CN109722247A - A kind of doping Fe3+The NaYF of ion4:Yb3+,Er3+The preparation method of upconversion fluorescence nano material - Google Patents
A kind of doping Fe3+The NaYF of ion4:Yb3+,Er3+The preparation method of upconversion fluorescence nano material Download PDFInfo
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Abstract
The invention discloses a kind of doping Fe3+The NaYF of ion4:Yb3+,Er3+The preparation method of upconversion fluorescence nano material, steps are as follows: sodium hydroxide, oleic acid and dehydrated alcohol mixing are generated the viscous solution of white by a.；B. NaF solution is added while stirring to above-mentioned solution, until forming translucent solution；C. respectively by Y (NO3)3·6H2O、Yb(NO3)3·5H2O、Er(NO3)3·5H2O、FeCl3·6H2Above-mentioned translucent solution is added while stirring and continues to stir for O solution；D. step c is prepared liquid to be transferred in polytetrafluoroethylene (PTFE) hydro-thermal autoclave, continuous heating under high temperature；E. cooling to reaction kettle, centrifugation washs precipitating with hexamethylene and dehydrated alcohol, and precipitating is dissolved in hexamethylene；F. step e acquired solution is centrifuged, drying.The present invention enriches the structure and drug loading space of nanoparticle, provides theoretical and experimental basis for the building of further probe and anticancer drug targeted delivery.
Description
Technical field
It is specifically a kind of by adulterating various concentration Fe the present invention relates to field of light emitting materials3+Ion regulation NaYF4:Yb3 +,Er3+The method of upconversion fluorescence nano material pattern and performance.
Background technique
Up-conversion nanoparticles (UCNPs) are the unique optical nano materials of one kind for adulterating lanthanide ion, by being mixed
There are a large amount of electron transitions, these nanoparticles can be by two or more low energy light in the 4f electron shell of miscellaneous lanthanide ion
A high-energy photon is converted on son.In the past decade, this unique anti-Stokes optics characteristic has been widely applied
Drug conveying, solar battery and super-resolution microscope etc. are triggered with various fields, including bio-sensing, light.
In fluoride, oxide, in the material of main parts such as vanadate and chloride, hexagonal phase NaYF4Due to its sub- energy in a low voice
Amount and low nonradiative loss and be considered as most effective material of main part, and be widely studied.In most cases,
Yb3+Ion is chosen as sensitizer, because it has single, relatively strong transition in visible light/near infrared spectrum.This
Outside,2F7/2→2F5/2Energy level transition be well matched with several electron transitions in common activator[1].There are many researchs will
Yb3+Ion is in conjunction with transition metal ions, and codope is into various main bodys[2], to realize the green strengthened[3], red[4]With it is white
Color[5]Up-conversion luminescence.Electronics residence time in the metastable intermediate of excitation is longer, it is more possible to by incident photon
Or nearby the energy transfer of ion excites again.Therefore, Er3+, Tm3+And Ho3+Ion due to Yb3+Resonance match and have
The intermediate excitation state of long-life is often used as activator.Wherein, Er3+Ion has more than four transition energy levels, and energy is close
10,200cm-1(980nm), to several specific wavelengths positioned at infrared region, there are stronger absorptions, and its green fluorescence has
Higher quenching concentration, therefore, Er3+Ion is to realize the infrared important activator to visible up-conversion fluorescence and laser material.
NaYF4: Yb, Er are as the most common rear-earth-doped up-conversion nano material, the nano particle of various patterns and and other materials
Complex be widely used in various fields.
Up-conversion nano material with the excellent characteristics of luminescence, high-resolution and sensitivity and its exciting light in addition to being located at
The characteristics of biological tissue " optical window " range, is expected to become luminescence imaging technology in next-generation organism.Moreover, and its
Outstanding physicochemical property provides possibility for multi-modality imaging.Such as in the synthesis process, by the way that by Gd, Sm, Fe etc. are different first
Element is doped in UCNPs structure or binding fluorescent dyes, iron oxide, gold nano, can make fluorescence imaging and other imaging technique phases
In conjunction with prepared UCNP also has the function of more multi-modality imagings.These compound UCNPs can be realized computerized tomography
It scans (CT), Magnetic resonance imaging (MRI), single-photon emission tomography (SPECT), positron emission computerized tomography (PET)
Equal multi-modality imagings.Multi-modal imaging compensates for the not foot point of independent UCL imaging, for more comprehensively, more accurately bio-imaging mentions
Possibility has been supplied, the research hotspot of diagnosis is become.
