CN111170633A - Thulium-ytterbium co-doped phosphate up-conversion luminescent glass and preparation method and application thereof - Google Patents

Thulium-ytterbium co-doped phosphate up-conversion luminescent glass and preparation method and application thereof Download PDF

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CN111170633A
CN111170633A CN202010064912.0A CN202010064912A CN111170633A CN 111170633 A CN111170633 A CN 111170633A CN 202010064912 A CN202010064912 A CN 202010064912A CN 111170633 A CN111170633 A CN 111170633A
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glass
thulium
ytterbium
conversion luminescent
doped phosphate
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张芳腾
韦丽娟
赵新捷
林中乔
张家骅
聂兆刚
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Guangdong University of Technology
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00Compositions for glass with special properties
    • C03C4/12Compositions for glass with special properties for luminescent glass; for fluorescent glass
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00Other methods of shaping glass
    • C03B19/02Other methods of shaping glass by casting molten glass, e.g. injection moulding
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B25/00Annealing glass products
    • C03B25/02Annealing glass products in a discontinuous way
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00Glass compositions
    • C03C3/12Silica-free oxide glass compositions
    • C03C3/16Silica-free oxide glass compositions containing phosphorus
    • C03C3/17Silica-free oxide glass compositions containing phosphorus containing aluminium or beryllium
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2201/00Type of glass produced
    • C03B2201/60Silica-free oxide glasses
    • C03B2201/70Silica-free oxide glasses containing phosphorus

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Abstract

The invention belongs to the technical field of up-conversion luminescent glass, and discloses thulium-ytterbium co-doped phosphate up-conversion luminescent glass, which comprises the component P2O5‑Al2O3–BaO‑Na2O–ZnO‑Yb2O3‑Tm2O3-a glass network framework modifier, wherein the molar percentages of the components are: p2O550~60%;Al2O310%;BaO 12%;Na2O 5%;ZnO 10%;Yb2O31~3%;Tm2O30.2-0.8% of glass network framework regulator and 1.8-10% of glass network framework regulator. The method of the inventionSimple, low cost of raw materials and simple required equipment. The phosphate up-conversion luminescent glass has the advantages of good permeability, high mechanical strength and up-conversion wavelength of about 800nm, and has important application prospect in the photoelectronic fields of near-infrared imaging, laser, detection and the like.

