CN105176515B - A kind of rare earth upconversion nano particle and its production and use - Google Patents
A kind of rare earth upconversion nano particle and its production and use Download PDFInfo
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- CN105176515B CN105176515B CN201510551274.4A CN201510551274A CN105176515B CN 105176515 B CN105176515 B CN 105176515B CN 201510551274 A CN201510551274 A CN 201510551274A CN 105176515 B CN105176515 B CN 105176515B
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- -1 erbium ion Chemical class 0.000 claims description 83
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 36
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 24
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 24
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 24
- 239000005642 Oleic acid Substances 0.000 claims description 24
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 24
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 24
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 24
- 229910052786 argon Inorganic materials 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 18
- 229910052783 alkali metal Inorganic materials 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- 229910052700 potassium Inorganic materials 0.000 claims description 16
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- DTQVDTLACAAQTR-UHFFFAOYSA-N trifluoroacetic acid Substances OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052691 Erbium Inorganic materials 0.000 claims description 13
- 229910052689 Holmium Inorganic materials 0.000 claims description 12
- 229910052775 Thulium Inorganic materials 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
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- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 claims description 6
- 229910021053 KNdF4 Inorganic materials 0.000 claims description 5
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- 238000002059 diagnostic imaging Methods 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 238000011953 bioanalysis Methods 0.000 claims description 2
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- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 2
- 239000012454 non-polar solvent Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 27
- 238000006862 quantum yield reaction Methods 0.000 abstract description 12
- 230000004913 activation Effects 0.000 abstract description 5
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- 238000005538 encapsulation Methods 0.000 abstract description 3
- 238000010792 warming Methods 0.000 description 14
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 13
- UYCAUPASBSROMS-UHFFFAOYSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-]C(=O)C(F)(F)F UYCAUPASBSROMS-UHFFFAOYSA-M 0.000 description 12
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- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention relates to a kind of rare earth upconversion nano particle and its production and use, the rare earth upconversion nano particle includes successively from inside to outside：Activator shell, energy transfer agent shell and sensitizer shell, and each layer contains Yb3+；Wherein, Yb3+Doping concentration successively reduce from inside to outside.The present invention is by setting ytterbium ion doping concentration gradient effectively to migrate the excited energy of sensitizer to activator, effectively increase the up-conversion luminescence quantum yield of rare earth upconversion nano particle, reach 0.22%, it is 2W/cm to realize in excitation source intensity2800nm continuous lasers excite, it can produce very strong up-conversion luminescence under infrared LED light source activation, it allow by the exclusive encapsulation of infrared LED light source and array technique, the portable detection equipment based on rare earth upconversion nano particle light-emitting probe is can be designed that, has further expanded application of the up-conversion luminescent material in biomedical sector.
Description
Technical field
The present invention relates to field of nanoparticles, and in particular to a kind of rare earth upconversion nano particle and preparation method thereof and use
On the way, more particularly to one kind can be used as the high brightness rare earth upconversion nano of excitation source by the use of infrarede emitting diode (LED)
Grain (UCNPs) and its production and use.
Background technology
Rare earth up-conversion luminescence nano particle (upconversion nanoparticles UCNPs) refers to utilize light more
Son absorbs energy transfer mechanism, and a kind of emerging life of the lower visible ray that can launch high-energy is excited in the near infrared light of low energy
Thing luminescence probe material.
In recent years, along with the fast development of nanosecond science and technology, UCNPs starts to show in bioanalysis and medical imaging field
Unique advantage：1st, autofluorescence and the scattering of biological tissue efficiently avoid as excitation source using near-infrared laser
The interference of light；2nd, because excitation source is located at biological organism optical window, therefore there is very strong biological penetration.Simultaneously as
The many advantages of rare earth nano material in itself, such as the luminescent lifetime of narrow emission, length, hypotoxicity, excellent chemical stability
With photostability etc. so that UCNPs has limitless application prospect in biomedical sector.But relatively low upper of UCNPs
Change luminous efficiency so that there is the up-conversion luminescence of sufficient intensity and the different kind organism medical application based on this, generally only
Can the completion under the exciting of LASER Light Source.Application of the laser in biomedicine is also subject to many limitations, and main cause is Gao Gong
Biological tissue's fire damage caused by the laser beam of rate.
CN103450875A discloses a kind of " core-shell structure copolymer-shell " rare earth upconversion nano particle using Nd as sensitizer, its
In, the rare earth upconversion nano particle shell layer contains Nd3+, and each layer contains Yb3+.This special Nd- sensitizations
UCNPs has bigger infrared Absorption intensity than traditional Yb- sensitizations UCNPs, so as to drastically increase upper conversion effect
Rate and luminous, also, Nd- sensitization UCNPs using 800nm laser as excitation source, have than traditional 980nm excitation sources
Smaller overheating effect and stronger biological tissue's penetration power.Nevertheless, but excited needed for the rare earth upconversion nano particle
The intensity of light source is higher, and it is still relatively low to change photoluminescence quantum yield thereon.
