CN1269755C - bismuth-doped germanium-based optical glass and preparation method thereof - Google Patents
bismuth-doped germanium-based optical glass and preparation method thereof Download PDFInfo
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- CN1269755C CN1269755C CN 200410054216 CN200410054216A CN1269755C CN 1269755 C CN1269755 C CN 1269755C CN 200410054216 CN200410054216 CN 200410054216 CN 200410054216 A CN200410054216 A CN 200410054216A CN 1269755 C CN1269755 C CN 1269755C
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- 239000005304 optical glass Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims description 8
- 229910052732 germanium Inorganic materials 0.000 title abstract 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title abstract 2
- 239000011521 glass Substances 0.000 claims abstract description 50
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000000137 annealing Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- CWCCJSTUDNHIKB-UHFFFAOYSA-N $l^{2}-bismuthanylidenegermanium Chemical compound [Bi]=[Ge] CWCCJSTUDNHIKB-UHFFFAOYSA-N 0.000 claims description 9
- 238000012546 transfer Methods 0.000 claims description 8
- 230000004927 fusion Effects 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- 229910005793 GeO 2 Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000000862 absorption spectrum Methods 0.000 abstract description 13
- 230000003287 optical effect Effects 0.000 abstract description 11
- 238000002189 fluorescence spectrum Methods 0.000 abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 abstract 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 abstract 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000005086 pumping Methods 0.000 description 34
- 239000000203 mixture Substances 0.000 description 21
- 230000005540 biological transmission Effects 0.000 description 10
- 238000004891 communication Methods 0.000 description 10
- 230000003321 amplification Effects 0.000 description 9
- 238000003199 nucleic acid amplification method Methods 0.000 description 9
- 239000013307 optical fiber Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 229910052797 bismuth Inorganic materials 0.000 description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000012190 activator Substances 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001195 gallium oxide Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical group 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005170 crystalloluminescence Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 210000001503 joint Anatomy 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 230000009022 nonlinear effect Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- -1 rare earth ion Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
-
- 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
- C03C3/253—Silica-free oxide glass compositions containing germanium
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The bismuth-doped germanium-based optical glass comprises the following components in percentage by mol: GeO290～99.98mol%；M＝Al2O3，Ta2O5，Ga2O3Or B2O30.01 to 9 mol%; bi2O30.01 to 5 mol%. The absorption spectrum of the glass covers a visible region to a near infrared region, the central wavelength of a fluorescence spectrum is about 1300nm, the fluorescence lifetime is more than 200 mu s, the full width at half maximum of the fluorescence is more than 200nm, and the glass can be pumped by lasers with the wavelengths of 532nm, 632.5nm and 808 nm. The optical glass is expected to be used in the technical fields of ultra-wideband optical amplifiers, high-power lasers, tunable lasers and the like.
Description
Technical field
The present invention relates to opticglass, particularly a kind of bismuth germanium base optical glass and preparation method thereof of mixing, this glass can be sent out near infrared communication band fluorescence, has long fluorescence lifetime, wide gain bandwidth is suitable as gain media and is applied to optical amplifier and/or laser apparatus.
Background technology
March 4 in 1998 order, the quiet patent (special permission discloses flat 11-29334) that waits the people to apply for being entitled as " mixing bismuth silica glass, optical fiber and image intensifer manufacture method " of the liana of Mitsubishi Cable Ind Ltd.They utilize the zeolite of bismuth exchange as dispersion medium, and comprehensive sol-gel method and high-temperature melting method have prepared and mixed the bismuth silica glass, draw out corresponding optical fiber, realized the light amplification at 1.3 μ m places under the 0.81 μ m pumping.The photoluminescence peak of this glass is positioned near the 1130nm, and maximum fluorescence halfwidth is 250nm, and maximum fluorescence lifetime is 650 μ s, and stimulated emission cross section is approximately 1.0 * 10
-20Cm
2.2001 on February 22,, liana is quiet to wait the people to apply for being entitled as " optical fiber and image intensifer " (the open 2002-252397 of special permission) again, and its basic glass consists of: Al
2O
3-SiO
2-Bi
2O
3, under 1750 ℃, found, draw out corresponding optical fiber, realized the light amplification at 1.3 μ m places under the 0.8 μ m pumping.
