CN107267149A - Red up-conversion luminescence nanomaterial and preparation method thereof - Google Patents
Red up-conversion luminescence nanomaterial and preparation method thereof Download PDFInfo
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- CN107267149A CN107267149A CN201610217246.3A CN201610217246A CN107267149A CN 107267149 A CN107267149 A CN 107267149A CN 201610217246 A CN201610217246 A CN 201610217246A CN 107267149 A CN107267149 A CN 107267149A
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Abstract
The invention discloses a kind of red up-conversion luminescence nanomaterial, it includes nano-crystal with core-shell structure, and the nano-crystal with core-shell structure has by rare earth compound Na0.52YbF3.52:Er3+The core of composition and by SrF2The shell of composition, the nano-crystal with core-shell structure has pure cubic structure phase.The invention also discloses the preparation method of the red up-conversion luminescence nanomaterial.The nano material good dispersion of the present invention, shape are homogeneous, with efficient red Upconversion luminescence and excellent nuclear magnetic resonance performance and CT performances, it is expected to be more widely used in the biomarker and therapeutic field of tumor of Form, and its preparation technology also has simple easily implementation, cost is low, yield is high, produce many advantages, such as being easy to amplification.
Description
Technical field
Present invention relates particularly to a kind of high efficiency red up-conversion luminescence nanomaterial and preparation method thereof, belong to luminous and led with Detection Techniques
Domain.
Background technology
Up-conversion luminescent material refers to but send the material of the photon of higher-energy when material absorbs energy relatively low photon.Pass through
The rare earth ion up-conversion luminescence that near-infrared is excited is because with tissue penetration is strong, stable luminescence, toxicity is low and background noise is small etc.
Advantage, has huge potential using value in terms of bioluminescence imaging, fluoroscopic examination.Due to abundant energy level, rare earth
Up-conversion luminescent material emission spectrum extends near infrared spectrum from VUV, shows abundant and unique optical spectra and hair
Light characteristic.Wherein, many rare earth ions have excellent magnetic property and X-ray attenuation performance again, and rare earth luminous nano material is used
The concern of more and more people is attracted in multi-functional biomarker.Green luminescence, near infrared light (700-1100 are arrived compared to ultraviolet
Nm) and feux rouges (600-700nm) is referred to as " optical window " of biological tissue, exciting light and transmitting light are respectively positioned on biological tissue
" optical window ", biological tissue is absorbed to it, scattered, autofluorescence etc. is greatly reduced, and contributes to rare earth upconversion nano material
Bio-imaging and oncotherapy applied to Form.In recent years, receiving for emitting red light is changed on the rare earth excited based on near-infrared
Rice material has been reported.However, the magnetic of intensity, purity and the rare earth nano material of existing upper conversion emitting red light in itself
Further raising can be still needed to CT performances.How to obtain and have efficient upper conversion imaging, Magnetic resonance imaging, CT imaging performances concurrently
Material, be still industry problem urgently to be resolved hurrily with the depth for realizing tumour, accurate treatment.
The content of the invention
In view of the shortcomings of the prior art, it is a primary object of the present invention to provide a kind of red up-conversion luminescence nanometer material of efficient stable
Material and preparation method thereof.
To realize aforementioned invention purpose, present invention employs following technical scheme：
The embodiments of the invention provide a kind of red up-conversion luminescence nanomaterial, it includes nano-crystal with core-shell structure, the nucleocapsid knot
Structure is nanocrystalline to be had by rare earth compound Na0.52YbF3.52:Er3+The core of composition and by SrF2The shell of composition, the nuclear shell structure nano
Crystalline substance has pure cubic structure phase.
Further, it is described it is nanocrystalline be hexagon nuclear shell structure nano piece that average grain diameter is 25~30nm, its center is averaged
Particle diameter is 20~25nm.
Further, it is described it is nanocrystalline can be in wavelength under 915nm light irradiation, in real in 625~700nm wavelength bands
Existing red up-conversion luminescence.