Mao etc.[6]By in NaYF4: various concentration Li is adulterated in Yb, Er crystal+And K+Ion discovery, with NaYF4:
Li in Yb, Er crystal+The increase of ion dose, their form become polyhedron, and the UC emissive porwer of crystal from stick to disk
It reduces.And adulterate K+The NaYF of ion4: the form of Yb, Er crystal keeps rodlike, and with K+The increase of ion, the UC hair of crystal
Penetrate intensity increase, it was demonstrated that the pattern and optical characteristics of the controllable rare earth mixing with nano crystal of doping of alkali metal.This is also mentioned
Show other metal ions doping may also pattern to upper conversion nano crystal and performance there is adjustment effect.There is research will
Fe3+Codope is into NaGdF4: Yb, Er nano particle, realizing feux rouges and green emission respectively enhances 30 and 34 times[7].Usually recognize
For, compared with the substituted ion in host lattice, the Doped ions with relatively large radius preferably induce hexagonal phase structure, and compared with
Small dopant ion advantageously forms cubic phase[8].Some researches show that adulterate Fe by regulation3+The concentration of ion can change
The crystalline structure of up-conversion nano material.Such as Fe3+Concentration controls in the range of 5mol% to 20mol%, can get pure six side
The NaYF of phase4:Yb,ErNano particle.Work as Fe3+When concentration is increased to 30mol%, conversion nano particle is a cube knot on this
Structure[9].Although this research and utilization changes Fe3+The up-conversion nano material that concentration obtains is nanoparticle, but it is but effectively
Change the crystalline structure of nanoparticle.
Bibliography
[1]Gainer C F,Romanowski M.A review of synthetic methods for the
production of upconverting lanthanide nanoparticles[J].Journal of Innovative
Optical Health Sciences,2014,07(02):1330007.
[2]Suyver J F,Aebischer A,Biner D,et al.Novel materials doped with
trivalent lanthanides and transition metal ions showing near-infrared to
visible photon upconversion[J].Optical Materials,2005,27(6):1111-1130.
[3]Li Z P,Dong B,He Y Y,et al.Selective enhancement of green
upconversion emissions of Er3+:Yb3Al5O12 nanocrystals by high excited state
energy transfer with Yb3+-Mn2+ dimer sensitizing[J].Journal of Luminescence,
2012,132(7):1646-1648.
[4]Dan H K,Zhou D,Wang R,et al.Effect of Mn2+,ions on the enhancement
red upconversion emission of Mn2+/Er3+/Yb3+,tri-doped in transparent glass-
ceramics[J].Optics&Laser Technology,2014,64(6):264-268.
[5]Kong Q,Wang J,Dong X,et al.Synthesis and luminescence properties
of Yb3+-Er3+,co-doped LaOCl nanostructures[J].Journal of Materials Science,
2014,49(7):2919-2931.
[6]Mao C,Yang X,Zhao L.Simultaneous morphology control and
upconversion fluorescence enhancement of NaYF4:Yb,Er crystals through alkali
ions doping[J].Chemical Engineering Journal,2013,229:429-435.
[7]Ramasamy P,Chandra P,Rhee S W,et al.Enhanced upconversion
luminescence in NaGdF4:Yb,Er nanocrystals by Fe3+ doping and their application
in bioimaging[J].Nanoscale,2013,5.
[8]Zeng S,Yi Z,Lu W,et al.Upconversion:Simultaneous Realization of
Phase/Size Manipulation,Upconversion Luminescence Enhancement,and Blood
Vessel Imaging in Multifunctional Nanoprobes Through Transition Metal Mn2+
Doping(Adv.Funct.Mater.26/2014)[J].Advanced Functional Materials,2014,24(26):
4051-4059.
[9]Selectively enhanced red upconversion luminescence and phase/size
manipulation via Fe3+ doping in NaYF4:Yb,Er nanocrystals[J].Nanoscale,2015,7.
