CN114634311B - Method for improving near-infrared fluorescence intensity of bismuth-doped quartz glass - Google Patents
Method for improving near-infrared fluorescence intensity of bismuth-doped quartz glass Download PDFInfo
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- CN114634311B CN114634311B CN202210329672.1A CN202210329672A CN114634311B CN 114634311 B CN114634311 B CN 114634311B CN 202210329672 A CN202210329672 A CN 202210329672A CN 114634311 B CN114634311 B CN 114634311B
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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
- C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B20/00—Processes specially adapted for the production of quartz or fused silica articles, not otherwise provided for
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
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Abstract
A method for improving the near-infrared fluorescence intensity of bismuth-doped quartz glass comprises the following steps: heating the bismuth-doped quartz glass to a molten state at 1600-1700 ℃ through high-temperature heat treatment, and preserving heat for 1-10min; quickly putting the melt into different cooling liquids, completely soaking, and carrying out quenching; and then taking out, and polishing the quenched glass to obtain the fluorescence-enhanced bismuth-doped quartz glass. The high-temperature heat source comprises a graphite furnace and oxyhydrogen flames. The cooling liquid comprises deionized water, dry ice, liquid nitrogen, liquid helium and the like. The method is beneficial to improving the concentration of bismuth-related active centers in the Bi-doped quartz glass, so that the fluorescence intensity of the bismuth-doped quartz glass in a near-infrared band is enhanced. The Bi-doped fiber laser has wide application as a gain medium of a Bi-doped fiber laser and a fiber amplifier.
Description
Technical Field
The invention belongs to the technical field of quartz glass, and particularly relates to a method for increasing the concentration of bismuth-related active centers and improving the near-infrared fluorescence intensity of bismuth-doped quartz glass through quenching and quenching.
Background
Rare earth doping (mainly Yb) 3+ ，Nd 3+ ，Pr 3+ ，Er 3+ And Tm 3+ Etc.) are very effective active media in the near infrared region, and are widely used in the fields of optical fiber amplifiers and the like. But spectral gaps still exist throughout the optical communication band. The near-infrared fluorescence of the Bi-doped glass can cover 1000-1700nm, the full width at half maximum of the fluorescence exceeds 300nm, and the Bi-doped glass has potential advantages in the aspect of realizing high-efficiency broadband optical fiber amplifiers. Since russian scientists realized laser and amplification output in the Bi-doped fiber for the first time in 2005, the Bi-doped silica fiber received much attention from researchers. The adoption of the Bi-doped optical fiber to realize the ultra-wideband amplification of the 1100-1700nm wave band greatly expands the bandwidth of optical communication, thereby improving the optical communication capacity.
On the other hand, although the fluorescence band width ratio of the existing bismuth-doped quartz glass is wide, the problems of low luminous efficiency, weak fluorescence intensity, uneven fluorescence peak shape and the like limit the application of bismuth-related ultra-wideband optical amplifiers, ultra-wideband light sources and the like.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a method for improving the near-infrared fluorescence intensity of bismuth-doped quartz glass, which comprises the steps of regulating and controlling the spectral properties of the bismuth-doped quartz glass through quenching, carrying out high-temperature heat treatment on the bismuth-doped quartz glass to a molten state, and then rapidly putting the molten glass into a cooling liquid for quenching treatment. The kind and proportion of the bismuth ion near-infrared active center are adjusted, so that the width of the covered optical communication wave band is improved, and flat broadband near-infrared luminescence is obtained.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for improving the near-infrared fluorescence intensity of bismuth-doped quartz glass is characterized by comprising the following steps:
(1) Cleaning the surface of the bismuth-doped quartz glass, and heating to a molten state;
(2) Placing the bismuth-doped quartz glass in a molten state into cooling liquid for quenching and quenching;
(3) And taking out the quenched bismuth-doped quartz glass, polishing, cleaning and drying.
Preferably, the step one: cleaning the surface of the prepared Bi-doped glass to prevent the introduction of impurities in the melting process;
preferably, step two: and (3) welding the glass sheet on the end face of the pure quartz rod through oxyhydrogen flame, and placing the pure quartz rod on a graphite furnace or an oxyhydrogen flame machine tool for rotating and heating for 5 minutes.
Preferably, step three: the bismuth-doped quartz glass which is subjected to heat treatment and is in a molten state at 1600-1800 ℃ is rapidly placed in cooling liquid.