The embodiments of the invention provide a kind of preparation method of red up-conversion luminescence nanomaterial, it includes：
(1) rare earth hybrid ionic salt is mixed with ethanol, water, oleic acid and sodium hydroxide, is subsequently added NH4F, 160~
200 DEG C of reaction more than 2h, are obtained by rare earth compound Na0.52YbF3.52:Er3+What is constituted is nanocrystalline, described nanocrystalline with pure cube
Structure phase；
(2) mixed nanocrystalline made from step (1) with oleic acid and octadecylene, then add trifluoroacetic acid strontium, in 270~
290 DEG C of 1~1.5h of reaction, obtain the nano-crystal with core-shell structure with pure cubic structure phase, and the nano-crystal with core-shell structure has by dilute
Earth compounds Na0.52YbF3.52:Er3+The core of composition and by SrF2The shell of composition.
Compared with prior art, the present invention at least has following good effect：
(1) the red up-conversion luminescence rare earth nano material good dispersion, shape are homogeneous, special with high efficiency red up-conversion luminescence
Property, Na0.52YbF3.52:Er3+Red light-emitting intensity be β-NaYF4:Yb3+/Er3+2.1 times of green luminescence intensity,
Na0.52YbF3.52:Er3+Feux rouges and the strength ratio of green glow reached 20.5, far above NaYb4:Er3+Feux rouges and green glow strength ratio
(3.8), growth core shell structure obtains nanocrystalline Na0.52YbF3.52:Er3+@SrF2Afterwards, the intensity of upper conversion emitting red light is improved again
17 times, while its material is in itself again with excellent nuclear magnetic resonance performance and CT performances, it is expected to Form biomarker and
Therapeutic field of tumor is more widely used；
(2) preparation technology of the red up-conversion luminescence rare earth nano material has simple easily implementation, cost is low, yield is high, production
Many advantages, such as being easy to amplification.
Brief description of the drawings
Fig. 1 a and Fig. 1 b are to obtain Na in the embodiment of the present invention 10.52YbF3.52:Er3+Nanocrystalline and Na0.52YbF3.52:Er3+@SrF2Nanometer
Brilliant transmission electron microscope bright field image photo.
Fig. 2 is to obtain Na in the embodiment of the present invention 10.52YbF3.52:Er3+Nanocrystalline and Na0.52YbF3.52:Er3+@SrF2Nanocrystalline XRD
Diffracting spectrum.
Fig. 3 is to obtain Na in the embodiment of the present invention 10.52YbF3.52:Er3+Nanocrystalline and Na0.52YbF3.52:Er3+@SrF2Nanocrystalline
Up-conversion luminescence spectrogram.
Fig. 4 is to obtain Na in the embodiment of the present invention 10.52YbF3.52:Er3+It is nanocrystalline with concentration hexagonal phase β-NaYF4:Yb3+/Er3+Receive
The comparison figure of meter Jing up-conversion luminescence spectrum.
Embodiment
In view of deficiency of the prior art, inventor is able to propose the technical side of the present invention through studying for a long period of time and largely putting into practice
Case.The technical scheme, its implementation process and principle etc. will be further explained as follows.
The one side of the embodiment of the present invention provides a kind of red up-conversion luminescence nanomaterial, and it includes nano-crystal with core-shell structure,
The nano-crystal with core-shell structure has by rare earth compound Na0.52YbF3.52:Er3+The core of composition and by SrF2The shell of composition.
Further, shown by powder x-ray diffraction analysis and transmission electron microscope observation, the nano-crystal with core-shell structure tool
There is pure cubic structure phase.
Further, it is described it is nanocrystalline be hexagon nuclear shell structure nano piece that average grain diameter is 25~30nm, its center is averaged
Particle diameter is 20~25nm.
Further, it is described it is nanocrystalline can wavelength for 915nm light irradiation under, in 625-700nm wavelength bands realize
Red up-conversion luminescence.