Summary of the invention
The invention proposes a kind of doping Fe3+The NaYF of ion4:Yb3+,Er3+The preparation side of upconversion fluorescence nano material
Method, it is intended that pass through Fe3+The different up-conversion nano material of pattern, such as nanometer rods, nano wire are prepared in the regulation of concentration, and
Performance causes one-dimensional up-conversion fluorescence nanometer material in conjunction with the characteristics of upconversion fluorescence nano material in terms of material is assigned with magnetics
Material has optics and magnetics bimodal imaging capability.
Present invention employs the following technical solutions.
A kind of doping Fe3+The NaYF of ion4:Yb3+,Er3+The preparation method of upconversion fluorescence nano material, including it is following
Step:
A. sodium hydroxide, oleic acid and ethanol solution are mixed, magnetic agitation 10-20 minutes, until it is viscous to generate white
Solution；
B. it weighs NaF solid and prepares solution, be added in the mixed solution that step a is obtained under magnetic agitation, continue magnetic force and stir
It mixes and obtains within about 10-20 minutes the translucent solution of milky；
C. Y (NO is weighed respectively3)3·6H2O、Yb(NO3)3·5H2O、Er(NO3)3·5H2O、FeCl3·6H2The preparation of O powder
Solution is added in the mixed solution that step b is obtained under magnetic agitation, continues magnetic agitation about 10-30 minutes to being completely dissolved；
D. the white suspension prepared by step c is transferred in polytetrafluoroethylene (PTFE) hydro-thermal autoclave, at 160-230 DEG C
Lower continuous heating 8-20 hours；
E. it is cooled to room temperature to polytetrafluoroethylene (PTFE) high-pressure hydrothermal reaction kettle, 2000-3000rpm is centrifuged 2-3 minutes, is used respectively
Alternately washing precipitates for hexamethylene and dehydrated alcohol, will finally be precipitated and dissolved in hexamethylene；
F. step e acquired solution 2000-3000rpm is centrifuged 2-3 minutes, obtains white precipitate and is dried, after dry
Solid powder is NaYF4:Yb3+,Er3+Upconversion fluorescence nano material.
Further, the ratio between the sodium hydroxide in step a and the amount of substance of ruthenium ion in step c are 15:1-30:1.
Further, the ratio between the sodium fluoride in step b and the amount of substance of total rare earth (TRE) ion in step c are 4:1.
Further, the ratio between amount of substance of ruthenium ion, ytterbium ion, erbium ion and iron ion is 60 in the step c:
18:2:0-80:18:2:20。
Further, the ratio between amount of substance of ruthenium ion, ytterbium ion, erbium ion and iron ion is 70 in the step c:
18:2:10, prepared nanoparticle are in corynebacterium structure.
Further, the ratio between amount of substance of ruthenium ion, ytterbium ion, erbium ion and iron ion is 80 in the step c:
18:2:0, prepared nanoparticle are in hexagonal disk-like structure.
Further, the ratio between amount of substance of ruthenium ion, ytterbium ion, erbium ion and iron ion is 60 in the step c:
18:2:20, prepared nanoparticle are in long club shaped structure structure.
Further, NaYF in the step f4:Yb3+,Er3+,Fe3+The draw ratio of up-conversion fluorescence nanometer rods is 1:2-
1:9。
Further, NaYF in the step f4:Yb3+,Er3+,Fe3+Upconversion fluorescence nano material respectively corresponds 0%,
10% and 20%Fe3+When doping, up-conversion fluorescence intensity rate are as follows: feux rouges: 1:20:29；Green light: 1:6:13.
Further, NaYF in the step f4:Yb3+,Er3+,Fe3+Upconversion fluorescence nano material respectively corresponds 10%
And 20%Fe3+When doping, saturation magnetization ratio is 3:8.
Present invention obtains following beneficial effects.
The present invention improves one step hydro thermal method, using oleic acid as surface stabilizer, passes through control sodium hydroxide and fluorine
Change sodium amount and with the substance of rare earth ion than etc. conditions achieve the purpose that change nano particle size and pattern, to close
At doping not same amount Fe3+The NaYF of ion4:Yb3+,Er3+Upconversion fluorescence nano material, and obtain hexagonal plate-like, receive
The rice different structures such as stub and nanometer rods.The luminescent material uniform particle diameter that the present invention obtains, dispersibility is preferable, and fluorescence intensity
By force, biggish surface area also provides bigger load area for further connection drug or targeting substance.In addition, the present invention changes
Hydro-thermal method after has many advantages, such as that easy to operate, process flow is short, cost is more cheap, in cell multi-modality imaging, cancer
And there is extensive clinical value in terms of the Clinics and Practices of other major diseases.