Description

Thulium-ytterbium co-doped phosphate up-conversion luminescent glass and preparation method and application thereof
Technical Field
The invention belongs to the technical field of up-conversion luminescent glass, and particularly relates to thulium-ytterbium co-doped phosphate up-conversion luminescent glass and a preparation method and application thereof.
Background
The up-conversion luminescent material is a material which absorbs low-energy photons and then emits high-energy photons, has a unique spectrum conversion function and has great application potential in various fields such as solid lasers, information storage, sensing, biological imaging, illumination light sources, three-dimensional display and the like, and is a research hotspot at home and abroad. In the up-conversion luminescent materials widely reported at present, inorganic materials taking crystal, glass and microcrystalline glass ceramics as matrixes are dominant. The up-conversion luminescent crystal material mainly refers to a fluorescent powder polycrystalline material and a single crystal material, the luminous intensity and the quantum efficiency of the up-conversion luminescent crystal material are generally high, but the preparation process is complex, plastic processing is not easy to perform, and large and complex structure devices are difficult to prepare. The up-conversion luminescent glass-ceramic combines the advantages of transparency and plasticity of glass and high luminous efficiency of ions in a microcrystalline environment, but the controllability of the size and the content of nanocrystals in the glass-ceramic is poor, so that the transmittance of the glass is greatly influenced, the transparent glass-ceramic is difficult to prepare, the preparation cost is far higher than that of directly preparing the glass, and the practical application of the up-conversion luminescent glass-ceramic is limited to a certain extent.
The upconversion luminescent glass is generally simple in preparation process, easy to realize molding control and bulk preparation, high in transparency and optical uniformity, and ideal in directions of laser, illumination, display and the like. Research shows that the existing up-conversion glass mainly comprises fluoride, germanate, tellurate and other low phonon energy glass, wherein the fluoride glass has unstable chemical property, poor mechanical strength and harsh preparation conditions, and the germanate and tellurate glass has high price. Therefore, there is a need for further development of low-cost, high-stability upconverting glass materials.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention provides thulium-ytterbium co-doped phosphate up-conversion luminescent glass, the up-conversion luminescent glass has a light emitting range of 780-820 nm under the excitation of 980nm, and two light emitting peak positions are respectively located near 794nm and 805 nm.
The invention also aims to provide a preparation method of the thulium-ytterbium co-doped phosphate up-conversion luminescent glass. The method has simple preparation process and low cost, and can be mass produced.
The invention further aims to provide application of the thulium-ytterbium co-doped phosphate up-conversion luminescent glass.
The above purpose of the invention is realized by the following technical scheme:
thulium-ytterbium co-doped phosphate up-conversion luminescent glass, wherein the up-conversion luminescent glass comprises the component P2O5-Al2O3–BaO-Na2O–ZnO-Yb2O3-Tm2O3-a glass network framework modifier, wherein the molar percentages of the components are respectively: p2O550~60%;Al2O310%;BaO 12%;Na2O 5%;ZnO 10%;Yb2O31~3%;Tm2O30.2-0.8% of glass network framework regulator and 1.8-10% of glass network framework regulator.
Preferably, the glass network skeleton regulator is SiO2、TeO2-WO3、B2O3
More preferably, the TeO2-WO3Medium TeO2And WO3The molar ratio of (1-2): (1-2).
The preparation method of the thulium-ytterbium co-doped phosphate up-conversion luminescent glass comprises the following specific steps:
s1, adding P2O5,Al2O3,BaO,Na2O,ZnO,Yb2O3,Tm2O3Mixing, grinding and stirring the mixture with a glass network framework regulator, transferring the mixture into an alumina crucible, melting the mixture at 1450-1550 ℃ to obtain a glass melt, pouring the glass melt onto a copper plate with the temperature kept at 250-300 ℃, and cooling the glass melt to obtain a glass block;
s2, annealing the glass block at 450-550 ℃, and cooling to room temperature along with the furnace to obtain the thulium-ytterbium co-doped phosphate up-conversion luminescent glass.
Preferably, the stirring time in the step S1 is 20-30 min.
Preferably, the melting time in the step S1 is 1-2 h.
Preferably, the annealing time in the step S2 is 3-6 h.
The thulium-ytterbium co-doped phosphate up-conversion luminescent glass is applied to the photoelectronic fields of near-infrared imaging, laser or detection and the like.
Compared with the prior art, the invention has the following beneficial effects:
1. the thulium-ytterbium co-doped phosphate up-conversion luminescent glass has the light emitting range of 780-820 nm under the excitation of 980nm, the two light emitting peak positions are respectively positioned near 794nm and 805nm, the strongest light emitting peak position is 794nm, and the thulium-ytterbium co-doped phosphate up-conversion luminescent glass can be used as a near-infrared laser gain medium, sensing, biological imaging and the like.
2. The phosphate up-conversion luminescent glass has the advantages of good permeability, high mechanical strength and up-conversion wavelength of about 800 nm.
