CN102674688B - Praseodymium-doped borophosphate base near-infrared ultra wide band luminescent glass and preparation method thereof - Google Patents
Praseodymium-doped borophosphate base near-infrared ultra wide band luminescent glass and preparation method thereof Download PDFInfo
- Publication number
- CN102674688B CN102674688B CN201210167643.6A CN201210167643A CN102674688B CN 102674688 B CN102674688 B CN 102674688B CN 201210167643 A CN201210167643 A CN 201210167643A CN 102674688 B CN102674688 B CN 102674688B
- Authority
- CN
- China
- Prior art keywords
- glass
- praseodymium
- preparation
- raw material
- borophosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
Disclosed are praseodymium-doped borophosphate base near-infrared ultra wide band luminescent glass and a preparation method thereof. The glass comprises 45-83 mol% of P2O5, 5-35 mol% of B2O3, 4-23 mol% of Al2O3, 6-22 mol% of Y2O3 and 0.1-3 mol% of Pr2O3. The preparation method of the glass includes the steps of raw material weighing, presintering, founding, pouring, annealing and the like. The preparation method is simple in process, high in ultra wide band near-infrared fluorescence-emission characteristic with emission wavelength of 830-1700nm and capable of improving the stability of the glass, reinforcing the luminous intensity of praseodymium ions, and satisfying the requirement of optical fiber wiredrawing.
Description
Technical field
The present invention relates to fluorescent glass, particularly a kind of praseodymium borophosphate base broadband infrared luminescence glass and preparation method thereof of mixing.
Background technology
1985, the erbium-doped fiber amplifier that is widely used in 1.55 microns of frequency ranges in opticfiber communication cable (referred to as EDFA) that Southampton University of Southampton is first successfully developed, was one of greatest invention in opticfiber communication.EDFA has greatly increased the capacity of opticfiber communication in the use of DWDM (dense wave division multipurpose) technology, become optical amplifier most widely used in current opticfiber communication.But, nowadays the gain bandwidth that is widely used in erbium-doped fiber amplifier (EDFA) in DWDM opticfiber communication cable and other rare earth ion doped fiber amplifier all in tens nanometer range and gain bandwidth uneven, and be merely able to cover third communication window in quartzy single-mode fiber (1.55 μ m), wavelength is fixed, adjustable wavelength is limited, and these are the development to higher and faster message transmission rate and larger data transmission capacity direction by the limit fibre communication technology greatly.Although raman amplifier is under suitable Raman pump source forcing, can amplify the signal of arbitrary wavelength in optical fiber window, and the gain spectral with the wide 300nm of reaching, but its required pumping light power is high, discrete is wanted several watts to tens watts, the distributed hundreds of milliwatt of wanting, add operating distance long, distributed operating distance wants tens to kms up to a hundred, be only suitable in the low noise amplification of long distance line net, pumping efficiency is low, be generally (10～20) % gain not high, generally lower than the output of 15dB high power pump, be difficult to accurately control, and its interchannel generation energy exchange, cause cross-talk, these make it be difficult to be widely used in WDWM communication system.So, development to advanced luminescent material, and then obtain the light amplification in wider wave band, rich communication bandwidth is fully utilized existing communication window, for example single mode silica fibre is positioned at 1260nm to 1675nm communication band O, E, S, C, L, U, will become in the existing optical communication system of a kind of breakthrough the lower and not high bottleneck effective means of transmission capacity of transfer rate.
Rare earth ion, transition metal ion and bismuth ion doping Reflection Optical Thin Film glass and fiber optic materials, be characterized near certain wavelength, demonstrating the fluorescence spectrum in broadband in communication band, the potential substrate material that becomes ultra-wideband-light amplification and novel optical fiber laser apparatus.The people such as the Mu Huan of the Shanghai Communications University (patent No.: 200510028444), the liana of Osaka, Japan university is quiet, this positive first-class (patent No.: 200680006145) of the bank of Nippon Sheet Glass Co Ltd, and the Wu Baitao of Shanghai Optics and Precision Mechanics institute, Chinese Academy of Sciences (patent No.: 200710047761), Ruan Jian (patent No.: 200710044174.8) etc. people aspect Reflection Optical Thin Film glass and fiber optic materials, carried out a large amount of research work and according to its achievement in research application the patent of invention of corresponding exercise question.
But, the opticglass of their invention is if practical, also exist at present broadband fluorescence and can not cover whole optical communicating waveband (800～1700nm), light emitting ionic is not high to the receptivity of pump light, fluorescent emission intensity is low, glass physicochemistry unstable properties, is not suitable for preparing optical fiber, the problems such as temperature of fusion height.The glass of particularly preparing optical fiber, the material property that needs covering and sandwich layer glass to have, i.e. (T
x-T
g) want large, the condition such as covering will mate with the specific refractory power of sandwich layer, and coefficient of thermal expansion differences is little.Therefore, if make this material practical, also must improve its luminescent properties, improve its stability, glass and physical and chemical performance, make glass transformation temperature, thermal expansivity and the refractive index match of covering and sandwich layer.
Summary of the invention
The present invention is exactly the problem for above-mentioned prior art, a kind of praseodymium borophosphate base broadband infrared luminescence glass and preparation method thereof of mixing is provided, to increase broadband fluorescent emission scope, improve the stability of glass, also by suitable doping ratio, strengthen the luminous intensity of praseodymium ion simultaneously, more advantageously met the needs of drawing optical fibers.
