CN107312520A - 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 cooperative 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+), x value is between 0~78%.The present invention realizes " 1+1 by the way that bare nucleus is overmolding into core shell structure>2 " cooperative effect, its fluorescence intensity has also obtained significant raising.
Description
Technical field
The invention belongs to up-conversion luminescent material technical field, and in particular to a kind of core shell structure with cooperative effect
LiRE1F4:Yb,RE2,Cd@LiRE1F4Upconversion fluorescence nano material and preparation method thereof.
Background technology
The luminous of rare earth luminous nano material is mainly based upon the radiation hair that rare earth ion is transitted to low-lying level by high level
Light.And be gradually reduced with the particle diameter of nano material, specific surface area gradually increases, skin effect enhancing, and skin effect is to luminous
The luminous influence of nano material is notable.Due to specific surface area increase so that the ligancy of the atom in nano particle face is not enough,
Particle surface produces substantial amounts of unsaturated bond, room, defect etc., forms luminous quenching centre；Skin effect increase, in receiving
In the presence of quenching centre more Non-radiative relaxation processes production occurs for the centre of luminescence (Doped ions) of rice grain near surface
Raw fluorescent quenching, so as to reduce the luminous intensity and luminous efficiency (Science, 2010,327,1634- of nano particle
1638).Skin effect largely reduces the luminescent properties of rare earth luminous nano material, also limit rare earth luminous nanometer
The application prospect of material.Surface modification is carried out to nano material, nano-material surface defect and radiationless relaxation can be reduced, carried
Its high luminous efficiency (Langmuir, 2008,24,12123-12125).
In order to obtain the more preferable nano material of luminescent properties, further modification is carried out to Illuminant nanometer material surface and seems outstanding
To be important.At present, the surface modification of Illuminant nanometer material mainly carries out shell cladding to nano material, and this method is received with one kind
Rice grain is core, and in one layer of uniform nanoshells of Surface coating, stable nucleocapsid knot is formed 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 knot
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
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 with good translucency, biocompatibility the features such as, and higher temperature can be born
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 existing compared with Macrolattice mismatch between core matrix material, nucleocapsid, further results between nucleocapsid and there is more lattice
Defect, these defects affect core material as new luminescence queenching center and lighted.
Homogeneity core shell structure, relative to heterogeneous core shell structure, core matrix material is identical with shell, in the absence of between nucleocapsid
Lattice mismatch issue, it is to avoid the formation at luminescence queenching center between nucleocapsid；Simultaneously for whole nano particle, identical core
Conchiolin material can also pass to the core centre of luminescence well equivalent to host material increase, the energy of shell matrix absorption,
Improve helpful for particle overall luminous efficacy.Under the exciting of 980nm near infrared lights, it is observed that a series of homogeneity cores
The upper conversion efficiency of shell up-conversion nanoparticles can strengthen 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 case of particle diameter identical,
(NaYF4:Yb3+/Er3+)@NaYF4The absolute quantum yield of nano-particle is no shell NaYF4:Yb3+/Er3+3 times of nano-particle
(J Opt Soc Am B,1998,15:996-1008), this result, which directly demonstrates homogeneity shell, can suppress surface quenching
Effect improves upper conversion efficiency.It is 980nm in wavelength, laser power density is 127W/cm2Under conditions of, (LiLuF4:Yb3+/
Tm3+)@LiLuF4 quantum yield is up to 7.6% (Nano Lett, 2012,12,2852-2858), very close to being even higher by
The upper conversion efficiency (Opt Lett, 2013,38,2101-2103) for the raw material reported before, further demonstrate homogeneity nucleocapsid
Structure can effectively suppress surface quenching effect.
Ion doping and structure core shell structure are two kinds of luminous effective means of enhancing, and both, which combine, can be achieved to cooperate with effect
Should, greatly enhance illumination effect.
