CN114752385B - Gd (Gd) type drug delivery device 3+ Doped microcrystalline material and preparation method and application thereof - Google Patents
Gd (Gd) type drug delivery device 3+ Doped microcrystalline material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of rare earth luminescent materials, and discloses a Gd 3+ Doped microcrystalline material, preparation method and application thereof, and preparation method and application thereofMicrocrystalline material through Gd 3+ Doped matrix material LiYF 4 :Yb 3+ /Ho 3+ Y-site of the microcrystal is obtained, gd 3+ The doping concentration of the rare earth elements in the micro-crystal material is less than or equal to 60mol percent of the total amount of the rare earth elements; the preparation method comprises the following steps: dispersing the dispersant in water solvent, adding RE element source and matrix source successively, mixing, maintaining at 210-250 deg.c for 24-60 hr to obtain micron crystal material. Gd for the invention 3+ Replacement part LiYF 4 Y in the crystal 3+ Causing LiYF to 4 Crystal lattice distortion, reduced symmetry of crystal field, transition probability and Ho 3+ Excited state particle number increases, yb 3+ With Ho 3+ Increased inter-energy transfer, ho 3+ Up-conversion luminescence enhancement of (c).
Description
Technical Field
The invention relates to the technical field of rare earth luminescent materials, in particular to Gd 3+ Doped microcrystalline material, and preparation method and application thereof are provided.
Background
In recent years, rare earth functional materials have wide application in various industries, and the application of rare earth luminescent materials has been the focus and hot spot of research. And the rare earth element has the optical property generated by the unique 4f electronic configuration, so that the rare earth element doped luminescent material has extremely rich luminescent color and good emission efficiency in a visible light wave band.
However, the existing rare earth luminescent material has low up-conversion fluorescence efficiency and low luminous intensity, so that the application of the rare earth luminescent material in various fields is limited.
To this end, the present invention provides a Gd 3+ Doped microcrystalline material, and preparation method and application thereof are provided.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a Gd 3+ Doped microcrystalline material, and preparation method and application thereof are provided.
Gd of the invention 3+ The doped microcrystalline material and the preparation method and application thereof are realized by the following technical scheme:
it is a first object of the present invention to provide a Gd 3+ Doped with microcrystalline material in LiYF 4 :Yb 3+ /Ho 3+ Microcrystals as matrix material and made of Gd 3+ Doped LiYF 4 :Yb 3+ /Ho 3+ The Y-site of the microcrystal is obtained and the chemical formula is LiYF 4 :Yb 3+ /Ho 3+ /Gd 3+ ；
Wherein Gd 3+ The doping concentration of the rare earth element is less than or equal to 60mol percent of the total amount of the rare earth element in the micrometer crystal material.
Further, yb 3+ The doping concentration of the rare earth element is 20mol% of the total amount of the rare earth elements in the micro-crystal material;
Ho 3+ the doping concentration of (2) is 1mol% of the total rare earth elements in the microcrystalline material.
Further, the micron crystal material realizes fluorescent emission with the wavelength of 450-770 nm under the excitation of 980nm laser.
Further, its main emission peaks include: a weak blue emission peak at 480nm, a strong green emission peak at 535-543 nm, a weak red emission peak at 638-657 nm, and a near infrared emission peak at 750 nm.
A second object of the present invention is to provide a method for preparing any of the above-mentioned microcrystalline materials, comprising the steps of:
dissolving and uniformly dispersing a dispersing agent in an aqueous solvent, then adding a rare earth element source, and uniformly mixing to obtain a first mixed material;
adding a matrix source into the first mixed material, uniformly mixing, and then preserving heat for 24-60 hours at the temperature of 210-250 ℃ to obtain Gd 3+ Doping the microcrystalline material;
wherein the matrix source comprises fluoride ions and lithium ions.
Further, the dispersing agent is one of EDTA, oleic acid, ethanol and polyethylene glycol.
Further, the rare earth element source comprises Gd 3+ 、Yb 3+ 、Ho 3+ And Y 3+ ；
Wherein Gd 3+ The molar concentration of (2) is less than or equal to 60mol% of the rare earth element source; yb 3+ Is 20mol% of the rare earth element source, ho 3+ The molar concentration of (2) is 1mol% of the rare earth element source.
Further, the rare earth element source is any one of nitrate, oxide and acetate of each rare earth element.
Further, the matrix source is LiF and NH 4 F, and LiF and NH 4 The molar ratio of F is 3-5:1.
