CN109369007B - 2.7-micron luminous high-concentration tellurium-gallium-zinc-doped laser glass and preparation method thereof - Google Patents
2.7-micron luminous high-concentration tellurium-gallium-zinc-doped laser glass and preparation method thereof Download PDFInfo
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- CN109369007B CN109369007B CN201811369202.8A CN201811369202A CN109369007B CN 109369007 B CN109369007 B CN 109369007B CN 201811369202 A CN201811369202 A CN 201811369202A CN 109369007 B CN109369007 B CN 109369007B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
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- C03C4/00—Compositions for glass with special properties
- C03C4/0071—Compositions for glass with special properties for laserable glass
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- 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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- 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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- 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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- 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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- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
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Abstract
The invention discloses 2.7 mu m luminous high-concentration tellurium-gallium-zinc doped laser glass and a preparation method thereof. The glass comprises the following components in percentage by mole: TeO2 62‑98%；Ga2O3 2‑20%；ZnO 2‑38%；Er2O30 to 4 percent. The glass is prepared by a melt-cooling process. The glass prepared by the invention has large glass forming area and low phonon energy (765 cm)‑1) And the fluorescence quenching concentration is high (3 mol%). Can obtain strong 2.7 mu m wave band fluorescence under 808nm and 980nm Laser Diode (LD) pumping, can directly monitor the attenuation life of the 2.7 mu m wave band fluorescence, and is suitable for the preparation and application of 2.7 mu m laser glass optical fiber, optical fiber amplifier and optical fiber laser.
Description
Technical Field
The invention belongs to the field of optical materials, and particularly relates to 2.7-micrometer luminous high-concentration tellurium-gallium-zinc-doped laser glass and a preparation method thereof.
Background
The 2.7 mu m wave band optical fiber laser has important potential application in medical operation, military, national defense and the like. The rare earth ion for realizing 2.7 mu m luminescence is Er3+Ion, corresponding to4I11/2→4I13/2And energy level transition, which has stronger absorption peaks at 808nm and 980nm, so that corresponding high-power semiconductor laser pumping can be adopted. At present, the glass matrix for realizing 2.7 mu m laser is only limited in fluoride glass, however, the fluoride glass has poor physical and chemical properties,the disadvantage of a low threshold for laser damage resistance, and therefore the search for new laser glass substrates is required.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide 2.7-micron luminescent high-concentration tellurium-gallium-zinc-doped laser glass and a preparation method thereof. Tellurate glass, especially tellurium-gallium-zinc glass, has high glass transition temperature, low phonon energy and high rare earth dissolving capacity, so that the tellurate glass may be used as 2.7 micron luminous matrix glass for 2.7 micron laser output.
The preparation method provided by the invention comprises the steps of taking tellurium oxide as a glass forming body, taking gallium oxide and zinc oxide as glass intermediates, forming a stable three-dimensional network structure, greatly widening the forming range of glass, improving the solubility of rare earth, and being used for the preparation and application of 2.7 mu m laser glass optical fibers, optical fiber amplifiers and optical fiber lasers.
The purpose of the invention is realized by the following technical scheme.
The invention provides 2.7 mu m luminous high-concentration tellurium-gallium-zinc doped laser glass, which comprises the following components in percentage by weight:
the sum of the above mole percentages is 100%.
Further, the method for preparing the 2.7-micron luminescent high-concentration tellurium-gallium-zinc-doped laser glass comprises the following steps of:
(1) weighing raw materials according to composition and proportion (the raw materials are all introduced in the form of oxides);
(2) fully mixing the raw materials obtained in the step (1) in an agate mortar to form a batch;
(3) transferring the batch in the step (2) into a corundum crucible, placing the corundum crucible in a high-temperature melting furnace for heating and heat preservation, and obtaining the bubble-free, calculus-free, transparent and uniform glass liquid after melting, clarification and homogenization;
(4) pouring the molten glass obtained in the step (3) on a stainless steel iron plate for molding to obtain a transparent glass block;
(5) and quickly transferring the formed transparent glass to a muffle furnace for annealing, preserving heat to remove the internal stress of the glass, and then cooling to room temperature along with the furnace to obtain the tellurium-gallium-zinc glass.
Further, the temperature rise in the step (3) is from room temperature to 800-1000 ℃, and the temperature is maintained for 30-60 minutes.