3. The thulium-ytterbium co-doped phosphate up-conversion luminescent glass has the advantages of simple preparation method, low cost and mass production.
4. According to the thulium-ytterbium co-doped phosphate up-conversion luminescent glass, the common 980nm semiconductor laser can be used as the pumping laser, and the thulium-ytterbium co-doped phosphate up-conversion luminescent glass is easy to obtain and convenient to use.
Drawings
Fig. 1 is an absorption spectrum of thulium ytterbium co-doped phosphate up-conversion luminescent glasses prepared in examples 1-4.
FIG. 2 shows fluorescence spectra of thulium-ytterbium co-doped phosphate up-conversion luminescent glasses prepared in examples 1-4.
Detailed Description
The invention is further described in the following description with reference to the figures and specific examples, which should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
The thulium-ytterbium co-doped phosphate up-conversion luminescent glass prepared in the embodiment has the composition of P2O5-Al2O3-BaO-Na2O-ZnO-Yb2O3-Tm2O3The mol percentages of the raw materials are respectively as follows: 60% P2O5,10%Al2O3,12%BaO,5%Na2O,10%ZnO,2.5%Yb2O3,0.5%Tm2O3
1. The raw materials are respectively weighed, poured into an agate mortar for grinding and stirring to be fully and uniformly mixed, and the uniformly ground batch is transferred into an alumina crucible. The glass was melted for 2h in a high temperature box-type resistance furnace at 1450 ℃ and then poured onto a smooth copper plate preheated to 300 ℃ to form a glass block.
2. And then, transferring the glass block into a muffle furnace at 480 ℃ for annealing for 3h, cooling to room temperature along with the furnace, taking out, cutting, polishing and forming into regular shapes, and thus obtaining the thulium-ytterbium co-doped phosphate up-conversion luminescent glass with smooth and transparent surface.
The absorption spectrum of the thulium-ytterbium co-doped phosphate up-conversion luminescent glass prepared in this example is shown in curve 1 in fig. 1, and the absorption peaks are respectively located near 350nm, 460nm, 700nm, 800nm, 900nm, 1200nm and 1650 nm. Among them, the strongest peak is 980nm and is derived from Yb3+From the ground state2F7/2To an excited state2F5/2Energy level transition, the rest peak positions are all from Tm3+Electron transition absorption from the ground state level to a different excited state level. Curve 1 in FIG. 2 is the upconversion emission spectrum of the thulium-ytterbium co-doped phosphate glass obtained in this example under 980nm excitation, and it can be seen that the thulium-ytterbium co-doped phosphate glass is 780-820 nm has strong up-conversion luminescence, the strongest luminescence peak is positioned at 794nm and is originated from Tm in glass3+Is/are as follows3H43H6Electron transition emission.
Example 2
The thulium-ytterbium co-doped phosphate up-conversion luminescent glass prepared in the embodiment has the composition of P2O5-TeO2-WO3-Al2O3-BaO-Na2O-ZnO-Yb2O3-Tm2O3The mole percentage of each raw material is as follows: 50% P2O5,5%TeO2,5%WO3,10%Al2O3,12%BaO,5%Na2O,10%ZnO,2.5%Yb2O3,0.5%Tm2O3
1. The raw materials are respectively weighed, poured into an agate mortar for grinding and stirring to be fully and uniformly mixed, and the uniformly ground batch is transferred into an alumina crucible. The glass was melted for 2 hours in a high temperature box-type resistance furnace at 1400 ℃ and then poured onto a smooth copper plate preheated to 300 ℃ to form a glass block.
2. And then, the glass block is moved into a muffle furnace at 450 ℃ for annealing for 4h, then is cooled to room temperature along with the furnace, and is taken out, cut and polished into a regular shape, so that the thulium-ytterbium co-doped phosphate up-conversion luminescent glass with a smooth and transparent surface is prepared.
The absorption spectrum of the thulium-ytterbium co-doped phosphate up-conversion luminescent glass prepared in the embodiment is shown as curve 2 in fig. 1, and the absorption peaks are respectively located near 350nm, 460nm, 700nm, 800nm, 900nm, 1200nm and 1650 nm. Among them, the strongest peak is 980nm and is derived from Yb3+From the ground state2F7/2To an excited state2F5/2Energy level transition, the rest peak positions are all from Tm3+Electron transition absorption from the ground state level to a different excited state level. Fig. 2 is a curve 2 in the upconversion emission spectrum of the thulium-ytterbium co-doped phosphate glass obtained in this embodiment under 980nm excitation, it can be seen that the thulium-ytterbium co-doped phosphate glass has very strong upconversion luminescence at 780-820 nm, the strongest luminescence peak is located at 794nm and is originated from Tm in the glass3+Is/are as follows3H43H6Electron transition emission.
Example 3
The thulium-ytterbium co-doped phosphate up-conversion luminescent glass prepared in the embodiment has the composition of P2O5-B2O3-Al2O3-BaO-Na2O-ZnO-Yb2O3-Tm2O3The mol percentages of the raw materials are respectively as follows: 50% P2O5,10%B2O3,10%Al2O3,12%BaO,5%Na2O,10%ZnO,2.5%Yb2O3,0.5%Tm2O3
1. The raw materials are respectively weighed, poured into an agate mortar for grinding and stirring to be fully and uniformly mixed, and the uniformly ground batch is transferred into an alumina crucible. The glass was melted for 2 hours in a high temperature box-type resistance furnace at 1500 ℃ and then poured onto a smooth copper plate preheated to 300 ℃ to form a glass block.
