CN108384536A - Er3+/Yb3+Codope calcium aluminum fluoride green up conversion luminescent material and preparation method thereof - Google Patents
Er3+/Yb3+Codope calcium aluminum fluoride green up conversion luminescent material and preparation method thereof Download PDFInfo
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- CN108384536A CN108384536A CN201810466151.4A CN201810466151A CN108384536A CN 108384536 A CN108384536 A CN 108384536A CN 201810466151 A CN201810466151 A CN 201810466151A CN 108384536 A CN108384536 A CN 108384536A
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7774—Aluminates
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Abstract
The invention belongs to phosphor technical fields, and in particular to the light activated Er of near-infrared3+/Yb3+Codope calcium aluminum fluoride green up conversion luminescent material and preparation method thereof.The present invention prepares Er using high temperature solid-state method3+/Yb3+Codope calcium aluminum fluoride, by high-purity Er2O3、Yb2O3、Al2O3、CaF2And CaCO3After raw material mixes in proportion, sintering obtains Er3+/Yb3+Codope calcium aluminum fluoride luminescent material.Luminescent material transmitting under the excitation of 980 nm near-infrared light is located at the green light of 550 rans, and up-conversion luminescence efficiency is higher；The stability of luminescent material of the present invention is good, environmentally friendly, at low cost, can be widely applied to 3 D stereo show, the fields such as biomolecule fluorescence labeling probe, fiber amplifier；The preparation method of the present invention is easily operated and industrialized production, production cost are low.
Description
Technical field
The invention belongs to phosphor technical fields, and in particular to Er3+/Yb3+A kind of calcium aluminum fluoride green of codope
Up-conversion luminescent material and preparation method thereof.
Background technology
Rare earth ion doped up-conversion luminescent material the sightless near infrared light of human eye is converted into one can see that
Visible light, Stokes shift is big, is not interfered by bias light, can be widely applied to Three-dimensional Display, laser anti-counterfeit, biology at
Picture, biological detection, pharmaceutical carrier and novel cancer photodynamic therapy etc..Current most of high efficiency up-conversion luminescence materials
The matrix such as fluoride, sulfide and the halide that material all uses phonon energy low, but the thermal stability of these matrix is poor, easily
It deliquesces, and not radiation hardness, preparation process is also complicated, to limit up-conversion luminescent material to a certain extent many special
The popularization and application in field.
Invention content
In view of the problems of the existing technology, good and can realize near infrared light purpose of the present invention is to prepare a kind of stability
The glimmering material of calcium aluminum fluoride Green upconversion luminescent of excitation, the luminescent material send out narrowband green light under near infrared light excitation, can
To overcome the defect of fluoride thermal stability difference, be conducive to the application field for extending up-conversion luminescent material.
In visible-range, Er3+Ion has2H11/2/4S3/2→4I15/2What transition (530nm and 550nm near) generated
Green light and4F9/2→4I15/2Two transmitting bands of feux rouges that transition (near 660nm) generates.By changing Yb3+The doping concentration of ion
The Up-conversion emission intensity of adjustable green light and feux rouges, can be obtained the transmitting of the green ratio of Different Red.
Host material of the present invention using broad-band gap calcium aluminum fluoride as doping.Since it is with good chemical stability
And temperature stability, and its energy gap has both greatly the excellent stability of oxide and the low phonon energy of fluoride, is well suited for
Do the matrix of luminescent material.
The present invention is prepared using high temperature solid-state method.Preparation method of the present invention is as follows：
(1) high-purity Er is weighed respectively according to stoichiometric ratio2O3、Yb2O3、Al2O3、CaF2And CaCO3Raw material is placed in agate
In mortar, dispersant grinding is done with absolute ethyl alcohol, grinding is dried after raw material is sufficiently mixed；
(2) it by the raw material after drying in 800-900 DEG C of pre-burning 1-3 hours, then grinds 1-2 hours；
(3) sufficient raw material will be mixed to calcine 6-10 hours for 1150-1300 DEG C in air atmosphere；
(4) after grinding, the light activated Er of near-infrared is obtained3+/Yb3+The calcium aluminum fluoride up-conversion luminescent material of codope
(Ca12Al14O32F2:Er,Yb)
The beneficial effects of the invention are as follows：
1. the present invention uses conventional high-temperature solid phase method, preparation process is simple, can be mass-produced, and has preferable market to apply
Foreground.