Infrarede emitting diode (LED) is due to its relatively low luminous power and the wider angle of departure so that it is using extremely
With higher security during biomedical sector.Meanwhile cheap price, preferable service life and the portability of LED, it is easy to
Use and operate, ripe encapsulation and the features such as permutation technology so that LED can be UCNPs in biology doctor as excitation source
Further research and utilization in terms of provide new thinking and scheme.
Therefore, how using infrarede emitting diode to improve rare earth up-conversion luminescence nano particle (UCNPs) in low work(
Luminous efficiency under rate light source activation and to be applied in portable detection equipment be current urgent problem to be solved.
The content of the invention
To solve the deficiencies in the prior art, an object of the present invention is to provide a kind of optimization ytterbium ion doping concentration
Rare earth upconversion nano particle (UCNPs).
The second object of the present invention is the preparation method for providing rare earth upconversion nano particle as described above.
The third object of the present invention is the purposes for providing rare earth upconversion nano particle as described above.
To use following technical scheme up to this purpose, the present invention：
In a first aspect, the invention provides a kind of rare earth upconversion nano particle, the rare earth upconversion nano particle by
It is interior and outer include successively：Activator shell, energy transfer agent shell and sensitizer shell, and each layer contains Yb3+；Wherein, Yb3 +Doping concentration successively reduce from inside to outside.
According to the present invention, excited energy preferentially moves in ytterbium ion energy transfer medium to the high region of ytterbium ion concentration
Move, therefore the ytterbium ion doping concentration gradient of the present invention effectively can migrate the excited energy of sensitizer to activator, have
Effect ground improves UCNPs up-conversion luminescence quantum yield, reaches 0.22%, it is 2W/cm to realize in excitation source intensity2's
800nm continuous lasers are excited, and very strong up-conversion luminescence can be produced under infrared LED light source activation.
Rare earth upconversion nano particle in the present invention is using erbium ion, thulium ion or holmium ion as activator, with neodymium
Ion is as sensitizer, the rare earth using ytterbium ion as energy transfer agent (connection activator and the direct energy transfer of sensitizer)
Upper conversion nano particle (UCNPs), the ytterbium ion doping concentration in the UCNPs near activator are more than the ytterbium near sensitizer
Ion doping concentration.
In the present invention, Yb in the activator shell3+Doping concentration be 25-40%, such as can be 25%, 28%,
29%th, 30%, 31%, 32%, 35%, 38%, 40%, preferably 28-35%, more preferably 30%.
In the present invention, Yb in the energy transfer agent shell3+Doping concentration be 15-23%, such as can be 15%,
16%th, 18%, 20%, 21%, 22%, 23%, preferably 18-20%, more preferably 20%.
In the present invention, Yb in the sensitizer shell3+Doping concentration be 6-14%, such as can be 6%, 7%, 8%,
9%th, 10%, 12%, 13%, 14%, preferably 8-10%, more preferably 10%.
As further improvement of the invention, the matrix structure of the rare earth upconversion nano particle is AYF4Or AGdF4,
Wherein A is Na or K.
In the present invention, material (such as the NaYF as matrix4, NaGdF4, KYF4, KGdF4Deng), can play prevents from handing over
The effect that fork relaxation and solubility are quenched, and itself has no effect on energy transfer process.
As further improvement of the invention, the rare earth upconversion nano particle is hexagonal phase.
In the present invention, the rare earth upconversion nano particle excites in the case where wavelength is 740-850nm LED light source, such as
It can be excited under 740nm, 750nm, 780nm, 800nm, 820nm, 850nm LED light source.
As further improvement of the invention, the activator shell (activator of the rare earth upconversion nano particle
Shell, AS) structure is：AYF4:Yb, X or AGdF4:Yb, X, wherein X are Er, Tm or Ho, and wherein A is Na or K.
As further improvement of the invention, the energy transfer agent shell of the rare earth upconversion nano particle
(migrator shell, MS) structure is：AYF4:Yb or AGdF4:Yb, wherein A are Na or K.
As further improvement of the invention, the sensitizer shell (sensitizer of the rare earth upconversion nano particle
Shell, SS) structure is：ANdF4:Yb, wherein A are Na or K.
As further improvement of the invention, the activator shell and sensitizer shell of the rare earth upconversion nano particle
Between contain 2-3 energy transfer agent shell.