The content of the invention
An object of the present invention is to propose a kind of core shell structure LiRE with cooperative effect1F4:Yb,RE2,Cd@
LiRE1F4Upconversion fluorescence nano material, its chemical expression is LiRE1 0.78-xF4:20%Yb, 2%RE2,xCd@LiRE1F4,
Wherein RE1For matrix ion, selected from Y3+、Gd3+、Lu3+In one kind；RE2For active ions, selected from Er3+、Tm3+、Ho3+、Nd3+
In one kind, x value is between 0~78%.
Another object of the present invention is to provide a kind of core shell structure LiRE with cooperative effect1F4:Yb,RE2,Cd@
LiRE1F4The preparation method of upconversion fluorescence nano material, comprises 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；Prepared and obtained using same method cadmium oxide (CdO)
Cd-TFA solution, is prepared and obtains RE respectively with rare earth oxide1- 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 well mixed to obtain mixed solution 1；In proportion by Li-TFA solution, RE1- TFA solution is well mixed must to mix molten
Liquid 2；
(c) mixed solution 1 obtained by step (b) is evaporated and obtains solid, add octadecylene (ODE) and oleic acid (OA), stirring
And heating makes solid dissolving, is removed water respectively, deoxygenation processing obtains solution A, mixed solution 2 is obtained using same method processing
Solution B；
(d) heated solution A under protective atmosphere, insulation reaction obtains solution C, is washed after solution C cooling through repeated multiple times ethanol
Wash, hexamethylene is scattered, separation of solid and liquid obtains solid；
(e) octadecylene, ultrasonic disperse and agitating and heating are added into solid obtained by step (d), solution B is reinjected and carries out instead
Should；
(f) through the washing of repeated multiple times ethanol, hexamethylene disperse, separation of solid and liquid obtains solid after reaction is completed, solid is produced
Thing is drying to obtain the core shell structure LiRE with cooperative effect1F4:Yb,RE2,Cd@LiRE1F4Upconversion fluorescence nano material.
According to such scheme, RE is prepared in step (a)1Rare earth oxide used in-TFA solution is selected from yittrium oxide
(Y2O3), gadolinium oxide (Gd2O3), luteium oxide (Lu2O3) in one kind, prepare Yb-TFA solution used in rare earth oxide be oxygen
Change ytterbium, prepare RE2Rare earth oxide used in-TFA solution is selected from erbium oxide (Er2O3), thulium oxide (Tm2O3), holimium oxide
(Ho2O3), neodymia (Nd2O3) in one kind.
According to such 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 x value be 0~78% between；Li, RE in mixed solution 21The ratio between amount of substance be 2：
1；1 rare earth ion and Cd in mixed solution2+The ratio between total material amount and the Rare Earth Ion total material amount of mixed solution 2 be 1:(1~
2)。
According to such scheme, step (c) is with the Rare Earth Ion of mixed solution 1 and Cd2+Total material amount 1mmol on the basis of,
The addition of octadecylene and oleic acid is 6mL.
According to such scheme, step (c) carries out removing water process, water removal under the conditions of vacuum, 70~80 DEG C to mixed solution
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 such scheme, insulation reaction temperature is 310~320 DEG C in step (d), and the reaction time is 30~40min.
According to such scheme, with the Rare Earth Ion of mixed solution 1 and Cd in step (e)2+Total material amount 1mmol be base
Standard, the addition of octadecylene is 2~4mL, and solution B is injected into mixed solution with 2~4mL/min speed below 260 DEG C
In, it is then heated to 310~320 DEG C of 30~40min of reaction.
According to such scheme, step (d) and step (f) the ethanol washing, hexamethylene disperse to specifically include：According to 3：7
Volume ratio ethanol is added in reaction solution, supernatant liquor is discarded after centrifugation and obtains solid, solid is distributed to hexamethylene
In, ethanol is added into dispersion liquid according to same ratio, centrifuges again and discards supernatant liquor and obtain solid.
According to such scheme, solid product drying temperature is 80 DEG C in step (f), and drying time is 12h.
