CN107033905A - A kind of rear-earth-doped lithium yttrium fluoride nano material and preparation method and application - Google Patents
A kind of rear-earth-doped lithium yttrium fluoride nano material and preparation method and application Download PDFInfo
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Abstract
The present invention relates to rear-earth-doped lithium yttrium fluoride nano material and its preparation method and application, there is upper conversion/luminous rear-earth-doped lithium yttrium fluoride nano material of lower transfer using improved high temperature Co deposited synthesis, epitaxial growth is carried out on the basis of kernel simultaneously, the individual layer core-shell structured nanomaterials being evenly coated can be made, further prepare based on many shell core-shell structure nano materials of lithium yttrium fluoride.Prepare three kinds of bill of materials good dispersions, uniform particle diameter, good luminescence properties of the present invention, after pickling processes, water miscible nano particle can be used for biological detection and bio-imaging.
Description
Technical field
The present invention relates to Study of Nanoscale Rare Earth Luminescent Materials field, more specifically lithium yttrium fluoride nano luminescent material and its system
Preparation Method and application.
Background technology
In recent years, rare earth mixing with nano luminescent material is shown in illumination, anti-fake code, information storage, opto-electronic device, too
Great application value is all shown in terms of positive energy battery and biomedicine.Rare earth mixing with nano material mainly has phosphoric acid
Salt, vanadate, oxide, sulfide and fluoride etc..Wherein, fluoride, because chemical stability is high, phonon energy is low, is one
The preferable rear-earth-doped host material of class.The research on rare-earth-doped fluoride is concentrated mainly on yttrium fluoride natrium at present
(NaYF4), gadolinium fluoride sodium (NaGdF4), lithium yttrium fluoride (LiYF4) or lithium lutetium fluoride (LiLuF4) etc. system, to lithium yttrium fluoride
(LiYbF4) research it is very few.
Lithium yttrium fluoride (the LiYbF of stoichiometric proportion4) there is Tetragonal (scheelite-type structure) crystal structure, space group is
I41/a。Yb3+It is doped to usually as sensitizer in parent lattice, to avoid influence of the concentration quenching to luminescent properties, Yb3+'s
Doping concentration is unsuitable too high, typically in up-conversion luminescent material, and its optimal doping concentration is 18~20% (molar concentrations).Make
For be both matrix composition and the Yb of sensitized ions3+Photon can not only be at utmost absorbed, energy can be made again in Yb3+Sublattice
Between migrate, promote Yb3+Energy transmission between ion and active ions, and then show different from low concentration Yb3+Doping body
The optical property and up-conversion luminescence efficiency of system.These special optical properties all make rear-earth-doped lithium yttrium fluoride nano material exist
The every field such as anti-fake code, FPD, biomedicine show potential application prospect.
At present, the synthesis of rear-earth-doped lithium yttrium fluoride nano material mainly uses solvent-thermal method and thermal decomposition method.Both
Nano particle pattern heterogeneity prepared by method, particle diameter are big, bad dispersibility, it is impossible to which meet bio-imaging and fluorescence labeling will
Ask.Further, since needing higher nucleation and crystallization temperature, traditional high temperature Co deposited synthesis can not obtain lithium yttrium fluoride and receive
Rice material.In addition, both at home and abroad, there is presently no on the rear-earth-doped lithium yttrium fluoride nano fluorescent marker material of monodisperse water soluble
Synthesis, the report of optical property and its application.
Therefore, it is still a series of for how controlling synthetic rare earth doped lithium yttrium fluoride nano material, improving its luminous efficiency etc.
Urgent problem to be solved.
The content of the invention
It is of the invention using improved high temperature Co deposited synthesis to there is upper conversion/lower transfer to light based on above mentioned problem
Rear-earth-doped lithium yttrium fluoride nano material, while carrying out extension on the basis of using rear-earth-doped lithium yttrium fluoride nano material as kernel
Growth, can be made the individual layer core-shell structured nanomaterials being evenly coated, can further prepare based on many shell cores of lithium yttrium fluoride
Shell structural nano material.The spectrum test result of product shows that the nano material luminous efficiency after cladding is substantially improved, quantum
Yield is also accordingly improved.Particularly LiYbF4:Relative intensities of the Tm in UV light region is high, can be excited as near-infrared built in
Light source nano-particle is applied to the biomedical sectors such as light-operated chemical reaction, photodynamic therapy and target drug-carrying.The present invention's
Bill of materials good dispersion, uniform particle diameter, good luminescence property, after pickling processes, available for biological detection and bio-imaging.
The present invention provides following technical scheme:
A kind of rear-earth-doped lithium yttrium fluoride nano material, consisting of:LiYb(1-x)LnxF4, wherein, Ln be selected from Ho, Er,
One or more in Tm, Tb, Eu, Ce, Sm, Dy, Nd, Pr, 0<X≤90mol%.
The present invention also provides a kind of rear-earth-doped lithium yttrium fluoride individual layer core-shell structured nanomaterials, and its chemical general formula is:
LiYb(1-x)LnxF4@LiAF4, wherein, Ln, x have definitions as described above, A be selected from Yb, Y, Ho, Er, Tm, Tb, Eu, Ce, Sm,
One or more in Dy, Nd, Pr, Gd, La, Sc, preferably A are Y or Gd.
The present invention further provides a kind of rear-earth-doped many shell core-shell structure nano materials of lithium yttrium fluoride, its chemical general formula
For:LiYb(1-x)LnxF4(@LiAF4)n, wherein, Ln, x, A have definitions as described above, and n is more than 2 integer, for example can be with
For 2,3,4,5,6,7,8,9,10 etc..
According to the present invention, rear-earth-doped lithium yttrium fluoride nano material, rear-earth-doped lithium yttrium fluoride individual layer nucleocapsid as described above
Structure nano material and many shell core-shell structure nano materials of rear-earth-doped lithium yttrium fluoride are pure tetragonal phase structure, and scale topography is equal
One, size range is 5-100nm.
According to the present invention, rear-earth-doped lithium yttrium fluoride nano material, rear-earth-doped lithium yttrium fluoride individual layer nucleocapsid as described above
Structure nano material and many shell core-shell structure nano materials of rear-earth-doped lithium yttrium fluoride can be oil solubility nanometer particle.Enter one
Step ground, when three kinds of materials are oil solubility nanometer particle, can obtain water-soluble nanoparticles further across pickling processes.