Further, the dosage ratio of the dispersing agent to the water solvent is 1 mmol:15-25 mL;
the volume ratio of the total molar weight of the rare earth elements in the rare earth element source to the water solvent is 1 mmol:15-25 mL;
the molar ratio of the matrix source to the rare earth element source is 20-30:1.
A third object of the present invention is to provide a Gd as defined above 3+ The application of doped micron crystal material in preparing anti-fake identifying material.
Compared with the prior art, the invention has the following beneficial effects:
the invention uses LiYF 4 :Yb 3+ /Ho 3+ Microcrystals as matrix material and made of Gd 3+ Doped LiYF 4 :Yb 3+ /Ho 3+ The Y-site of the microcrystal is obtained by Gd 3+ Y of ion co-doping substitution part 3+ After the ion position, liYF 4 The crystal lattice of the crystal is distorted, thereby reducing LiYF 4 So that the probability of transition and Ho 3+ Increasing the number of excited state particles and simultaneously making Yb 3+ Ion and Ho 3+ Between ionsThe energy transfer rate of (2) is also increased, thereby enabling Ho 3+ The up-conversion luminescence of the ions is significantly enhanced.
The invention successfully prepares Gd by a hydrothermal synthesis method 3+ Doped with microcrystalline material and prepared Gd 3+ The doped microcrystalline material has a pure tetragonal phase with highly stable and efficient up-conversion luminescence properties, a monodisperse octahedral shape with a size of about 60 μm. And Gd 3+ The luminous intensity of the doped microcrystal material is greatly improved compared with that of undoped microcrystal material, such as Gd 3+ The micro-crystal with the doping concentration of 30mol percent is compared with the undoped Gd 3+ The luminous intensity of (C) was increased by about 3 times as a whole, indicating Gd 3+ Incorporation into LiYF 4 The lattice distortion of the crystal improves the up-conversion luminous efficiency and the up-conversion luminous intensity of the sample.
At excitation power of 0.5-1.5W, the ratio of green to red intensity (I) R /I G ) Only about 13% change occurred, indicating that the prepared microcrystals of the present invention have high stability green luminescence at different excitation powers.
The anti-counterfeiting ink is prepared from the microparticle crystal prepared by the invention, the anti-counterfeiting pattern prepared by screen printing does not emit light in a natural light environment, and the pattern shows bright green light under the irradiation of 980nm laser, which indicates that the microparticle crystal prepared by the invention has good up-conversion luminescence performance, thereby having wide application prospect in the anti-counterfeiting technical field.
Drawings
FIG. 1 is an X-ray diffraction pattern of comparative example 1, example 1-example 6 microns crystals of the present invention;
FIG. 2 is an X-ray diffraction pattern of a microcrystal of the present invention; wherein, fig. 2 (a), 2 (b) and (c) are SEM spectra of the microcrystalline materials of comparative example 1, example 3 and example 5, respectively;
FIG. 3 shows the fluorescence spectrum test results of the microcrystalline materials of comparative example 1 and example 6 of the present invention; wherein, FIG. 3 (a) is a fluorescence spectrum of the microcrystalline materials of comparative example 1, example 1-example 6, and FIG. 3 (b) is a luminescence spectrum of the microcrystalline materials of comparative example 1, example 1-example 6 irradiated with 980nm laser light in dark environment;
FIG. 4 (a) is a graph showing the comparison of fluorescence intensities of the crystals of comparative example 1 and example 3; FIG. 4 (b) is a schematic representation of the energy level transition of the microcrystals of the present invention under excitation by 980nm laser;
FIG. 5 (a) is a graph showing the change in intensity of the strongest up-conversion luminescence portion (green luminescence) of the microcrystalline materials of comparative example 1, examples 1-6 of the present invention under 980nm laser excitation; FIG. 5 (b) is the ratio of the integrated intensities of the green emission peak and the red emission peak of the microcrystalline materials of comparative example 1, examples 1-6 of the present invention;
FIG. 6 is a graph showing fluorescence change at different excitation powers for the microcrystals of example 3 of the present invention; FIG. 6 (a) is a graph showing fluorescence spectra of the crystals of example 3 according to the present invention under excitation with 980nm laser having a variable excitation power of 0.5 to 1.5W, and FIG. 6 (b) is a graph showing the ratio (I) of the intensity of red light emission to the intensity of green light emission of the crystals of example 3 according to the present invention under excitation power of 0.5 to 1.5W R /I G )；
FIG. 7 (a) is a screen printing process diagram of the security pattern of the present invention; fig. 7 (b) is a schematic diagram of an up-conversion luminescent anti-counterfeiting pattern prepared by the method, wherein the left side of fig. 7 (b) is an anti-counterfeiting pattern printed on glass under natural light, and the right side of fig. 7 (b) is a luminescent picture of the anti-counterfeiting pattern under 980nm laser irradiation.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. In the following examples of the present invention, gd 3+ The doping concentration of (a) refers to Gd 3+ Occupy LiYF 4 :Yb 3+ /Ho 3 + /Gd 3+ Mole percent of total rare earth elements in the microcrystalline material.