Preferably, the concrete structure of the rare earth upconversion nano particle is：
AS@MS@MS@SS；
AS@MS@MS@MS@SS；
SS@MS@MS@AS；
SS@MS@MS@MS@AS。
According to the present invention, it need to meet that doping from high to low is dense to SS, the doping concentration of ytterbium ion again from AS to the MS
Spend gradient.
As further improvement of the invention, the concrete structure of the rare earth upconversion nano particle is：
NaYF4:Yb,X@NaYF4:Yb@NaYF4:Yb@NaNdF4:Yb；
NaGdF4:Yb,X@NaGdF4:Yb@NaGdF4:Yb@NaNdF4:Yb；
KYF4:Yb,X@KYF4:Yb@KYF4:Yb@KNdF4:Yb；
KGdF4:Yb,X@KGdF4:Yb@KGdF4:Yb@KNdF4:Yb；
Wherein X is Er, Tm or Ho.
Second aspect, present invention also offers a kind of preparation side of the particle of rare earth upconversion nano as described in relation to the first aspect
Method, comprise the following steps：
(1) nano particle with activator shell structurre is prepared；
(2) nano particle with activator shell and energy transfer agent shell structurre is prepared；
(3) nano particle with activator shell, energy transfer agent shell and sensitizer shell structurre is prepared.
As further improvement of the invention, methods described comprises the following steps：
(1) nano particle with AS structures is prepared；
(2) nano particle with AS@MS structures is prepared；
(3) nano particle with AS@MS@MS structures is prepared；
(4) nano particle with AS@MS@MS@SS structures is prepared.
Preferably, the described method comprises the following steps：
(1) by trifluoroacetic acid rare-earth salts or rare earth fluoride salt and trifluoroacetic acid alkali metal salt or fluorination alkali metal salt massage that
Than (Na or K):(Y or Gd):Yb:X=1:(0.7-0.9):(0.3-0.35):The mixed-powder that (0.005-0.02) is prepared adds
In the mixed system for entering oleic acid and octadecylene, wherein X=Er, Tm or Ho, stirring, then heat to 260-340 DEG C and persistently add
Hot a period of time, after cooling, centrifuge, disperseed with non-polar solven, obtain dispersion liquid I；
(2) the dispersion liquid I is added containing in molar ratio (Na or K):Y:Yb=(0.3-0.6):(0.2-0.5):
The trifluoroacetic acid rare-earth salts or rare earth fluoride salt of (0.25-0.3) and trifluoroacetic acid alkali metal salt or fluorination alkali metal salt, oleic acid and
In the mixed solution of octadecylene, stirring, then heating to 260-340 DEG C, simultaneously for a period of time, after cooling, centrifugation divides continuous heating
From being disperseed with non-polar solven, obtain dispersion liquid II；
(3) the dispersion liquid II is added containing in molar ratio (Na or K):Y:Yb=1:(0.7-0.9):(0.2-0.25's)
The mixing of trifluoroacetic acid rare-earth salts or rare earth fluoride salt and trifluoroacetic acid alkali metal salt or fluorination alkali metal salt, oleic acid and octadecylene
In solution, stirring, 260-340 DEG C and continuous heating are then heated to for a period of time, after cooling, centrifuged, with nonpolar molten
Agent disperses, and obtains dispersion liquid III；
(4) the dispersion liquid III is added containing in molar ratio (Na or K):Nd:Yb=(0.5-1):(0.5-1):(0.15-
0.2) trifluoroacetic acid rare-earth salts or rare earth fluoride salt and trifluoroacetic acid alkali metal salt or fluorination alkali metal salt, oleic acid and octadecylene
Mixed solution in, stirring, then heat to 260-340 DEG C and continuous heating for a period of time, after cooling, centrifuge, obtain
The rare earth upconversion nano particle.
As further improvement of the invention, in step (1)-(4), the stirring is carried out under vacuo, the heating
Carried out under argon gas protection.
As further improvement of the invention, in step (1)-(4), 0.5-2h is reacted at described 260-340 DEG C,
After centrifugation, washed with ethanol；The non-polar solven is preferably hexamethylene.
The third aspect, present invention also offers the rare earth upconversion nano particle according to first aspect to prepare biology point
Purposes in analysis or medical imaging reagent and portable detection equipment.
Fourth aspect, present invention also offers a kind of portable detection equipment, it is with as described in relation to the first aspect on rare earth
Conversion nano particle is used as excitation source as luminescence probe using infrared LED.