As example, rear-earth-doped lithium yttrium fluoride nano material of the present invention, rear-earth-doped lithium yttrium fluoride individual layer nucleocapsid
Structure nano material and many shell core-shell structure nano materials of rear-earth-doped lithium yttrium fluoride can be selected from following oil solubility nanometer
One or more in grain or water-soluble nanoparticles:LiYbF4:2mol%Er nano particles, LiYbF4:2mol%Ho nanometers
Grain, LiYbF4:1mol%Tm nano particles, LiYbF4:30mol%Tb nano particles, LiYbF4:90mol%Tb nano particles,
LiYbF4:2mol%Er@LiYF4Individual layer Core-shell Structure Nanoparticles, LiYbF4:30mol%Tb@LiYF4Individual layer core shell structure is received
Rice grain or LiYbF4:2mol%Er@LiYF4:20mol%Yb@LiYbF4:20mol%Yb, 20mol%Nd@LiYF4:
20mol%Yb@LiYbF4:1mol%Tm@LiYF4Many shell core-shell structure nano particles.
The present invention also provides rear-earth-doped lithium yttrium fluoride nano material LiYb as described above(1-x)LnxF4Preparation method, bag
Include following steps:
(1) salting liquid is prepared;
(2) methanol solution of ammonium fluoride is added in the solution obtained to step (1), reaction obtains oil solubility nanometer particle;
With
Optionally, (3) mix the oil solubility nanometer particle obtained by step (2) with acid ethanol solution, obtain water solubility
Nano material LiYb(1-x)LnxF4。
According to the present invention, in step (1), the salting liquid can be metal salt solution, be selected from Li, Yb and Ho, Er,
One or more inorganic or organic slat solutions in Tm, Tb, Eu, Ce, Sm, Dy, Nd, Pr, such as halide solution, acetate is molten
Liquid or nitrate solution, preferably halide solution or Acetate Solution, more preferably Acetate Solution;
As example, the Acetate Solution is selected from lithium acetate, acetic acid ytterbium and acetic acid erbium, acetic acid holmium, acetic acid thulium, acetic acid
One or more in terbium, acetic acid europium, cerous acetate, acetic acid samarium, acetic acid dysprosium, acetic acid neodymium, praseodymium acetate;
According to the present invention, the consumption of metal salt meets LiYb in the metal salt solution(1-x)LnxF4In mol ratio, its
Middle x, Ln have definitions as described above.
According to the present invention, in step (1), the solvent that the metal salt solution is used can be that oleic acid and trioctylamine are mixed
Liquid, both volume ratios are (1-10):(1-100), be such as (2-6):(2-50), such as be 2 using volume ratio:3 oleic acid and
The mixed liquor of trioctylamine is used as solvent.
According to the present invention, metal salt is preferably dissolved in oleic acid and three by the operation of step (1) under 5-50 DEG C (such as room temperature)
In octylame solvent, 100-160 DEG C is further preferably warming up under inert gas shielding, 30min is incubated, is then down to 5-50 DEG C
(such as room temperature), obtains settled solution.
According to one embodiment of the invention, in step (2), mole of ammonium fluoride in the methanol solution of the ammonium fluoride
Amount can be in step (1) 4 times of lithium salts mole in the metal lithium salt solution that uses.
According to one embodiment of the invention, in step (2), the temperature of reaction is 300-350 DEG C, and the time of reaction is
5-180min。
According to one embodiment of the invention, in step (3), the acid ethanol solution is pH=1-5 organic acid
Or the acid ethanol solution of inorganic acid, the acid ethanol solution for example prepared using concentrated hydrochloric acid.
The present invention also provides the preparation method of rear-earth-doped lithium yttrium fluoride individual layer core-shell structured nanomaterials as described above, bag
Include following steps:
(a1) the oil solubility nanometer particle for obtaining step (2) is used as kernel seed crystal;
(a2) prepare salting liquid and be used as shell precursor solution;
(a3) kernel seed crystal described in step (a1) is added into step (a2) solution;
(a4) methanol solution of ammonium fluoride is added in the solution obtained to step (a3);
(a5) solution reaction that step (a4) is obtained obtains the rear-earth-doped lithium yttrium fluoride individual layer nuclear shell structure nano of oil-soluble
Material;With
Optionally, (a6) is by the rear-earth-doped lithium yttrium fluoride individual layer core-shell structured nanomaterials of oil-soluble obtained by step (a5)
Mixed with acid ethanol solution, obtain water-solubility rare-earth doping lithium yttrium fluoride individual layer core-shell structured nanomaterials.
According to the present invention, in step (a2), the salting liquid can be metal salt solution, be selected from Li and Yb, Ho,
One or more inorganic or organic slat solutions in Er, Tm, Tb, Eu, Ce, Sm, Dy, Nd, Pr, Gd, La, Sc, such as halide
Solution, Acetate Solution or nitrate solution, preferably halide solution or Acetate Solution, more preferably acetate are molten
Liquid;
As example, the Acetate Solution is selected from lithium acetate and acetic acid ytterbium, acetic acid yttrium, acetic acid erbium, acetic acid holmium, acetic acid
In thulium, acetic acid terbium, acetic acid europium, cerous acetate, acetic acid samarium, acetic acid dysprosium, acetic acid neodymium, praseodymium acetate, gadolinium acetate, lanthanum acetate, acetic acid scandium
It is one or more;
According to the present invention, the consumption of metal salt meets LiYb in the metal salt solution(1-x)LnxF4@LiAF4Outer layer knot
Structure LiAF4Mol ratio, wherein x, Ln, A have definitions as described above.
According to the present invention, in step (a2), the solvent that the metal salt solution is used is the mixed liquor of oleic acid and trioctylamine,
Its volume ratio is (1-10):(1-100), be such as (2-6):(2-50), such as be 2 using volume ratio:3 oleic acid and trioctylamine
Mixed liquor is used as solvent.
According to the present invention, metal salt is preferably dissolved in oleic acid and three by the operation of step (a2) under 5-50 DEG C (such as room temperature)
In octylame solvent, 100-160 DEG C is further preferably warming up under inert gas shielding, 30min is incubated, is then down to 5-50 DEG C
(such as room temperature), obtains settled solution.
According to one embodiment of the invention, shell presoma in the kernel seed crystal and step (a3) in step (a2)
Mol ratio can be 4:1-1:5.
