CN117164250A - Method for improving near infrared luminous bandwidth and intensity of bismuth-doped quartz-based material - Google Patents
Method for improving near infrared luminous bandwidth and intensity of bismuth-doped quartz-based material Download PDFInfo
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- CN117164250A CN117164250A CN202310992464.4A CN202310992464A CN117164250A CN 117164250 A CN117164250 A CN 117164250A CN 202310992464 A CN202310992464 A CN 202310992464A CN 117164250 A CN117164250 A CN 117164250A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 title claims abstract description 33
- 239000010453 quartz Substances 0.000 title claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- 239000007789 gas Substances 0.000 claims abstract description 57
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 239000011261 inert gas Substances 0.000 claims abstract description 22
- 239000011521 glass Substances 0.000 claims description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 27
- CWCCJSTUDNHIKB-UHFFFAOYSA-N $l^{2}-bismuthanylidenegermanium Chemical compound [Bi]=[Ge] CWCCJSTUDNHIKB-UHFFFAOYSA-N 0.000 claims description 22
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 20
- 229910052805 deuterium Inorganic materials 0.000 claims description 19
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 claims description 17
- 238000004321 preservation Methods 0.000 claims description 17
- 229910052734 helium Inorganic materials 0.000 claims description 13
- 239000001307 helium Substances 0.000 claims description 13
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- 229910000577 Silicon-germanium Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 238000004891 communication Methods 0.000 abstract description 14
- 229910052797 bismuth Inorganic materials 0.000 abstract description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract description 8
- 230000001965 increasing effect Effects 0.000 abstract description 6
- 239000012159 carrier gas Substances 0.000 description 19
- 238000004020 luminiscence type Methods 0.000 description 12
- 239000013307 optical fiber Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 9
- 229910001451 bismuth ion Inorganic materials 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000005498 polishing Methods 0.000 description 8
- 230000005855 radiation Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 230000005284 excitation Effects 0.000 description 5
- 238000005086 pumping Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 230000008707 rearrangement Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002419 bulk glass Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Abstract
The preferred method for improving the near infrared luminous bandwidth and intensity of the bismuth-doped quartz-based material comprises the following steps: placing the bismuth-doped quartz-based material into a closed reaction kettle, and introducing mixed gas of reducing gas and inert gas to enable the reaction kettle to be in a high-pressure state; heating the reaction kettle to a certain temperature and preserving heat for a period of time, wherein the heating temperature is not lower than 100 ℃, and the preserving heat time is 50-400h. Under the high-temperature and high-pressure treatment of the mixed gas of the reducing gas and the inert gas in a proper proportion, the quantity of near infrared luminous centers of bismuth can be increased, the fluorescent half-width of the obtained bismuth-doped quartz-based material in a near infrared band can be widened, the fluorescent intensity is improved, and the bismuth-doped quartz-based material has a wide application prospect in expanding a communication band.
Description
Technical Field
The invention belongs to the technical field of quartz glass, and particularly relates to a method for improving near infrared luminous bandwidth and intensity of bismuth-doped quartz-based materials.
Background
Optical fiber communication is an important mode of modern communication, popularization of 5G communication and popularization of the Internet of things put more severe requirements on transmission capacity of optical communication and the like, so that the communication capacity of a single optical fiber is improved. The erbium-doped fiber amplifier (EDFA) adopted by the optical fiber communication system used at the present stage has the action wave band of only C+L wave band, the bandwidth of about 100nm, and compared with the whole quartz optical fiber low-loss communication window of 1200nm-1700nm, the utilization rate is less than 20%, which can not meet the high-speed increasing communication requirement. Bismuth doped glass materials are considered as potential gain media for high speed communications because they emit light over a broad bandwidth tunable in the 1000-1800nm band and have a full width at half maximum (FWMH) of greater than 300 nm.
On the other hand, the currently reported bismuth-doped quartz-based glass has luminescence peak positions between 1100nm and 1460nm and between 1600 and 1800nm, and has weaker fluorescence intensity in the C+L band range widely used for communication, which also hinders the wide application of bismuth-doped quartz-based materials. Patent CN103601364A, CN114634311A, CN10588491A, CN116375349a and the like propose many methods for increasing the fluorescence intensity of bismuth-doped glass, but none of them relates to a method capable of effectively controlling the main peak of fluorescence in the c+l band range.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a method for improving near infrared luminous bandwidth and intensity of bismuth-doped quartz-based materials, and the spectral properties of the bismuth-doped quartz-based materials are adjusted through high-pressure high-temperature carrier gas treatment.