The one side of the embodiment of the present invention additionally provides a kind of preparation method of red up-conversion luminescence nanomaterial, and it includes：
(1) rare earth hybrid ionic salt is mixed with ethanol, water, oleic acid and sodium hydroxide, is subsequently added NH4F, 160~
200 DEG C of reaction more than 2h, are obtained by rare earth compound Na0.52YbF3.52:Er3+What is constituted is nanocrystalline, described nanocrystalline with pure cube
Structure phase；
(2) mixed nanocrystalline made from step (1) with oleic acid and octadecylene, fluoroacetic acid strontium is then added, in 270~290 DEG C
1~1.5h is reacted, the nano-crystal with core-shell structure with pure cubic structure phase is obtained, the nano-crystal with core-shell structure has by rare earth chemical combination
Thing Na0.52YbF3.52:Er3+The core of composition and by SrF2The shell of composition.
More preferred, step (1) includes：Rare earth hybrid ionic salting liquid is dissolved in water and forms transparent settled solution, second is added
Alcohol, water, the mixed liquor of oleic acid and sodium hydroxide, make in the mixed system to be formed aqueous, ethanol, the volume ratio of oleic acid be
1:2:4, and the concentration of sodium hydroxide is 0.015~0.03g/mL in the mixed system, being then added dropwise to concentration is
0.8~1.2mol/L ammonium fluoride aqueous solution, is sufficiently stirred for, and reacts 2~24h at 160~200 DEG C, then isolates solid-state therein
Product, after scrubbed, drying, is obtained described nanocrystalline.
More preferred, step (2) includes：It is sufficiently mixed nanocrystalline made from step (1) with oleic acid, octadecylene, then
Trifluoroacetic acid strontium is added, the nanocrystalline mol ratio with trifluoroacetic acid strontium is 1：0.5~2, afterwards 280~290 DEG C be incubated 1~
1.5h, isolates solid product therein, the nano-crystal with core-shell structure is obtained after scrubbed, drying.
Further, the preparation method includes：After solid product is washed with ethanol and hexamethylene mixed liquor, in 80 DEG C of drying.
Further, the rare earth hybrid ionic salt includes the nitrate containing rare earth element (such as, but not limited to Yb, Er), chlorination
Silver or acetate.
The present invention is with NaxYbF3+xNanocrystalline is rear-earth-doped matrix material, by rare earth ion Yb3+And F-The regulation and control of concentration ratio are real
Now to NaxYbF3+xNanocrystalline luminescent spectrum is regulated and controled in optical window wave band, has been finally given and has been changed in the red with high-purity
Luminous rare-earth nano-crystal Na0.52YbF3.52:Er3+.And then strengthen the principle of up-conversion luminescence using core shell structure, it is nanocrystalline in gained
Outgrowth SrF2Shell, has obtained highly efficient red up-conversion luminescence nanometer crystal Na0.52YbF3.52:Er3+@SrF2。
In a typical embodiments, the preparation method includes：The first step is that rare earth hybrid ionic salt is added into ethanol, water, oil
In the mixed liquor of acid and sodium hydroxide, ammonium fluoride aqueous solution is then added dropwise to, solvent thermal reaction is finally carried out at a certain temperature appropriate
Time, obtain the uniform hexagon piece of size dimension.Second step is by the nanocrystalline and oleic acid obtained by the first step, octadecylene and three
Fluoroacetic acid strontium is mixed, and pyrolysis appropriate time is carried out at a certain temperature, the nano-crystal with core-shell structure needed for obtaining.
In one more specifically embodiment, the preparation method can include：According to mol ratio Yb3+:Er3+=0.98:0.02 configuration is dilute
Native hybrid ionic salt, is added to 3mL deionized waters, and stirring is formed after transparent settled solution, is added dropwise to 10mL ethanol, 2mL
In the mixed liquor of deionized water, 20mL oleic acid and 0.6g sodium hydroxides, 1.0mol/L ammonium fluoride aqueous solution 4mL is then added dropwise to,
It is moved into after being sufficiently stirred in 50mL water heating kettles, finally carries out solvent thermal reaction at a temperature of 160~200 DEG C, soaking time is 2~
24h.After products therefrom is washed with ethanol and hexamethylene mixed liquor, Na is obtained after being dried in 80 DEG C0.52YbF3.52:Er3+It is nanocrystalline.
