CN111646695A - Heavy metal oxide glass with broadband mid-infrared light emitting characteristic and preparation method thereof - Google Patents

Heavy metal oxide glass with broadband mid-infrared light emitting characteristic and preparation method thereof Download PDF

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CN111646695A
CN111646695A CN202010487516.9A CN202010487516A CN111646695A CN 111646695 A CN111646695 A CN 111646695A CN 202010487516 A CN202010487516 A CN 202010487516A CN 111646695 A CN111646695 A CN 111646695A
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metal oxide
heavy metal
glass
oxide glass
raw materials
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王鹏飞
于晋
王顺宾
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Suzhou Kaiwen Baoni Optoelectronics Technology Co ltd
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Suzhou Kaiwen Baoni Optoelectronics Technology Co ltd
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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
    • C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
    • 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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B25/00—Annealing glass products
    • 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
    • C03B5/235—Heating the glass
    • 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
    • C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
    • H01S3/05—Construction or shape of optical resonators; Accommodation of active medium therein; Shape of active medium
    • H01S3/06—Construction or shape of active medium
    • H01S3/063—Waveguide lasers, i.e. whereby the dimensions of the waveguide are of the order of the light wavelength
    • H01S3/067—Fibre lasers
    • H01S3/06708—Constructional details of the fibre, e.g. compositions, cross-section, shape or tapering
    • H01S3/06716—Fibre compositions or doping with active elements

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Abstract

The invention discloses heavy metal oxide glass with broadband mid-infrared luminescence characteristics, wherein the matrix molar composition of the heavy metal oxide glass is represented by a chemical formula as follows: xPbO- (57-x) PbF2‑25Bi2O3‑18Ga2O3Wherein x is 37-57, and Er is doped with the concentration of 1mol percent3+Ions. The preparation method comprises the following steps: calculating the mass ratio of the high-purity raw materials according to the mol percentage and then weighingGrinding and stirring to fully mix various raw materials; putting the uniformly mixed raw materials into a platinum crucible and heating; and pouring the molten glass onto a preheated copper plate at 250-350 ℃, and placing the copper plate in an annealing furnace for annealing. The PBG glass prepared by the invention has the characteristics of high transparency, high luminous intensity, high stability and the like, the preparation process is simple, and mass production can be realized; in addition, it has important applications in the field of fiber lasers due to its excellent thermal stability and processability.