Detailed description of the invention
Fig. 1 is NaYF prepared by the embodiment of the present invention 14: 18%Yb3+, 2%Er3+, 10%Fe3+Up-conversion fluorescence nanometer rods
Transmission electron microscope photo；
Fig. 2 is NaYF prepared by the embodiment of the present invention 14: 18%Yb3+, 2%Er3+, 10%Fe3+Up-conversion fluorescence nanometer rods
X ray diffracting spectrum；
Fig. 3 is NaYF prepared by the embodiment of the present invention 1 under 980nm laser irradiation4: 18%Yb3+, 2%Er3+, 10%
Fe3+The up-conversion fluorescence spectrogram of nanometer rods；
Fig. 4 is the NaYF prepared with superconducting quantum interference device (SQUID) to the embodiment of the present invention 14: 18%Yb3+, 2%Er3+, 10%
Fe3+The magnetic result figure that up-conversion fluorescence nanometer rods measure；
Fig. 5 is NaYF prepared by the embodiment of the present invention 24: 18%Yb3+, 2%Er3+Up-conversion fluorescence nanometer plate transmission electron microscope
Photo；
Fig. 6 is NaYF prepared by the embodiment of the present invention 24: 18%Yb3+, 2%Er3+The X-ray of up-conversion fluorescence nanometer plate is spread out
Penetrate map；
Fig. 7 is NaYF prepared by the embodiment of the present invention 2 under 980nm laser irradiation4: 18%Yb3+, 2%Er3+Nanometer plate
Up-conversion fluorescence spectrogram；
Fig. 8 is NaYF prepared by the embodiment of the present invention 34: 18%Yb3+, 2%Er3+, 20%Fe3+Up-conversion fluorescence nanometer
Stick transmission electron microscope photo；
Fig. 9 is NaYF prepared by the embodiment of the present invention 34: 18%Yb3+, 2%Er3+, 20%Fe3+Up-conversion fluorescence nanometer rods
X ray diffracting spectrum；
Figure 10 is NaYF prepared by the embodiment of the present invention 3 under 980nm laser irradiation4: 18%Yb3+, 2%Er3+, 20%
Fe3+The up-conversion fluorescence spectrogram of nanometer rods；
Figure 11 is the NaYF prepared with superconducting quantum interference device (SQUID) to the embodiment of the present invention 34: 18%Yb3+, 2%Er3+, 20%
Fe3+The magnetic result figure that up-conversion fluorescence nanometer rods measure.
Specific embodiment
Referring to the drawings and the present invention is further detailed in embodiment.
Embodiment 1
A kind of NaYF4: 18%Yb3+, 2%Er3+, 10%Fe3+The preparation method of up-conversion fluorescence nanometer rods, including it is following
Step:
A. by 0.7g sodium hydroxide, 7.95mL oleic acid and 12.66mL dehydrated alcohol as in 50mL plastic beaker, magnetic force is stirred
It mixes 20 minutes, mixes well it, until generating the viscous solution of white；
B. 0.2435g NaF solid is weighed, 10mL aqueous solution is prepared, is added what 8.3mL was obtained in step a under magnetic agitation
In mixed solution, continue to obtain the translucent solution of milky in magnetic agitation about 20 minutes；
C. Y (NO is weighed3)3·6H2O、Yb(NO3)3·5H2O、Er(NO3)3·5H2O、FeCl3·6H2O powder, makes respectively
For the aqueous solution of 1M, 1M, 0.1M, 0.2M out, take 0.84mL, 0.216mL, 0.24mL, 0.6mL that step is added under magnetic agitation respectively
In the mixed solution that rapid b is obtained, continue magnetic agitation about 20 minutes to being completely dissolved；
D. the white suspension prepared by step c is transferred in polytetrafluoroethylene (PTFE) hydro-thermal autoclave, is held at 180 DEG C
Continuous heating 12 hours；
E. it is cooled to room temperature to polytetrafluoroethylene (PTFE) high-pressure hydrothermal reaction kettle, 2000-3000rpm is centrifuged 3 minutes, uses ring respectively
Alternately washing precipitates for hexane and dehydrated alcohol, will finally be precipitated and dissolved in hexamethylene；
F. step e acquired solution 2000-3000rpm is centrifuged 3 minutes, obtains white precipitate and is dried, it is red after drying
Color solid powder is NaYF4: 18%Yb3+, 2%Er3+, 10%Fe3+Up-conversion fluorescence nanometer rods.