Compared with prior art, beneficial effects of the present invention are：(1) using conventional reagent, preparation technology is simply easily grasped
Make, bare nucleus is directly scattered in 18 weak solutions, save except hexamethylene operation, it is to avoid hexamethylene and solvent formation vapor of mixture
Thing is difficult to situation about removing；(2) core shell structure of upconversion fluorescence nano material is remarkably reinforced its fluorescence.
Brief description of the drawings
Fig. 1 is the LiY that the embodiment of the present invention 1 is prepared0.68Yb0.2Er0.02Cd0.1F4The XRD and LiYF of bare nucleus4's
Standard card JCPDS 17-0874 comparison diagram；
Fig. 2 is LiY prepared by the embodiment of the present invention 10.68Yb0.2Er0.02Cd0.1F4The TEM figures of bare nucleus；
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 cooperative effect prepared by the embodiment of the present invention 10.68Yb0.2Er0.02Cd0.1F4@
LiYF4The TEM figures of the brilliant material of upper conversion nano；
Fig. 5 is the core shell structure LiY with cooperative effect prepared by the embodiment of the present invention 10.68Yb0.2Er0.02Cd0.1F4@
LiYF4The grain size distribution of the brilliant material of upper conversion nano；
Fig. 6 is LiY prepared by the embodiment of the present invention 10.68Yb0.2Er0.02Cd0.1F4Bare nucleus and the nucleocapsid with cooperative effect
Structure LiY0.68Yb0.2Er0.02Cd0.1F4@LiYF4The XPS figures of up-conversion nano material；
Fig. 7 is LiY prepared by the embodiment of the present invention 10.68Yb0.2Er0.02Cd0.1F4Bare nucleus and the nucleocapsid with cooperative effect
Structure LiY0.68Yb0.2Er0.02Cd0.1F4@LiYF4The fluorescence spectra of up-conversion nano material.
Embodiment
To make those of ordinary skill in the art fully understand technical scheme 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 cooperative effect, to prepare
LiY0.68Yb0.2Er0.02Cd0.1F4@LiYF4Exemplified by, specifically include following steps：
(1) lithium hydroxide (LiOH) is mixed with appropriate amount of deionized water, stirs and heat, trifluoroacetic acid is then added dropwise
(CF3COOH), settled solution 1mol/L Li-TFA is obtained after solid is completely dissolved；It can be similarly made with cadmium oxide (CdO)
0.2mol/L Cd-TFA, 1mol/L Y-TFA, 0.2mol/L Yb-TFA can be made with rare earth oxide, 0.02mol/L's
ER-TFA。
(2) Y in molar ratio：Yb：Er：Cd=0.68：0.2：0.02：0.01 measures the standard liquid (Y- that total amount is 1mmol
TFA+Yb-TFA+Er-TFA+Cd-TFA), it is put into three-necked flask together with 2mmol Li-TFA, is clear solution 1.Adopt
3mmol Li-TFA and the 1.5mmol Y-TFA measured is put into three-necked flask together with same method, is clear solution
2。
(3) step (2) resulting solution 1 is placed in fume hood, is evaporated in 80 DEG C obtains solid under magnetic stirring, cooled down
6mL ODE and 6mL OA are added afterwards, are heated to 60 DEG C of insulations until solid is completely dissolved.Then continue to be warming up to 80 DEG C simultaneously
Vacuumize 15min to be removed water, be then turned off vavuum pump and be passed through Ar gas, be heated to 100 DEG C of insulation 40min and carry out deoxygenation, obtain
Solution A.Solution 2 obtains solution B using same method processing.
(4) solution A is to slowly warm up to 320 DEG C under the conditions of Ar protective atmospheres, insulation reaction 35min obtains yellow transparent
Solution C, question response liquid closes protection gas after being slowly cooled to room temperature.
(5) reaction solution is pressed：Ethanol=7：3 volume ratio adds ethanol into solution C, and upper strata is discarded after 10000rpm centrifugations
Clear liquid obtains white pigmented samples, then with hexamethylene divided white sample, then by reaction solution：Ethanol=7：3 volume ratio adds second
Alcohol is centrifuged with 10000rpm.