The design of LED array is as shown in figure 5, it is with simple circuit (including 16 volts of batteries), by 9 in the present invention
Group near-infrared LED bulb is in parallel, and each of which group contains the near-infrared LED bulb of 5 series connection.Every group of LED connects one again to be had
There is the resistance of different resistances to adjust size of current, so as to adjust the luminous intensity of these series LEDs.These LED bulb strings
Power density is 230,201,178,153,126,98,77,64 and 51mW/cm2(from left to right), sent out so as to form a LED
Light intensity gradient.In this case, when the detection chip coated with UCNPs is placed on the near-infrared luminous diode array inspection
When surveying on device, a up-conversion luminescence bar can be observed with the naked eye clearly (as shown in Figure 5).The length of the up-conversion luminescence bar
Degree is directly related with the concentration of the UCNPs on chip, and this is due to that the detection chip of the UCNPs with higher concentration can be by more
More hairs of the near-infrared LED series excitation with relatively low luminous intensity.Therefore, by simply checking that the length of up-conversion luminescence bar can
Directly to read the concentration of UCNPs in detection chip (0.02-1 mg/mls).
Compared with prior art, the present invention at least has the advantages that：
(1) present invention by set ytterbium ion doping concentration gradient can effectively by the excited energy of sensitizer migrate to
Activator, UCNPs up-conversion luminescence quantum yield is drastically increased, 0.22% is reached, realizes in excitation source
Intensity is 2W/cm2800nm continuous lasers excite.
(2) rare earth upconversion nano particle of the present invention can produce very strong upper conversion under infrared LED light source activation
It is luminous, fuel factor caused by traditional 980nm laser irradiation biological sample is not only effectively prevent, and drastically increase and excite
The penetration depth of light source, improve luminous efficiencies of the UCNPs in the case where low power sources excite so that it can be by infrared LED
The exclusive encapsulation of light source and array technique, design the portable detection equipment based on UCNPs luminescence probes, have expanded upper conversion hair
Application of the luminescent material in biological field.
Brief description of the drawings
Fig. 1 is commercially available 740-nm, and the transmitting spectrogram (a) of 850-nm and 940-nm LED light sources and the UCNPs of embodiment 1 exist
740-nm, 850-nm and 940-nm LED light source excite spectrogram (b)；
Fig. 2 is to adulterate the UCNPs of erbium ion, thulium ion and holmium ion in embodiment 1-3 respectively in 740-nm, 850-nm and
Luminous photo figure and corresponding luminescent spectrum figure under 940-nm LED light source excitations；
Wherein, Fig. 2 a-2d are the UCNPs of doping erbium ion in 740-nm (a), 850-nm (b) and 940-nm (c) LED light
Luminous photo figure and corresponding luminescent spectrum figure (d) under source excitation；Fig. 2 e-2h are the UCNPs of doping thulium ion in 740-
Luminous photo figure and corresponding luminescent spectrum figure (h) under nm (e), 850-nm (f) and 940-nm (g) LED light source excitation；Figure
2i-2l is luminous photographs of the UCNPs of doping holmium ion under 740-nm (i), 850-nm (j) and 940-nm (k) LED light source excitation
Piece figure and corresponding luminescent spectrum figure (l)；
Fig. 3 is with different Yb ion doping concentration gradients (α:β:γ refers to activator shell respectively from left to right, energy moves
Move the doping concentration of Yb ions in agent shell and sensitizer shell) UCNPs luminescent spectrum figure compare；
Wherein, Fig. 3 a-3c are that total concentration of the Yb ions in UCNPs is 10mol% (a), 20mol% (b) and 30mol%
(c)；Fig. 3 d-3f are Yb ions in α:β:γ=30:20:The schematic diagram (d) of distribution situation, transmission electron microscope picture in 10 UCNPs
And corresponding energy dispersion X-ray spectrum linear sweep graph (f) (e)；
Fig. 4 is α:β:γ=30:20:The absolute quantum yield that 10 UCNPs is measured under different excitation light power density；
Fig. 5 is the design using infrared LED as the portable detection equipment of excitation source using UCNPs as luminescence probe
Schematic diagram (a) and the detection chip with different UCNPs concentration show that the upper conversion of different length is sent out on the detection device
Striation (b).
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in understanding the present invention, is not construed as the concrete restriction to the present invention.
Embodiment 1：Rare earth upconversion nano particle NaYF4:Yb,Er@NaYF4:Yb@NaNdF4:Yb
To stoichiometrically CF3COONa:(CF3COO)3Y:(CF3COO)3Yb:(CF3COO)3Er=1mmol:
0.78mmol:0.3mmol:The mixed-powder that 0.02mmol has been configured adds oleic acid (10mL), the mixture of octadecylene (20mL)
In system, 30min is stirred at 120 DEG C of vacuum, then 320 DEG C is warming up under argon gas protection and continues 1h；After cooling, centrifugation point
After being washed 1-2 times from, ethanol, disperseed with 2mL hexamethylenes, obtain dispersion liquid I.