In order to achieve the above purpose, the present invention provides a method for improving near infrared luminescence bandwidth and intensity of bismuth doped quartz-based materials, comprising the following steps:
(1) Placing the bismuth-doped quartz-based material into a closed reaction kettle, vacuumizing, and introducing mixed gas of reducing gas and inert gas to enable the reaction kettle to be in a high-pressure state;
(2) Heating the reaction kettle, and heating and preserving heat.
Preferably, the bismuth-doped quartz-based material is a material taking bismuth-doped silicon-based glass as a main component, the silicon oxide content is more than 45% (mole percent), and the bismuth oxide content is 0.001% -1% (mole percent).
Preferably, the bismuth-doped quartz-based material is bismuth-germanium co-doped quartz glass or bismuth-germanium-doped silicon-based glass.
Preferably, the component (mole percent) of the bismuth-doped quartz-based material is 49.98SiO 2 -50GeO 2 -0.02Bi 2 O 3 The component (mole percent) of the bismuth-doped quartz-based material is 79.98SiO 2 -20GeO 2 -0.02Bi 2 O 3 。
Preferably, the reducing gas is one or more of hydrogen, deuterium, and carbon monoxide; the inert gas is one or more of nitrogen, helium and argon.
Preferably, the pressure ratio of the reducing gas to the inert gas in the mixed gas is x MPa (5-x) MPa, and x is more than 0 and less than 5.
Preferably, the pressure ratio of the reducing gas in the mixed gas is not less than 40%, and the pressure ratio of the inert gas is not less than 40%.
Preferably, the mixture is a mixture of deuterium and helium.
Preferably, the pressure ratio of deuterium gas to helium gas is 2MPa to 3MPa.
Preferably, in the step (1), a mixed gas of reducing gas and inert gas is introduced into a closed reaction kettle, so that the total pressure in the reaction kettle is ensured to be 4-6 MPa at room temperature; in the step (2), the total pressure in the reaction kettle is kept between 10 and 15MPa in the heat preservation process of the reaction kettle.
Preferably, in the step (1), the high pressure state is 5MPa; in the step (2), the heating temperature is 100-500 ℃, and the heat preservation time is 50-400h.
Compared with the prior art, the invention has the beneficial effects that:
1) Based on the high-pressure effect generated by the mixed gas of the reducing gas and the inert gas, the gas molecules are promoted to enter a glass network to sensitize bismuth ions, and the quantity of near infrared luminescence centers of low-valence bismuth is increased under the neutralization of the inert gas.
2) In the carrier gas treatment process, a high-temperature environment provides driving force for bismuth ion local coordination atom rearrangement, so that a new near infrared luminescence center is generated, and the bismuth ion luminescence range is expanded.
3) The invention is suitable for bismuth doped quartz glass, optical fiber preformed rod and optical fiber, and has universality.
4) The bismuth-doped quartz-based material after carrier gas has high-concentration bismuth near infrared active center and associated different near infrared luminescent center. Under 808nm excitation, compared with the original non-carrier gas glass, the fluorescence peak position intensity is enhanced, the half-width is widened, and the E, S, C, L, U (1360-1675 nm) communication wave band is covered.
Drawings
FIG. 1 is a graph showing the comparison of 808nm excitation fluorescence spectra before and after the glass carrier gas of examples 1 to 3 and comparative example 1.
FIG. 2 is a graph showing the comparison of 808nm excitation fluorescence spectra before and after the glass carrier gas of examples 4-6 and comparative example 2.
Detailed Description
For further understanding of the features and technical means of the present invention, and the objects and functions achieved thereby. Specific embodiments of the invention will be further described with reference to the drawings, but the scope of the claims is not limited thereto.
The invention discloses a method for improving near infrared luminous bandwidth and intensity of bismuth-doped quartz-based materials, which comprises the following steps:
(1) Placing the bismuth-doped quartz-based material into a closed reaction kettle, and introducing mixed gas of reducing gas and inert gas to enable the reaction kettle to be in a high-pressure state;
(2) Heating the reaction kettle, and heating and preserving heat.