Description

Heavy metal oxide glass with broadband mid-infrared light emitting characteristic and preparation method thereof
Technical Field
The invention relates to the technical field of luminescent materials and optical fiber lasers, in particular to heavy metal oxide glass with broadband mid-infrared luminescence characteristics and a preparation method thereof.
Background
Mid-infrared (2.5-25 μm) lasers have important applications in many fields. Taking 2.7 μm laser as an example, the laser can be used in the field of medical minimally invasive surgery because the luminescence peak position of the laser is partially overlapped with the absorption peak of water; in addition, many gases have strong absorption peaks around 3 μm, and thus, can be used in the fields of gas sensing and detection. Due to Er3+The ions have rich energy level distribution, and can be used as a powerful selection for generating infrared laser with different wave bands in various matrixes, such as 1.55 microns, 2.7 microns and the like. Furthermore, Er3+The ions have an energy level that can be matched to a 980nm commercial laser, thus ensuring their possibility for large-scale use.
With the development of optical communication and lasers, there is an objective demand for smaller-sized lasers and higher power outputs, and thus, high demands are made on physical properties and optical gain characteristics of working substances. For a glass-like gain medium, a higher refractive index means a higher gain characteristic, and thus the laser can be effectively downsized. In 1992, Dambaugh et al first proposed glasses made with heavy metal oxides as the major component to increase the refractive index of the glass product while ensuring or even improving its thermal and chemical stability. In addition, compared with common fluoride glass, the glass has lower phonon energy, so that the luminous intensity of the laser in the mid-infrared band is obviously improved. Therefore, the heavy metal oxide glass is one of the powerful choices for the working substance of the laser in the mid-infrared band due to the characteristics of low phonon energy, high refractive index, large transmission window and the like.
Therefore, those skilled in the art have made an effort to develop a heavy metal oxide glass having a broadband mid-infrared emission characteristic and a method of preparing the same.
Disclosure of Invention
In view of the above-mentioned defects of the prior art, the technical problem to be solved by the present invention is to provide a heavy metal oxide glass having a wider bandwidth mid-infrared luminescence property compared with other common fluoride glasses, and a preparation method thereof.
In order to achieve the above purpose, the present invention provides a heavy metal oxide glass having broadband mid-infrared luminescence characteristics, wherein the matrix molar composition of the heavy metal oxide glass is represented by the chemical formula: xPbO- (57-x) PbF2-25Bi2O3-18Ga2O3Wherein x is 37-57, the sum of the mole percentages of the components is 100%, and Er with the doping concentration of 1mol percent3+Ions.
Further, the Er3+Er as ion2O3The form is doped.
The invention also provides a preparation method of the heavy metal oxide glass with broadband mid-infrared luminescence characteristics, which comprises the following steps:
step 1, calculating the mass ratio of high-purity raw materials according to the mole percentage, weighing, grinding and stirring to fully mix various raw materials;
step 2, putting the uniformly mixed raw materials into a platinum crucible and heating;
and 3, pouring the molten glass onto a copper plate preheated at the temperature of 250-350 ℃, and placing the copper plate in an annealing furnace for annealing.
Further, the various raw materials in step 1 include Pb, Bi, Ga, and Er.
Further, the matrix molar composition of the heavy metal oxide glass with broadband mid-infrared luminescence property in the step 1 is represented by a chemical formula: xPbO- (57-x) PbF2-25Bi2O3-18Ga2O3Wherein x is 37-57, the sum of the mole percentages of the components is 100%, and Er with the doping concentration of 1mol percent3+Ions.
Further, the Er3+Er as ion2O3The form is doped.
Further, the heating in the step 2 is specifically: heating the mixture in an electric furnace at 850-950 ℃ for 25-45 min.
Further, the annealing in the step 3 specifically includes: keeping the temperature at 250-350 ℃ for 1.5-4 h, and cooling to room temperature along with the furnace.
Further, all the steps of the preparation method should be performed in a dry glove box.
Further, the preparation method further comprises the following steps:
and 4, cutting and polishing the prepared glass.
The invention has the beneficial effects that:
the prepared PBG glass has the characteristics of high transparency, high luminous intensity, high stability and the like, the preparation process is simple, and mass production can be realized. The needed pumping light source is a 980nm laser, so that the device can be applied to a plurality of fields such as medical operation, gas monitoring and sensing and the like in a large scale. In addition, such glasses have important applications in the field of fiber lasers due to their excellent thermal stability and processability.
Drawings
FIG. 1 is a differential thermal analysis curve of a glass according to a preferred embodiment of the present invention;
FIG. 2 is a transmission curve of a glass according to a preferred embodiment of the present invention;
FIG. 3 is a comparison of the luminescence at 2.7 μm for the glass of a preferred embodiment of the present invention versus several fluoride glasses.
Detailed Description
The preferred embodiments of the present invention will be described below with reference to the accompanying drawings for clarity and understanding of technical contents. The present invention may be embodied in many different forms of embodiments and the scope of the invention is not limited to the embodiments set forth herein.
Example (b):
the mole percent of each raw material of the glass matrix can be expressed as: 47PbO-10PbF2-25Bi2O3-18Ga2O3(PBG glass), PbO and PbF2Total mole percentage of (1)57 percent of the rare earth ions are Er3+Ions, concentration 1 mol%, based on oxide (Er)2O3) The form is doped.
TABLE 1
Figure BDA0002519598730000031
Figure BDA0002519598730000041
The preparation method comprises the following steps:
weighing high-purity raw materials with corresponding weights by using an electronic balance according to the weight of each raw material shown in the table 1, and fully grinding and mixing the raw materials in an agate mortar; placing the mixture in a 30ml platinum crucible, placing the crucible in a thermocouple electric furnace at 900 ℃ for melting for 30min, pouring the crucible on a copper plate preheated at 300 ℃, placing the crucible in a precision annealing furnace for heat preservation for 2h, then turning off a power supply, and cooling the crucible to room temperature.
In addition, in the melting process, if the water content in the glass is too high, the luminous intensity of 2.7 microns can be greatly reduced, and the glass is easy to crystallize, so that the whole manufacturing process of the glass is filled with dry N2And O2And preferably the mix is left to stand in the glove box for 24 hours prior to melting to perform the physical dewatering process.
The test flow comprises the following steps:
cutting and polishing the prepared heavy metal oxide glass to 10 × 2mm3Performing a correlation optical test; taking a proper amount of leftover materials, placing the leftover materials in an agate mortar, grinding the leftover materials into tiny powder, and taking 10mg of powder to perform DSC differential thermal analysis test.
And (3) testing results:
(1) DSC differential thermal test:
the test results are shown in fig. 1, and it can be seen that the transition temperature is 310 ℃, the crystallization starting temperature is 391 ℃, and the corresponding thermal stability parameter Δ T is 81 ℃, which is higher than other common fluoride glasses, indicating that the thermal stability is better than that of fluoride glasses.
(2) And (3) transmission test:
the test result is shown in figure 2, the transmission window is 475 nm-8 μm, and the infrared cut-off wavelength is higher than that of common fluoride glass; the transmittance was about 74%, which is slightly lower than that of the comparative glass.
(3)2.7 μm luminescence comparison test:
the PBG glass of the invention is used as a pumping source by using a 980nm laser diode light source, the luminous intensity of the PBG glass is tested to be near 2.7 mu m, and Er with the same concentration as other doped PBG glass3+The results of comparing the ionic fluoride glasses under the same test conditions are shown in FIG. 3, and the emission intensity is PBG glass, fluorine indium based glass, fluorine Zirconium Based (ZBLAN) glass, and fluorine aluminum based glass in the order of strong to weak. The half-height width of the light-emitting band of the PBG glass is 184.44nm, which is wider than the fluoride glasses, and is 140.95nm (fluorine indium based glass), 147.99nm (ZBLAN glass) and 133.82nm (fluorine aluminum based glass). The test result shows that the light emitting characteristic of the PBG glass at 2.7 mu m is far better than that of the fluoride glasses, and the application of the PBG glass at a middle infrared band is facilitated.
Experiments and tests prove that the glass substrate obtained by the invention has higher thermal stability, the parameter delta T is more than 80 ℃, the infrared cut-off wavelength is 8 mu m, and the glass is suitable for being used as a medium-infrared luminous substrate material; the refractive index is about 2.3, which shows that the gain characteristic is larger; the 2.7 mu m luminescence is stronger than other fluoride glasses, and the bandwidth difference is about 40nm, which shows that the luminescence property is more excellent.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.