Example 1
The present embodiment provides a Gd 3+ Doped microcrystalline material, in this embodiment, of the formula LiYF 4 :Yb 3+ /Ho 3+ /Gd 3+ And Gd 3+ Is doped at LiYF 4 :Yb 3+ /Ho 3+ /Gd 3+ 10mol% of the total amount of the rare earth elements, yb 3+ Is doped at LiYF 4 :Yb 3+ /Ho 3+ /Gd 3+ 20mol% of the total amount of the rare earth elements, ho 3+ Is doped at LiYF 4 :Yb 3+ /Ho 3+ /Gd 3+ 1mol% of the total amount of rare earth elements, the microcrystalline material of this example is denoted as LiY 0.69 F 4 :Yb 0.2 /Ho 0.01 /Gd 0.1 。
And the preparation method of the microcrystalline material of the embodiment is as follows:
placing 1mmol of dispersant EDTA into 20mL of water, heating at a constant temperature of 60 ℃ and stirring at a speed of 1200r/min for 10min to enable EDTA to be fully dissolved and uniformly dispersed in the water, then adding 1mmol of rare earth element source, continuously stirring at a speed of 1200r/min for 10min, and uniformly mixing to obtain a first mixed material;
adding a matrix source into the first mixed material, stirring at a speed of 1200r/min for 30min to make the solution milky, slowly pouring the solution into a 100mL high-pressure reaction kettle, then placing the solution at a temperature of 230 ℃ for 48h, carrying out solid-liquid separation, washing the obtained white solid with absolute ethyl alcohol and ultrapure water respectively to remove impurities, and then drying the washed solid in a vacuum drying oven at 60 ℃ for 12h to obtain Gd 3+ Doping the microcrystalline material.
In this embodiment, the rare earth element source is Y (NO 3 ) 3 ·6H 2 O、Gd(NO 3 ) 3 ·6H 2 O、Yb(NO 3 ) 3 ·5H 2 O and Ho (NO) 3 ) 3 ·5H 2 Mixed solution of O, and Y (NO 3 ) 3 ·6H 2 O、Gd(NO 3 ) 3 ·6H 2 O、Yb(NO 3 ) 3 ·5H 2 O and Ho (NO) 3 ) 3 ·5H 2 The molar ratio of O was 0.69:0.1:0.2:0.01.
In this example, the substrate source is 20mmol LiF and 5mmol NH 4 Mixed solution of F.
Example 2
The embodiment provides a Gd-doped material 3+ LiYF of (F) 4 :Yb 3+ /Ho 3+ The microcrystalline material, in this example, has the formula LiYF 4 :Yb 3+ /Ho 3+ /Gd 3+ And Gd 3+ Is doped at LiYF 4 :Yb 3+ /Ho 3+ /Gd 3+ 20mol% of total rare earth elements, yb 3+ Is doped at LiYF 4 :Yb 3+ /Ho 3+ /Gd 3+ 20mol% of the total amount of the rare earth elements, ho 3+ Is doped at LiYF 4 :Yb 3+ /Ho 3+ /Gd 3+ The microcrystalline material of this example was designated as LiY with 1mol% of the total amount of rare earth elements 0.59 F 4 :Yb 0.2 /Ho 0.01 /Gd 0.2 。
And the preparation method of the microcrystalline material of this embodiment is different from that of embodiment 1 only in that:
in this embodiment, the rare earth element source is Y (NO 3 ) 3 ·6H 2 O、Gd(NO 3 ) 3 ·6H 2 O、Yb(NO 3 ) 3 ·5H 2 O and Ho (NO) 3 ) 3 ·5H 2 Mixed solution of O, and Y (NO 3 ) 3 ·6H 2 O、Gd(NO 3 ) 3 ·6H 2 O、Yb(NO 3 ) 3 ·5H 2 O and Ho (NO) 3 ) 3 ·5H 2 The molar ratio of O was 0.59:0.2:0.2:0.01.