Specifically, the bismuth-doped silica-based material is a material mainly composed of bismuth-doped silica-based glass, such as bismuth-doped silica bulk glass, bismuth-doped silica optical fiber preform, bismuth-doped silica optical fiber, and the like. In the embodiment of the invention, the bismuth-doped quartz-based material is bismuth-germanium co-doped quartz glass and bismuth-germanium-doped silicon-based glass. However, it is known that bismuth-doped silica optical fiber preforms and bismuth-doped silica optical fibers are based on bismuth-doped silica-based glass, and their near infrared emission characteristics are almost completely dependent on the core material. Therefore, the invention is also applicable to other bismuth-doped quartz-based materials which take bismuth-doped silica-based glass as a main component.
In particular, the reducing gas includes, but is not limited to, hydrogen (H 2 ) Deuterium (D) 2 ) And one or more of carbon monoxide (CO).
In particular, inert gases include, but are not limited to, nitrogen (N 2 ) Helium (H) 2 ) And one or more of argon (Ar). Preferably, in the step (1), the bismuth-doped quartz-based material is placed in a closed reaction kettle, and after being pumped into vacuum by an external vacuum pump, mixed gas of reducing gas and inert gas is introduced so as to prevent oxygen in air from reacting with the reducing gas. In a specific embodiment, the external vacuum pump is evacuated for 10 minutes.
Preferably, in the step (1), a mixed gas of reducing gas and inert gas is introduced into the closed reaction kettle, so that the total pressure in the reaction kettle is ensured to be 4-6 MPa at room temperature. In a specific embodiment, the total pressure in the reaction kettle is 5MPa. Preferably, the introduced mixed gas is a mixed gas of deuterium and helium. Preferably, the pressure ratio of deuterium gas to helium gas is 3MPa to 2MPa.
Preferably, in the step (2), the total pressure in the reaction kettle is kept between 10 and 15MPa in the heat preservation process of the reaction kettle.
Preferably, in the step (2), the heating temperature is 100-500 ℃, and the heat preservation time is 50-400h.
Example 1 (see FIG. 1 and Table 1)
In this example, the sample is bismuth germanium co-doped quartz glass, and the glass comprises the following components in percentage by mole: 79.98SiO 2 -20GeO 2 -0.02Bi 2 O 3 . The carrier gas process of the bismuth germanium co-doped quartz glass comprises the following steps: (1) Putting bismuth germanium co-doped quartz glass into a closed reaction kettle, and externally connecting a vacuum pump for vacuum-pumping for 10 minutes; (2) Introducing hydrogen into the reaction kettle to enable the pressure in the reaction kettle to reach 3MPa, and then introducing nitrogen to enable the total pressure in the reaction kettle to reach 5MPa; (3) The reaction kettle is arranged in an infrared radiation heating furnace,setting heating and cooling procedures, and preserving heat for 50 hours at 500 ℃, wherein the pressure in the reaction kettle is kept between 12 and 15MPa in the heat preservation process. In the step (2), the pressure ratio of the hydrogen to the nitrogen is 3MPa to 2MPa. And (3) taking out the sample after the procedure of the step (3) is finished, cleaning, polishing the two sides and carrying out optical characterization.
Example 2 (see FIG. 1 and Table 1)
In this example, the sample is bismuth germanium co-doped quartz glass, and the glass comprises the following components in percentage by mole: 79.98SiO 2 -20GeO 2 -0.02Bi 2 O 3 . The carrier gas process of the bismuth germanium co-doped quartz glass comprises the following steps: (1) Putting bismuth germanium co-doped quartz glass into a closed reaction kettle, and externally connecting a vacuum pump for vacuum-pumping for 10 minutes; (2) Deuterium is introduced into the reaction kettle to enable the pressure in the reaction kettle to reach 2MPa, and then nitrogen is introduced to enable the total pressure in the reaction kettle to reach 5MPa; (3) The reaction kettle is placed in an infrared radiation heating furnace, heating and cooling procedures are set, the temperature is kept at 400 ℃ for 100 hours, and the pressure in the reaction kettle is kept at 12MPa in the heat preservation process. In the step (2), the pressure ratio of deuterium gas to nitrogen gas is 2MPa to 3MPa. And (3) taking out the sample after the procedure of the step (3) is finished, cleaning, polishing the two sides and carrying out optical characterization.