2. And then, transferring the glass block into a muffle furnace at 480 ℃ for annealing for 4h, cooling to room temperature along with the furnace, taking out, cutting, polishing and forming into regular shapes, and thus obtaining the thulium-ytterbium co-doped phosphate up-conversion luminescent glass with smooth and transparent surface.
The absorption spectrum of the thulium-ytterbium co-doped phosphate up-conversion luminescent glass prepared in this example is shown in curve 3 in fig. 1, and the absorption peaks are respectively located near 350nm, 460nm, 700nm, 800nm, 900nm, 1200nm and 1650 nm. Among them, the strongest peak is 980nm and is derived from Yb3+From the ground state2F7/2To an excited state2F5/2Energy level transition, the rest peak positions are all from Tm3+Electron transition absorption from the ground state level to a different excited state level. Fig. 2 is a curve 3 of the upconversion emission spectrum of the thulium-ytterbium co-doped phosphate glass obtained in this embodiment under 980nm excitation, it can be seen that the thulium-ytterbium co-doped phosphate glass has strong upconversion luminescence at 780-820 nm, the strongest luminescence peak is located at 794nm and is originated from Tm in the glass3+Is/are as follows3H43H6Electron transition emission.
Example 4
The thulium-ytterbium co-doped phosphate up-conversion luminescent glass prepared in the embodiment has the composition of P2O5-SiO2-Al2O3-BaO-Na2O-ZnO-Yb2O3-Tm2O3The mol percentages of the raw materials are respectively as follows: 50% P2O5,10%SiO2,10%Al2O3,12%BaO,5%Na2O,10%ZnO,2.5%Yb2O3,0.5%Tm2O3
1. The raw materials are respectively weighed, poured into an agate mortar for grinding and stirring to be fully and uniformly mixed, and the uniformly ground batch is transferred into an alumina crucible. The glass was melted for 2 hours in a high temperature box-type resistance furnace at 1500 ℃ and then poured onto a smooth copper plate preheated to 300 ℃ to form a glass block.
2. And then, the glass block is moved into a muffle furnace at 500 ℃ for annealing for 4h, then is cooled to room temperature along with the furnace, and is taken out, cut and polished into a regular shape, so that the thulium-ytterbium co-doped phosphate up-conversion luminescent glass with a smooth and transparent surface is prepared.
The absorption spectrum of the thulium-ytterbium co-doped phosphate up-conversion luminescent glass prepared in this example is shown in curve 4 in fig. 1, and the absorption peaks are respectively located near 350nm, 460nm, 700nm, 800nm, 900nm, 1200nm and 1650 nm. Among them, the strongest peak is 980nm and is derived from Yb3+From the ground state2F7/2To an excited state2F5/2Energy level transition, the rest peak positions are all from Tm3+Electron transition absorption from the ground state level to a different excited state level. Fig. 2 is a curve 4 of the upconversion emission spectrum of the thulium-ytterbium co-doped phosphate glass obtained in this embodiment under 980nm excitation, it can be seen that the thulium-ytterbium co-doped phosphate glass has strong upconversion luminescence at 780-820 nm, the strongest luminescence peak is located at 794nm and is originated from Tm in the glass3+Is/are as follows3H43H6Electron transition emission.
Example 5
The thulium-ytterbium co-doped phosphate up-conversion luminescent glass prepared in the embodiment has the composition of P2O5-SiO2-Al2O3-BaO-Na2O-ZnO-Yb2O3-Tm2O3The mol percentages of the raw materials are respectively as follows: 55% P2O5,2%TeO2-4%WO3,10%Al2O3,12%BaO,5%Na2O,10%ZnO,1.5%Yb2O3,0.5%Tm2O3
Example 6
The thulium-ytterbium co-doped phosphate up-conversion luminescent glass prepared in the embodiment has the composition of P2O5-SiO2-Al2O3-BaO-Na2O-ZnO-Yb2O3-Tm2O3The mol percentages of the raw materials are respectively as follows: 50% P2O5,9.2%B2O3,10%Al2O3,12%BaO,5%Na2O,10%ZnO,3%Yb2O3,0.8%Tm2O3
Example 7
The thulium-ytterbium co-doped phosphate up-conversion luminescent glass prepared in the embodiment has the composition of P2O5-SiO2-Al2O3-BaO-Na2O-ZnO-Yb2O3-Tm2O3The mol percentages of the raw materials are respectively as follows: 55% P2O5,5.5%SiO2,10%Al2O3,12%BaO,5%Na2O,10%ZnO,2%Yb2O3,0.5%Tm2O3
Example 8
The thulium-ytterbium co-doped phosphate up-conversion luminescent glass prepared in the embodiment has the composition of P2O5-SiO2-Al2O3-BaO-Na2O-ZnO-Yb2O3-Tm2O3The mol percentages of the raw materials are respectively as follows: 60% P2O5,1.8%SiO2,10%Al2O3,12%BaO,5%Na2O,10%ZnO,1%Yb2O3,0.2%Tm2O3
Example 9
The thulium-ytterbium co-doped phosphate up-conversion luminescent glass prepared in the embodiment has the composition of P2O5-SiO2-Al2O3-BaO-Na2O-ZnO-Yb2O3-Tm2O3The mol percentages of the raw materials are respectively as follows: 52% P2O5,6%TeO2-3%WO3,10%Al2O3,12%BaO,5%Na2O,10%ZnO,1.5%Yb2O3,0.5%Tm2O3
Example 10
The thulium-ytterbium co-doped phosphate up-conversion luminescent glass prepared in the embodiment has the composition of P2O5-SiO2-Al2O3-BaO-Na2O-ZnO-Yb2O3-Tm2O3The mol percentages of the raw materials are respectively as follows: 52% P2O5,6%TeO2-3%WO3,10%Al2O3,12%BaO,5%Na2O,10%ZnO,1.5%Yb2O3,0.4%Tm2O3
Example 11
The thulium-ytterbium co-doped phosphate up-conversion luminescent glass prepared in the embodiment has the composition of P2O5-SiO2-Al2O3-BaO-Na2O-ZnO-Yb2O3-Tm2O3The mol percentages of the raw materials are respectively as follows: 53% P2O5,7.9%SiO2,10%Al2O3,12%BaO,5%Na2O,10%ZnO,1.5%Yb2O3,0.6%Tm2O3
Example 12
The thulium-ytterbium co-doped phosphate up-conversion luminescent glass prepared in the embodiment has the composition of P2O5-SiO2-Al2O3-BaO-Na2O-ZnO-Yb2O3-Tm2O3Mole percent of each raw materialRespectively as follows: 54% P2O5,7.2%B2O3,10%Al2O3,12%BaO,5%Na2O,10%ZnO,1.5%Yb2O3,0.3%Tm2O3
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.