According to one embodiment of the invention, in step (a4), ammonium fluoride rubs in the methanol solution of the ammonium fluoride
Your amount can be in step (a2) 4 times of lithium salts mole in the metal lithium salt solution that uses.
According to one embodiment of the invention, in step (a5), the temperature of reaction is 300-350 DEG C, the time of reaction
For 5-180min.
According to one embodiment of the invention, in step (a6), the acid ethanol solution is pH=1-5 organic acid
Or the acid ethanol solution of inorganic acid, the acid ethanol solution for example prepared using concentrated hydrochloric acid.
The present invention also provides the preparation method of many shell core-shell structure nano materials of the rear-earth-doped lithium yttrium fluoride, including
Following steps:
(b1) using the rear-earth-doped lithium yttrium fluoride individual layer core-shell structured nanomaterials of oil-soluble of synthesis in step (a5) as
Kernel seed crystal;
(b2) prepare salting liquid and be used as shell precursor solution;
(b3) the kernel seed crystal added into step (b2) solution in step (b1);
(b4) methanol solution of ammonium fluoride is added into step (b3) resulting solution;
(b5) step (b4) resulting solution reaction obtains many shell core-shell structure nanos of the rear-earth-doped lithium yttrium fluoride of oil-soluble
Material;
(b6) many shell core-shell structure nano materials of the rear-earth-doped lithium yttrium fluoride of oil-soluble obtained step (b5) as
Seed crystal, repeat step (b1)-(b5) can prepare two layers and more than two layers of core-shell structured nanomaterials;With
Optionally, (b7) is by many shell core-shell structure nano materials of the rear-earth-doped lithium yttrium fluoride of oil-soluble obtained by step (b6)
Material is mixed with acid ethanol solution, obtains the water-solubility rare-earth doping many shell core-shell structure nano materials of lithium yttrium fluoride.
According to the present invention, in step (b2), the salting liquid can be metal salt solution, be selected from Li and Yb, Ho,
One or more common inorganic or organic slat solutions in Er, Tm, Tb, Eu, Ce, Sm, Dy, Nd, Pr, Gd, La, Sc, such as halogen
Compound solution, Acetate Solution or nitrate solution, preferably halide solution or Acetate Solution, more preferably acetic acid
Salting liquid;
As example, the Acetate Solution is selected from lithium acetate and acetic acid yttrium, acetic acid ytterbium, acetic acid erbium, acetic acid holmium, acetic acid
In thulium, acetic acid terbium, acetic acid europium, cerous acetate, acetic acid samarium, acetic acid dysprosium, acetic acid neodymium, praseodymium acetate, gadolinium acetate, lanthanum acetate, acetic acid scandium
It is one or more;
According to the present invention, the consumption of metal salt meets LiYb in the metal salt solution(1-x)Lnx F4(@LiAF4)nExcept step
Suddenly the mol ratio of other layers in (b1) outside seed crystal, wherein, x, n, Ln, A have definitions as described above.
According to the present invention, in step (b2), the solvent that the metal salt is used is the mixed liquor of oleic acid and trioctylamine, its body
Product is than being (1-10):(1-100), be such as (2-6):(2-50), such as be 2 using volume ratio:The mixing of 3 oleic acid and trioctylamine
Liquid is used as solvent.
According to the present invention, metal salt is preferably dissolved in oleic acid and three by the operation of step (b2) under 5-50 DEG C (such as room temperature)
In octylame solvent, 100-160 DEG C is further preferably warming up under inert gas shielding, 30min is incubated, is then down to 5-50 DEG C
(such as room temperature), obtains settled solution.
According to one embodiment of the invention, shell presoma in the kernel seed crystal and step (b3) in step (b2)
Mol ratio can be 4:1-1:5.
According to one embodiment of the invention, in step (b4), ammonium fluoride rubs in the methanol solution of the ammonium fluoride
Your amount can be in step (b2) 4 times of lithium salts mole in the metal lithium salt solution that uses.
According to one embodiment of the invention, in step (b5), the temperature of reaction is 300-350 DEG C, the time of reaction
For 5-180min.
In step (b7), the acid ethanol solution can be pH=1-5 organic acid or the acidic ethanol of inorganic acid
Solution, the acid ethanol solution for example prepared using concentrated hydrochloric acid.
The many shell core-shell structure nano materials of rear-earth-doped lithium yttrium fluoride of the present invention can according to the need for use and
The different numbers of plies are prepared, are further many shell core-shell structure nano materials of different-thickness.
The present invention also provides rear-earth-doped lithium yttrium fluoride nano material, rear-earth-doped lithium yttrium fluoride individual layer nucleocapsid as described above
The purposes of structure nano material and many shell core-shell structure nano materials of rear-earth-doped lithium yttrium fluoride, including for optical storage,
Illuminate in terms of display, fluorescence labeling detection, bio-imaging, optical anti-counterfeiting and coding, for example, detected for fluorescence labeling and raw
Thing is imaged.
" optionally " of the invention means to carry out or without the step.
The beneficial effects of the present invention are:
1) present invention controls synthetic rare earth doped lithium yttrium fluoride nano material using high temperature coprecipitation, pungent with oleic acid and three
Amine mixed liquor is solvent, improves crystallization temperature, the nano particle monodispersity of preparation is good, pattern is homogeneous, and size is controllable, pickling it
The rear-earth-doped lithium yttrium fluoride nano material of good water solubility is obtained afterwards, it is adaptable to bio-imaging and detection.
2) the rear-earth-doped lithium yttrium fluoride nano material of the invention prepared, rear-earth-doped lithium yttrium fluoride individual layer nucleocapsid knot
Structure nano material, can be water-soluble or oil-soluble, its structure is pure tetragonal phase structure, and scale topography is homogeneous, and luminescent properties are excellent
It is different.
3) many shell core-shell structure nano materials of lithium yttrium fluoride, the nanometer material are based on invention further provides one kind
Material list good dispersion, scale topography is homogeneous;Dependent on the change of power, its luminescent properties shows green and arrives yellow to yellowish green,
Bluish violet is arrived again to the gradual change of white, and showing should in the potential of field such as optical storage, illumination display, optical anti-counterfeiting and codings
Use prospect.