2. Er prepared by the present invention3+/Yb3+The excites scope of codope calcium aluminum fluoride is concentrated mainly near infrared range
Near 980 nanometers, which has stronger tissue penetration, interference not damaged to biological tissue, without background fluorescence, this
A little characteristics make it be controlled in Three-dimensional Display, laser anti-counterfeit, bio-imaging, biological detection, pharmaceutical carrier and novel cancer photodynamics
Treat etc. has huge application potential.
3. the up-conversion luminescent material of the present invention, the advantages of having, are as follows：
(1) upper conversion calcium aluminum fluoride luminescent material of the invention under being excited at 980 nanometers, can emit main peak and be located at 550
The green light of nanometer, luminance purity is high, and performance is stablized.
(2) up-conversion luminescent material matrix thermal stability of the invention is good, radiation hardness, is conducive to expand up-conversion luminescence material
Expect the application in special dimension, such as the application under cosmic space and hot conditions.
(3) rich reserves in the raw material nature of up-conversion luminescent material of the invention, it is cheap, production material at
This is low, and the object for preparing sample is mutually pure.
(4) preparation process of the present invention is simple, and output is efficient, favorable repeatability, and non-pollutant discharge in preparation process is one
The environmental-friendly phosphor of kind
Description of the drawings
Fig. 1 is that the embodiment of the present invention 1 prepares sample Ca11.98Al14O32F2:Er0.002/Yb0.018X-ray powder diffraction figure
Spectrum.
Fig. 2 is that the embodiment of the present invention 1 prepares sample Ca11.98Al14O32F2:Er0.002/Yb0.018In 980 nm near-infrared light
The up-conversion luminescence spectrogram obtained under excitation.
Specific implementation mode
It is worth the Er of a variety of doping concentrations according to the step of going out given in invention content3+/Yb3+Codope calcium aluminum fluoride is green
Color up-conversion luminescent material.
Example 1
(1) CaCO is weighed3(99.99%) 1.1771g, Al2O3(99.99%) 0.71372g, CaF2(99.99%)
0.07808g、Er2O3(99.99%) 0.00459g, Yb2O3(99.99%) 0.04256g is placed in mortar, use ethyl alcohol as
Dispersant is ground, and grinding is dried after so that raw material is sufficiently mixed；
(2) it by the raw material after drying in 850 DEG C of pre-burnings 2 hours, then grinds 1 hour；
(3) sufficient raw material will be mixed to calcine 10 hours for 1200 DEG C in air atmosphere；
(4) after grinding, the light activated Er of near-infrared is obtained3+/Yb3+The calcium aluminum fluoride up-conversion luminescent material of codope
(Ca11.98Al14O32F2:Er0.002/Yb0.018)
Embodiment 2
(1) CaCO is weighed3(99.99%) 1.1963g, Al2O3(99.99%) 0.71372g, CaF2(99.99%)
0.07808g、Er2O3(99.99%) 0.00459g, Yb2O3(99.99%) 0.047g is placed in mortar, use ethyl alcohol as point
Powder is ground, and grinding is dried after so that raw material is sufficiently mixed；
(2) it by the raw material after drying in 900 DEG C of pre-burnings 2 hours, then grinds 1 hour；
(3) sufficient raw material will be mixed to calcine 6 hours for 1250 DEG C in air atmosphere；
(4) after grinding, the light activated Er of near-infrared is obtained3+/Yb3+The calcium aluminum fluoride up-conversion luminescent material of codope
(Ca11.996Al14O32F2:Er0.002/Yb0.002)
Example 3
(1) CaCO is weighed3(99.99%) 2.3494g, Al2O3(99.99%) 1.42744g, CaF2(99.99%)
0.15616g、Er2O3(99.99%) 0.00918g, Yb2O3(99.99%) 0.0946g is placed in mortar, use ethyl alcohol as point
Powder is ground, and grinding is dried after raw material is sufficiently mixed；
(2) it by the raw material after drying in 850 DEG C of pre-burnings 2 hours, then grinds 1 hour；
(3) sufficient raw material will be mixed to calcine 10 hours for 1300 DEG C in air atmosphere；