Example 3
The embodiment provides a Gd-doped material 3+ LiYF of (F) 4 :Yb 3+ /Ho 3+ The microcrystalline material, in this example, has the formula LiYF 4 :Yb 3+ /Ho 3+ /Gd 3+ And Gd 3+ Is doped at LiYF 4 :Yb 3+ /Ho 3+ /Gd 3+ 30mol% of the total amount of the medium rare earth elements, yb 3+ Is doped at LiYF 4 :Yb 3+ /Ho 3+ /Gd 3+ 20mo of total amount of rare earth elementsl％，Ho 3+ Is doped at LiYF 4 :Yb 3+ /Ho 3+ /Gd 3+ The microcrystalline material of this example was designated as LiY with 1mol% of the total amount of rare earth elements 0.49 F 4 :Yb 0.2 /Ho 0.01 /Gd 0.3 . And the preparation method of the microcrystalline material of this embodiment is different from that of embodiment 1 only in that:
in this embodiment, the rare earth element source is Y (NO 3 ) 3 ·6H 2 O、Gd(NO 3 ) 3 ·6H 2 O、Yb(NO 3 ) 3 ·5H 2 O and Ho (NO) 3 ) 3 ·5H 2 Mixed solution of O, and Y (NO 3 ) 3 ·6H 2 O、Gd(NO 3 ) 3 ·6H 2 O、Yb(NO 3 ) 3 ·5H 2 O and Ho (NO) 3 ) 3 ·5H 2 The molar ratio of O was 0.49:0.3:0.2:0.01.
Example 4
The embodiment provides a Gd-doped material 3+ LiYF of (F) 4 :Yb 3+ /Ho 3+ The microcrystalline material, in this example, has the formula LiYF 4 :Yb 3+ /Ho 3+ /Gd 3+ And Gd 3+ Is doped at LiYF 4 :Yb 3+ /Ho 3+ /Gd 3+ 40mol% of the total amount of the medium rare earth elements, yb 3+ Is doped at LiYF 4 :Yb 3+ /Ho 3+ /Gd 3+ 20mol% of the total amount of the rare earth elements, ho 3+ Is doped at LiYF 4 :Yb 3+ /Ho 3+ /Gd 3+ The microcrystalline material of this example was designated as LiY with 1mol% of the total amount of rare earth elements 0.39 F 4 :Yb 0.2 /Ho 0.01 /Gd 0.4 . And the preparation method of the microcrystalline material of this embodiment is different from that of embodiment 1 only in that:
in this embodiment, the rare earth element source is Y (NO 3 ) 3 ·6H 2 O、Gd(NO 3 ) 3 ·6H 2 O、Yb(NO 3 ) 3 ·5H 2 O and Ho (NO) 3 ) 3 ·5H 2 Mixed solution of O, and Y (NO 3 ) 3 ·6H 2 O、Gd(NO 3 ) 3 ·6H 2 O、Yb(NO 3 ) 3 ·5H 2 O and Ho (NO) 3 ) 3 ·5H 2 The molar ratio of O was 0.39:0.4:0.2:0.01.
Example 5
The embodiment provides a Gd-doped material 3+ LiYF of (F) 4 :Yb 3+ /Ho 3+ The microcrystalline material, in this example, has the formula LiYF 4 :Yb 3+ /Ho 3+ /Gd 3+ And Gd 3+ Is doped at LiYF 4 :Yb 3+ /Ho 3+ /Gd 3+ 50mol% of the total amount of the medium rare earth elements, yb 3+ Is doped at LiYF 4 :Yb 3+ /Ho 3+ /Gd 3+ 20mol% of the total amount of the rare earth elements, ho 3+ Is doped at LiYF 4 :Yb 3+ /Ho 3+ /Gd 3+ The microcrystalline material of this example was designated as LiY with 1mol% of the total amount of rare earth elements 0.29 F 4 :Yb 0.2 /Ho 0.01 /Gd 0.5 . And the preparation method of the microcrystalline material of this embodiment is different from that of embodiment 1 only in that:
in this embodiment, the rare earth element source is Y (NO 3 ) 3 ·6H 2 O、Gd(NO 3 ) 3 ·6H 2 O、Yb(NO 3 ) 3 ·5H 2 O and Ho (NO) 3 ) 3 ·5H 2 Mixed solution of O, and Y (NO 3 ) 3 ·6H 2 O、Gd(NO 3 ) 3 ·6H 2 O、Yb(NO 3 ) 3 ·5H 2 O and Ho (NO) 3 ) 3 ·5H 2 The molar ratio of O is 0.29:0.5:0.2:0.01.