Then it is added to gained is nanocrystalline in the mixed solution of 10mL oleic acid and 10mL octadecylenes, adds a certain amount of trifluoroacetic acid strontium,
Na0.52YbF3.52:Er3+The nanocrystalline mol ratio with trifluoroacetic acid strontium is 1:0.5~2, heat point is finally carried out at a temperature of 280~290 DEG C
Solution reaction, soaking time is 1~1.5h.After products therefrom is washed with ethanol and hexamethylene mixed liquor, obtained after being dried in 80 DEG C
Na0.52YbF3.52:Er3+@SrF2It is nanocrystalline.
The preparation method of the present invention has the advantages that technique is simple, cost is low, yield is high, production is easy to amplification, and obtained product point
Scattered property is good, shape is homogeneous, with high efficiency red Upconversion luminescence, while there is excellent nuclear magnetic resonance performance and CT performances,
It is expected to be used widely in the biomarker and therapeutic field of tumor of Form, below in conjunction with some embodiments and accompanying drawing to this hair
Bright technical scheme is further described.
0.98mmol ytterbium nitrates and 0.02mmol erbium nitrates are added in 3mL deionized waters by embodiment 1, and stirring forms transparent clear
After clear solution, in the mixed liquor for being added dropwise to 10mL ethanol, 2mL deionized waters, 20mL oleic acid and 0.6g sodium hydroxides,
1.0mol/L ammonium fluoride aqueous solution 4mL is then added dropwise to, is moved into after being sufficiently stirred in 50mL water heating kettles, finally at 200 DEG C
At a temperature of carry out solvent thermal reaction, soaking time is 8 hours.After products therefrom is washed with ethanol and hexamethylene mixed liquor, in
Na is obtained after 80 DEG C of drying0.52YbF3.52:Er3+It is nanocrystalline.Then the Na obtained by 0.5mmol is taken0.52YbF3.52:Er3+It is nanocrystalline, with
0.5mmol trifluoroacetic acids strontium is mixed, and in the mixed solution for being added to 10mL oleic acid and 10mL octadecylenes, is entered at a temperature of 280 DEG C
Row pyrolysis, soaking time is 1 hour.After products therefrom is washed with ethanol and hexamethylene mixed liquor, after 80 DEG C dry
Obtain Na0.52YbF3.52:Er3+@SrF2It is nanocrystalline.
0.98mmol ytterbium nitrates and 0.02mmol erbium nitrates are added in 3mL deionized waters by embodiment 2, and stirring forms transparent clear
After clear solution, in the mixed liquor for being added dropwise to 10mL ethanol, 2mL deionized waters, 20mL oleic acid and 0.6g sodium hydroxides,
1.0mol/L ammonium fluoride aqueous solution 4mL is then added dropwise to, is moved into after being sufficiently stirred in 50mL water heating kettles, finally at 200 DEG C
At a temperature of carry out solvent thermal reaction, soaking time is 16 hours.After products therefrom is washed with ethanol and hexamethylene mixed liquor, in
Na is obtained after 80 DEG C of drying0.52YbF3.52:Er3+It is nanocrystalline.Then the Na obtained by 0.5mmol is taken0.52YbF3.52:Er3+It is nanocrystalline, with
0.5mmol trifluoroacetic acids strontium is mixed, and in the mixed solution for being added to 10mL oleic acid and 10mL octadecylenes, is entered at a temperature of 280 DEG C
Row pyrolysis, soaking time is 1 hour.After products therefrom is washed with ethanol and hexamethylene mixed liquor, after 80 DEG C dry
Obtain Na0.52YbF3.52:Er3+@SrF2It is nanocrystalline.