The NaYF that the present embodiment is prepared4: 18%Yb3+, 2%Er3+, 10%Fe3+TEM photo as shown in Figure 1, receiving
Rice corpuscles is in corynebacterium structure, and diameter about 100nm, length about 200nm, dispersibility is preferably.Fig. 2 is NaYF4: 18%Yb3+, 2%
Er3+, 10%Fe3+The XRD spectrum of nanometer rods, as shown, nano stick crystal phase structure is hexagonal phase.It is excited in 980nm near-infrared
Under, NaYF4: 18%Yb3+, 2%Er3+, 10%Fe3+Up-conversion fluorescence spectrogram as shown in figure 3, in 406-459nm, 518-
There are three up-conversion fluorescence peaks, respectively blue, green and red emission band at 598nm and 648-704nm, correspond to Er
Ion2H9/2—4I15/2、2H11/2,4S3/2—4I15/2、4F9/2—4I15/2Energy level transition, wherein green emitted peak intensity is most strong, and
Blue emission peak is most weak, and green emitted peak is about 97 times of blue emission peak, is 11 times or so of red emission peak, and undoped
Fe3+The nano particle of ion compares (embodiment 2), and green, red emissive porwer is enhanced to 6 times and 20 times respectively.It is surveyed with SQUID
NaYF4: 18%Yb3+, 2%Er3+, 10%Fe3+The hysteresis loop of nanometer rods is as shown in figure 4, as seen from the figure, which has
There is ferromagnetism, saturation magnetic intensity is about 1.5 × 10-5Emu/g, coercivity are about 11Oe.
Embodiment 2
A kind of NaYF4: 18%Yb3+, 2%Er3+The preparation method of up-conversion fluorescence nanometer plate, comprising the following steps:
A. by 0.7g sodium hydroxide, 7.95mL oleic acid and 12.66mL dehydrated alcohol as in 50mL plastic beaker, magnetic force is stirred
It mixes 20 minutes, mixes well it, until generating the viscous solution of white；
B. 0.2435g NaF solid is weighed, 10mL aqueous solution is prepared, is added what 8.3mL was obtained in step a under magnetic agitation
In mixed solution, continue to obtain the translucent solution of milky in magnetic agitation about 20 minutes；
C. Y (NO is weighed3)3·6H2O、Yb(NO3)3·5H2O、Er(NO3)3·5H2O powder, prepare respectively 1M, 1M,
The aqueous solution of 0.1M takes under magnetic agitation 0.96mL, 0.216mL, 0.24mL to be added in the mixed solution that step b is obtained respectively,
Continue magnetic agitation about 20 minutes to being completely dissolved；
D. the white suspension prepared by step c is transferred in polytetrafluoroethylene (PTFE) hydro-thermal autoclave, is held at 180 DEG C
Continuous heating 12 hours；
E. it is cooled to room temperature to polytetrafluoroethylene (PTFE) high-pressure hydrothermal reaction kettle, 2000-3000rpm is centrifuged 3 minutes, uses ring respectively
Alternately washing precipitates for hexane and dehydrated alcohol, will finally be precipitated and dissolved in hexamethylene；
F. step e acquired solution 2000-3000rpm is centrifuged 3 minutes, obtains white precipitate and is dried, it is red after drying
Color solid powder is NaYF4: 18%Yb3+, 2%Er3+Up-conversion fluorescence nanometer plate.
The NaYF that the present embodiment is prepared4: 18%Yb3+, 2%Er3+TEM photo as shown in figure 5, nanoparticle be in six
Angle disk-like structure, diameter about 200-300nm, thickness about 50-100nm, dispersibility is preferably.Fig. 6 is NaYF4: 18%Yb3+, 2%
Er3+The XRD spectrum of nanometer plate, as shown, nanometer plate crystal phase structure is hexagonal phase.Under the excitation of 980nm near-infrared, NaYF4:
18%Yb3+, 2%Er3+Up-conversion fluorescence spectrogram as shown in fig. 7, there are two at 517-602nm and 656-683nm
Up-conversion fluorescence peak, respectively green and red emission band, correspond to Er ion2H11/2,4S3/2—4I15/2、4F9/2—4I15/2's
Energy level transition, wherein green emitted peak intensity is stronger, about 34 of red emission peak times or so.