Example 6
The embodiment provides a Gd-doped material 3+ LiYF of (F) 4 :Yb 3+ /Ho 3+ The microcrystalline material, in this example, has the formula LiYF 4 :Yb 3+ /Ho 3+ /Gd 3+ And Gd 3+ Is doped at LiYF 4 :Yb 3+ /Ho 3+ /Gd 3+ 60mol% of the total amount of the medium rare earth elements, yb 3+ Is doped at LiYF 4 :Yb 3+ /Ho 3+ /Gd 3+ 20mol% of the total amount of the rare earth elements, ho 3+ Is doped at LiYF 4 :Yb 3+ /Ho 3+ /Gd 3+ The microcrystalline material of this example was designated as LiY with 1mol% of the total amount of rare earth elements 0.19 F 4 :Yb 0.2 /Ho 0.01 /Gd 0.6 . And the preparation method of the microcrystalline material of this example is different from that of comparative example 1 only in that:
in this embodiment, the rare earth element source is Y (NO 3 ) 3 ·6H 2 O、Gd(NO 3 ) 3 ·6H 2 O、Yb(NO 3 ) 3 ·5H 2 O and Ho (NO) 3 ) 3 ·5H 2 Mixed solution of O, and Y (NO 3 ) 3 ·6H 2 O、Gd(NO 3 ) 3 ·6H 2 O、Yb(NO 3 ) 3 ·5H 2 O and Ho (NO) 3 ) 3 ·5H 2 The molar ratio of O is 0.19:0.6:0.2:0.01.
Example 7
The embodiment provides a Gd-doped material 3+ LiYF of (F) 4 :Yb 3+ /Ho 3+ The microcrystalline material and this example differs from example 3 only in that:
in this embodiment, the substrate sources are LiF and NH 4 Mixed solution of F, and LiF and NH 4 The molar ratio of F is 3:1.
In this example, the dispersant to water solvent ratio was 1mmol to 15mL.
In this example, the hydrothermal reaction temperature was 210℃and the incubation time was 60 hours.
In this embodiment, the rare earth element source is a mixture of yttrium acetate, gadolinium acetate, ytterbium acetate and holmium acetate.
Example 8
The embodiment provides a Gd-doped material 3+ LiYF of (F) 4 :Yb 3+ /Ho 3+ Microcrystalline material, and is present inThe preparation method of the microcrystalline material of the example differs from that of example 3 only in that:
in this embodiment, the substrate sources are LiF and NH 4 Mixed solution of F, and LiF and NH 4 The molar ratio of F is 5:1.
In this example, the dispersant to water solvent ratio was 1 mmol/25 mL.
In this example, the hydrothermal reaction temperature was 250℃and the incubation time was 24 hours.
In this embodiment, the rare earth element source is a mixture of yttrium oxide, gadolinium oxide, ytterbium oxide, and holmium oxide.
Comparative example 1
This comparative example provides a LiYF 4 :Yb 3+ /Ho 3+ Microcrystalline materials, i.e. Gd 3+ Is doped at LiYF 4 :Yb 3 + /Ho 3+ /Gd 3+ 0mol% of the total amount of the rare earth elements, yb 3+ Is doped at LiYF 4 :Yb 3+ /Ho 3+ /Gd 3+ 20mol% of the total amount of the rare earth elements, ho 3+ Is doped at LiYF 4 :Yb 3+ /Ho 3+ /Gd 3+ The microcrystalline material of this comparative example was designated as LiY with 1mol% of the total amount of rare earth elements 0.79 F 4 :Yb 0.2 /Ho 0.01 。
And the preparation method of the microcrystalline material of the comparative example is as follows:
placing 1mmol of dispersant EDTA into 20mL of water, heating at a constant temperature of 60 ℃ and stirring at a speed of 1200r/min for 10min to enable EDTA to be fully dissolved and uniformly dispersed in the water, then adding 1mmol of rare earth element source, continuously stirring at a speed of 1200r/min for 10min, and uniformly mixing to obtain a first mixed material;
adding a matrix source into the first mixed material, stirring at a speed of 1200r/min for 30min to make the solution milky, slowly pouring the solution into a 100mL high-pressure reaction kettle, then placing the solution at a temperature of 230 ℃ for heat preservation for 48h, performing solid-liquid separation, washing the obtained white solid with absolute ethyl alcohol and ultrapure water respectively to remove impurities, and then washing the washed solidDrying in vacuum drying oven at 60deg.C for 12 hr to obtain LiYF 4 :Yb 3+ /Ho 3+ A microcrystalline material.