(6) centrifugation terminates rear abandoning supernatant, and 4mL octadecylenes are added thereto, by mixed solution ultrasonic disperse and are stirred
Heating, solution B is injected wherein, be continuously heating to 320 DEG C of insulation reaction 35min at 260 DEG C with 4mL/min speed.
(7) reaction solution is sucked in centrifuge tube, by reaction solution：Ethanol=7：3 volume ratio adds ethanol, 10000rpm from
Gains in depth of comprehension, with hexamethylene divided white sample, add ethanol sedimentation centrifugation, such cyclic washing at least three times to white pigmented samples.
Then product is placed under vacuum condition in 80 DEG C of dry 12h, white powdery solids product, as up-conversion fluorescence material is obtained
Expect LiY0.68Yb0.2Er0.02Cd0.1F4@LiYF4。
The LiY that this example is prepared0.68Yb0.2Er0.02Cd0.1F4The XRD of bare nucleus is as shown in figure 1, bare nucleus
LiY0.68Yb0.2Er0.02Cd0.1F4TEM figures it is as shown in Figure 2.It is synthesized rear-earth-doped 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.Can from Fig. 3
To find out LiY0.68Yb0.2Er0.02Cd0.1F4Size is uniform, and dimensions length is in 171nm or so, and width is naked in 74nm or so
Core assumes diamond in shape.Core shell structure LiY with cooperative effect prepared by this example0.68Yb0.2Er0.02Cd0.1F4@LiYF4Upper conversion is received
The TEM of the brilliant material of rice as shown in figure 4, bare nucleus and core shell structure XPS as shown in Figure 6 therefrom we can see that
LiY0.68Yb0.2Er0.02Cd0.1F4@LiYF4With core shell structure.LiY prepared by this example0.68Yb0.2Er0.02Cd0.1F4Upper conversion
Nanocrystalline material and LiY0.68Yb0.2Er0.02Cd0.1F4@LiYF4The fluorescence spectrum contrast 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 respectively
Place, when the brilliant material of upper conversion nano 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, to prepare
LiY0.68Yb0.2Tm0.02Cd0.1F4@LiYF4Exemplified by, specifically include following steps：
(1) lithium hydroxide (LiOH) is mixed with appropriate amount of deionized water, stirs and heat, trifluoroacetic acid is then added dropwise
(CF3COOH), settled solution 1mol/L Li-TFA is obtained after solid is completely dissolved；It can be similarly made with cadmium oxide (CdO)
0.2mol/L Cd-TFA, 1mol/L Y-TFA, 0.2mol/L Yb-TFA can be made with rare earth oxide, 0.02mol/L's
Tm-TFA。
(2) Y in molar ratio：Yb：Tm：Cd=0.68：0.2：0.02：0.01 measures the standard liquid (Y- that total amount is 1mmol
TFA+Yb-TFA+Tm-TFA+Cd-TFA), it is put into three-necked flask together with 2mmol Li-TFA, is clear solution 1.Adopt
3mmol Li-TFA and the 1.5mmol Y-TFA measured is put into three-necked flask together with same method, is clear solution
2。
(3) step (b) resulting solution is placed in fume hood, is evaporated in 80 DEG C obtains solid under magnetic stirring, cooled down
6mLODE and 6mLOA is added afterwards, is heated to 60 DEG C of insulations until solid is completely dissolved.Then continue to be warming up to 80 DEG C and take out
Vacuum 15min is removed water, and is then turned off vavuum pump and is passed through Ar gas, is heated to 100 DEG C of insulation 40min and is carried out deoxygenation, obtains molten
Liquid A.Solution 2 obtains solution B using same method processing.
(4) solution A is to slowly warm up to 320 DEG C under the conditions of Ar protective atmospheres, insulation reaction 35min obtains yellow transparent
Solution C, question response liquid closes protection gas after being slowly cooled to room temperature.