Claims (9)

1. Thulium-ytterbium co-doped phosphate up-conversion luminescent glass is characterized in that the up-conversion luminescent glass comprises P2O5-Al2O3–BaO-Na2O–ZnO-Yb2O3-Tm2O3-a glass network framework modifier, wherein the molar percentages of the components are: p2O550~60%;Al2O310%;BaO 12%;Na2O 5%;ZnO 10%;Yb2O31~3%;Tm2O30.2-0.8% of glass network framework regulator and 1.8-10% of glass network framework regulator.
2. The thulium ytterbium co-doped phosphate up-conversion luminescent glass according to claim 1, wherein the glass network framework modifier is SiO2、TeO2-WO3Or B2O3
3. The thulium ytterbium co-doped phosphate up-conversion luminescent glass according to claim 2, wherein the TeO is2-WO3Medium TeO2And WO3The molar ratio of (1-2): (1-2).
4. The thulium and ytterbium co-doped phosphate up-conversion luminescent glass according to claim 1, wherein the up-conversion luminescent glass has a wavelength of 780-820 nm under excitation of 980 nm.
5. The method for preparing thulium ytterbium co-doped phosphate up-conversion luminescent glass according to any of claims 1 to 4, characterized in that it comprises the following specific steps:
s1, adding P2O5,Al2O3,BaO,Na2O,ZnO,Yb2O3,Tm2O3Mixing, grinding and stirring the mixture with a glass network framework regulator, transferring the mixture into an alumina crucible, melting the mixture at 1450-1550 ℃ to obtain a glass melt, pouring the glass melt onto a copper plate with the temperature kept at 250-300 ℃, and cooling the glass melt to obtain a glass block;
s2, annealing the glass block at 450-550 ℃, and cooling to room temperature along with the furnace to obtain the thulium-ytterbium co-doped phosphate up-conversion luminescent glass.
6. The method for preparing thulium-ytterbium co-doped phosphate up-conversion luminescent glass according to claim 5, wherein the stirring time in step S1 is 20-30 min.
7. The method for preparing thulium-ytterbium co-doped phosphate up-conversion luminescent glass according to claim 5, wherein the melting time in step S1 is 1-2 h.
8. The method for preparing thulium-ytterbium co-doped phosphate up-conversion luminescent glass according to claim 5, wherein the annealing time in step S2 is 3-6 h.
9. Use of the thulium ytterbium co-doped phosphate up-conversion luminescent glass according to any of claims 1 to 4 in the near infrared imaging, laser or detection optoelectronic field.
CN202010064912.0A 2020-01-20 2020-01-20 Thulium-ytterbium co-doped phosphate up-conversion luminescent glass and preparation method and application thereof Pending CN111170633A (en)

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CN113620599A (en) * 2021-06-15 2021-11-09 福建江夏学院 Novel long-afterglow luminescent glass-ceramic and preparation method thereof

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Application publication date: 20200519