December 13 calendar year 2001, on June 18th, 2002, on December 25th, 2002, this positive first-class of the bank of Nippon Sheet Glass Co Ltd has applied for being entitled as the patent (special permission open 2003-183047,2004-20994,2003-283028) of " red glass and transparent glass-ceramics thereof ", " light amplification glass optical fiber ", " infrared lumious material and optical amplification medium " continuously, and its basic glass consists of A
2O-BO-Al
2O
3-SiO
2-Bi
2O
3(A=basic metal; The B=alkaline-earth metal).Corresponding product presents red or red-brown; Red glass its color after crystallization is handled does not have obvious change, but character such as its thermotolerance and physical strength obviously strengthen; Pumping wavelength pumping with being positioned at 400～850nm zone can access the fluorescence that highest peak is positioned at 1000～1600nm interval, and can realize the light amplification of wavelength between 1000～1400nm; Bismuth oxide, aluminum oxide and silicon-dioxide etc. are the necessary basal component of this luminescent material of preparation.
Be developed into erbium-doped fiber amplifier (EDFA) from the end of the eighties to the beginning of the nineties, and begin to be applied to have promoted opticfiber communication and developed since the opticfiber communication cable of 1.55mm frequency range, and technological development and the commercialization of present EDFA are the most ripe to full optical transmission direction; The EDFA fiber amplifier has been abandoned traditional photoelectricity light data-transmission mode, and directly optical signal is amplified, thereby effectively overcome the electronic bottleneck problem in the original transmission mode, this image intensifer also has in real time simultaneously, high gain, broadband, online, lower noise, low-loss full optical amplification function, is requisite Primary Component in the opticfiber communication cable of new generation; Because this technology has not only solved the restriction of decay to optical-fiber network transfer rate and distance, the more important thing is that it has started the wavelength-division multiplex of 1550nm frequency range, thereby ultra-high speed, vast capacity, over distance wavelength-division multiplex (WDM), dense wave division multipurpose (DWDM), full light transmission, soliton transmission etc. will be become a reality, and be epoch-making milestones on the opticfiber communication development history.At present widely used is that its operation window of C-band EDFA is at 1530～1565nm, it is minimum to have fibre loss, output rating is big, gain is high,, amplification characteristic low with polarization irrelevant, noise figure has nothing to do with systematic bits rate and data layout, and amplify a series of characteristics such as multichannel wavelength signals simultaneously, in long-distance optical communication system, obtained using widely.Its deficiency is that the gain bandwidth of C-Band EDFA has only 35nm, only covers the part of quartzy single-mode fiber low loss window, has restricted the intrinsic wavelength channel number that can hold of optical fiber; Yet along with developing rapidly and the quickening of IT application process of Internet technology, require the transmission capacity of ferry optical transmission system constantly to enlarge, and will enlarge transmission capacity, mainly contain three kinds of solution routes at present: (1) increases the transfer rate of each wavelength; (2) reduce channel separation; (3) increase total transmission bandwidth.For first kind of way, will bring new dispersion compensation problem if speed is brought up to 10Gbit/s, moreover present electronic system also exists what is called " electronic bottleneck " effect problem.If second kind of way is reduced to 50GHz or 25GHz will bring four-wave mixing non-linear effects such as (FWM) to system with sitgnal distancel from 100GHz, and requires system to adopt Wavelength stabilized technology.The EDFA that studies new fiber amplifier such as L-band is increase total transmission bandwidth a kind of, and it expands to L-band 1570～1605nm with the EDFA operation wavelength by C-band 1530～1560nm, makes the gain amplifier spectrum of EDFA expand one times.Although the wavelength of L-band EDFA has covered the afterbody of EDF gain spectral, but still can compare favourably with advanced in performance C-band EDFA product: for example both basic structure is similar, and the design and fabrication technology of most of C-band EDFA still can be applicable to L-band EDFA development; L-band EDFA has less radiation and the absorption and the lower average counter-rotating factor, and the gain fluctuation coefficient is much smaller than C-band EDFA, and existence brings the passive fiber loss bigger because the EDF of L-band EDFA is long, amplifies the big slightly deficiency that waits of noise.Though EDFA can make bandwidth increase to some extent from C-Band to the L-Band development, but be based on rare earth ion as the optical amplifier of activator because the restriction of the luminosity of himself, very difficult acquisition has bigger gain bandwidth, the luminescent material of shorter wavelength region (for example 1500nm or shorter).