Dispersion liquid I is added and contains CF3COONa:(CF3COO)3Y:(CF3COO)3Yb=0.3mmol:0.27mmol:
0.9mmol, oleic acid (20mL), in the mixed solution of octadecylene (20mL), 30min is stirred at 120 DEG C of vacuum, then protected in argon gas
300 DEG C are warming up under shield and continues 1h；After cooling, centrifuge, after ethanol washs 1-2 times, disperseed with 2mL hexamethylenes, obtained
Dispersion liquid II.
Dispersion liquid II is added and contains CF3COONa:(CF3COO)3Y:(CF3COO)3Yb=1mmol:0.7mmol:
0.25mmol, oleic acid (10mL), in the mixed solution of octadecylene (20mL), 30min is stirred at 120 DEG C of vacuum, then in argon gas
300 DEG C are warming up under protection and continues 1h；After cooling, centrifuge, after ethanol washs 1-2 times, disperseed with 2mL hexamethylenes, obtained
To dispersion liquid III.
Dispersion liquid III is added and contains CF3COONa:(CF3COO)3Nd:(CF3COO)3Yb=0.5mmol:0.7mmol:
0.15mmol, oleic acid (10mL), in the mixed solution of octadecylene (20mL), 30min is stirred at 120 DEG C of vacuum, then in argon gas
300 DEG C are warming up under protection and continues 1h；After cooling, centrifuge, after ethanol washs 1-2 times, last 70 DEG C are dried in vacuo
To the UCNPs.
Fig. 1 is commercially available 740-nm, the transmitting spectrogram (a) of 850-nm and 940-nm LED light sources and the UCNPs of the present embodiment
Excite spectrogram (b).It will be seen from figure 1 that 740-nm LED emission peak and UCNPs excite the peak match preferable, therefore this is specially
Profit is using 740-nm LED as excitation source.
Embodiment 2：Rare earth upconversion nano particle NaYF4:Yb,Tm@NaYF4:Yb@NaNdF4:Yb
To stoichiometrically CF3COONa:(CF3COO)3Y:(CF3COO)3Yb:(CF3COO)3Tm=1mmol:
0.71mmol:0.32mmol:The mixed-powder that 0.005mmol has been configured adds oleic acid (10mL), the mixing of octadecylene (20mL)
In system, 30min is stirred at 120 DEG C of vacuum, then 320 DEG C is warming up under argon gas protection and continues 1h；After cooling, centrifugation point
After being washed 1-2 times from, ethanol, disperseed with 2mL hexamethylenes, obtain dispersion liquid I.
Dispersion liquid I is added and contains CF3COONa:(CF3COO)3Y:(CF3COO)3Yb=1mmol:0.75mmol:
0.25mmol, oleic acid (20mL), in the mixed solution of octadecylene (20mL), 30min is stirred at 120 DEG C of vacuum, then in argon gas
300 DEG C are warming up under protection and continues 1h；After cooling, centrifuge, after ethanol washs 1-2 times, disperseed with 2mL hexamethylenes, obtained
To dispersion liquid II.
Dispersion liquid II is added and contains CF3COONa:(CF3COO)3Y:(CF3COO)3Yb=0.2mmol:0.14mmol:
0.5mmol, oleic acid (10mL), in the mixed solution of octadecylene (20mL), 30min is stirred at 120 DEG C of vacuum, then protected in argon gas
300 DEG C are warming up under shield and continues 1h；After cooling, centrifuge, after ethanol washs 1-2 times, disperseed with 2mL hexamethylenes, obtained
Dispersion liquid III.
Dispersion liquid III is added and contains CF3COONa:(CF3COO)3Nd:(CF3COO)3Yb=0.6mmol:0.7mmol:
0.18mmol, oleic acid (10mL), in the mixed solution of octadecylene (20mL), 30min is stirred at 120 DEG C of vacuum, then in argon gas
300 DEG C are warming up under protection and continues 1h；After cooling, centrifuge, after ethanol washs 1-2 times, last 70 DEG C are dried in vacuo
To the UCNPs.
Embodiment 3：Rare earth upconversion nano particle NaYF4:Yb,Ho@NaYF4:Yb@NaNdF4:Yb
To stoichiometrically CF3COONa:(CF3COO)3Y:(CF3COO)3Yb:(CF3COO)3Ho=1mmol:
0.9mmol:0.35mmol:The mixed-powder that 0.015mmol has been configured adds oleic acid (10mL), the mixture of octadecylene (20mL)
In system, 30min is stirred at 120 DEG C of vacuum, then 320 DEG C is warming up under argon gas protection and continues 1h；After cooling, centrifugation point
After being washed 1-2 times from, ethanol, disperseed with 2mL hexamethylenes, obtain dispersion liquid I.