4) trioctylamine that preparation method of the invention uses boiling point higher improves reaction temperature for solvent, can prepare crystallization
The property controllable rear-earth-doped lithium yttrium fluoride nano material of good, scale topography, further prepares rear-earth-doped lithium yttrium fluoride individual layer core
Shell structural nano material and many shell core-shell structure nano materials of the adjustable lithium yttrium fluoride of shell thickness.
Brief description of the drawings
Fig. 1:The LiYbF that embodiment 4 and embodiment 7 are prepared4:30mol%Tb nano particles and LiYbF4:30mol%
Tb@LiYF4The powder diagram of individual layer Core-shell Structure Nanoparticles.
Fig. 2:The LiYbF that embodiment 1 and embodiment 8 are prepared4:2mol%Er nano particles and LiYbF4:2mol%
Er@LiYF4:20mol%Yb@LiYF4:20mol%Yb, 20mol%Nd@LiYF4:20mol%Yb@LiYbF4:1mol%Tm@
LiYF4The powder diagram of many shell core-shell structure nano particles.
Fig. 3:The LiYbF that embodiment 4 is prepared4:The X-ray energy spectrum analysis chart of 30mol%Tb nano particles.
Fig. 4:(a) LiYbF that embodiment 1 is prepared4:2mol%Er nano particles, (b) embodiment 4 are prepared
LiYbF4:The LiYbF that 30mol%Tb nano particles, (c) embodiment 6 are prepared4:2mol%Er@LiYF4Individual layer core shell structure
The LiYbF that nano particle and (d) embodiment 7 are prepared4:30mol%Tb@LiYF4The transmission of individual layer Core-shell Structure Nanoparticles
Electron microscope.
Fig. 5:The LiYbF that embodiment 1 is prepared4:The Up-conversion emission spectrogram of 2mol%Er nano particles (is excited
980nm)。
Fig. 6:The LiYbF that embodiment 2 is prepared4:The Up-conversion emission spectrogram of 2mol%Ho nano particles (is excited
980nm)。
Fig. 7:The LiYbF that embodiment 3 is prepared4:The Up-conversion emission spectrogram of 1mol%Tm nano particles (is excited
980nm)。
Fig. 8:The LiYbF that embodiment 4 is prepared4:The Up-conversion emission spectrogram of 30mol%Tb nano particles (is excited
980nm)。
Fig. 9:The LiYbF that embodiment 4 is prepared4:The lower transfer excitation-emission spectrogram of 30mol%Tb nano particles.
Figure 10:The LiYbF that embodiment 7 is prepared4:30mol%Tb@LiYF4Before individual layer Core-shell Structure Nanoparticles pickling
Up-conversion emission spectrogram (exciting 980nm) afterwards.
Figure 11:The multicolor luminous photo (exciting 980nm) of embodiment 9.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.Furthermore, it is to be understood that after described content of the invention has been read, this area skill
Art personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within limited range of the present invention.
Unless otherwise indicated, the raw material and reagent used in embodiment is commercial materials, or passes through known method
Prepare.
It is MiniFlex2 that product of the embodiment of the present invention, which carries out powder diffraction and characterizes the INSTRUMENT MODEL used, and producer is
Rigaku, copper target radiation wavelength is λ=0.154187nm.
It is JEM-2010 that product of the embodiment of the present invention, which carries out X-ray energy spectrum and analyzes the INSTRUMENT MODEL used, and producer is JEOL.
Product of the embodiment of the present invention carries out transmission electron microscope and detects that the INSTRUMENT MODEL used is TECNAI G2F20, producer is
FEI。
Product of the embodiment of the present invention carries out Up-conversion emission spectral characterization (exciting 980nm) INSTRUMENT MODEL for using
FSP920-C, producer is Edinburgh.
It is FLS980 that product of the embodiment of the present invention, which carries out lower transfer excitation-emission spectrogram and characterizes the INSTRUMENT MODEL used,
Producer is Edinburgh, and excitation source is xenon lamp.
Embodiment 1:LiYbF4:The preparation of 2mol%Er nano particles.Weigh 1mmol CH3COOLi·3H2O、
0.02mmol Er(CH3COO)3·4H2O and 0.98mmol Yb (CH3COO)3·4H2O, then adds 8mL oleic acid and 12mL tri-
Octylame, logical nitrogen is heated to 120 DEG C and is incubated 30 minutes, forms clear solution A, is then down to room temperature;Weigh 4mmol's
NH4F, is dissolved in 10mL methanol, and is added dropwise in solution A, continues stirring 10min and is allowed to abundant mixing, is warming up to 60 DEG C,
30min is incubated, clear solution B is formed;320 DEG C are warming up to, 1h is incubated, is down to room temperature;20mL ethanol precipitations are added to separate and wash
Wash for several times, obtain 22nm or so oil-soluble LiYbF4:2mol%Er nano particles.By 112 μ L concentrated hydrochloric acids be added to 15mL without
PH=1 acid solution is prepared in water-ethanol.Oil solubility nanometer particle is dispersed in above-mentioned acid ethanol solution, 30 points of ultrasound
Centrifuged after clock, with absolute ethyl alcohol and water, alternately washing can obtain water-soluble LiYbF for several times4:2mol%Er nano particles.
Embodiment 2:LiYbF4:The preparation of 2mol%Ho nano particles.Weigh 1mmol CH3COOLi·3H2O、
0.02mmol Ho(CH3COO)3·4H2O and 0.98mmol Yb (CH3COO)3·4H2O, then adds 8mL oleic acid and 12mL tri-
Octylame, logical nitrogen is heated to 120 DEG C and is incubated 30 minutes, forms clear solution A, is then down to room temperature;Weigh 4mmol's
NH4F, is dissolved in 10mL methanol, and is added dropwise in solution A, continues stirring 10min and is allowed to abundant mixing, is warming up to 60 DEG C,
30min is incubated, clear solution B is formed;320 DEG C are warming up to, 1h is incubated, is down to room temperature;20mL ethanol precipitations are added to separate and wash
Wash for several times, obtain 22nm or so oil-soluble LiYbF4:2mol%Ho nano particles.By 112 μ L concentrated hydrochloric acids be added to 15mL without
PH=1 acid solution is prepared in water-ethanol.Oil solubility nanometer particle is dispersed in above-mentioned acid ethanol solution, 30 points of ultrasound
Centrifuged after clock, with absolute ethyl alcohol and water, alternately washing can obtain water-soluble LiYbF for several times4:2mol%Ho nano particles.