0.98mmol ytterbium nitrates and 0.02mmol erbium nitrates are added in 3mL deionized waters by embodiment 3, and stirring forms transparent clear
After clear solution, in the mixed liquor for being added dropwise to 10mL ethanol, 2mL deionized waters, 20mL oleic acid and 0.6g sodium hydroxides,
1.0mol/L ammonium fluoride aqueous solution 4mL is then added dropwise to, is moved into after being sufficiently stirred in 50mL water heating kettles, finally at 200 DEG C
At a temperature of carry out solvent thermal reaction, soaking time is 24 hours.After products therefrom is washed with ethanol and hexamethylene mixed liquor, in
Na is obtained after 80 DEG C of drying0.52YbF3.52:Er3+It is nanocrystalline.Then the Na obtained by 0.5mmol is taken0.52YbF3.52:Er3+It is nanocrystalline, with
0.5mmol trifluoroacetic acids strontium is mixed, and in the mixed solution for being added to 10mL oleic acid and 10mL octadecylenes, is entered at a temperature of 280 DEG C
Row pyrolysis, soaking time is 1 hour.After products therefrom is washed with ethanol and hexamethylene mixed liquor, after 80 DEG C dry
Obtain Na0.52YbF3.52:Er3+@SrF2It is nanocrystalline.
0.98mmol ytterbium nitrates and 0.02mmol erbium nitrates are added in 3mL deionized waters by embodiment 4, and stirring forms transparent clear
After clear solution, in the mixed liquor for being added dropwise to 10mL ethanol, 2mL deionized waters, 20mL oleic acid and 0.6g sodium hydroxides,
1.0mol/L ammonium fluoride aqueous solution 4mL is then added dropwise to, is moved into after being sufficiently stirred in 50mL water heating kettles, finally at 200 DEG C
At a temperature of carry out solvent thermal reaction, soaking time is 2 hours.After products therefrom is washed with ethanol and hexamethylene mixed liquor, in
Na is obtained after 80 DEG C of drying0.52YbF3.52:Er3+It is nanocrystalline.Then the Na obtained by 0.5mmol is taken0.52YbF3.52:Er3+It is nanocrystalline, with
0.5mmol trifluoroacetic acids strontium is mixed, and in the mixed solution for being added to 10mL oleic acid and 10mL octadecylenes, is entered at a temperature of 280 DEG C
Row pyrolysis, soaking time is 1 hour.After products therefrom is washed with ethanol and hexamethylene mixed liquor, after 80 DEG C dry
Obtain Na0.52YbF3.52:Er3+@SrF2It is nanocrystalline.
0.98mmol ytterbium nitrates and 0.02mmol erbium nitrates are added in 3mL deionized waters by embodiment 5, and stirring forms transparent clear
After clear solution, in the mixed liquor for being added dropwise to 10mL ethanol, 2mL deionized waters, 20mL oleic acid and 0.6g sodium hydroxides,
1.0mol/L ammonium fluoride aqueous solution 4mL is then added dropwise to, is moved into after being sufficiently stirred in 50mL water heating kettles, finally at 180 DEG C
At a temperature of carry out solvent thermal reaction, soaking time is 8 hours.After products therefrom is washed with ethanol and hexamethylene mixed liquor, in
Na is obtained after 80 DEG C of drying0.52YbF3.52:Er3+It is nanocrystalline.Then the Na obtained by 0.5mmol is taken0.52YbF3.52:Er3+It is nanocrystalline, with
0.5mmol trifluoroacetic acids strontium is mixed, and in the mixed solution for being added to 10mL oleic acid and 10mL octadecylenes, is entered at a temperature of 280 DEG C
Row pyrolysis, soaking time is 1 hour.After products therefrom is washed with ethanol and hexamethylene mixed liquor, after 80 DEG C dry
Obtain Na0.52YbF3.52:Er3+@SrF2It is nanocrystalline.
0.98mmol ytterbium nitrates and 0.02mmol erbium nitrates are added in 3mL deionized waters by embodiment 6, and stirring forms transparent clear
After clear solution, in the mixed liquor for being added dropwise to 10mL ethanol, 2mL deionized waters, 20mL oleic acid and 0.6g sodium hydroxides,
1.0mol/L ammonium fluoride aqueous solution 4mL is then added dropwise to, is moved into after being sufficiently stirred in 50mL water heating kettles, finally at 160 DEG C
At a temperature of carry out solvent thermal reaction, soaking time is 8 hours.After products therefrom is washed with ethanol and hexamethylene mixed liquor, in
Na is obtained after 80 DEG C of drying0.52YbF3.52:Er3+It is nanocrystalline.Then the Na obtained by 0.5mmol is taken0.52YbF3.52:Er3+It is nanocrystalline, with
0.5mmol trifluoroacetic acids strontium is mixed, and in the mixed solution for being added to 10mL oleic acid and 10mL octadecylenes, is entered at a temperature of 280 DEG C
Row pyrolysis, soaking time is 1 hour.After products therefrom is washed with ethanol and hexamethylene mixed liquor, after 80 DEG C dry
Obtain Na0.52YbF3.52:Er3+@SrF2It is nanocrystalline.