Dispersion liquid I is added and contains CF3COONa:(CF3COO)3Y:(CF3COO)3Yb=1mmol:0.9mmol:0.9mmol,
Oleic acid (20mL), in the mixed solution of octadecylene (20mL), 30min is stirred at 120 DEG C of vacuum, then heated up under argon gas protection
To 300 DEG C and continue 1h；After cooling, centrifuge, after ethanol washs 1-2 times, disperseed with 2mL hexamethylenes, obtain dispersion liquid II.
Dispersion liquid II is added and contains CF3COONa:(CF3COO)3Y:(CF3COO)3Yb=0.2mmol:0.18mmol:
0.5mmol, oleic acid (10mL), in the mixed solution of octadecylene (20mL), 30min is stirred at 120 DEG C of vacuum, then protected in argon gas
300 DEG C are warming up under shield and continues 1h；After cooling, centrifuge, after ethanol washs 1-2 times, disperseed with 2mL hexamethylenes, obtained
Dispersion liquid III.
Dispersion liquid III is added and contains CF3COONa:(CF3COO)3Nd:(CF3COO)3Yb=1mmol:1mmol:0.2mmol,
Oleic acid (10mL), in the mixed solution of octadecylene (20mL), 30min is stirred at 120 DEG C of vacuum, then heated up under argon gas protection
To 300 DEG C and continue 1h；After cooling, centrifuge, after ethanol washs 1-2 times, last 70 DEG C of vacuum drying obtain described
UCNPs。
Fig. 2 is to adulterate the UCNPs of erbium ion, thulium ion and holmium ion in embodiment 1-3 respectively in 740-nm, 850-nm and
Luminous photo figure and corresponding luminescent spectrum figure under 940-nm LED light source excitations.Figure it is seen that embodiment 1-3
UCNPs bright up-conversion luminescence can be produced under the exciting of LED light source；And the UCNPs of 740-nm LED light source excitations
With stronger up-conversion luminescence.
Fig. 3 is with different Yb ion doping concentration gradients (α:β:γ refers to activator shell respectively from left to right, energy moves
Move the doping concentration of Yb ions in agent shell and sensitizer shell) UCNPs luminescent spectrum figure compare.Fig. 4 is α:β:γ=
30:20:The absolute quantum yield that 10 UCNPs is measured under different excitation light power density.
Table 1 shows the inductivity coupled plasma mass spectrometry of the UCNPs with different Yb ion doping concentration gradients, display
Yb ions gross mass content in UCNPs.
By Fig. 3 and table 1 as can be seen that when total Yb ion dopings concentration keeps constant in UCNPs, have from high to low
The UCNPs of Yb ion doping concentration gradients show stronger up-conversion luminescence.As seen from Figure 4, excitation light power is worked as
Density is 2W/cm2When, the measured value of UCNPs absolute quantum yield is 0.22%.
Table 1
Embodiment 4：Rare earth upconversion nano particle KYF4:Yb,Er@KYF4:Yb@KNdF4:Yb
To stoichiometrically CF3COOK:(CF3COO)3Y:(CF3COO)3Yb:(CF3COO)3Er=1mmol:
0.8mmol:0.32mmol:The mixed-powder that 0.01mmol has been configured adds oleic acid (10mL), the mixture of octadecylene (20mL)
In system, 30min is stirred at 120 DEG C of vacuum, then 320 DEG C is warming up under argon gas protection and continues 1h；After cooling, centrifugation point
After being washed 1-2 times from, ethanol, disperseed with 2mL hexamethylenes, obtain dispersion liquid I.
Dispersion liquid I is added and contains CF3COOK:(CF3COO)3Y:(CF3COO)3Yb=0.35mmol:0.27mmol:
0.9mmol, oleic acid (20mL), in the mixed solution of octadecylene (20mL), 30min is stirred at 120 DEG C of vacuum, then protected in argon gas
300 DEG C are warming up under shield and continues 1h；After cooling, centrifuge, after ethanol washs 1-2 times, disperseed with 2mL hexamethylenes, obtained
Dispersion liquid II.
Dispersion liquid II is added and contains CF3COOK:(CF3COO)3Y:(CF3COO)3Yb=1mmol:0.75mmol:
0.23mmol, oleic acid (10mL), in the mixed solution of octadecylene (20mL), 30min is stirred at 120 DEG C of vacuum, then in argon gas
300 DEG C are warming up under protection and continues 1h；After cooling, centrifuge, after ethanol washs 1-2 times, disperseed with 2mL hexamethylenes, obtained
To dispersion liquid III.