Example 3 (see FIG. 1 and Table 1)
In this example, the sample is bismuth germanium co-doped quartz glass, and the glass comprises the following components in percentage by mole: 79.98SiO 2 -20GeO 2 -0.02Bi 2 O 3 . The carrier gas process of the bismuth germanium co-doped quartz glass comprises the following steps: (1) Putting bismuth germanium co-doped quartz glass into a closed reaction kettle, and externally connecting a vacuum pump for vacuum-pumping for 10 minutes; (2) Introducing mixed gas of 95% helium and 5% deuterium into the reaction kettle to enable the total pressure in the reaction kettle to reach 5MPa; (3) The reaction kettle is placed in an infrared radiation heating furnace, heating and cooling procedures are set, the temperature is kept at 100 ℃ for 400 hours, and the pressure in the reaction kettle is kept at 10MPa in the heat preservation process. And (3) taking out the sample after the procedure of the step (3) is finished, cleaning, polishing the two sides and carrying out optical characterization.
Comparative example 1 (see FIG. 1 and Table 1)
In this example, the sample is bismuth germanium co-doped quartz glass, and the glass comprises the following components in percentage by mole: 79.98SiO 2 -20GeO 2 -0.02Bi 2 O 3 . The heat preservation process of the bismuth-germanium co-doped quartz glass comprises the following steps: (1) Putting bismuth germanium co-doped quartz glass into a closed reaction kettle, and externally connecting a vacuum pump for vacuum-pumping for 10 minutes; (2) The reaction kettle is placed in an infrared radiation heating furnace, heating and cooling programs are set, the temperature is kept at 400 ℃ for 100 hours, and a vacuum pump continuously works in the heat-preserving process. And (3) taking out the sample after the procedure of the step (2) is finished, cleaning, polishing the two sides and carrying out optical characterization.
The results of fluorescence tests of bismuth germanium co-doped silica glass of examples 1 to 3 and comparative example 1 using a laser for excitation at 808nm are shown in FIG. 1. The obvious difference is that the heat preservation treatment of the bismuth-germanium co-doped quartz glass in the comparative example 1 does not influence the spectrum shape and the intensity of the bismuth-germanium co-doped quartz glass; in the embodiment 1, the main luminescence peak of bismuth-germanium co-doped quartz glass subjected to heat preservation treatment by adopting mixed gas carrier gas of hydrogen and nitrogen is red-shifted from 1400nm to 1550nm, and the half-height peak width is widened from 187nm to 385nm; in the embodiment 2, the light-emitting main peak of the bismuth germanium co-doped quartz glass subjected to heat preservation treatment by adopting the carrier gas of the mixed gas of deuterium and nitrogen is red-shifted from 1400nm to 1580nm, and the half-height peak width is widened from 187nm to 330nm; in example 3, the mixed gas carrier gas of helium and a very small amount of deuterium is adopted, and the luminescence main peak of bismuth germanium co-doped quartz glass subjected to heat preservation treatment is unchanged, the half-height peak width is widened from 187nm to 273nm, the effect of enhancing the fluorescence intensity of bismuth ions can be achieved by treatment under the weak reducing condition, but compared with the mixed gas with strong reducing condition, a small amount of new luminescence centers can be induced under the condition. The bismuth germanium co-doped quartz glass emission band treated by the high-pressure high-temperature carrier gas provided by the invention covers a E, S, C, L, U (1360-1675 nm) communication band.
This indicates that: the mixed gas based on the reducing gas and the inert gas generates a high-pressure effect, so that gas molecules are promoted to enter a glass network to sensitize bismuth ions, and the quantity of near infrared luminescence centers of low-valence bismuth is increased under the neutralization effect of the inert gas; meanwhile, under the action of high temperature, the glass structure is relatively loose, the rearrangement of coordination atoms around the bismuth ions in low valence state is promoted, and a new near infrared luminescence center is generated.