Embodiment 3
A kind of NaYF4: 18%Yb3+, 2%Er3+, 20%Fe3+The preparation method of up-conversion fluorescence nanometer rods, including it is following
Step:
A. by 0.7g sodium hydroxide, 7.95mL oleic acid and 12.66mL dehydrated alcohol as in 50mL plastic beaker, magnetic force is stirred
It mixes 20 minutes, mixes well it, until generating the viscous solution of white；
B. 0.2435g NaF solid is weighed, 10mL aqueous solution is prepared, is added what 8.3mL was obtained in step a under magnetic agitation
In mixed solution, continue to obtain the translucent solution of milky in magnetic agitation about 20 minutes；
C. Y (NO is weighed3)3·6H2O、Yb(NO3)3·5H2O、Er(NO3)3·5H2O、FeCl3·6H2O powder, makes respectively
For the aqueous solution of 1M, 1M, 0.1M, 0.2M out, take 0.72mL, 0.216mL, 0.24mL, 1.2mL that step is added under magnetic agitation respectively
In the mixed solution that rapid b is obtained, continue magnetic agitation about 20 minutes to being completely dissolved；
D. the white suspension prepared by step c is transferred in polytetrafluoroethylene (PTFE) hydro-thermal autoclave, is held at 180 DEG C
Continuous heating 12 hours；
E. it is cooled to room temperature to polytetrafluoroethylene (PTFE) high-pressure hydrothermal reaction kettle, 2000-3000rpm is centrifuged 3 minutes, uses ring respectively
Alternately washing precipitates for hexane and dehydrated alcohol, will finally be precipitated and dissolved in hexamethylene；
F. step e acquired solution 2000-3000rpm is centrifuged 3 minutes, obtains white precipitate and is dried, it is red after drying
Color solid powder is NaYF4: 18%Yb3+, 2%Er3+, 20%Fe3+Up-conversion fluorescence nanometer rods.
The NaYF that the present embodiment is prepared4: 18%Yb3+, 2%Er3+, 20%Fe3+TEM photo as shown in figure 8, receiving
Rice corpuscles is in long club shaped structure, and diameter about 50nm, length about 500nm, dispersibility is preferably.Fig. 9 is NaYF4: 18%Yb3+, 2%
Er3+, 20%Fe3+The XRD spectrum of nanometer rods, as shown, nano stick crystal phase structure is hexagonal phase.It is excited in 980nm near-infrared
Under, NaYF4: 18%Yb3+, 2%Er3+, 20%Fe3+Up-conversion fluorescence spectrogram it is as shown in Figure 10, in 406-459nm, 518-
There are three up-conversion fluorescence peaks, respectively blue, green and red emission band at 598nm and 648-704nm, correspond to Er
Ion2H9/2—4I15/2、2H11/2,4S3/2—4I15/2、4F9/2—4I15/2Energy level transition, wherein green emitted peak intensity is most strong, and
Blue emission peak is not most weak, and green emitted peak intensity is about 55 times of blue emission peak, is 16 times or so of red emission peak, and not
Adulterate Fe3+The nano particle of ion compares (embodiment 2), and green, red emissive porwer is enhanced to 13 times and 29 times respectively.With
SQUID surveys NaYF4: 18%Yb3+, 2%Er3+, 20%Fe3+The hysteresis loop of nanometer rods is as shown in figure 11, and as seen from the figure, this is received
Rice material has ferromagnetism, and saturation magnetic intensity is about 4 × 10-5Emu/g, coercivity are about 13Oe.