The Raman amplifier can provide gain in big bandwidth range, the highest bandwidth that 300nm is provided of this amplification, but this needs higher drawing power (for length less than the optical fiber of 100m greater than 1 watt), thus communication system is had higher requirement.
As the active ions of crystalline host material, (1000～1500nm) can send the fluorescence with big bandwidth to transition metal, such as the sapphire (Ti:Al of Doped with Titanium in the near-infrared region for they for a long time
2O
3) can provide optical gain, Cr for another example at 650-1100nm
4+Ion is as the crystallo-luminescence material of activator, 1988, people such as V.Petricevic obtained the output of 1167～1345nm tunable laser, same year in mixing the forsterite of chromium, people such as Angert have also realized 1350～1500 interval tunable Cr at YAG:Cr among the Ca
4+Laser output.Owing to have suitable wavelength region and bandwidth, so the material of doped transition metal ions just can be used for communication field.But, because general transmission medium all is the glass optical fiber material, therefore crystalline material is docked in the communication system with regard to difficult, so very natural people just expect transition metal ion is mixed in the glass host material, above-mentioned like this butt joint problem just can be readily solved.2000, SetsuhisaTanabe and Xian Feng were with Cr
4+Mix in the aluminate glass, obtained the fluorescence that is positioned at 1.3 μ m 2003 that bandwidth surpasses 200nm, Fujimoto and Nakatsuka realized mixing the light amplification of bismuth silica glass at 1.3 μ m.
The melt temperature of silica glass is higher, even if report fusion under 1760 ℃ high temperature in the document still has a large amount of bubbles and exists.
Summary of the invention
The objective of the invention is for the higher shortcoming of the melt temperature that overcomes above-mentioned silica glass, a kind of bismuth germanium base optical glass and preparation method thereof of mixing is provided, this glass melting temperature is obviously much lower, thereby eliminate influence of air bubbles will easier realization, and has an optical property of the ultra broadband that can cover whole communication band, be expected at ultra broadband optics amplifier, superpower laser, technical fields such as tunable laser are applied.
Technology of the present invention solves that to put case as follows:
A kind of bismuth germanium base optical glass of mixing, each is composed as follows to it is characterized in that this glass:
Form mol%
GeO
2 90～99.98；
M=Al
2O
3, Ta
2O
5, Ga
2O
3Or B
2O
30.01～9;
Bi
2O
3 0.01～5。
The described preparation method who mixes bismuth germanium base optical glass comprises the following steps:
1. selected glass is formed and content mol%, and each raw material by the certain total amount of this proportioning weighing grinds half an hour in agate mortar;
2. then 500 ℃ of following pre-burnings 7 hours, take out grinding after, again 1550 ℃ of fusions 2 hours;
3. melt is poured over fast on the stainless steel plate and with another block plate and flattens, and transfers in the annealing furnace, naturally cools to room temperature with stove in annealing under 500 ℃ after 7 hours, and taking-up promptly gets this and mixes bismuth germanium base optical glass.
In this glass ingredient, GeO
2Be glass network former, Bi
2O
3Provide the raw material of light emitting ionic, can form the luminescence center relevant with bismuth, M is that glass network is modified body, the viscosity of reduction glass melting liquid that can be suitable, be beneficial to from crucible and pour out, be again the essential composition that this glass can produce fluorescence, also can disperse luminescence center to a certain extent simultaneously, play the effect of dispersion agent.
