CN109369007A - 2.7 mu m luminous high-concentration dopant tellurium gallium zinc laser glasses of one kind and preparation method thereof - Google Patents
2.7 mu m luminous high-concentration dopant tellurium gallium zinc laser glasses of one kind and preparation method thereof Download PDFInfo
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- CN109369007A CN109369007A CN201811369202.8A CN201811369202A CN109369007A CN 109369007 A CN109369007 A CN 109369007A CN 201811369202 A CN201811369202 A CN 201811369202A CN 109369007 A CN109369007 A CN 109369007A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C4/00—Compositions for glass with special properties
- C03C4/0071—Compositions for glass with special properties for laserable glass
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
- C03B25/02—Annealing glass products in a discontinuous way
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/06—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture in pot furnaces
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/122—Silica-free oxide glass compositions containing oxides of As, Sb, Bi, Mo, W, V, Te as glass formers
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/60—Silica-free oxide glasses
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Abstract
The invention discloses a kind of 2.7 mu m luminous high-concentration dopant tellurium gallium zinc laser glasses and preparation method thereof.The molar percentage compositing range of the glass are as follows: TeO262-98%;Ga2O32-20%;ZnO 2-38%;Er2O30-4%.The glass passes through melting cooling method preparation.Glass prepared by the present invention has into glass area big, the low (765cm of phonon energy‑1), the characteristics of fluorescent quenching concentration high (3mol%).Very strong 2.7 mu m waveband fluorescence can be obtained under 808nm and 980nm laser diode (LD) pumping, the Decay that can directly monitor 2.7 mu m waveband fluorescence simultaneously, is suitable for the preparation and application of 2.7 μm of laser glass optical fiber, fiber amplifier and optical fiber laser.
Description
Technical field
The invention belongs to optical material fields, and in particular to a kind of 2.7 mu m luminous high-concentration dopant tellurium gallium zinc laser glasses
And preparation method thereof.
Background technique
2.7 mu m waveband optical fiber lasers have important potential application in medical operating and military and national defense etc..Realize 2.7 μm
Luminous rare earth ion is Er3+Ion, it is corresponding4I11/2→4I13/2Energy level transition has stronger suction in 808nm and 980nm
Peak is received, therefore can be pumped using corresponding high-power semiconductor laser.The glass matrix only office of 2.7 μm of laser is realized at present
Limit is in fluoride glass, however fluoride glass there are physico-chemical properties poor, the lower disadvantage of threshold for resisting laser damage, therefore
Need to explore novel laser glass matrix.
Summary of the invention
In order to overcome the disadvantages mentioned above and deficiency of the prior art, the object of the present invention is to provide one kind 2.7 is mu m luminous highly concentrated
Degree doping tellurium gallium zinc laser glass and preparation method thereof.Tellurate glass especially tellurium gallium zinc glass vitrifying with higher turns
Temperature, lower phonon energy, higher rare earth solvability, therefore can be used as 2.7 mu m luminous host glasses, it is expected to
Realize 2.7 μm of laser outputs.
Preparation method provided by the invention includes using tellurium oxide as glass former, and gallium oxide and zinc oxide are among glass
Body can form stable three-dimensional net structure, greatly widen the formation range of glass, improve rare earth solubility, can be used for 2.7
The preparation and application of μm laser glass optical fiber, fiber amplifier and optical fiber laser.
The purpose of the present invention is achieved through the following technical solutions.
A kind of 2.7 mu m luminous high-concentration dopant tellurium gallium zinc laser glass provided by the invention, the glass composition and ratio are as follows:
Above-mentioned molar percentage summation is 100%.
Further, the method for preparing above-mentioned 2.7 mu m luminous high-concentration dopant tellurium gallium zinc laser glasses, including following step
It is rapid:
(1) weigh raw material according to composition and ratio (raw material introduces in the form of the oxide);
(2) raw material obtained in step (1) is thoroughly mixed to form batch in the agate mortar;
(3) batch in step (2) is transferred to corundum crucible, is placed in high-temperature smelting pot and heats up and keep the temperature, melted, is clear
Bubble-free is obtained after cleer and peaceful homogenizing, without calculus, transparent, uniform glass metal;
(4) glass metal that step (3) obtains is cast on stainless steel iron plate and is formed, obtain transparent glass block;
(5) molding transparent glass is transferred quickly to anneal in Muffle furnace, is kept the temperature to remove the internal stress of glass, then
It cools to room temperature with the furnace, obtains the tellurium gallium zinc glass.
Further, to be temperature rise to 800-1000 DEG C from room temperature for step (3) heating, keeps the temperature 30-60 minutes.
Further, the temperature of step (5) described annealing is 300-350 DEG C.
Further, the time of step (5) described heat preservation is 2-4 hours.
Further, the rate of step (5) described cooling is 10-20 DEG C/h.
The tellurium gallium zinc glass can be made by above-mentioned preparation method.