0.98mmol ytterbium nitrates and 0.02mmol erbium nitrates are added in 3mL deionized waters by embodiment 7, and stirring forms transparent clear
After clear solution, in the mixed liquor for being added dropwise to 10mL ethanol, 2mL deionized waters, 20mL oleic acid and 0.6g sodium hydroxides,
1.0mol/L ammonium fluoride aqueous solution 4mL is then added dropwise to, is moved into after being sufficiently stirred in 50mL water heating kettles, finally at 200 DEG C
At a temperature of carry out solvent thermal reaction, soaking time is 8 hours.After products therefrom is washed with ethanol and hexamethylene mixed liquor, in
Na is obtained after 80 DEG C of drying0.52YbF3.52:Er3+It is nanocrystalline.Then the Na obtained by 0.5mmol is taken0.52YbF3.52:Er3+It is nanocrystalline, with
0.25mmol trifluoroacetic acids strontium is mixed, in the mixed solution for being added to 10mL oleic acid and 10mL octadecylenes, at a temperature of 280 DEG C
Pyrolysis is carried out, soaking time is 1 hour.After products therefrom is washed with ethanol and hexamethylene mixed liquor, in 80 DEG C of drying
After obtain Na0.52YbF3.52:Er3+@SrF2It is nanocrystalline.
0.98mmol ytterbium nitrates and 0.02mmol erbium nitrates are added in 3mL deionized waters by embodiment 8, and stirring forms transparent clear
After clear solution, in the mixed liquor for being added dropwise to 10mL ethanol, 2mL deionized waters, 20mL oleic acid and 0.6g sodium hydroxides,
1.0mol/L ammonium fluoride aqueous solution 4mL is then added dropwise to, is moved into after being sufficiently stirred in 50mL water heating kettles, finally at 200 DEG C
At a temperature of carry out solvent thermal reaction, soaking time is 8 hours.After products therefrom is washed with ethanol and hexamethylene mixed liquor, in
Na is obtained after 80 DEG C of drying0.52YbF3.52:Er3+It is nanocrystalline.Then the Na obtained by 0.5mmol is taken0.52YbF3.52:Er3+It is nanocrystalline, with
1.0mmol trifluoroacetic acids strontium is mixed, and in the mixed solution for being added to 10mL oleic acid and 10mL octadecylenes, is entered at a temperature of 280 DEG C
Row pyrolysis, soaking time is 1 hour.After products therefrom is washed with ethanol and hexamethylene mixed liquor, after 80 DEG C dry
Obtain Na0.52YbF3.52:Er3+@SrF2It is nanocrystalline.
0.98mmol ytterbium nitrates and 0.02mmol erbium nitrates are added in 3mL deionized waters by embodiment 9, and stirring forms transparent clear
After clear solution, in the mixed liquor for being added dropwise to 10mL ethanol, 2mL deionized waters, 20mL oleic acid and 0.6g sodium hydroxides,
1.0mol/L ammonium fluoride aqueous solution 4mL is then added dropwise to, is moved into after being sufficiently stirred in 50mL water heating kettles, finally at 200 DEG C
At a temperature of carry out solvent thermal reaction, soaking time is 8 hours.After products therefrom is washed with ethanol and hexamethylene mixed liquor, in
Na is obtained after 80 DEG C of drying0.52YbF3.52:Er3+It is nanocrystalline.Then the Na obtained by 0.5mmol is taken0.52YbF3.52:Er3+It is nanocrystalline, with
0.5mmol trifluoroacetic acids strontium is mixed, and in the mixed solution for being added to 10mL oleic acid and 10mL octadecylenes, is entered at a temperature of 280 DEG C
Row pyrolysis, soaking time is 1.5 hours.After products therefrom is washed with ethanol and hexamethylene mixed liquor, in 80 DEG C of drying
After obtain Na0.52YbF3.52:Er3+@SrF2It is nanocrystalline.