Preferably, step four: and taking out the cooled glass, and cutting, polishing two sides, cleaning and drying.
And continuously preserving the heat for 1-10 minutes when the bismuth-doped quartz glass is heated to a molten state at 1600-1800 ℃.
The cooling liquid includes, but is not limited to, deionized water, dry ice, liquid nitrogen, liquid helium, and the like.
Preferably, the heat treatment source is H 2 /O 2 An oxyhydrogen flame of = 1-4.
Preferably, the cooling liquid is liquid helium.
Compared with the prior art, the invention has the beneficial effects that:
1) The rapid quenching at the melting temperature increases the fictive temperature of the glass, increases the degree of disorder of the internal structure, and increases asymmetry, thereby promoting the increase of the species of Bi-related active centers. Is beneficial to improving the concentration of bismuth-related active centers in the Bi-doped quartz glass, thereby enhancing the fluorescence intensity of the bismuth-doped quartz glass in the near infrared band
2) When heated by high-temperature oxyhydrogen flame, the reduction environment is provided, which is beneficial to the reduction of Bi so as to generate low-price Bi, increase the number of active centers of Bi and promote near-infrared luminescence.
3) According to the invention, through low-content bismuth doping, the phenomena of glass darkening, transmittance reduction, luminescence quenching and the like easily generated in the heat treatment and quenching processes caused by high-Bi content doping are avoided.
4) Under the excitation of 500nm, compared with the original un-quenched glass, the bismuth-doped quartz glass after the rapid cold quenching has the advantages that the main fluorescence peak is red-shifted from 1170nm to 1402nm, the full width at half maximum of the fluorescence can reach 356nm, and the communication wavelength range which can be covered by the bismuth-doped quartz glass is greatly increased.
Drawings
FIG. 1 is a comparison graph of absorption spectra before and after quenching and quenching of Bi/P co-doped quartz glass of the present invention.
FIG. 2 is a comparison of fluorescence intensities of Bi/P co-doped quartz glass before and after quenching.
FIG. 3 is a graph showing the fluorescence intensity vs. line of the Bi/P co-doped quartz glass of the present invention at around 1400nm under different heating modes.
FIG. 4 is a graph showing the fluorescence intensity contrast curves of the Bi/P co-doped quartz glass of the present invention in different quenching quenches around 1400 nm.
Detailed Description
The present invention has been made in an effort to provide a more complete understanding of the features and technical means of the present invention, as well as the objects and functions attained. Specific embodiments of the present invention are further described below in conjunction with the appended drawings, but the scope of the claims is not limited thereto
Example 1: (see FIG. 1, FIG. 2, FIG. 3 and Table 1)
The Bi/P co-doped quartz glass of the embodiment comprises the following components (mol percent): 0.1Bi 2 O 3 -10P 2 O 5 -89.9SiO 2 。
The quenching process of the Bi/P co-doped quartz glass comprises the following steps:
(1) Firstly, cleaning the surface of the glass by using acetone or alcohol, and avoiding the introduction of impurities during high-temperature heat treatment;
(2) And fusing the bismuth-doped quartz glass on the end face of one side of the pure quartz glass tube. Warp H 2 /O 2 Heating oxyhydrogen flame of =1 to a molten state at 1600-1800 ℃;
(3) Rapidly placing the bismuth-doped quartz glass in a molten state into deionized water at 25 ℃, completely soaking, and performing rapid quenching treatment;
(4) And taking out the quenched sample, processing the sample into a preset size, polishing two surfaces of the sample, and then cleaning and drying the sample.
The test results are shown in fig. 1 and 2. The significant difference is that the absorption at 430nm of the quenched BiP co-doped quartz glass is significantly enhanced. And the bismuth active center absorption peak related to silicon appears near 820 and 1400 nm. A xenon lamp is adopted for excitation at 500nm, the main luminescence peak of the quenched Bi/P-doped quartz glass is red-shifted to 1402nm from 1170nm, and the half-height width is increased to 356nm from 254. The emission band may cover 1000-1700nm.