Compared with prior art, the invention has the advantages that and effect:
Glass prepared by the present invention has into glass area big, the low (765cm of phonon energy-1), fluorescent quenching concentration is high
The characteristics of (3mol%).Very strong 2.7 mu m waveband fluorescence can be obtained under 808nm and 980nm laser diode (LD) pumping,
The Decay that can directly monitor 2.7 mu m waveband fluorescence simultaneously, is suitable for 2.7 μm of laser glass optical fiber, fiber amplifiers
With the preparation and application of optical fiber laser.
Detailed description of the invention
Fig. 1 is the formation area figure (dash area represents practical at glass range) of the resulting tellurium gallium zinc laser glass of the present invention,
Hollow circled numerals corresponding embodiment 1-7 in figure;
Fig. 2 is the Raman spectrum of present invention gained 6 tellurium gallium zinc laser glass of embodiment;
Fig. 3 is the emission spectrum of present invention gained 6 tellurium gallium zinc laser glass of embodiment;
Fig. 4 is the life time decay curve of present invention gained 6 tellurium gallium zinc laser glass of embodiment, excitation wavelength 980nm, prison
Survey wavelength is 2715nm).
Specific embodiment
Embodiments of the present invention are further detailed below in conjunction with specific embodiment and attached drawing, but of the invention
Embodiment is without being limited thereto.
The composition and ratio of glass made from 7 specific embodiments of the invention see the table below 1, wherein Er2O3The mode mixed in addition
It is introduced into glass composition.
Table 1
The preparation step of tellurium gallium zinc laser glass is as follows in embodiment 1-2:
(1) according to composition and ratio accurate weighing raw material 20g, raw material is high pure raw material (> 99.99%), wherein implementing
The raw material of example 1 are as follows: TeO2: 14.68g, Ga2O3: 4.74g, ZnO:0.57g, Er2O3: 0g;The raw material of embodiment 2 are as follows: TeO2:
14.78g Ga2O3: 4.38g, ZnO:0.56g, Er2O3: 0.29g;
(2) raw material obtained in step (1) is mixed to form batch in the agate mortar;
(3) the uniform batch of grinding in step (2) is transferred to corundum crucible, is placed in high-temperature smelting pot and is warming up to 800 DEG C
(embodiment 1-3) obtains bubble-free, without calculus, transparent, uniform glass metal after melting 30 minutes;
(4) glass metal after clarification and homogenization is cast on stainless steel iron plate and is formed, obtain transparent glass block;
(5) molding transparent glass is transferred in Muffle furnace and anneals in 300 DEG C and keeps the temperature 2 hours to remove in glass
Then stress cools to room temperature with the furnace with 20 DEG C/h of cooling rate, obtain tellurium gallium zinc glass.
The preparation step of tellurium gallium zinc laser glass is as follows in embodiment 3-5:
(1) according to composition and ratio accurate weighing raw material 20g, the wherein raw material of embodiment 3 are as follows: TeO2: 14.21g,
Ga2O3: 4.61g, ZnO:0.8g, Er2O3: 0.47g;The raw material of embodiment 4 are as follows: TeO2: 14.7g, Ga2O3: 4.43g, ZnO:
0.19g, Er2O3: 0.68g;The raw material of embodiment 5 are as follows: TeO2: 15.74g, Ga2O3: 2.31g, ZnO:1g, Er2O3: 1.55g;
(2) raw material obtained in step (1) is mixed to form batch in the agate mortar;
(3) the uniform batch of grinding in step (2) is transferred to corundum crucible, is placed in high-temperature smelting pot and is melted at 1000 DEG C
Bubble-free is obtained after sixty minutes, without calculus, transparent, uniform glass metal;
(4) glass metal after clarification and homogenization is cast on stainless steel iron plate and is formed, obtain transparent glass block;
(5) molding transparent glass is transferred in Muffle furnace and anneals in 350 DEG C and keeps the temperature 4 hours to remove in glass
Then stress cools to room temperature with the furnace with 15 DEG C/h of cooling rate, obtain tellurium gallium zinc glass.
The preparation step of tellurium gallium zinc laser glass is as follows in embodiment 6-7:
(1) according to composition and ratio accurate weighing raw material 20g, the wherein raw material of embodiment 6 are as follows: TeO2: 16.48g,
Ga2O3: 1.14g, ZnO:0.99g, Er2O3: 1.39g;The raw material of embodiment 7 are as follows: TeO2: 18.14g, Ga2O3: 0.22g, ZnO:
0.09g, Er2O3: 0.68g;
(2) raw material obtained in step (1) is mixed to form batch in the agate mortar;
(3) the uniform batch of grinding in step (2) is transferred to corundum crucible, is placed in high-temperature smelting pot and is melted at 900 DEG C
Bubble-free is obtained after forty minutes, without calculus, transparent, uniform glass metal;
(4) glass metal after clarification and homogenization is cast on stainless steel iron plate and is formed, obtain transparent glass block;
(5) molding transparent glass is transferred in Muffle furnace and anneals in 320 DEG C and keeps the temperature 3 hours to remove in glass
Then stress cools to room temperature with the furnace with 10 DEG C/h of cooling rate, obtain tellurium gallium zinc glass.