In this comparative example, the rare earth element source is Y (NO 3 ) 3 ·6H 2 O、Yb(NO 3 ) 3 ·5H 2 O and Ho (NO) 3 ) 3 ·5H 2 Mixed solution of O, and Y (NO 3 ) 3 ·6H 2 O、Yb(NO 3 ) 3 ·5H 2 O and Ho (NO) 3 ) 3 ·5H 2 The molar ratio of O was 0.79:0.2:0.01.
In this comparative example, the substrate source was 20mmol LiF and 5mmol NH 4 Mixed solution of F.
Test section
X-ray diffraction test
The invention adopts BUKER D8ADVANCE X-ray diffractometer to test the phase purity of the micrometer crystal materials of comparative examples 1-6, the test results are shown in figure 1, and the parameters of the testing instrument are as follows: 40mA and 40kV, cu target K alpha, lambda is 0.1546nm,2 theta range is 10-80 degrees.
LiYF in tetragonal phase is shown in FIG. 1 from bottom to top 4 X-ray diffraction patterns of standard card PDF #17-0874, comparative example 1, example 2, example 3, example 4, example 5, and example 6. As can be seen from FIG. 1, the X-ray diffraction peaks of the microcrystalline materials of comparative example 1, examples 1-6 of the present invention are all similar to LiYF in tetragonal phase 4 Is fully corresponding to standard card PDF #17-0874, only when higher concentrations of Gd 3+ Ion doping to LiYF 4 :Yb 0.2 /Ho 0.01 Some weak GdF appears when in the subject of (C) 3 Is a characteristic peak of (2). Shows that the experiment successfully synthesizes the pure tetragonal LiYF 4 :Yb 3+ /Ho 3+ /Gd 3+ And (3) microcrystals.
(II) scanning electron microscope test
The invention adopts a Zeiss ZEISS sigma 500 field emission scanning electron microscope to test the crystal morphology and the size of the micron crystal materials of comparative example 1, example 3 and example 5 respectively, and the test results are shown in figure 2.
FIGS. 2 (a), 2 (b) and (c) are SEM images of the microcrystalline materials of comparative examples 1, 3 and 5, respectively, and as can be seen in FIG. 2, the morphology of the microcrystalline material of comparative example 1 is octahedral shape with an average size of about 65 μm; the average size of the microcrystalline materials of examples 3 and 5 was about 60 μm.
In conclusion, the micron crystal prepared by the invention has the advantages of octahedral structure, regular shape, uniform dispersion and smoother overall crystal surface, and along with Gd 3+ The doping concentration of ions is improved, gd 3+ Is incorporated instead of part Y 3+ The crystal size is not significantly changed but LiYF is caused 4 Lattice distortion of the crystal.
(III) Up-conversion luminescence Performance test
The invention adopts a 980nm laser with adjustable power of 0-2W as a pumping light source for excitation, adopts a Hitachi F-4500 type fluorescence spectrometer for respectively carrying out fluorescence spectrum test on the micrometer crystal materials of comparative example 1 and examples 1-6, and the test results are shown in figure 3.
Fig. 3 (a) is a fluorescence spectrum of the microcrystalline materials of comparative example 1, example 1 to example 6, and fig. 3 (b) is a luminescence spectrum of the microcrystalline materials of comparative example 1, example 1 to example 6 irradiated with 980nm laser light in dark environment. As can be seen from FIG. 3 (a), example 3 (Gd) 3+ The luminescent intensity of the microcrystal is strongest with a doping concentration of 30 mol%).
And the major emission peaks of the example 1-example 6 microns crystals include a weak blue emission peak at 480nm, a strong green emission peak at 535-543 nm, a weak red emission peak at 638-657 nm, and a near infrared emission peak at 750 nm.
(1)Gd 3+ Effect of ion doping concentration on the upconversion luminescence properties of the microcrystals of the present invention
Comparative example 1 (Gd) 3+ 0 mol%) and example 3 (Gd) 3+ For example, a doping concentration of 30 mol%) is used to illustrate the present invention in the case of a microcrystalGd 3+ Influence of ion doping concentration on conversion luminescence properties on the microcrystals.
FIG. 4 (a) is Gd 3+ Doping concentrations are respectively comparative example 1 (Gd 3+ 0 mol%) and example 3 (Gd) 3+ As is evident from the graph, the up-conversion luminescence intensity is improved by about 3 times as a whole.