Claims (10)
1. a kind of doping Fe3+The NaYF of ion4:Yb3+,Er3+The preparation method of upconversion fluorescence nano material, it is characterised in that:
The following steps are included:
A. sodium hydroxide, oleic acid and ethanol solution are mixed, magnetic agitation 10-20 minutes, until generating the viscous solution of white；
B. it weighs NaF solid and prepares solution, be added in the mixed solution that step a is obtained under magnetic agitation, continue magnetic agitation about
Obtain within 10-20 minutes the translucent solution of milky；
C. Y (NO is weighed respectively3)3·6H2O、Yb(NO3)3·5H2O、Er(NO3)3·5H2O、FeCl3·6H2O powder prepares molten
Liquid is added in the mixed solution that step b is obtained under magnetic agitation, continues magnetic agitation about 10-30 minutes to being completely dissolved；
D. the white suspension prepared by step c is transferred in polytetrafluoroethylene (PTFE) hydro-thermal autoclave, is held at 160-230 DEG C
Continuous heating 8-20 hours；
E. it is cooled to room temperature to polytetrafluoroethylene (PTFE) high-pressure hydrothermal reaction kettle, 2000-3000rpm is centrifuged 2-3 minutes, uses hexamethylene respectively
Alternately washing precipitates for alkane and dehydrated alcohol, will finally be precipitated and dissolved in hexamethylene；
F. step e acquired solution 2000-3000rpm is centrifuged 2-3 minutes, obtains white precipitate and is dried, the solid after drying
Powder is NaYF4:Yb3+,Er3+Upconversion fluorescence nano material.
2. a kind of doping Fe according to claim 13+The NaYF of ion4:Yb3+,Er3+The system of upconversion fluorescence nano material
Preparation Method, it is characterised in that: the ratio between the amount of substance of ruthenium ion in sodium hydroxide and step c in step a is 15:1-30:
1。
3. a kind of doping Fe according to claim 13+The NaYF of ion4:Yb3+,Er3+The system of upconversion fluorescence nano material
Preparation Method, it is characterised in that: the ratio between the amount of substance of total rare earth (TRE) ion in sodium fluoride and step c in step b is 4:1.
4. a kind of doping Fe according to claim 13+The NaYF of ion4:Yb3+,Er3+The system of upconversion fluorescence nano material
Preparation Method, it is characterised in that: the ratio between amount of substance of ruthenium ion, ytterbium ion, erbium ion and iron ion is 60 in the step c:
18:2:0-80:18:2:20。
5. a kind of doping Fe according to claim 43+The NaYF of ion4:Yb3+,Er3+The system of upconversion fluorescence nano material
Preparation Method, it is characterised in that: the ratio between amount of substance of ruthenium ion, ytterbium ion, erbium ion and iron ion is 70 in the step c:
18:2:10, prepared nanoparticle are in corynebacterium structure.
6. a kind of doping Fe according to claim 43+The NaYF of ion4:Yb3+,Er3+The system of upconversion fluorescence nano material
Preparation Method, it is characterised in that: the ratio between amount of substance of ruthenium ion, ytterbium ion, erbium ion and iron ion is 80 in the step c:
18:2:0, prepared nanoparticle are in hexagonal disk-like structure.
7. a kind of doping Fe according to claim 43+The NaYF of ion4:Yb3+,Er3+The system of upconversion fluorescence nano material
Preparation Method, it is characterised in that: the ratio between amount of substance of ruthenium ion, ytterbium ion, erbium ion and iron ion is 60 in the step c:
18:2:20, prepared nanoparticle are in long club shaped structure structure.
8. a kind of doping Fe according to claim 13+The NaYF of ion4:Yb3+,Er3+The system of upconversion fluorescence nano material
Preparation Method, it is characterised in that: NaYF in the step f4:Yb3+,Er3+,Fe3+The draw ratio of up-conversion fluorescence nanometer rods is 1:2-
1:9。
9. a kind of doping Fe according to claim 13+The NaYF of ion4:Yb3+,Er3+The system of upconversion fluorescence nano material
Preparation Method, it is characterised in that: NaYF in the step f4:Yb3+,Er3+,Fe3+Upconversion fluorescence nano material respectively corresponds 0%,
10% and 20%Fe3+When doping, up-conversion fluorescence intensity rate are as follows: feux rouges: 1:20:29；Green light: 1:6:13.
10. a kind of doping Fe according to claim 13+The NaYF of ion4:Yb3+,Er3+Upconversion fluorescence nano material
Preparation method, it is characterised in that: NaYF in the step f4:Yb3+,Er3+,Fe3+Upconversion fluorescence nano material respectively corresponds
10% and 20%Fe3+When doping, saturation magnetization ratio is 3:8.
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