Claims (10)

1. The heavy metal oxide glass with broadband mid-infrared luminescence characteristics is characterized in that a matrix of the heavy metal oxide glassThe molar composition is expressed by the chemical formula: xPbO- (57-x) PbF2-25Bi2O3-18Ga2O3Wherein x is 37-57, the sum of the mole percentages of the components is 100%, and Er with the doping concentration of 1mol percent3+Ions.
2. The heavy metal oxide glass having broadband mid-infrared emission characteristics according to claim 1, wherein said Er is3+Er as ion2O3The form is doped.
3. A preparation method of heavy metal oxide glass with broadband mid-infrared luminescence characteristics is characterized by comprising the following steps:
step 1, calculating the mass ratio of high-purity raw materials according to the mole percentage, weighing, grinding and stirring to fully mix various raw materials;
step 2, putting the uniformly mixed raw materials into a platinum crucible and heating;
and 3, pouring the molten glass onto a copper plate preheated at the temperature of 250-350 ℃, and placing the copper plate in an annealing furnace for annealing.
4. The method according to claim 3, wherein the raw materials in step 1 include Pb, Bi, Ga and Er.
5. The method according to claim 3, wherein the molar composition of the matrix of the heavy metal oxide glass with broadband mid-infrared emission characteristic in the step 1 is represented by a chemical formula: xPbO- (57-x) PbF2-25Bi2O3-18Ga2O3Wherein x is 37-57, the sum of the mole percentages of the components is 100%, and Er with the doping concentration of 1mol percent3+Ions.
6. The method of claim 5The preparation method of the heavy metal oxide glass with the broadband mid-infrared luminescence characteristic is characterized in that the Er3+Er as ion2O3The form is doped.
7. The method for preparing the heavy metal oxide glass with the broadband mid-infrared luminescence property according to claim 3, wherein the heating in the step 2 is specifically: heating the mixture in an electric furnace at 850-950 ℃ for 25-45 min.
8. The method for preparing the heavy metal oxide glass with the broadband mid-infrared luminescence property according to claim 3, wherein the annealing in the step 3 is specifically as follows: keeping the temperature at 250-350 ℃ for 1.5-4 h, and cooling to room temperature along with the furnace.
9. The method of claim 3, wherein the steps of the method are performed in a dry glove box.
10. The method of preparing a heavy metal oxide glass having broadband mid-infrared emission characteristics according to claim 3, further comprising:
and 4, cutting and polishing the prepared glass.
CN202010487516.9A 2020-06-02 2020-06-02 Heavy metal oxide glass with broadband mid-infrared light emitting characteristic and preparation method thereof Pending CN111646695A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111574051A (en) * 2020-06-05 2020-08-25 哈尔滨工程大学 PBG Er-doped3+Heavy metal oxide glass

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103030275A (en) * 2013-01-17 2013-04-10 中国科学院上海光学精密机械研究所 Erbium ion doped intermediate infrared luminous fluorine tellurate glass

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103030275A (en) * 2013-01-17 2013-04-10 中国科学院上海光学精密机械研究所 Erbium ion doped intermediate infrared luminous fluorine tellurate glass

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
EMERSON A. DOS SANTOS: "Evaluation of laser level populations of erbium-doped glasses", 《JOURNAL OF LUMINESCENCE》 *
HIROKI YAMAUCHI: "Spectroscopic properties of Tm3+ ions in PbO-PbF2-Bi2O3-Ga2O3 glasses for S-band optical amplifications", 《JOURNAL OF APPLIED PHYSICS》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111574051A (en) * 2020-06-05 2020-08-25 哈尔滨工程大学 PBG Er-doped3+Heavy metal oxide glass

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