Further, the annealing temperature in the step (5) is 300-350 ℃.
Further, the heat preservation time in the step (5) is 2-4 hours.
Further, the cooling rate of the step (5) is 10-20 ℃/hour.
The tellurium-gallium-zinc glass can be prepared by the preparation method.
Compared with the prior art, the invention has the following advantages and effects:
the glass prepared by the invention has large glass forming area and low phonon energy (765 cm)-1) And the fluorescence quenching concentration is high (3 mol%). Can obtain strong 2.7 mu m wave band fluorescence under 808nm and 980nm Laser Diode (LD) pumping, can directly monitor the attenuation life of the 2.7 mu m wave band fluorescence, and is suitable for the preparation and application of 2.7 mu m laser glass optical fiber, optical fiber amplifier and optical fiber laser.
Drawings
FIG. 1 is a diagram of the formation region of the tellurium-gallium-zinc laser glass obtained in the present invention (the shaded area represents the actual glass forming range), in which the numbers of the hollow circles correspond to those of examples 1-7;
FIG. 2 is a Raman spectrum of example 6 CZT laser glass obtained by the present invention;
FIG. 3 is an emission spectrum of example 6 of a CZT laser glass obtained in the present invention;
FIG. 4 is a life attenuation curve of the example 6 Te-Ga-Zn laser glass obtained in the present invention, wherein the excitation wavelength is 980nm and the monitoring wavelength is 2715 nm).
Detailed Description
The embodiments of the present invention will be further described below with reference to specific examples and drawings, but the embodiments of the present invention are not limited thereto.
The compositions and proportions of the glasses produced in the 7 embodiments of the invention are given in Table 1 below, where Er is2O3Is introduced into the glass composition in an external doping manner.
TABLE 1
The preparation steps of the tellurium-gallium-zinc laser glass in the embodiment 1-2 are as follows:
(1) raw materials of 20g are accurately weighed according to composition and proportion, and are all high-purity raw materials (more than 99.99%), wherein the raw materials of the embodiment 1 are as follows: TeO2：14.68g，Ga2O3：4.74g，ZnO：0.57g，Er2O3: 0g of a compound; the raw materials of example 2 were: TeO2：14.78g，Ga2O3：4.38g，ZnO：0.56g，Er2O3：0.29g；
(2) Mixing the raw materials obtained in the step (1) in an agate mortar to form a batch;
(3) transferring the uniformly ground batch in the step (2) into a corundum crucible, putting the corundum crucible into a high-temperature furnace, heating to 800 ℃ (embodiment 1-3), and melting for 30 minutes to obtain a transparent and uniform glass liquid without bubbles and stones;
(4) pouring the clarified and homogenized molten glass on a stainless steel iron plate for molding to obtain a transparent glass block;
(5) and transferring the formed transparent glass to a muffle furnace, annealing at 300 ℃, preserving heat for 2 hours to remove the internal stress of the glass, and then cooling to room temperature along with the furnace at a cooling rate of 20 ℃/hour to obtain the tellurium-gallium-zinc glass.
The preparation steps of the tellurium-gallium-zinc laser glass in the embodiments 3-5 are as follows:
(1) accurately weighing 20g of raw materials according to composition and proportion, wherein the raw materials of the embodiment 3 are as follows: TeO2：14.21g，Ga2O3：4.61g，ZnO：0.8g，Er2O3: 0.47 g; the starting materials for example 4 were: TeO2：14.7g，Ga2O3：4.43g，ZnO：0.19g，Er2O3: 0.68 g; the starting materials for example 5 were: TeO2：15.74g，Ga2O3：2.31g，ZnO：1g，Er2O3：1.55g；
(2) Mixing the raw materials obtained in the step (1) in an agate mortar to form a batch;
(3) transferring the batch ground uniformly in the step (2) into a corundum crucible, and placing the corundum crucible in a high-temperature melting furnace to melt for 60 minutes at 1000 ℃ to obtain bubble-free, stone-free, transparent and uniform glass liquid;
(4) pouring the clarified and homogenized molten glass on a stainless steel iron plate for molding to obtain a transparent glass block;
(5) and transferring the formed transparent glass into a muffle furnace, annealing at 350 ℃, preserving heat for 4 hours to remove the internal stress of the glass, and then cooling to room temperature along with the furnace at a cooling rate of 15 ℃/hour to obtain the tellurium-gallium-zinc glass.