This glass sample is because of Bi
2O
3Concentration different and present pink, purplish red or reddish-brown; All samples are all transparent and do not have bubble and exist.Test shows: different luminosity and the fluorescence lifetimes of forming glass are different, wavelength be respectively 532,632.5 and the pumping of 808nm light source under, all samples all can produce fluorescence halfwidth (FWHM) greater than 200nm, fluorescence lifetime is greater than the fluorescence that is positioned at 1000～1700nm of 200 μ s.
Description of drawings
Fig. 1 is glass 96GeO of the present invention
23Al
2O
31.0Bi
2O
3Absorption spectrum
Fig. 2 is glass 96GeO of the present invention
23Al
2O
31.0Bi
2O
3Fluorescence spectrum under different pumping wavelengths
Fig. 3 is glass 96GeO of the present invention
23Ta
2O
51.0Bi
2O
3Absorption spectrum
Fig. 4 glass 96GeO of the present invention
23Ta
2O
51.0Bi
2O
3Fluorescence spectrum under different pumping wavelengths
Fig. 5 is glass 96GeO of the present invention
23Ga
2O
31.0Bi
2O
3Absorption spectrum
Fig. 6 glass 96GeO of the present invention
23Ga
2O
31.0Bi
2O
3Fluorescence spectrum under different pumping wavelengths
Fig. 7 is glass 96GeO of the present invention
23B
2O
31.0Bi
2O
3Absorption spectrum
Fig. 8 glass 96GeO of the present invention
23B
2O
31.0Bi
2O
3Fluorescence spectrum under different pumping wavelengths
Embodiment
The invention will be further described below in conjunction with embodiment and accompanying drawing, but should not limit protection scope of the present invention with this.
Table 1, table 2, table 3 and table 4 have been listed M=Al in the glass composition of the present invention respectively
2O
3, Ta
2O
5, Ga
2O
3, B
2O
3Composition and the molar percentage thereof of four groups of embodiment, the color of corresponding glass, fluorescence position and halfwidth thereof, the test result of fluorescence lifetime, wherein embodiment 1,4,21,24,31,34,41 and 44 is Comparative Examples.
The preparation method is as follows: the batching of pressing the about 20g of proportioning weighing of table 1, in agate mortar, grind half an hour, then 500 ℃ of following pre-burnings 7 hours, after taking out grinding, again in 1550 ℃ of fusions 2 hours, so that thoroughly eliminate bubble, melt is poured over fast on the stainless steel plate and with another block plate and flattens, transfer in the annealing furnace and naturally cool to room temperature with stove after 7 hours, take out and promptly get sample in annealing under 500 ℃.Glass sample is because of Bi
2O
3Concentration different and present pink, purplish red or reddish-brown; All samples are all transparent and do not have bubble and exist.Sample cuts into 10 * 10 * 1mm
3, the polishing back is for the usefulness of test.Table 1 has listed file names with the luminosity and the fluorescence lifetime of the glass of these compositions.As seen from the table, corresponding 99GeO
21.0Bi
2O
3The glass of forming, promptly Comparative Examples 1, no matter is the laser pumping of 532nm, and still 632.5 and the pumping of 808nm is neither can produce fluorescence, only just can produce fluorescence later on mixing aluminum oxide, the adding of visible aluminum oxide is to produce the fluorescence essential condition; The centre wavelength of fluorescence is with Bi
2O
3The increase gradually of concentration, clocklike move to long wave; Fluorescence has dependency to pumping wavelength.Fig. 1 is for consisting of 96GeO
23Al
2O
31.0Bi
2O
3Absorption spectrum, by 500,700,800 and four absorption bands of 1000nm form, cover from seeing the zone of infrared broadness like this, this makes it the easier pumping source that searches out coupling, the absorption spectrum of the glass of other compositions with it with.Fig. 2 is for consisting of 96GeO
23Al
2O
31.0Bi
2O
3The fluorescence spectrum under different pumping wavelengths, present the characteristics of ultra broadband, and disclose and can but can find its pumping source in 450～1000nm interval, also the glassy phase of composition is seemingly therewith for the glass of other compositions.