Example 2: (see FIG. 1, FIG. 2, FIG. 3 and Table 1)
The Bi/P co-doped quartz glass of the embodiment comprises the following components (mol percent): 0.1Bi 2 O 3 -10P 2 O 5 -89.9SiO 2 。
The quenching process of the Bi/P co-doped quartz glass comprises the following steps:
(1) The surface of the glass is cleaned by acetone or alcohol, so that the introduction of impurities caused by high-temperature heat treatment is avoided;
(2) And fusing the bismuth-doped quartz glass on the end face of one side of the pure quartz glass tube. Heating to 16001800 deg.C molten state in graphite furnace;
(3) Rapidly placing the bismuth-doped quartz glass in a molten state into deionized water at 25 ℃, completely soaking, and performing rapid quenching treatment;
(4) Taking out the quenched sample, processing the sample into a preset size, polishing the two sides of the sample, and then cleaning and drying the sample
Example 3: (see FIG. 1, FIG. 2, FIG. 3 and Table 1)
The Bi/P co-doped quartz glass of the embodiment comprises the following components (mol percent): 0.1Bi 2 O 3 -10P 2 O- 5 89.9SiO 2 。
The quenching process of the Bi/P co-doped quartz glass comprises the following steps:
(1) The surface of the glass is cleaned by acetone or alcohol, so that the introduction of impurities caused by high-temperature heat treatment is avoided;
(2) And fusing the bismuth-doped quartz glass on the end face of one side of the pure quartz glass tube. Warp H 2 /O 2 Heating oxyhydrogen flame of =2 to a molten state at 1600-1800 ℃;
(3) Rapidly placing the bismuth-doped quartz glass in a molten state into deionized water at 25 ℃, completely soaking, and performing rapid quenching treatment;
(4) Taking out the quenched sample, processing the sample into a preset size, polishing two sides of the sample, and then cleaning and drying the sample
Example 4: (see FIG. 1, FIG. 2, FIG. 3 and Table 1)
The Bi/P co-doped quartz glass of the embodiment comprises the following components (mol percent): 0.1Bi 2 O 3 -10P 2 O 5 -89.9SiO 2 。
The quenching process of the Bi/P co-doped quartz glass comprises the following steps:
(1) The surface of the glass is cleaned by acetone or alcohol, so that the introduction of impurities caused by high-temperature heat treatment is avoided;
(2) And fusing the bismuth-doped quartz glass on the end face of one side of the pure quartz glass tube. Warp H 2 /O 2 Heating oxyhydrogen flame of =4 to a molten state at 1600-1800 ℃;
(3) Rapidly placing the bismuth-doped quartz glass in a molten state into deionized water at 25 ℃, completely soaking, and performing rapid quenching treatment;
(4) Taking out the quenched sample, processing the sample into a preset size, polishing two sides of the sample, and then cleaning and drying the sample
The normalized results of the fluorescence spectra of the glass obtained by quenching under different heating modes are shown in FIG. 3. The obvious difference is that the oxyhydrogen flame promotes the reduction of Bi so as to generate low-valence Bi, thereby promoting the increase of the number of Bi active centers and the increase of near-infrared fluorescence intensity. However, excessive reduction causes a decrease in Bi transmittance and the generation of luminescence quenching clusters, resulting in a decrease in fluorescence intensity.
Example 5: (see FIG. 4 and Table 1)
The Bi/P co-doped quartz glass of the embodiment comprises the following components (mol percent): 0.1Bi 2 O 3 -10P 2 O 5 -89.9SiO 2 。
The quenching process of the Bi/P co-doped quartz glass comprises the following steps:
(1) The surface of the glass is cleaned by acetone or alcohol, so that the introduction of impurities caused by high-temperature heat treatment is avoided;
(2) And fusing the bismuth-doped quartz glass on the end face of one side of the pure quartz glass tube. Warp H 2 /O 2 Heating oxyhydrogen flame of =2 to a molten state at 1600-1800 ℃;
(3) Rapidly placing the bismuth-doped quartz glass in a molten state into dry ice, completely soaking, and performing rapid quenching treatment;
(4) Taking out the quenched sample, processing the sample into a preset size, polishing two sides of the sample, and then cleaning and drying the sample
Example 6: (see FIG. 4 and Table 1)
The Bi/P co-doped quartz glass of the embodiment comprises the following components (mol percent): 0.1Bi 2 O 3 -10P 2 O 5 -89.9SiO 2 。
The quenching process of the Bi/P co-doped quartz glass comprises the following steps:
(1) The surface of the glass is cleaned by acetone or alcohol, so that the introduction of impurities caused by high-temperature heat treatment is avoided;