The preparation steps of the tellurium-gallium-zinc laser glass in the embodiments 6 to 7 are as follows:
(1) accurately weighing 20g of raw materials according to composition and proportion, wherein the raw materials of the embodiment 6 are as follows: TeO2：16.48g，Ga2O3：1.14g，ZnO：0.99g，Er2O3: 1.39 g; the starting materials for example 7 were: TeO2：18.14g，Ga2O3：0.22g，ZnO：0.09g，Er2O3：0.68g；
(2) Mixing the raw materials obtained in the step (1) in an agate mortar to form a batch;
(3) transferring the batch ground uniformly in the step (2) into a corundum crucible, and placing the corundum crucible in a high-temperature melting furnace to melt for 40 minutes at 900 ℃ to obtain bubble-free, stone-free, transparent and uniform glass liquid;
(4) pouring the clarified and homogenized molten glass on a stainless steel iron plate for molding to obtain a transparent glass block;
(5) and transferring the formed transparent glass into a muffle furnace, annealing at 320 ℃, preserving heat for 3 hours to remove the internal stress of the glass, and then cooling to room temperature along with the furnace at the cooling rate of 10 ℃/hour to obtain the tellurium-gallium-zinc glass.
FIG. 1 is a diagram of the formation region of the tellurium-gallium-zinc laser glass obtained by the present invention (the shaded area represents the actual glass forming range), and the numbers of the open circles in the diagram correspond to the examples 1-7. From fig. 1, it can be seen that the glass forming region of the tellurium-gallium-zinc glass of the invention is very large. FIG. 2 shows that the maximum phonon energy of the glass is only 765cm-1Lower maximum phonon energy is beneficial to obtaining high-efficiency mid-infrared luminescence. FIG. 3 is the mid-infrared fluorescence spectrum, Er, of the CdZnTe glass of example 63+A strong 2.7 μm fluorescence was observed at concentrations up to 3 mol%. Er can be seen in FIG. 43+Ion(s)4I11/2The lifetime of the energy level is 0.4 ms. The glass forming area of the film prepared by the above embodiment is large, and the phonon energy is low (765 cm)-1) And the fluorescence quenching concentration is high (3 mol%). Can obtain strong 2.7 mu m wave band fluorescence under the pump of 980nm Laser Diode (LD), can directly monitor the attenuation life of the 2.7 mu m wave band fluorescence, and is suitable for the preparation and application of 2.7 mu m laser glass optical fiber, optical fiber amplifier and optical fiber laser.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (6)
1. A2.7 μm luminous high-concentration tellurium-gallium-zinc-doped laser glass is characterized by comprising the following components in percentage by weight:
TeO2 62-98%；
Ga2O3 2-20%；
ZnO 2-38%；
Er2O3 0.5-4%；
the mole percentage composition and the mixture ratio are 100 percent.
2. A method for preparing 2.7 μm luminescent high-concentration tellurium-gallium-zinc-doped laser glass as claimed in claim 1, characterized by comprising the steps of:
(1) weighing raw materials according to composition and proportion;
(2) mixing the raw materials obtained in the step (1) to form a batch;
(3) placing the uniformly ground batch in the step (2) into a high-temperature smelting furnace for melting to obtain transparent and uniform glass liquid without bubbles and stones;
(4) pouring the molten glass obtained in the step (3) on a stainless steel iron plate for molding to obtain a transparent glass block;
(5) and transferring the formed transparent glass to a muffle furnace for annealing, preserving heat to remove the internal stress of the glass, and then cooling to room temperature along with the furnace to obtain the tellurium-gallium-zinc glass.
3. The method according to claim 2, wherein the step (3) is carried out in a high temperature furnace at a temperature of from room temperature to 800-1000 ℃ for 30-60 minutes.
4. The method as claimed in claim 2, wherein the annealing temperature in step (5) is 300-350 ℃.
5. The method according to claim 2, wherein the holding time in the step (5) is 2 to 4 hours.
6. The method as set forth in claim 2, wherein the cooling in the step (5) is performed at a rate of 10 to 20 ℃/hr.
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