(4) after grinding, the light activated Er of near-infrared is obtained3+/Yb3+The calcium aluminum fluoride up-conversion luminescent material of codope
(Ca11.978Al14O32F2:Er0.002/Yb0.02)
Example 4
(1) CaCO is weighed3(99.99%) 1.1867g, Al2O3(99.99%) 0.71372g, CaF2(99.99%)
0.07808g、Er2O3(99.99%) 0.00459g, Yb2O3(99.99%) 0.0236g is placed in mortar, use ethyl alcohol as point
Powder is ground, and grinding is dried after raw material is sufficiently mixed；
(2) it by the raw material after drying in 900 DEG C of pre-burnings 2 hours, then grinds 1 hour；
(3) sufficient raw material will be mixed to calcine 8 hours for 1200 DEG C in air atmosphere；
(4) after grinding, the light activated Er of near-infrared is obtained3+/Yb3+The calcium aluminum fluoride up-conversion luminescent material of codope
(Ca11.988Al14O32F2:Er0.002/Yb0.010)。
Claims (2)
1. the light activated Er of near-infrared3+/Yb3+Codope calcium aluminum fluoride green up conversion luminescent material, it is characterised in that：The material
Chemical formula be Ca12-x-yAl14O32F2:Erx/Yby, wherein x is erbium ion-doped molar ratio, and y is mole of ytterbium ion doping
Than, 0.001≤x≤0.005,0.01≤y≤0.05.
2. the light activated Er of near-infrared according to claim 13+/Yb3+Codope calcium aluminum fluoride Green upconversion luminescent material
The preparation method of material, may be used high temperature solid-state method, which is characterized in that specifically comprise the following steps：
（1）By chemical formula Ca12-x-yAl14O32F2:Erx/YbyThe stoichiometric ratio of middle each element weighs high-purity Er respectively2O3、
Yb2O3、Al2O3、CaF2And CaCO3Raw material is placed in agate mortar, does dispersant grinding with absolute ethyl alcohol, grinding makes raw material fill
It is dried after dividing mixing；
（2）By pre-burning 1-2 times in air atmosphere of the raw material after drying, sintering temperature is 800-900 DEG C, and the pre-sintering time is 1-
It 3 hours, after its natural cooling, then grinds 1-2 hours；
（3）Sufficient raw material will be mixed to calcine 6-10 hours for 1150-1300 DEG C in air atmosphere；
（4）The light activated Er of near-infrared is obtained after grinding uniformly3+/Yb3+Codope calcium aluminum fluoride green up conversion luminescent material
（Ca12Al14O32F2:Er/Yb）.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110872512A (en) * | 2018-08-30 | 2020-03-10 | 长春理工大学 | Bismuth ion activated calcium fluoroaluminate blue fluorescent powder and preparation method thereof |
| WO2023175222A1 (en) * | 2022-03-18 | 2023-09-21 | Ancor Tecnológica Canaria, S.L. | Biocidal product with luminescent marker additive for textile surfaces or the like |
| WO2023175220A1 (en) * | 2022-03-18 | 2023-09-21 | Ancor Tecnológica Canaria, S.L. | Biocidal and photoluminescent treatment of viscose fibre immediately following the addition of carbon disulfide in the conversion of cellulose into viscose (xanthation) |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110872512A (en) * | 2018-08-30 | 2020-03-10 | 长春理工大学 | Bismuth ion activated calcium fluoroaluminate blue fluorescent powder and preparation method thereof |
| WO2023175222A1 (en) * | 2022-03-18 | 2023-09-21 | Ancor Tecnológica Canaria, S.L. | Biocidal product with luminescent marker additive for textile surfaces or the like |
| WO2023175220A1 (en) * | 2022-03-18 | 2023-09-21 | Ancor Tecnológica Canaria, S.L. | Biocidal and photoluminescent treatment of viscose fibre immediately following the addition of carbon disulfide in the conversion of cellulose into viscose (xanthation) |
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| ES2952015A1 (en) * | 2022-03-18 | 2023-10-26 | Ancor Tecnologica Canaria S L | BIOCIDAL AND PHOTOLUMINESCENT TREATMENT OF VISCOSE FIBER IMMEDIATELY AFTER THE ADDITION OF CARBON DISULFIDE IN THE PROCESS OF CONVERSION OF CELLULOSE INTO VISCOSE (XANTATHYATION) (Machine-translation by Google Translate, not legally binding) |
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