FIG. 4 (b) is LiYF under excitation of 980nm laser 4 :Yb 3+ /Ho 3+ /Gd 3+ Schematic representation of energy level transitions of microcrystalline particles, yb 3+ Ion first from 2 F 7/2 Transition of energy level to 2 F 5/2 The energy levels, then, induce a subsequent series of radiative transitions through the ET1 (energy transfer) process and ET2, ET3, and MPR (multi-phonon relaxation process) caused by CR1 (cross relaxation) and CR2, including: ho 3+ Ion at 480nm 3 K 8 5 F 2 5 F 3 → 5 I 8 ) Weak blue emission peak 535nm 5 F 4 → 5 I 8 ) And 543 nm% 5 S 2 → 5 I 8 ) Strong green emission peak of 638 nm% 3 K 8 、 5 F 2 、 5 F 3 → 5 I 7 ) And 657 nm% 5 F 5 → 5 I 8 ) Is less than 750nm 5 F 4 ， 5 S 2 → 5 I 7 ) Is a weak near infrared emission peak. Since the blue emission intensity at 480nm is very weak, the light emission intensity for the range of 450 to 500nm (gray shaded portion) in fig. 4 (a) is multiplied by 10 times.
The following studies of the light emission performance of the present invention are mainly conducted on green light emission (535 nm, 543 nm) and red light emission (638 nm, 657 nm).
Referring to FIG. 5, FIG. 5 (a) shows LiYF at different concentrations under excitation of 980nm laser with a certain power 4 :Yb 3+ /Ho 3+ /Gd 3+ Variation of intensity of strongest up-conversion luminescence portion (green luminescence) of microcrystalline materialA drawing. When Gd 3+ When the ion doping concentration is 0 to 30mol percent, the Gd is along with 3+ Continuously increasing ion doping concentration, liYF 4 :Yb 3+ /Ho 3+ /Gd 3+ The luminous intensity of the micro-crystal material is improved, and Gd is used as 3+ The luminescence intensity reached the highest at an ion doping concentration of 30mol%, but with Gd 3+ The improvement of the luminous intensity of the ion is also limited, and when the doping concentration is between 30 and 60mol percent, the ion is along with Gd 3+ The ion doping concentration is continuously increased, and the luminous intensity is reduced. This is mainly due to Gd 3+ The ionic radius of (a) is slightly larger than Y 3+ In LiYF 4 In the crystal, gd 3+ Co-doping of ions replaces part of Y 3+ The location of the ions will result in LiYF 4 The crystal lattice of the crystal is distorted, resulting in LiYF 4 The symmetry of the crystal field of (a) is reduced and this lattice distortion causes the probability of transition and Ho 3+ Excited state particle number increases, yb 3+ Ion and Ho 3+ The rate of energy transfer between ions is also increased, such that Ho 3+ The up-conversion luminescence of the ions is significantly enhanced. Selecting the optimal concentration Gd 3+ Ion doped LiYF 4 :Yb 3+ /Ho 3+ /Gd 3+ The micron crystal material is used as the raw material of the anti-counterfeiting ink.
FIG. 5 (b) is a different Gd 3+ LiYF of ion doping concentration 4 :Yb 3+ /Ho 3+ /Gd 3+ The ratio of the integrated intensities of the green emission peak and the red emission peak of the microcrystalline material. With Gd 3+ The increase in co-doping concentration, the sample showed a dominant green emission and a faint red emission, and the green emission intensity ratio and the red emission intensity ratio were almost unchanged (δr% =r% max -R％ min ＝0.2％，δG％＝G％ max -G％ min =0.4%). Thus, different Gd 3+ Samples with ion co-doping concentrations all emit highly stable green light.
(2) Influence of excitation Power on the luminescence Properties of the conversion on the microcrystals of the present invention
FIG. 6 (a) is a graph showing fluorescence spectra of the microcrystals of example 3 under excitation by 980nm laser with variable excitation power of 0.5 to 1.5W. It can be seen that as the excitation power increases, the luminous intensity of the microcrystal of example 3 increases as a whole.
FIG. 6 (b) shows the ratio (I) of the red light emission intensity to the green light emission intensity of the microcrystal of example 3 at an excitation power of 0.5 to 1.5W R /I G ). It can be seen that in the range of 0.5 to 1.5W, the ratio of red and green emission intensities of the sample increased by only about 13% with increasing excitation power, indicating that the upconversion luminescence monochromaticity of the microcrystal of example 3 is highly stable, and the change in excitation power has little influence on the upconversion luminescence property thereof, and such stable and efficient luminescence property has very important significance for application in anti-counterfeit identification.