Embodiment 3:LiYbF4:The preparation of 1mol%Tm nano particles.Weigh 1mmol CH3COOLi·3H2O、
0.01mmol Tm(CH3COO)3·4H2O and 0.99mmolYb (CH3COO)3·4H2O, then adds 8mL oleic acid and 12mL tri- is pungent
Amine, logical nitrogen is heated to 120 DEG C and is incubated 30 minutes, forms clear solution A, is then down to room temperature;Weigh 4mmol NH4F,
It is dissolved in 10mL methanol, and is added dropwise in solution A, continues stirring 10min and be allowed to abundant mixing, be warming up to 60 DEG C, insulation
30min, forms clear solution B;320 DEG C are warming up to, 1h is incubated, is down to room temperature;20mL ethanol precipitations are added to separate and wash number
It is secondary, obtain 22nm or so oil-soluble LiYbF4:1mol%Tm nano particles.112 μ L concentrated hydrochloric acids are added to the anhydrous second of 15mL
PH=1 acid solution is prepared in alcohol.Oil solubility nanometer particle is dispersed in above-mentioned acid ethanol solution, ultrasound is after 30 minutes
Centrifugation, with absolute ethyl alcohol and water, alternately washing can obtain water-soluble LiYbF for several times4:1mol%Tm nano particles.
Embodiment 4:LiYbF4:The preparation of 30mol%Tb nano particles.Weigh 1mmol CH3COOLi·3H2O、
0.3mmol Tb(CH3COO)3·4H2O and 0.7mmol Yb (CH3COO)3·4H2O, then adds 8mL oleic acid and 12mL tri- is pungent
Amine, logical nitrogen is heated to 120 DEG C and is incubated 30 minutes, forms clear solution A, is then down to room temperature;Weigh 4mmol NH4F,
It is dissolved in 10mL methanol, and is added dropwise in solution A, continues stirring 10min and be allowed to abundant mixing, be warming up to 60 DEG C, insulation
30min, forms clear solution B;320 DEG C are warming up to, 1h is incubated, is down to room temperature;20mL ethanol precipitations are added to separate and wash number
It is secondary, obtain 12nm or so oil-soluble LiYbF4:30mol%Tb nano particles.112 μ L concentrated hydrochloric acids are added to the anhydrous second of 15mL
PH=1 acid solution is prepared in alcohol.Oil solubility nanometer particle is dispersed in above-mentioned acid ethanol solution, ultrasound is after 30 minutes
Centrifugation, with absolute ethyl alcohol and water, alternately washing can obtain water-soluble LiYbF for several times4:30mol%Tb nano particles.
Embodiment 5:LiYbF4:The preparation of 90mol%Tb nano particles.Weigh 1mmol CH3COOLi·3H2O、
0.9mmol Tb(CH3COO)3·4H2O and 0.1mmol Yb (CH3COO)3·4H2O, then adds 8mL oleic acid and 12mL tri- is pungent
Amine, logical nitrogen is heated to 120 DEG C and is incubated 30 minutes, forms clear solution A, is then down to room temperature;Weigh 4mmol NH4F,
It is dissolved in 10mL methanol, and is added dropwise in solution A, continues stirring 10min and be allowed to abundant mixing, be warming up to 60 DEG C, insulation
30min, forms clear solution B;320 DEG C are warming up to, 1h is incubated, is down to room temperature;20mL ethanol precipitations are added to separate and wash number
It is secondary, obtain 12nm or so oil-soluble LiYbF4:90mol%Tb nano particles.112 μ L concentrated hydrochloric acids are added to the anhydrous second of 15mL
PH=1 acid solution is prepared in alcohol.Oil solubility nanometer particle is dispersed in above-mentioned acid ethanol solution, ultrasound is after 30 minutes
Centrifugation, with absolute ethyl alcohol and water, alternately washing can obtain water-soluble LiYbF for several times4:90mol%Tb nano particles.
Embodiment 6:LiYbF4:2mol%Er@LiYF4The preparation of nano particle.Weigh 1mmol CH3COOLi·3H2O、
0.02mmol Er(CH3COO)3·4H2O and 0.98mmol Yb (CH3COO)3·4H2O, then adds 8mL oleic acid and 12mL tri-
Octylame, logical nitrogen is heated to 120 DEG C and is incubated 30 minutes, forms clear solution A, is then down to room temperature;Weigh 4mmol's
NH4F, is dissolved in 10mL methanol, and is added dropwise in solution A, continues stirring 10min and is allowed to abundant mixing, is warming up to 60 DEG C,
30min is incubated, clear solution B is formed;320 DEG C are warming up to, 1h is incubated, is down to room temperature;20mL ethanol precipitations are added to separate and wash
Wash for several times, obtain 22nm or so oil-soluble LiYbF4:2mol%Er nano particles.By oil-soluble LiYbF4:2mol%Er nanometers
Particle carries out nucleocapsid cladding as kernel seed crystal.Weigh 1mmol Y (CH3COO)3·4H2O and 1mmol CH3COOLi·3H2O,
Then 8mL oleic acid and 12mL trioctylamines are added, logical nitrogen is heated to 120 DEG C and is incubated 30 minutes, forms clear solution C, plus
Enter 1mmolLiYbF4:2mol%Er kernel seed crystals.Continue stirring 10min and be allowed to abundant mixing, weigh 4mmol NH4F, is dissolved in
In 10mL methanol, and it is added dropwise in solution C, continues stirring 10min and be allowed to abundant mixing, be warming up to 60 DEG C, insulation
30min, forms clear solution D;320 DEG C are warming up to, 1h is incubated, is down to room temperature;20mL ethanol precipitations are added to separate and wash number
It is secondary, obtain 30nm or so oil-soluble LiYbF4:2mol%Er@LiYF4Nano particle.By 112 μ L concentrated hydrochloric acids be added to 15mL without
PH=1 acid solution is prepared in water-ethanol.Oil solubility nanometer particle is dispersed in above-mentioned acid ethanol solution, 30 points of ultrasound
Centrifuged after clock, with absolute ethyl alcohol and water, alternately washing can obtain water-soluble LiYbF for several times4:2mol%Er@LiYF4Individual layer nucleocapsid
Structure nano particles.