Example 4 (see FIG. 2 and Table 1)
In this example, the sample is bismuth-doped germanium-silicon-based glass, and the glass comprises the following components in percentage by mole: 49.98SiO 2 -50GeO 2 -0.02Bi 2 O 3 . The carrier gas process of the bismuth-doped germanium silicon-based glass comprises the following steps: (1) Placing the bismuth-doped germanium silicon-based glass into a closed reaction kettle, and externally connecting a vacuum pump for vacuumizing for 10 minutes; (2) Introducing hydrogen into the reaction kettle to enable the pressure in the reaction kettle to reach 3MPa, and then introducing nitrogen to enable the total pressure in the reaction kettle to reach 5MPa; (3) The reaction kettle is placed in an infrared radiation heating furnace, heating and cooling procedures are set, the temperature is kept at 500 ℃ for 50 hours, and the pressure in the reaction kettle is kept at 12-15 MPa in the heat-preserving process. In the step (2), the pressure ratio of the hydrogen to the nitrogen is 3MPa to 2MPa. And (3) taking out the sample after the procedure of the step (3) is finished, cleaning, polishing the two sides and carrying out optical characterization.
Example 5 (see FIG. 2 and Table 1)
In this embodiment, the sample is bismuth-doped silicon germanium-based glass, and the glass comprises the following components in percentage by mole: 49.98SiO 2 -50GeO 2 -0.02Bi 2 O 3 . The carrier gas process of the bismuth-doped germanium silicon-based glass comprises the following steps: (1) Placing the bismuth-doped germanium silicon-based glass into a closed reaction kettle, and externally connecting a vacuum pump for vacuumizing for 10 minutes; (2) Deuterium is introduced into the reaction kettle to enable the pressure in the reaction kettle to reach 2MPa, and then nitrogen is introduced to enable the total pressure in the reaction kettle to reach 5MPa; (3) The reaction kettle is placed in an infrared radiation heating furnace, heating and cooling procedures are set, the temperature is kept at 400 ℃ for 100 hours, and the pressure in the reaction kettle is kept at 12MPa in the heat preservation process. In the step (2), the pressure ratio of deuterium gas to nitrogen gas is 2MPa to 3MPa. And (3) taking out the sample after the procedure of the step (3) is finished, cleaning, polishing the two sides and carrying out optical characterization.
Example 6 (see FIG. 2 and Table 1)
In this embodiment, the sample is bismuth-doped silicon germanium-based glass, and the glass comprises the following components in percentage by mole: 49.98SiO 2 -20GeO 2 -0.02Bi 2 O 3 . The carrier gas process of the bismuth-doped germanium silicon-based glass comprises the following steps: (1) Placing the bismuth-doped germanium silicon-based glass into a closed reaction kettle, and externally connecting a vacuum pump for vacuumizing for 10 minutes; (2) Introducing mixed gas of 95% helium and 5% deuterium into a reaction kettle to reactThe total pressure in the kettle reaches 5MPa; (3) The reaction kettle is placed in an infrared radiation heating furnace, heating and cooling procedures are set, the temperature is kept at 100 ℃ for 400 hours, and the pressure in the reaction kettle is kept at 10MPa in the heat preservation process. And (3) taking out the sample after the procedure of the step (3) is finished, cleaning, polishing the two sides and carrying out optical characterization.
Comparative example 2 (see FIG. 2 and Table 1)
In this example, the sample is bismuth-doped germanium-silicon-based glass, and the glass comprises the following components in percentage by mole: 49.98SiO 2 -50GeO 2 -0.02Bi 2 O 3 . The carrier gas process of the bismuth-doped germanium silicon-based glass comprises the following steps: (1) Placing the bismuth-doped germanium silicon-based glass into a closed reaction kettle, and externally connecting a vacuum pump for vacuumizing for 10 minutes; (2) The reaction kettle is placed in an infrared radiation heating furnace, heating and cooling programs are set, the temperature is kept at 400 ℃ for 100 hours, and a vacuum pump continuously works in the heat-preserving process. And (3) taking out the sample after the procedure of the step (2) is finished, cleaning, polishing the two sides and carrying out optical characterization.