(5) reaction solution is pressed：Ethanol=7：3 volume ratio adds ethanol into solution C, and upper strata is discarded after 10000rpm centrifugations
Clear liquid obtains white pigmented samples, then with hexamethylene divided white sample, then by reaction solution：Ethanol=7：3 volume ratio adds second
Alcohol is centrifuged with 10000rpm.
(6) centrifugation terminates rear abandoning supernatant, and 4mL octadecylenes are added thereto, by mixed solution ultrasonic disperse and are stirred
Heating, solution B is injected wherein, be continuously heating to 320 DEG C of insulation reaction 35min at 260 DEG C with 4mL/min speed.
(7) reaction solution is sucked in centrifuge tube, by reaction solution：Ethanol=7：3 volume ratio adds ethanol, 10000rpm from
Gains in depth of comprehension, with hexamethylene divided white sample, add ethanol sedimentation centrifugation, such cyclic washing at least three times to white pigmented samples.
Then product is placed under vacuum condition in 80 DEG C of dry 12h, white powdery solids product, as up-conversion fluorescence material is obtained
Expect LiY0.68Yb0.2Tm0.02Cd0.1F4。
Claims (10)
1. a kind of core shell structure LiRE with cooperative effect1F4:Yb,RE2,Cd@LiRE1F4Upconversion fluorescence nano material, its
It is characterised by, its chemical expression is LiRE1 0.78-xF4:20%Yb, 2%RE2,xCd@LiRE1F4, wherein RE1For matrix ion,
Selected from Y3+、Gd3+、Lu3+In one kind；RE2For active ions, selected from Er3+、Tm3+、Ho3+、Nd3+In one kind, x value is 0
Between~78%.
2. a kind of core shell structure LiRE with cooperative effect1F4:Yb,RE2,Cd@LiRE1F4The system of upconversion fluorescence nano material
Preparation Method, it is characterised in that comprise the following steps：
(a) lithium hydroxide is mixed with appropriate amount of deionized water, stirs and heat, trifluoroacetic acid is then added dropwise, treat that solid is completely molten
Li-TFA solution is obtained after solution；Prepared using same method cadmium oxide and obtain Cd-TFA solution, 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 well mixed to obtain mixed solution 1；In proportion by Li-TFA solution, RE1- TFA solution is well mixed to obtain mixed solution 2；
(c) mixed solution 1 obtained by step (b) is evaporated and obtains solid, add octadecylene and oleic acid, stirring and heating makes solid molten
Solution, is removed water, deoxygenation processing obtains solution A, mixed solution 2 obtains solution B using same method processing respectively；
(d) heated solution A under protective atmosphere, insulation reaction obtains solution C, through the washing of repeated multiple times ethanol, ring after solution C cooling
Hexane is scattered, separation of solid and liquid obtains solid；
(e) octadecylene, ultrasonic disperse and agitating and heating are added into solid obtained by step (d), solution B is reinjected and is reacted；
(f) through the washing of repeated multiple times ethanol, hexamethylene disperse, separation of solid and liquid obtains solid after reaction is completed, solid product is done
The dry core shell structure LiRE produced with cooperative effect1F4:Yb,RE2,Cd@LiRE1F4Upconversion fluorescence nano material.
3. a kind of core shell structure LiRE with cooperative 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
The one kind of compound in yittrium oxide, gadolinium oxide, luteium oxide, it is oxidation to prepare rare earth oxide used in Yb-TFA solution
Ytterbium, prepares RE2The one kind of rare earth oxide in erbium oxide, thulium oxide, holimium oxide, neodymia used in-TFA solution.
4. a kind of core shell structure LiRE with cooperative 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, wherein x value be 0~78% between；Li, RE in mixed solution 21
The ratio between amount of substance be 2：1；1 rare earth ion and Cd in mixed solution2+Total material amount and the total thing of the Rare Earth Ion of mixed solution 2
Mass ratio is 1:(1~2).