Embodiment 7:LiYbF4:30mol%Tb@LiYF4The preparation of nano particle.Weigh 1mmol CH3COOLi·3H2O、
0.3mmol Tb(CH3COO)3·4H2O and 0.7mmol Yb (CH3COO)3·4H2O, then adds 8mL oleic acid and 12mL tri- is pungent
Amine, logical nitrogen is heated to 120 DEG C and is incubated 30 minutes, forms clear solution A, is then down to room temperature;Weigh 4mmol NH4F,
It is dissolved in 10mL methanol, and is added dropwise in solution A, continues stirring 10min and be allowed to abundant mixing, be warming up to 60 DEG C, insulation
30min, forms clear solution B;320 DEG C are warming up to, 1h is incubated, is down to room temperature;20mL ethanol precipitations are added to separate and wash number
It is secondary, obtain 12nm or so oil-soluble LiYbF4:2mol%Er nano particles.By oil-soluble LiYbF4:30mol%Tb nanometers
Grain carries out nucleocapsid cladding as kernel seed crystal.Weigh 1mmol Y (CH3COO)3·4H2O and 1mmol CH3COOLi·3H2O, so
After add 8mL oleic acid and 12mL trioctylamines, logical nitrogen is heated to 120 DEG C and is incubated 30 minutes, forms clear solution C, adds
1mmolLiYbF4:30mol%Tb kernel seed crystals.Continue stirring 10min and be allowed to abundant mixing, weigh 4mmol NH4F, is dissolved in
In 10mL methanol, and it is added dropwise in solution C, continues stirring 10min and be allowed to abundant mixing, be warming up to 60 DEG C, insulation
30min, forms clear solution D;320 DEG C are warming up to, 1h is incubated, is down to room temperature;20mL ethanol precipitations are added to separate and wash number
It is secondary, obtain 30nm or so oil-soluble LiYbF4:30mol%Tb@LiYF4Nano particle.112 μ L concentrated hydrochloric acids are added to 15mL
PH=1 acid solution is prepared in absolute ethyl alcohol.Oil solubility nanometer particle is dispersed in above-mentioned acid ethanol solution, ultrasound 30
Centrifuged after minute, with absolute ethyl alcohol and water, alternately washing can obtain water-soluble LiYbF for several times4:30mol%Tb@LiYF4Individual layer
Core-shell Structure Nanoparticles.
Embodiment 8:LiYbF4:2mol%Er@LiYF4:20mol%Yb@LiYF4:20mol%Yb, 20mol%Nd@
LiYF4:20mol%Yb@LiYbF4:1mol%Tm@LiYF4The preparation of nano particle.Weigh 1mmol CH3COOLi·3H2O、
0.02mmol Er(CH3COO)3·4H2O and 0.98mmol Yb (CH3COO)3·4H2O, then adds 8mL oleic acid and 12mL tri-
Octylame, logical nitrogen is heated to 120 DEG C and is incubated 30 minutes, forms clear solution A, is then down to room temperature;Weigh 4mmol's
NH4F, is dissolved in 10mL methanol, and is added dropwise in solution A, continues stirring 10min and is allowed to abundant mixing, is warming up to 60 DEG C,
30min is incubated, clear solution B is formed;320 DEG C are warming up to, 1h is incubated, is down to room temperature;20mL ethanol precipitations are added to separate and wash
Wash for several times, obtain 22nm or so oil-soluble LiYbF4:2mol%Er nano particles.By oil-soluble LiYbF4:2mol%Er nanometers
Particle carries out nucleocapsid cladding as kernel seed crystal.Weigh 0.8mmol Y (CH3COO)3·4H2O、0.2mmol Yb
(CH3COO)3·4H2O and 1mmol CH3COOLi·3H2O, then adds 8mL oleic acid and 12mL trioctylamines, leads to nitrogen heating
To 120 DEG C and be incubated 30 minutes, formed clear solution C, add 1mmolLiYbF4:2mol%Er kernel seed crystals.Continue to stir
10min is allowed to abundant mixing, weighs 4mmol NH4F, is dissolved in 10mL methanol, and is added dropwise in solution C, continues to stir
10min is allowed to abundant mixing, is warming up to 60 DEG C, is incubated 30min, forms clear solution D;320 DEG C are warming up to, 1h is incubated, is down to
Room temperature;Add 20mL ethanol precipitations to separate and wash for several times, obtain 30nm or so oil-soluble LiYbF4:2mol%Er@LiYF4:
20mol%Yb nano particles.It is repeated 5 times above-mentioned steps, you can obtain the nano particle of 5 layers of cladding, different shell presoma roots
Prepared according to proper proportion, finally obtain oil-soluble LiYbF4:2mol%Er@LiYF4:20mol%Yb@LiYF4:20mol%Yb,
20mol%Nd@LiYF4:20mol%Yb@LiYbF4:1mol%Tm@LiYF4Many shell core-shell structure nano particles.
Embodiment 9:The LiYbF for taking 5mg embodiments 8 to prepare4:2mol%Er@LiYF4:20mol%Yb@LiYF4:
20mol%Yb, 20mol%Nd@LiYF4:20mol%Yb@LiYbF4:1mol%Tm@LiYF4Many shell core-shell structure nanometers
Grain is scattered in 3mL hexamethylene organic solvents.980 or 808nm laser irradiating sample is respectively adopted, testing its power density is
0.1~50W/cm2Fluorescence spectrum.Further, under dark fieid conditions, its corresponding power density (0.1~50W/cm is shot2)
Luminous photo, its color shows green to yellowish green to yellow from right-to-left, then to bluish violet to white gradual change.Realize
The polychrome up-conversion luminescence regulation and control that 980/808nm is excited.
More than, embodiments of the present invention are illustrated.But, the present invention is not limited to above-mentioned embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvements done etc., should be included in the guarantor of the present invention
Within the scope of shield.
Claims (10)
1. a kind of rear-earth-doped lithium yttrium fluoride nano material, consisting of:LiYb(1-x)LnxF4, wherein, Ln be selected from Ho, Er, Tm,
One or more in Tb, Eu, Ce, Sm, Dy, Nd, Pr, 0<X≤90mol%.
2. a kind of rear-earth-doped lithium yttrium fluoride individual layer core-shell structured nanomaterials, its chemical general formula is:LiYb(1-x)LnxF4@
LiAF4, wherein, one or more of the Ln in Ho, Er, Tm, Tb, Eu, Ce, Sm, Dy, Nd, Pr, 0<X≤90mol%, A are selected
From the one or more in Yb, Y, Ho, Er, Tm, Tb, Eu, Ce, Sm, Dy, Nd, Pr, Gd, La, Sc, preferably A is Y or Gd.