0.98mmol ytterbium nitrates and 0.02mmol erbium nitrates are added in 3mL deionized waters by embodiment 10, and stirring forms transparent
After settled solution, the mixed liquor of 10mL ethanol, 2mL deionized waters, 20mL oleic acid and 0.6g sodium hydroxides is added dropwise to
In, 1.0mol/L ammonium fluoride aqueous solution 4mL is then added dropwise to, is moved into 50mL water heating kettles, finally exists after being sufficiently stirred for
Solvent thermal reaction is carried out at a temperature of 200 DEG C, soaking time is 8 hours.After products therefrom is washed with ethanol and hexamethylene mixed liquor,
Na is obtained after being dried in 80 DEG C0.52YbF3.52:Er3+It is nanocrystalline.Then the Na obtained by 0.5mmol is taken0.52YbF3.52:Er3+It is nanocrystalline, with
0.5mmol trifluoroacetic acids strontium is mixed, and in the mixed solution for being added to 10mL oleic acid and 10mL octadecylenes, is entered at a temperature of 290 DEG C
Row pyrolysis, soaking time is 1 hour.After products therefrom is washed with ethanol and hexamethylene mixed liquor, after 80 DEG C dry
Obtain Na0.52YbF3.52:Er3+@SrF2It is nanocrystalline.
Pattern, thing phase and the light conversion properties of the obtained product of embodiment 1 can see Fig. 1-Fig. 3, and 2~embodiment of embodiment 10 obtains production
Thing also has the pattern and performance close with the embodiment 1.
β-the NaYF of comparative example 14:Yb3+/Er3+Nanocrystalline, preparation is comprised the following steps that：
0.80mmol yttrium chlorides, 0.18mmol ytterbium chlorides and 0.02mmol erbium chlorides are added to the mixed of 6mL oleic acid and 15mL octadecylenes
Close in solution, 150 DEG C of insulation 1h, untill the mixed solution for forming fully transparent clarification, are cooled to room temperature under the atmosphere of nitrogen,
Then the methanol mixed solution of 4mmol ammonium fluorides and 2.5mmol sodium hydroxides is slowly added dropwise, first 70 DEG C are incubated 20min, then 120 DEG C
10min is incubated, finally 310 DEG C of insulation reaction 1h under nitrogen atmosphere.Reaction adds ethanol that product is collected by centrifugation after terminating, and gained is produced
After thing is washed with ethanol and hexamethylene mixed liquor, in 80 DEG C of drying, NaYF is obtained4:Yb3+/Er3+It is nanocrystalline.NaYF4:Yb3+/Er3+
Be upper conversion nano it is brilliant in classical efficient up-conversion luminescence nanometer crystal, with efficient upper conversion green emitting, but with
Na0.52YbF3.52:Er3+Compare, thereon change green intensity be only Na0.52YbF3.52:Er3+The 1/2.1 of upper conversion red light intensity.
α-the NaYbF of comparative example 24:Er3+Nanocrystalline, preparation is comprised the following steps that：
By 0.98mmol trifluoroacetic acids ytterbium, 0.02mmol trifluoroacetic acids erbium and 1.0mmol sodium trifluoroacetates be added to 10mL oleic acid and
In 10mL octadecylenes, the heating stirring under the atmosphere of nitrogen is first incubated 1h, to the solution for obtaining fully transparent clarification at 120 DEG C
Untill, then it is to slowly warm up to 300 DEG C, insulation reaction 1h.After cooling down to room temperature, plus ethanol is collected by centrifugation, by products therefrom
Washed with ethanol and hexamethylene mixed liquor, α-NaYbF are obtained after being dried in 80 DEG C4:Er3+It is nanocrystalline.α-NaYbF4:Er3+Nanocrystalline
Upper conversion emitting red light, into 3.8, is far below and Na with the upper strength ratio for changing green emitting0.52YbF3.52:Er3+Upper conversion feux rouges with it is green
Light strength ratio (being 20.5) and Na0.52YbF3.52:Er3+@SrF2Upper change feux rouges and green intensity ratio (into 5.8).