Application of the micron crystal material in preparing anti-fake identifying material
The rare earth doped luminescent material can be applied to various aspects such as anti-counterfeiting identification, fingerprint identification, biomedicine and the like. The rare earth doped up-conversion luminescent material has high luminescent performance, so the anti-counterfeiting identification is particularly outstanding. The anti-counterfeiting pattern is manufactured by screen printing, and the manufacturing process is shown in fig. 7 (a).
LiYF prepared in example 3 according to the invention 4 :Yb 3+ /Ho 3+ /Gd 3+ The micron crystal material is taken as an example, the micron crystal material is fully ground and then is uniformly mixed with silk screen metal ink according to the proportion of 5mg sample/1 mL ink to prepare anti-counterfeiting ink, the prepared anti-counterfeiting ink is poured on a silk screen printing template and then repeatedly brushed by using a brush applicator, so that the anti-counterfeiting pattern of western character can be successfully printed on a glass sheet below the silk screen printing template, and the up-conversion luminous anti-counterfeiting pattern is obtained. After the printed anti-counterfeiting pattern is dried in a drying oven, the luminous anti-counterfeiting pattern is shot in dark and matt environment by using a single lens reflex under the irradiation of 980nm laser. In order to ensure shooting quality, an optical filter is additionally arranged in front of the camera to filter interference of strong excitation light.
FIG. 7 (b) is a luminescent security pattern of the "Siemens" letter pattern that has been completed, the security pattern printed on glass under natural light on the left, the luminescent image of the security pattern under 980nm laser irradiation on the right, and bright green luminescence can be observed. The prepared anti-counterfeiting mark pattern has the advantages of good adhesive force on the surface of the glass substrate, difficult falling, high luminous intensity, good monochromaticity, easy identification, clear details and the like, and is a good luminous anti-counterfeiting material.
It should be apparent that the embodiments described above are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (6)
1. Gd (Gd) type drug delivery device 3+ Doped with a microcrystalline material characterized by the presence of LiYF 4 :Yb 3+ /Ho 3+ Microcrystals as matrix material and made of Gd 3+ Doped LiYF 4 :Yb 3+ /Ho 3+ The Y-site of the microcrystal is obtained and the chemical formula is LiYF 4 :Yb 3+ /Ho 3+ /Gd 3+ ；
Wherein Gd 3+ The doping concentration of the rare earth elements in the micro-crystal material is less than or equal to 30mol percent of the total amount of the rare earth elements;
Yb 3+ the doping concentration of the rare earth element is 20mol% of the total amount of the rare earth elements in the micro-crystal material;
Ho 3+ the doping concentration of the rare earth element is 1mol% of the total amount of the rare earth elements in the micro-crystal material;
the micron crystal material realizes fluorescent emission with the wavelength of 450-770 nm under the excitation of 980-nm laser.
2. Gd as claimed in claim 1 3+ Doped microcrystalline material characterized in that its main emission peaks comprise: 480 A weak blue emission peak at nm, a strong green emission peak at 535-543 nm, a weak red emission peak at 638-657 nm, and a near infrared emission peak at 750-nm.
3. A method according to any one of claims 1-2The Gd 3+ A method for preparing a doped microcrystalline material comprising the steps of:
dissolving and uniformly dispersing a dispersing agent in an aqueous solvent, then adding a rare earth element source, and uniformly mixing to obtain a first mixed material;
adding a matrix source into the first mixed material, uniformly mixing, and then, preserving heat for 24-60 hours at the temperature of 210-250 ℃ to obtain Gd 3+ Doping the microcrystalline material;
wherein the matrix source comprises fluoride ions and lithium ions;
the dispersing agent is one of EDTA, oleic acid, ethanol and polyethylene glycol;
the rare earth element source comprises Gd 3+ 、Yb 3+ 、Ho 3+ And Y 3+ ；
Wherein Gd 3+ The molar concentration of (2) is less than or equal to 30mol% of the rare earth element source; yb 3+ Is 20mol% of the rare earth element source, ho 3+ The molar concentration of (2) is 1mol% of the rare earth element source;
the matrix source is LiF and NH 4 F, and LiF and NH 4 The molar ratio of F is 3-5:1.
4. The method of claim 3, wherein the rare earth element source is any one of nitrate, oxide and acetate of each rare earth element.
5. The method of claim 3, wherein the dispersant to water solvent ratio is 1mmol:15 to 25ml;
the volume ratio of the total molar quantity of the rare earth elements in the rare earth element source to the water solvent is 1 mmol:15-25 mL;
the molar ratio of the matrix source to the rare earth element source is 20-30:1.
6. Gd according to any one of claims 1-2 3+ The application of doped micron crystal material in preparing anti-fake identifying material.
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