Fig. 1 is the formation area figure (dash area represents practical at glass range) of the resulting tellurium gallium zinc laser glass of the present invention,
Hollow circled numerals corresponding embodiment 1-7 in figure.Tellurium gallium zinc glass of the invention is very big at glass area as can be seen from Figure 1.Fig. 2
It can be seen that the maximum phonon energy of glass is only 765cm-1, lower maximum phonon energy help to obtain infrared in efficient
It shines.Fig. 3 is the middle IR fluorescence spectrum of the tellurium gallium zinc glass of embodiment 6, Er3+It can be observed when at concentrations up to 3mol% strong
2.7 μm of fluorescence.It can be seen that Er in Fig. 43+Ion4I11/2The service life of energy level is 0.4ms.It is prepared in the above embodiments to have into glass
Qu great, the low (765cm of phonon energy-1), the characteristics of fluorescent quenching concentration high (3mol%).It is pumped at 980nm laser diode (LD)
Very strong 2.7 mu m waveband fluorescence can be obtained under Pu, while can directly monitor the Decay of 2.7 mu m waveband fluorescence, fitted
Together in the preparation and application of 2.7 μm of laser glass optical fiber, fiber amplifier and optical fiber laser.
Above embodiments are only preferrred embodiment of the present invention, for explaining only the invention, are not intended to limit the present invention, this
Field technical staff should belong to guarantor of the invention without departing from change made under spirit of the invention, replacement, modification etc.
Protect range.
Claims (6)
1. a kind of 2.7 mu m luminous high-concentration dopant tellurium gallium zinc laser glasses, which is characterized in that its composition and ratio are as follows:
TeO262-98%;
Ga2O32-20%;
ZnO 2-38%;
Er2O3 0-4%;
Above-mentioned molar percentage summation is 100%.
2. the method for preparing 2.7 mu m luminous high-concentration dopant tellurium gallium zinc laser glasses described in claim 1, which is characterized in that packet
Include following steps:
(1) raw material is weighed according to composition and ratio;
(2) raw material obtained in step (1) is mixed to form batch;
(3) will the uniform batch of grinding in step (2), be placed in high-temperature smelting pot after melting obtain bubble-free, without calculus, thoroughly
Bright, uniform glass metal;
(4) step (3) resulting glass metal is cast on stainless steel iron plate and is formed, obtain transparent glass block;
(5) molding transparent glass is transferred in Muffle furnace and is annealed, kept the temperature to remove the internal stress of glass, then furnace cooling
To room temperature, the tellurium gallium zinc glass is obtained.
3. preparation method according to claim 2, which is characterized in that step (3) heating is that temperature rises to from room temperature
800-1000 DEG C, keep the temperature 30-60 minutes.
4. preparation method according to claim 2, which is characterized in that the temperature of step (5) described annealing is 300-350
℃。
5. preparation method according to claim 2, which is characterized in that the time of step (5) described heat preservation is 2-4 hours.
6. preparation method according to claim 2, which is characterized in that the rate of step (5) described cooling be 10-20 DEG C/
Hour.
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CN201811369202.8A CN109369007B (en) | 2018-11-16 | 2018-11-16 | 2.7-micron luminous high-concentration tellurium-gallium-zinc-doped laser glass and preparation method thereof |
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CN109369007B CN109369007B (en) | 2021-02-19 |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112110647A (en) * | 2020-09-23 | 2020-12-22 | 中国计量大学 | High-color-rendering-index fluorescent glass applied to laser illumination and preparation method thereof |
Citations (2)
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US20030045421A1 (en) * | 2001-08-15 | 2003-03-06 | Agilent Technologies, Inc. | Optical tellurite glasses for optical waveguide amplifiers and oscillators, and process for producing them |
CN103058516A (en) * | 2013-01-17 | 2013-04-24 | 中国科学院上海光学精密机械研究所 | High-concentration erbium ion doped tellurium tungstate glass capable of emitting light at mid-infrared 2.7 microns |
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2018
- 2018-11-16 CN CN201811369202.8A patent/CN109369007B/en active Active
Patent Citations (2)
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US20030045421A1 (en) * | 2001-08-15 | 2003-03-06 | Agilent Technologies, Inc. | Optical tellurite glasses for optical waveguide amplifiers and oscillators, and process for producing them |
CN103058516A (en) * | 2013-01-17 | 2013-04-24 | 中国科学院上海光学精密机械研究所 | High-concentration erbium ion doped tellurium tungstate glass capable of emitting light at mid-infrared 2.7 microns |
Non-Patent Citations (3)
Title |
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PURUSHOTTAM JOSHI: "Erbium-Ion-Doped Tellurite Glasss Fibers and Waveguides — Devices and Future Prospective: PART I", 《INTERNATIONAL JOURNAL OF APPLIED GLASS SCIENCE》 * |
YANYAN GUO: "Erbium doped heavy metal oxide glasses for mid-infrared laser materials", 《JOURNAL OF NON-CRYSTALLINE SOLIDS》 * |
赵纯: "Tm3+/Yb3+共掺碲镓酸盐玻璃上转换光谱研究", 《武汉理工大学学报》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112110647A (en) * | 2020-09-23 | 2020-12-22 | 中国计量大学 | High-color-rendering-index fluorescent glass applied to laser illumination and preparation method thereof |
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