of solid and liquid after the reaction was completed, solid product is done
The dry core-shell structure LiRE with synergistic effect1F4:Yb,RE2,Cd@LiRE1F4Upconversion fluorescence nano material.
3. a kind of core-shell structure LiRE with synergistic effect according to claim 21F4:Yb,RE2,Cd@LiRE1F4On
Fluorescent nano material converted preparation method, it is characterised in that: RE is prepared in step (a)1Rare earth oxygen used in-TFA solution
Compound is selected from one of yttrium oxide, gadolinium oxide, luteium oxide, and preparing rare earth oxide used in Yb-TFA solution is oxidation
Ytterbium prepares RE2Rare earth oxide used in-TFA solution is selected from one of erbium oxide, thulium oxide, holimium oxide, neodymia.
4. a kind of core-shell structure LiRE with synergistic effect according to claim 21F4:Yb,RE2,Cd@LiRE1F4On
Fluorescent nano material converted preparation method, it is characterised in that: Li, Cd, RE in mixed solution 1 obtained by step (b)1、Yb、RE2's
The ratio between amount of substance is 2:x:(0.78-x): 0.2:0.02,0 < x≤78%；Li, RE in mixed solution 21The ratio between amount of substance be
2:1；1 rare earth ion and Cd in mixed solution2+Total material amount and mixed solution 2 in the ratio between rare earth ion total material amount be 1:(1
~2).
5. a kind of core-shell structure LiRE with synergistic effect according to claim 21F4:Yb,RE2,Cd@LiRE1F4On
Fluorescent nano material converted preparation method, it is characterised in that: step (c) is with rare earth ion and Cd in mixed solution 12+Total object
On the basis of quality 1mmol, the additional amount of octadecylene and oleic acid is 6mL.
6. a kind of core-shell structure LiRE with synergistic effect according to claim 21F4:Yb,RE2,Cd@LiRE1F4On
Fluorescent nano material converted preparation method, it is characterised in that: step (c) is under the conditions of vacuum, 70~80 DEG C to mixed solution
It carries out except water process, the water removal time is 10~20min；Deoxygenation processing, deoxygenation are carried out under the conditions of argon atmosphere, 100~120 DEG C
Time is 40~60min.
7. a kind of core-shell structure LiRE with synergistic effect according to claim 21F4:Yb,RE2,Cd@LiRE1F4On
Fluorescent nano material converted preparation method, it is characterised in that: insulation reaction temperature is 310~320 DEG C in step (d), reaction
Time is 30~40min.
8. a kind of core-shell structure LiRE with synergistic effect according to claim 21F4:Yb,RE2,Cd@LiRE1F4On
Fluorescent nano material converted preparation method, it is characterised in that: with rare earth ion and Cd in mixed solution 1 in step (e)2+It is total
On the basis of amount of substance 1mmol, the additional amount of octadecylene is 2~4mL, 260 DEG C or less by solution B with the rate of 2~4mL/min
It is injected into mixed solution, is then heated to 310~320 DEG C of 30~40min of reaction.
9. a kind of core-shell structure LiRE with synergistic effect according to claim 21F4:Yb,RE2,Cd@LiRE1F4On
Fluorescent nano material converted preparation method, it is characterised in that: step (d) and step (f) ethanol washing, hexamethylene disperse
It specifically includes: ethyl alcohol being added in reaction solution according to the volume ratio of 3:7, supernatant liquor is discarded after centrifuge separation and obtains solid, it will
Solid is distributed in hexamethylene, and ethyl alcohol is added into dispersion liquid according to same ratio, is centrifugated again and to discard upper layer clear
Liquid obtains solid.
10. a kind of core-shell structure LiRE with synergistic effect according to claim 21F4:Yb,RE2,Cd@LiRE1F4On
Fluorescent nano material converted preparation method, it is characterised in that: solid product drying temperature is 80 DEG C in step (f), when dry
Between be 12h.
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