5. a kind of core shell structure LiRE with cooperative effect according to claim 21F4:Yb,RE2,Cd@LiRE1F4On
Fluorescent nano material converted preparation method, it is characterised in that：Step (c) is with the Rare Earth Ion of mixed solution 1 and Cd2+Total thing
On the basis of quality 1mmol, the addition of octadecylene and oleic acid is 6mL.
6. a kind of core shell structure LiRE with cooperative 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
Carry out removing 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 cooperative 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 cooperative effect according to claim 21F4:Yb,RE2,Cd@LiRE1F4On
Fluorescent nano material converted preparation method, it is characterised in that：With the Rare Earth Ion of mixed solution 1 and Cd in step (e)2+It is total
On the basis of amount of substance 1mmol, the addition of octadecylene is 2~4mL, by solution B with 2~4mL/min speed below 260 DEG C
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 cooperative 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) the ethanol washing, hexamethylene disperse
Specifically include：According to 3：Ethanol is added in reaction solution by 7 volume ratio, and supernatant liquor is discarded after centrifugation and obtains solid, will
Solid is distributed in hexamethylene, and ethanol is added into dispersion liquid according to same ratio, centrifuges again and to discard upper strata clear
Liquid obtains solid.
10. a kind of core shell structure LiRE with cooperative 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 drying
Between be 12h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107892913A (en) * | 2017-11-06 | 2018-04-10 | 哈尔滨工程大学 | A kind of method for improving the enhanced rare earth up-conversion fluorescence efficiency of impurity |
| CN108384547A (en) * | 2018-04-25 | 2018-08-10 | 华中科技大学 | A kind of list doping-enrichment nucleocapsid up-conversion luminescent material and preparation method thereof |
| CN111117620A (en) * | 2020-03-11 | 2020-05-08 | 福州大学 | Preparation method of nano up-conversion fluorescent powder with strong ultraviolet light emission |
| CN112898976A (en) * | 2020-11-24 | 2021-06-04 | 武汉理工大学 | LiGdF with core-shell structure4Crystal and method for producing same |
| CN114350361A (en) * | 2022-01-19 | 2022-04-15 | 福州大学 | Up-conversion rare earth doped nano material with high fluorescence intensity and preparation method thereof |
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| CN102925157A (en) * | 2012-11-27 | 2013-02-13 | 哈尔滨工业大学 | Preparation method of NaY(98-X)% F4:X%Yb, 2%Er@NaDyF4 in core-shell structure |
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| CN102925157A (en) * | 2012-11-27 | 2013-02-13 | 哈尔滨工业大学 | Preparation method of NaY(98-X)% F4:X%Yb, 2%Er@NaDyF4 in core-shell structure |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107892913A (en) * | 2017-11-06 | 2018-04-10 | 哈尔滨工程大学 | A kind of method for improving the enhanced rare earth up-conversion fluorescence efficiency of impurity |
| CN108384547A (en) * | 2018-04-25 | 2018-08-10 | 华中科技大学 | A kind of list doping-enrichment nucleocapsid up-conversion luminescent material and preparation method thereof |
| CN108384547B (en) * | 2018-04-25 | 2020-05-19 | 华中科技大学 | Up-conversion luminescent material with single-doped-enriched core-shell structure and preparation method thereof |
| CN111117620A (en) * | 2020-03-11 | 2020-05-08 | 福州大学 | Preparation method of nano up-conversion fluorescent powder with strong ultraviolet light emission |
| CN111117620B (en) * | 2020-03-11 | 2022-11-22 | 福州大学 | Preparation method of nano up-conversion fluorescent powder with strong ultraviolet light emission |
| CN112898976A (en) * | 2020-11-24 | 2021-06-04 | 武汉理工大学 | LiGdF with core-shell structure4Crystal and method for producing same |
| CN114350361A (en) * | 2022-01-19 | 2022-04-15 | 福州大学 | Up-conversion rare earth doped nano material with high fluorescence intensity and preparation method thereof |
| CN114350361B (en) * | 2022-01-19 | 2023-08-25 | 福州大学 | Up-conversion rare earth doped nano material with high fluorescence intensity and preparation method thereof |
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