The fluorescence test results of the bismuth-doped germanium-silicon-based glasses of examples 4-6 and comparative example 2 are shown in FIG. 2, using a laser for excitation at 808 nm. The obvious difference is that the comparative example 2 only carries out heat preservation treatment on bismuth-doped germanium-silicon-based glass and only expands the half-width of the luminescence peak; the carrier gas treatment of the mixed gas of hydrogen/nitrogen (example 4) or the mixed gas of 95% helium and 5% deuterium (example 6) can greatly change the luminescence spectrum shape of the bismuth-doped germanium-silicon-based glass, namely the main luminescence peak of 1400nm is converted into the broad spectrum of the double peak superposition of 1400nm and 1560nm, the half-height peak width is widened from 238nm to more than 400nm, and the transmitting band covers the communication wave band of O, E, S, C, L, U (1260-1675 nm); in example 5, the main luminescence peak of the bismuth-doped germanium-silicon-based glass after the carrier gas of the mixed gas of deuterium and nitrogen is red-shifted from 1400nm to 1600nm, and the half-height peak width is widened from 238nm to 312nm.
This indicates that: based on the high-pressure effect generated by the mixed gas of the reducing gas and the inert gas, the gas molecules are promoted to enter a glass network to sensitize bismuth ions, and the quantity of near infrared luminescence centers of low-valence bismuth is increased under the neutralization effect of the inert gas. Meanwhile, under the action of high temperature, the glass structure is relatively loose, the rearrangement of coordination atoms around the bismuth ions in low valence state is promoted, and a new near infrared luminescence center is generated.
Table 1 shows the main peak positions, half-height peak widths, and fluorescence change ratios at 1400nm and 1550nm of examples 1 to 6 and comparative examples 1 to 2, respectively, compared with the original samples.
TABLE 1
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalent substitutions and improvements made within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (11)
1. The method for improving the near infrared luminous bandwidth and intensity of the bismuth-doped quartz-based material is characterized by comprising the following steps of:
(1) Placing the bismuth-doped quartz-based material into a closed reaction kettle, vacuumizing, and introducing mixed gas of reducing gas and inert gas to enable the reaction kettle to be in a high-pressure state;
(2) Heating the reaction kettle, and heating and preserving heat.
2. The method according to claim 1, wherein the bismuth-doped quartz-based material is a material comprising bismuth-doped silica-based glass as a main component, the silicon oxide content is more than 45% (mol%) and the bismuth oxide content is 0.001% -1% (mol%).
3. The method of claim 2, wherein the bismuth-doped quartz-based material is bismuth-germanium co-doped quartz glass or bismuth-doped silicon germanium-based glass.
4. A method according to claim 3, wherein the bismuth-doped quartz-based material has a composition (mole percent) of 49.98SiO 2 -50GeO 2 -0.02Bi 2 O 3 The component (mole percent) of the bismuth-doped quartz-based material is 79.98SiO 2 -20GeO 2 -0.02Bi 2 O 3 。
5. The method of claim 1, wherein the reducing gas is one or more of hydrogen, deuterium, and carbon monoxide; the inert gas is one or more of nitrogen, helium and argon.
6. The method according to claim 1, wherein the pressure ratio of the reducing gas to the inert gas in the mixture is x MPa (5-x) MPa,0 < x <5.
7. The method of claim 6, wherein the reducing gas pressure ratio in the mixture is not less than 40% and the inert gas pressure ratio is not less than 40%.
8. The method of claim 5, wherein the gas mixture is a mixture of deuterium and helium.
9. The method of claim 8, wherein the pressure ratio of deuterium gas to helium gas is 2mpa to 3mpa.
10. The method according to claim 1, wherein in the step (1), a mixed gas of a reducing gas and an inert gas is introduced into the closed reaction kettle to ensure that the total pressure in the reaction kettle is 4-6 MPa at room temperature; in the step (2), the total pressure in the reaction kettle is kept between 10 and 15MPa in the heat preservation process of the reaction kettle.
11. The method according to claim 10, wherein in the step (1), the high pressure state is 5MPa; in the step (2), the heating temperature is 100-500 ℃, and the heat preservation time is 50-400h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310992464.4A CN117164250A (en) | 2023-08-08 | 2023-08-08 | Method for improving near infrared luminous bandwidth and intensity of bismuth-doped quartz-based material |
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