Dispersion liquid III is added and contains CF3COOK:(CF3COO)3Nd:(CF3COO)3Yb=0.56mmol:0.79mmol:
0.18mmol, oleic acid (10mL), in the mixed solution of octadecylene (20mL), 30min is stirred at 120 DEG C of vacuum, then in argon gas
300 DEG C are warming up under protection and continues 1h；After cooling, centrifuge, after ethanol washs 1-2 times, last 70 DEG C are dried in vacuo
To the UCNPs.
Embodiment 5：The LED array of rare earth upconversion nano particle comprising embodiment 1
Fig. 5 is the design using infrared LED as the portable detection equipment of excitation source using UCNPs as luminescence probe
Schematic diagram (a) and the detection chip with different UCNPs concentration show that the upper conversion of different length is sent out on the detection device
Striation (b).As seen from Figure 5, by simply checking that the length of up-conversion luminescence bar can be directly to read detection chip
Upper UCNPs concentration (0.02-1 mg/mls).
As can be seen from the above-described embodiment, the present invention in, excited energy in ytterbium ion energy transfer medium preferentially to
The high zone migration of ytterbium ion concentration, therefore the ytterbium ion doping concentration gradient effectively can move the excited energy of sensitizer
Activator is moved to, effectively improves UCNPs up-conversion luminescence quantum yield (0.22%；2W/cm2800nm continuous lasers swash
Hair), it has exceeded current neodymium ion sensitization UCNPs and had reported highest quantum yield (i.e. disclosed in CN103450875A
The up-conversion luminescence quantum yield of rare earth upconversion nano particle (UCNPs) with " core-shell structure copolymer-shell " structure is 0.11%；
20W/cm2800nm continuous lasers excite).It is significant to note that UCNPs quantum yield and the light intensity of excitation source
It is directly proportional, excitation source intensity 2W/cm of the present invention2Far below 20W/cm2, therefore the UCNPs of the present invention upper conversion hair
Quantum yield has been greatly improved, thus UCNPs of the present invention can be produced under infrared LED light source activation it is very strong
Up-conversion luminescence.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (21)
1. a kind of rare earth upconversion nano particle, it is characterised in that the rare earth upconversion nano particle wraps successively from inside to outside
Include：Activator shell, energy transfer agent shell and sensitizer shell, and each layer contains Yb3+；Wherein, Yb3+Doping concentration
Successively reduce from inside to outside；
The matrix structure of the rare earth upconversion nano particle is AYF4Or AGdF4, wherein A is Na or K；
The rare earth upconversion nano particle is using erbium ion, thulium ion or holmium ion as activator, using neodymium ion as quick
Agent, energy transfer agent is used as using ytterbium ion；
Yb in the activator shell3+Doping concentration be 25-40%；
Yb in the energy transfer agent shell3+Doping concentration be 15-23%；
Yb in the sensitizer shell3+Doping concentration be 6-14%.
2. rare earth upconversion nano particle according to claim 1, it is characterised in that Yb in the activator shell3+'s
Doping concentration is 28-35%.
3. rare earth upconversion nano particle according to claim 2, it is characterised in that Yb in the activator shell3+'s
Doping concentration is 30%.
4. rare earth upconversion nano particle according to claim 1, it is characterised in that Yb in the energy transfer agent shell3 +Doping concentration be 18-20%.
5. rare earth upconversion nano particle according to claim 4, it is characterised in that Yb in the energy transfer agent shell3 +Doping concentration be 20%.
6. rare earth upconversion nano particle according to claim 1, it is characterised in that Yb in the sensitizer shell3+'s
Doping concentration is 8-10%.
7. rare earth upconversion nano particle according to claim 6, it is characterised in that Yb in the sensitizer shell3+'s
Doping concentration is 10%.
8. rare earth upconversion nano particle according to claim 1, it is characterised in that the rare earth upconversion nano particle
For hexagonal phase.
9. rare earth upconversion nano particle according to claim 1, it is characterised in that the rare earth upconversion nano particle
Excited in the case where wavelength is 740-850nm LED light source.
10. rare earth upconversion nano particle according to claim 1, it is characterised in that the rare earth upconversion nano
Grain activator shell structurre be：AYF4:Yb, X or AGdF4:Yb, X, wherein X are Er, Tm or Ho, and wherein A is Na or K.
11. rare earth upconversion nano particle according to claim 1, it is characterised in that the rare earth upconversion nano
Grain energy transfer agent shell structurre be：AYF4:Yb or AGdF4:Yb, wherein A are Na or K.
12. rare earth upconversion nano particle according to claim 1, it is characterised in that the rare earth upconversion nano
Grain sensitizer shell structurre be：ANdF4:Yb, wherein A are Na or K.