Press the batching of the proportioning weighing 20g of table 2, in agate mortar, grind half an hour, then 500 ℃ of following pre-burnings 7 hours, after taking out grinding, again in 1550 ℃ of fusions 2 hours, so that thoroughly eliminate bubble, melt is poured over fast on the stainless steel plate and with another block plate and flattens, transfer in the annealing furnace and naturally cool to room temperature with stove after 7 hours, take out and promptly get sample in annealing under 500 ℃.Glass sample is because of Bi
2O
3Concentration different and present pink, purplish red or reddish-brown; All samples are all transparent and do not have bubble and exist.Sample cuts into 10 * 10 * 1mm
3, the polishing back is for the usefulness of test.Table 2 has listed file names with the luminosity and the fluorescence lifetime of the glass of these compositions.As seen from the table, corresponding 99GeO
21.0Bi
2O
3The glass of forming, promptly Comparative Examples 21, no matter are the laser pumpings of 532nm, and still 632.5 and the pumping of 808nm is neither can produce fluorescence, only just can produce fluorescence later on mixing tantalum oxide, the adding of visible tantalum oxide is to produce the fluorescence essential condition; The centre wavelength of fluorescence is with Bi
2O
3The increase gradually of concentration, clocklike move to the long wave direction; Fluorescence has dependency to pumping wavelength.Fig. 3 is for consisting of 96GeO
23Ta
2O
51.0Bi
2O
3Absorption spectrum, by 508,712,800 and four absorption bands of 1000nm form, cover from seeing the zone of infrared broadness like this, this makes it the easier pumping source that searches out coupling, the absorption spectrum of the glass of other compositions with it with.Fig. 4 is for consisting of 96GeO
23Ta
2O
51.0Bi
2O
3The fluorescence spectrum under different pumping wavelengths, present the characteristics of ultra broadband, and disclose and can all can find its pumping source in 450～1000nm interval, also the glassy phase of composition is seemingly therewith for the glass of other compositions.
Press the batching of the proportioning weighing 20g of table 3, in agate mortar, grind half an hour, then 500 ℃ of following pre-burnings 7 hours, after taking out grinding, again in 1550 ℃ of fusions 2 hours, so that thoroughly eliminate bubble, melt is poured over fast on the stainless steel plate and with another block plate and flattens, transfer in the annealing furnace and naturally cool to room temperature with stove after 7 hours, take out and promptly get sample in annealing under 500 ℃.Glass sample is because of Bi
2O
3Concentration different and present pink, purplish red or reddish-brown; All samples are all transparent and do not have bubble and exist.Sample cuts into 10 * 10 * 1mm
3, the polishing back is for the usefulness of test.Table 3 has listed file names with the luminosity and the fluorescence lifetime of the glass of these compositions.As seen from the table, corresponding 99GeO
21.0Bi
2O
3The glass of forming, promptly Comparative Examples 31, no matter are the laser pumpings of 532nm, and still 632.5 and the pumping of 808nm is neither can produce fluorescence, only just can produce fluorescence later on mixing gallium oxide, the adding of visible gallium oxide is to produce the fluorescence essential condition; The centre wavelength of fluorescence is with Bi
2O
3The increase gradually of concentration, clocklike move to the long wave direction; Fluorescence has dependency to pumping wavelength.Fig. 5 is for consisting of 96GeO
23Ga
2O
31.0Bi
2O
3Absorption spectrum, by 501,708,800 and four absorption bands of 1000nm form, cover from seeing the zone of infrared broadness like this, this makes it the easier pumping source that searches out coupling, the absorption spectrum of the glass of other compositions with it with.Fig. 6 is for consisting of 96GeO
23Ga
2O
31.0Bi
2O
3The fluorescence spectrum under different pumping wavelengths, present the characteristics of ultra broadband, and disclose and can all can find its pumping source in 450～1000nm interval, also the glassy phase of composition is seemingly therewith for the glass of other compositions.