3. a kind of many shell core-shell structure nano materials of rear-earth-doped lithium yttrium fluoride, its chemical general formula is:LiYb(1-x)LnxF4(@
LiAF4)n, wherein, one or more of the Ln in Ho, Er, Tm, Tb, Eu, Ce, Sm, Dy, Nd, Pr, 0<X≤90mol%, A
One or more in Yb, Y, Ho, Er, Tm, Tb, Eu, Ce, Sm, Dy, Nd, Pr, Gd, La, Sc, preferably A are Y or Gd, n
For more than 2 integer, such as can be 2,3,4,5,6,7,8,9,10.
4. rear-earth-doped lithium yttrium fluoride nano material, rear-earth-doped lithium yttrium fluoride individual layer core as described in claim any one of 1-3
Shell structural nano material or many shell core-shell structure nano materials of rear-earth-doped lithium yttrium fluoride are pure tetragonal phase structure, scale topography
Homogeneous, size range is 5-100nm;
Preferably, the rear-earth-doped lithium yttrium fluoride nano material, rear-earth-doped lithium yttrium fluoride individual layer core-shell structured nanomaterials
Or the rear-earth-doped many shell core-shell structure nano materials of lithium yttrium fluoride can be oil solubility nanometer particle;Further, when three kinds
When material is oil solubility nanometer particle, water-soluble nanoparticles can be obtained further across pickling processes;
Preferably, the rear-earth-doped lithium yttrium fluoride nano material, rear-earth-doped lithium yttrium fluoride individual layer core-shell structured nanomaterials
Or the rear-earth-doped many shell core-shell structure nano materials of lithium yttrium fluoride are selected from following oil solubility nanometer particle or water-soluble nano
One or more in grain:LiYbF4:2mol%Er nano particles, LiYbF4:2mol%Ho nano particles, LiYbF4:1mol%
Tm nano particles, LiYbF4:30mol%Tb nano particles, LiYbF4:90mol%Tb nano particles, LiYbF4:2mol%Er@
LiYF4Individual layer Core-shell Structure Nanoparticles, LiYbF4:30mol%Tb@LiYF4Individual layer Core-shell Structure Nanoparticles or LiYbF4:
2mol%Er@LiYF4:20mol%Yb@LiYbF4:20mol%Yb, 20mol%Nd@LiYF4:20mol%Yb@LiYbF4:
1mol%Tm@LiYF4Many shell core-shell structure nano particles.
5. the preparation method of rear-earth-doped lithium yttrium fluoride nano material, comprises the following steps as described in claim 1 or 4:
(1) salting liquid is prepared;
(2) methanol solution of ammonium fluoride is added in the solution obtained to step (1), oil solubility nanometer particle is reacted to obtain;With
Optionally, (3) mix the oil solubility nanometer particle obtained by step (2) with acid ethanol solution, obtain water-soluble nano
Material LiYb(1-x)LnxF4;
Preferably, wherein in step (1), the salting liquid can be metal salt solution, be selected from Li, Yb and Ho, Er, Tm,
One or more common inorganic or organic slat solutions in Tb, Eu, Ce, Sm, Dy, Nd, Pr, such as halide solution, acetate
Solution or nitrate solution, preferably halide solution or Acetate Solution, more preferably Acetate Solution;
Preferably, the acetate is selected from lithium acetate, acetic acid ytterbium and acetic acid erbium, acetic acid holmium, acetic acid thulium, acetic acid terbium, acetic acid europium, vinegar
It is one kind of multiple in sour cerium, acetic acid samarium, acetic acid dysprosium, acetic acid neodymium, praseodymium acetate;
Preferably, the consumption of metal salt meets LiYb in the metal salt solution(1-x)LnxF4In mol ratio, wherein x, Ln have
Definition as claimed in claim 1;
Preferably, in step (1), the solvent that the metal salt solution is used can be oleic acid and trioctylamine mixed liquor, both
Volume ratio is (1-10):(1-100), be such as (2-6):(2-50), such as be 2 using volume ratio:3 oleic acid and trioctylamine it is mixed
Close liquid and be used as solvent;
Preferably, the operation of step (1) is entered to be dissolved in metal salt in oleic acid and trioctylamine solvent under 5-50 DEG C (such as room temperature)
One step is preferably warming up to 100-160 DEG C under inert gas shielding, is incubated 30min, is then down to 5-50 DEG C (such as room temperature), obtains
Settled solution;
Preferably, in step (2), the mole of ammonium fluoride is the gold that uses in step (1) in the methanol solution of the ammonium fluoride
Belong to 4 times of lithium salts mole in lithium salt solution;
Preferably, in step (2), the temperature of reaction is 300-350 DEG C, and the time of reaction is 5-180min;
Preferably, in step (3), the acid ethanol solution is that pH=1-5 organic acid or the acidic ethanol of inorganic acid are molten
Liquid, the acid ethanol solution for example prepared using concentrated hydrochloric acid.
6. the preparation method of rear-earth-doped lithium yttrium fluoride individual layer core-shell structured nanomaterials as described in claim 2 or 4, including with
Lower step:
(a1) the oil solubility nanometer particle for obtaining step described in claim 5 (2) is used as kernel seed crystal;
(a2) prepare salting liquid and be used as shell precursor solution;
(a3) kernel seed crystal described in step (a1) is added in the solution obtained to step (a2);
(a4) methanol solution of ammonium fluoride is added in the solution obtained to step (a3);
(a5) solution reaction that step (a4) is obtained obtains the rear-earth-doped lithium yttrium fluoride individual layer core-shell structured nanomaterials of oil-soluble;
With
Optionally, (a6) by the rear-earth-doped lithium yttrium fluoride individual layer core-shell structured nanomaterials of oil-soluble obtained by step (a5) with acid
Property ethanol solution mixing, obtain water-solubility rare-earth doping lithium yttrium fluoride individual layer core-shell structured nanomaterials.