13. rare earth upconversion nano particle according to claim 1, it is characterised in that the rare earth upconversion nano
Contain 2-3 energy transfer agent shell between the activator shell and sensitizer shell of grain.
14. rare earth upconversion nano particle according to claim 1, it is characterised in that the rare earth upconversion nano
Grain concrete structure be：
NaYF4:Yb,X@NaYF4:Yb@NaYF4:Yb@NaNdF4:Yb；
NaGdF4:Yb,X@NaGdF4:Yb@NaGdF4:Yb@NaNdF4:Yb；
KYF4:Yb,X@KYF4:Yb@KYF4:Yb@KNdF4:Yb；
KGdF4:Yb,X@KGdF4:Yb@KGdF4:Yb@KNdF4:Yb；
Wherein X is Er, Tm or Ho.
15. the preparation method of the rare earth upconversion nano particle according to claim any one of 1-14, it is characterised in that institute
The method of stating comprises the following steps：
(1) nano particle with activator shell structurre is prepared；
(2) nano particle with activator shell and energy transfer agent shell structurre is prepared；
(3) nano particle with activator shell, energy transfer agent shell and sensitizer shell structurre is prepared.
16. according to the method for claim 15, it is characterised in that the described method comprises the following steps：
(1) by trifluoroacetic acid rare-earth salts or rare earth fluoride salt and trifluoroacetic acid alkali metal salt or fluorination alkali metal salt in molar ratio
(Na or K):(Y or Gd):Yb:X=1:(0.7-0.9):(0.3-0.35):The mixed-powder that (0.005-0.02) is prepared adds
In the mixed system of oleic acid and octadecylene, wherein X=Er, Tm or Ho, stirring, 260-340 DEG C of simultaneously continuous heating is then heated to
For a period of time, after cooling, centrifuge, disperseed with non-polar solven, obtain dispersion liquid I；
(2) the dispersion liquid I is added containing in molar ratio (Na or K):Y:Yb=(0.3-0.6):(0.2-0.5):(0.25-
0.3) trifluoroacetic acid rare-earth salts or rare earth fluoride salt and trifluoroacetic acid alkali metal salt or fluorination alkali metal salt, oleic acid and octadecylene
Mixed solution in, stirring, then heat to 260-340 DEG C and continuous heating for a period of time, after cooling, centrifuge, use is non-
Polar solvent disperses, and obtains dispersion liquid II；
(3) the dispersion liquid II is added containing in molar ratio (Na or K):Y:Yb=1:(0.7-0.9):The trifluoro of (0.2-0.25)
Acetic acid rare-earth salts or rare earth fluoride salt and trifluoroacetic acid alkali metal salt or fluorination alkali metal salt, the mixed solution of oleic acid and octadecylene
In, stirring, then heat to 260-340 DEG C and continuous heating for a period of time, after cooling, centrifuge, with non-polar solven point
Dissipate, obtain dispersion liquid III；
(4) the dispersion liquid III is added containing in molar ratio (Na or K):Nd:Yb=(0.5-1):(0.5-1):(0.15-0.2)
Trifluoroacetic acid rare-earth salts or rare earth fluoride salt and trifluoroacetic acid alkali metal salt or fluorination alkali metal salt, oleic acid and octadecylene it is mixed
Close in solution, stirring, then heat to 260-340 DEG C and continuous heating for a period of time, after cooling, centrifuge, obtain described
Rare earth upconversion nano particle.
17. according to the method for claim 16, it is characterised in that in step (1)-(4), the stirring is entered under vacuo
OK, the heating is carried out under argon gas protection.
18. according to the method for claim 16, it is characterised in that in step (1)-(4), at described 260-340 DEG C
0.5-2h is reacted, after centrifugation, is washed with ethanol.
19. according to the method for claim 16, it is characterised in that in step (1)-(3), the non-polar solven is ring
Hexane.
20. the rare earth upconversion nano particle according to claim any one of 1-14 is preparing bioanalysis or medical imaging
Purposes in reagent and portable detection equipment.
21. a kind of portable detection equipment, it is characterised in that it is to be changed as described in claim any one of 1-14 on rare earth
Nano particle is used as excitation source as luminescence probe using infrared LED.
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| CN112898977B (en) * | 2021-01-21 | 2022-04-29 | 广州大学 | Terbium ion doped up-conversion nano material and preparation method thereof |
| CN112724978B (en) * | 2021-01-21 | 2022-04-29 | 广州大学 | Core-shell structure up-conversion nano material and preparation method thereof |
| CN115029136A (en) * | 2021-03-03 | 2022-09-09 | 上海交通大学 | Fluidized chemical mass production method of rare earth fluoride nanoparticles |
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