(2) And fusing the bismuth-doped quartz glass on the end face of one side of the pure quartz glass tube. Warp H 2 /O 2 Heating oxyhydrogen flame of =2 to a molten state at 1600-1800 ℃;
(3) Rapidly placing the bismuth-doped quartz glass in a molten state in liquid nitrogen, completely soaking, and performing rapid quenching treatment;
(4) Taking out the quenched sample, processing the sample into a preset size, polishing two sides of the sample, and then cleaning and drying the sample
Example 7: (see FIG. 4 and Table 1)
The Bi/P co-doped quartz glass of the embodiment comprises the following components (mol percent): 0.1Bi 2 O 3 -10P 2 O 5 -89.9SiO 2 。
The quenching process of the Bi/P co-doped quartz glass comprises the following steps:
(1) The surface of the glass is cleaned by acetone or alcohol, so that the introduction of impurities caused by high-temperature heat treatment is avoided;
(2) And fusing the bismuth-doped quartz glass on the end face of one side of the pure quartz glass tube. Warp H 2 /O 2 Heating oxyhydrogen flame of =2 to a molten state at 1600-1800 ℃;
(3) Rapidly placing the bismuth-doped quartz glass in a molten state into liquid helium, completely soaking, and performing rapid quenching treatment;
(4) Taking out the quenched sample, processing the sample into a preset size, polishing the two sides of the sample, and then cleaning and drying the sample
The fluorescence normalization results of the samples obtained by quenching with different cooling liquids are shown in FIG. 4. The obvious difference is that the increase of the fictive temperature of the glass, the increase of the disorder degree of the internal structure and the increase of the asymmetry are caused under different cooling rates, thereby promoting the difference of the increase range of the Bi-related active center types and the concentration. The higher the cooling rate, the more significant the increase in fluorescence intensity.
TABLE 1 percent increase in fluorescence intensity at 1170nm and around 1400nm for the heating and cooling modes of examples 1-7 compared to the original sample
It will be appreciated by those skilled in the art that the foregoing is only a preferred embodiment of the invention and is not intended to limit the invention, and that any modification, variation or equivalent arrangement within the spirit and scope of the invention should be considered as falling within the scope of the invention.
Claims (3)
1. A method for improving the near-infrared fluorescence intensity of bismuth-doped quartz glass is characterized by comprising the following steps:
(1) Cleaning the surface of the bismuth-doped quartz glass, and heating to a molten state;
(2) Placing the bismuth-doped quartz glass in a molten state in cooling liquid for quenching and quenching;
(3) Taking out the quenched bismuth-doped quartz glass, polishing, cleaning and drying;
the heating adopts a graphite furnace or H 2 And O 2 Oxyhydrogen flame with the proportion of 1-4 is used as a heating source;
the rapid quenching refers to transferring the molten bismuth-doped quartz glass into cooling liquid within 1-3 seconds;
the cooling liquid is deionized water, dry ice, liquid nitrogen or liquid helium;
the bismuth-doped quartz glass comprises the following components: 0.1Bi 2 O 3 -10P 2 O 5 -89.9SiO 2 。
2. The method for increasing the near-infrared fluorescence intensity of bismuth-doped silica glass according to claim 1, wherein the heating temperature is 1600 to 1800 ℃.
3. The method for increasing the near-infrared fluorescence intensity of bismuth-doped quartz glass according to claim 1 or 2, characterized in that the temperature is maintained in the molten state for 1 to 10 minutes.
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| CN101817636A (en) * | 2009-11-17 | 2010-09-01 | 昆明理工大学 | Bismuth-doped silicon-aluminum-calcium optical glass and preparation method thereof |
| CN101749642B (en) * | 2009-12-18 | 2011-09-21 | 天津工业大学 | Fluorescent glass lens for blue light excited white light LED and preparation method thereof |
| CN103524037B (en) * | 2013-07-26 | 2016-08-10 | 宁波大学 | A kind of silver nano-grain composite block bismuthate glass material and preparation method thereof |
| CN104193141A (en) * | 2014-08-01 | 2014-12-10 | 浙江大学 | Method for preparing Bi-doped glass material with mid-infrared luminescence |
| WO2016086013A1 (en) * | 2014-11-26 | 2016-06-02 | Corning Incorporated | Method for making halogen doped optical element |
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