7. the preparation method of rear-earth-doped lithium yttrium fluoride individual layer core-shell structured nanomaterials as claimed in claim 6, wherein step
(a2) in, the salting liquid can be metal salt solution, be selected from Li and Yb, Ho, Er, Tm, Tb, Eu, Ce, Sm, Dy, Nd,
One or more common inorganic or organic slat solutions in Pr, Gd, La, Sc, such as halide solution, Acetate Solution or nitric acid
Salting liquid, preferably halide solution or Acetate Solution, more preferably Acetate Solution;
Preferably, the acetate is selected from lithium acetate and acetic acid ytterbium, acetic acid yttrium, acetic acid erbium, acetic acid holmium, acetic acid thulium, acetic acid terbium, vinegar
It is one kind of multiple in sour europium, cerous acetate, acetic acid samarium, acetic acid dysprosium, acetic acid neodymium, praseodymium acetate, gadolinium acetate, lanthanum acetate, acetic acid scandium;
Preferably, the consumption of metal salt meets LiYb in the metal salt solution(1-x)LnxF4@LiAF4Layer structure LiAF4's
Mol ratio, wherein x, Ln, A have the definition described in claim 2;
Preferably, in step (a2), the solvent that the metal salt solution is used is the mixed liquor of oleic acid and trioctylamine, its volume ratio
For (1-10):(1-100), be such as (2-6):(2-50), such as be 2 using volume ratio:3 oleic acid and the mixed liquor of trioctylamine are made
For solvent;
Preferably, the operation of step (a2) is to be dissolved in metal salt in oleic acid and trioctylamine solvent under 5-50 DEG C (such as room temperature),
100-160 DEG C is further preferably warming up under inert gas shielding, 30min is incubated, is then down to 5-50 DEG C (such as room temperature), obtains
To settled solution;
Preferably, the mol ratio of shell presoma is 4 in the kernel seed crystal and step (a3) in step (a2):1-1:5;
Preferably, in step (a4), the mole of ammonium fluoride is to use in step (a2) in the methanol solution of the ammonium fluoride
4 times of lithium salts mole in metal lithium salt solution;
Preferably, in step (a5), the temperature of reaction is 300-350 DEG C, and the time of reaction is 5-180min;
Preferably, in step (a6), the acid ethanol solution is that pH=1-5 organic acid or the acidic ethanol of inorganic acid are molten
Liquid, the acid ethanol solution for example prepared using concentrated hydrochloric acid.
8. the preparation method of the rear-earth-doped many shell core-shell structure nano materials of lithium yttrium fluoride as described in claim 3 or 4, including
Following steps:
(b1) by the rear-earth-doped lithium yttrium fluoride individual layer core shell structure of oil-soluble of synthesis in step described in claim 6 or 7 (a5)
Nano material is used as kernel seed crystal;
(b2) prepare salting liquid and be used as shell precursor solution;
(b3) the kernel seed crystal added into step (b2) solution in step (b1);
(b4) methanol solution of ammonium fluoride is added into step (b3) resulting solution;
(b5) step (b4) resulting solution reaction obtains many shell core-shell structure nano materials of the rear-earth-doped lithium yttrium fluoride of oil-soluble;
(b6) many shell core-shell structure nano materials of the rear-earth-doped lithium yttrium fluoride of oil-soluble obtained step (b5) as seed crystal,
Repeat step (b1)-(b5) can prepare two layers and more than two layers of core-shell structured nanomaterials;With
Optionally, (b7) is by many shell core-shell structure nano materials of the rear-earth-doped lithium yttrium fluoride of oil-soluble obtained by step (b6) and acid
Property ethanol solution mixing, obtain water-solubility rare-earth doping many shell core-shell structure nano materials of lithium yttrium fluoride.
9. the preparation method of the rear-earth-doped many shell core-shell structure nano materials of lithium yttrium fluoride as claimed in claim 8, wherein walking
Suddenly in (b2), the salting liquid can be metal salt solution, be selected from Li and Yb, Ho, Er, Tm, Tb, Eu, Ce, Sm, Dy,
One or more inorganic or organic slat solutions in Nd, Pr, Gd, La, Sc, such as halide solution, Acetate Solution or nitric acid
Salting liquid, preferably halide solution or Acetate Solution, more preferably Acetate Solution;
Preferably, the acetate is selected from lithium acetate and acetic acid yttrium, acetic acid ytterbium, acetic acid erbium, acetic acid holmium, acetic acid thulium, acetic acid terbium, vinegar
It is one kind of multiple in sour europium, cerous acetate, acetic acid samarium, acetic acid dysprosium, acetic acid neodymium, praseodymium acetate, gadolinium acetate, lanthanum acetate, acetic acid scandium;
Preferably, the consumption of metal salt meets LiYb in the metal salt solution(1-x)LnxF4(@LiAF4)nExcept seed in step (b1)
The mol ratio of other layers outside crystalline substance, wherein, x, n, Ln, A have definition as claimed in claim 3;
Preferably, in step (b2), the solvent that the metal salt is used is the mixed liquor of oleic acid and trioctylamine, and its volume ratio is
(1-10):(1-100), be such as (2-6):(2-50), such as be 2 using volume ratio:The mixed liquor conduct of 3 oleic acid and trioctylamine
Solvent;
Preferably, the operation of step (b2) is to be dissolved in metal salt in oleic acid and trioctylamine solvent under 5-50 DEG C (such as room temperature),
100-160 DEG C is further preferably warming up under inert gas shielding, 30min is incubated, is then down to 5-50 DEG C (such as room temperature), obtains
To settled solution;
Preferably, the mol ratio of shell presoma is 4 in the kernel seed crystal and step (b3) in step (b2):1-1:5;
Preferably, in step (b4), the mole of ammonium fluoride is to use in step (b2) in the methanol solution of the ammonium fluoride
4 times of lithium salts mole in metal lithium salt solution;
Preferably, in step (b5), the temperature of reaction is 300-350 DEG C, and the time of reaction is 5-180min;
Preferably, in step (b7), the acid ethanol solution is that pH=1-5 organic acid or the acidic ethanol of inorganic acid are molten
Liquid, the acid ethanol solution for example prepared using concentrated hydrochloric acid.
10. rear-earth-doped lithium yttrium fluoride nano material, rear-earth-doped lithium yttrium fluoride individual layer core as described in claim any one of 1-4
The purposes of shell structural nano material and many shell core-shell structure nano materials of rear-earth-doped lithium yttrium fluoride, for optical storage, shines
Substantially show, fluorescence labeling detection, bio-imaging, in terms of optical anti-counterfeiting and coding, be preferred for fluorescence labeling detection and biological
Imaging.
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