Embodiment group 4
Press the batching of the proportioning weighing 20g of table 4, in agate mortar, grind half an hour, then 500 ℃ of following pre-burnings 7 hours, after taking out grinding, again in 1550 ℃ of fusions 2 hours, so that thoroughly eliminate bubble, melt is poured over fast on the stainless steel plate and with another block plate and flattens, transfer in the annealing furnace and naturally cool to room temperature with stove after 7 hours, take out and promptly get sample in annealing under 500 ℃.Glass sample is because of Bi
2O
3Concentration different and present pink, purplish red or reddish-brown; All samples are all transparent and do not have bubble and exist.Sample cuts into 10 * 10 * 1mm
3, the polishing back is for the usefulness of test.Table 4 has listed file names with the luminosity and the fluorescence lifetime of the glass of these compositions.As seen from the table, corresponding 99GeO
21.0Bi
2O
3The glass of forming, promptly Comparative Examples 41, no matter are the laser pumpings of 532nm, and still 632.5 and the pumping of 808nm is neither can produce fluorescence, only just can produce fluorescence later on mixing boron oxide, the adding of visible boron oxide is to produce the fluorescence essential condition; The centre wavelength of fluorescence is with Bi
2O
3The increase gradually of concentration, clocklike move to the long wave direction; Fluorescence has dependency to pumping wavelength.Fig. 7 is for consisting of 96GeO
23B
2O
31.0Bi
2O
3Absorption spectrum, by 508,705,800 and four absorption bands of 1000nm form, cover from seeing the zone of infrared broadness like this, this makes it the easier pumping source that searches out coupling, the absorption spectrum of the glass of other compositions with it with.Fig. 8 is for consisting of 96GeO
23B
2O
31.0Bi
2O
3The fluorescence spectrum under different pumping wavelengths, present the characteristics of ultra broadband, and disclose and can but can find its pumping source in 450～1000nm interval, also the glassy phase of composition is seemingly therewith for the glass of other compositions.
Table 1
Table 1
Table 2
Table 3
Table 4
*Semiconductor laser diode pumping with 808nm.
Claims (2)
1, a kind of bismuth germanium base optical glass of mixing, each is composed as follows to it is characterized in that this glass:
Form molar percentage
GeO
2 90～99.98；
M=Al
2O
3, Ta
2O
5, Ga
2O
3Or B
2O
30.01～9;
Bi
2O
3 0.01～5。
2, the preparation method who mixes bismuth germanium base optical glass according to claim 1 is characterized in that this method comprises the following steps:
1. selected glass is formed and content mol%, and each raw material by the certain total amount of this proportioning weighing grinds half an hour in agate mortar;
2. then 500 ℃ of following pre-burnings 7 hours, take out grinding after, again 1550 ℃ of fusions 2 hours;
3. melt is poured over fast on the stainless steel plate and with another block plate and flattens, and transfers in the annealing furnace, naturally cools to room temperature with stove in annealing under 500 ℃ after 7 hours, and taking-up promptly gets this and mixes bismuth germanium base optical glass.
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| CN103086601B (en) * | 2012-12-13 | 2015-06-03 | 昆明理工大学 | Bismuth-doped germinate ultra wideband optical glass and preparation method thereof |
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| CN105068178B (en) * | 2015-07-17 | 2018-02-27 | 华南理工大学 | A kind of near-infrared luminous bismuth doping multicomponent optical fiber and preparation method |
| CN108233165B (en) * | 2018-01-22 | 2020-03-17 | 暨南大学 | Near-infrared bismuth-tantalum double-doped laser crystal facing 0.95-1.65 micron all-solid-state laser |
| CN110752283A (en) * | 2019-10-12 | 2020-02-04 | 华南理工大学 | Broadband near-infrared LED device |
| CN114477764B (en) * | 2022-01-26 | 2023-04-21 | 华南理工大学 | Bismuth-thulium co-doped gain glass with high-efficiency broadband and preparation method thereof |
| CN116354598A (en) * | 2023-03-01 | 2023-06-30 | 华南理工大学 | Bismuth-gallium co-doped gain fiber serving as gain medium and preparation method thereof |
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