It should be appreciated that the technical concepts and features of above-described embodiment only to illustrate the invention, its object is to allow be familiar with technique
Personage can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is all smart according to the present invention
The equivalent change or modification that refreshing essence is made, should all be included within the scope of the present invention.
Claims (8)
1. a kind of red up-conversion luminescence nanomaterial, it is characterised in that comprising nano-crystal with core-shell structure, the nano-crystal with core-shell structure
With by rare earth compound Na0.52YbF3.52:Er3+The core of composition and by SrF2The shell of composition, the nano-crystal with core-shell structure has pure
Cubic structure phase.
2. red up-conversion luminescence nanomaterial according to claim 1, it is characterised in that：It is described it is nanocrystalline be that average grain diameter is
25~30nm hexagon nuclear shell structure nano piece, the average grain diameter of its center is 20~25nm.
3. red up-conversion luminescence nanomaterial according to claim 1 or 2, it is characterised in that：It is described it is nanocrystalline can be
Under wavelength irradiates for 915nm light, in the red up-conversion luminescence of realization in 625~700nm wavelength bands.
4. a kind of preparation method of red up-conversion luminescence nanomaterial, it is characterised in that including：
(1) rare earth hybrid ionic salt is mixed with ethanol, water, oleic acid and sodium hydroxide, is subsequently added NH4F, 160~
200 DEG C of reaction more than 2h, are obtained by rare earth compound Na0.52YbF3.52:Er3+What is constituted is nanocrystalline, described nanocrystalline with pure cube
Structure phase；
(2) mixed nanocrystalline made from step (1) with oleic acid and octadecylene, then add trifluoroacetic acid strontium, in 270~
290 DEG C of 1~1.5h of reaction, obtain the nano-crystal with core-shell structure with pure cubic structure phase, and the nano-crystal with core-shell structure has by dilute
Earth compounds Na0.52YbF3.52:Er3+The core of composition and by SrF2The shell of composition.
5. the preparation method of red up-conversion luminescence nanomaterial according to claim 4, it is characterised in that step (1)
Including：Rare earth hybrid ionic salting liquid is dissolved in water and forms transparent settled solution, ethanol, water, oleic acid and sodium hydroxide is added
Mixed liquor, make in the mixed system to be formed aqueous, ethanol, the volume ratio of oleic acid be 1:2:4, and the hydrogen-oxygen in the mixed system
The concentration for changing sodium is 0.015~0.03g/mL, is then added dropwise to the ammonium fluoride aqueous solution that concentration is 0.8~1.2mol/L, fully stirs
Mix, and in 160~200 DEG C of 2~24h of reaction, then solid product therein is isolated, after scrubbed, drying, obtain the nanometer
It is brilliant.
6. the preparation method of red up-conversion luminescence nanomaterial according to claim 4, it is characterised in that step (2) is wrapped
Include：Be sufficiently mixed nanocrystalline made from step (1) with oleic acid, octadecylene, then add trifluoroacetic acid strontium, it is described it is nanocrystalline with
The mol ratio of trifluoroacetic acid strontium is 1：0.5~2,1~1.5h is incubated at 280~290 DEG C afterwards, solid product therein is isolated,
The nano-crystal with core-shell structure is obtained after scrubbed, dry.
7. the preparation method of the red up-conversion luminescence nanomaterial according to claim 5 or 6, it is characterised in that including：Will
After solid product is with ethanol and the washing of hexamethylene mixed liquor, in 80 DEG C of drying.
8. the preparation method of the red up-conversion luminescence nanomaterial according to any one of claim 4-5, it is characterised in that：
The rare earth hybrid ionic salt include the nitrate containing rare earth element, chlorate or acetate, the rare earth element include Yb and
Er。
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