Thought of the present invention is in glass ingredient, to have increased in large quantities B
2o
3and Y
2o
3, so not only improved the preparation condition of glass, regulated the melt temperature of glass, thermal expansivity, the transition temperatures of glass etc., have improved the stability of glass, have also strengthened the luminous intensity of praseodymium ion.Meanwhile, this glass forms the needs that can more advantageously meet drawing optical fibers.This opticglass can obtain the near infrared ultra broadband fluorescent emission (830～1700nm) of remarkable enhancing under the pumping of 445nm laser apparatus, make the praseodymium ion doped-glass can be at wideband adjustable amplifier, superpower laser, the field application such as tunable laser and fibre-optical drawing become possibility.In addition, the development of high power semi-conductor blue laser may be expanded the range of application of rare earth ion, for example use this glass, under 445nm laser pumping, can realize 1064nm Laser output, make band gap-photonic crystal fiber, can obtain two low loss window of widespread use in opticfiber communication cable: 1.55 mu m wavebands and 1.31 mu m wavebands.
Technical solution of the present invention is as follows:
Mix a praseodymium borophosphate base broadband infrared luminescence glass, its feature is that this glass respectively forms and molar percentage is as follows:
The described preparation method who mixes praseodymium borophosphate base broadband infrared luminescence glass, is characterized in that the concrete steps of the method are as follows:
1. according to each of selected glass, form and molar percentage weighs the raw material of certain total amount, and will to adopt primary ammonium phosphate be P
2o
5introducing raw material, in corundum mortar, fully ground and mixed is even;
2. pre-burning: fully pre-burning at 800～1000 ℃, to discharge moisture and the composition in raw material completely, after treating the abundant pre-burning of frit, again grind abundant ground and mixed even;
3. found: by the uniform raw material of abundant ground and mixed, found 90-120min in 1450～1600 ℃, frit melts completely, and homogenizing is clarified as glass metal;
4. cast: glass metal is cast on the steel plate grinding tool that is preheating in advance 350 ℃;
5. annealing: after glass ware forming, this glass sample, in 590～620 ℃ of annealing 4-6 hour, is then cooled to room temperature with stove.
Technique effect of the present invention is as follows:
The composition of this glass has been compared significantly different from other broadband fluorescent glass composition:
One, adopted Pr
3+for luminescent active ion;
Two, in glass ingredient, increased B
2o
3, add B
2o
3can better improve the preparation condition of glass, regulate the melt temperature of glass, thermal expansivity, the transition temperature of glass etc., and then the stability of raising glass, the luminous intensity of enhancing praseodymium ion, the glass of founding out like this can more advantageously meet the needs of drawing optical fibers;
Three, Y in this glass
2o
3content high, and the Y of high-content
2o
3not only be conducive to strengthen praseodymium ion near infrared ultra broadband fluorescent emission intensity, can also regulate the performances such as the specific refractory power of glass and material property.
During this opticglass forms, P
2o
5, B
2o
3as the Network former of glass, it is the main component of glass; Pr
2o
3it is the raw material of light emitting ionic; Al
2o
3it is glass network intermediate, both can become glass network former may be also to modify body, can suitably adjust the viscosity of glass to a certain extent, improve the chemical stability of glass, disperse luminescent active ion, and then make fluorescent line widen the ultra-wideband near-infrared luminous performance that strengthens praseodymium ion, be can produce the important component of ultra broadband fluorescence in gain media.Y
2o
3in glass, can reach hexa-coordinate [YO
6] make light emitting ionic energy level broadening, and then make fluorescent line widen the ultra-wideband near-infrared luminous performance that strengthens praseodymium ion, be can produce the important component of ultra broadband fluorescence in gain media.
Because this glass sample moiety is different, glass melting temperature and melting time are different, and its fluorescence intensity is not identical with fluorescence lifetime, and color is water white transparency.
Experimental result and test data show, the glass fluorescent emission performance that component is different and corresponding fluorescence lifetime are different, under 445nm laser pumping excites, all glass sample all can produce stronger Infrared fluorescence transmitting, three peak wavelength ~ 1040,1163 and effective fluorescence halfwidth (FWHM) of 1470nm position be respectively 108,147 and 205nm, and there is longer fluorescence lifetime, be respectively 68,321 and 68 μ s, fluorescence wave band coverage is 830～1700nm.Glass of the present invention under 445nm laser pumping excites, all has stronger fluorescence intensity respectively, 1040,1163 and the stimulated emission cross section at 1470nm place be respectively 7.82 * 10-20,1.99 * 10-20 and 1.61 * 10-19cm2.Product (the σ of stimulated emission cross section (σ) and fluorescence lifetime (T)
t) be an important parameter weighing laserable material optical property, this is because laser threshold and σ
tbe inversely proportional to.The σ that this glass is total
tbe 3.44 * 10-23cm2s, its numeric ratio Ti:Al
2o
3(σ
t=1.4 * 10-24cm2s) large nearly 24.6 times.
Experiment shows, glass preparation technique of the present invention is simple, has the ultra broadband near-infrared fluorescent emission characteristic that 830～1700nm is stronger, improves the stability of glass, strengthened the luminous intensity of praseodymium ion, more advantageously meets the needs of drawing optical fibers.Make band gap-photonic crystal fiber, can obtain two low loss window of widespread use in opticfiber communication cable: 1.55 mu m wavebands and 1.31 mu m wavebands.
Accompanying drawing explanation
Fig. 1 is the fluorescence emission spectrograms of embodiment 15 mother glasses under 445nm pump light excites, and solid line is test spectral, and dotted line 1-3 is Gauss's swarming;
Fig. 2 is the absorption spectrum of embodiment 15 samples, and sample is at 445nm, 588nm, and 805nm, 972nm, near absorption peak 1499nm and 1906nm marks;
Fig. 3 is that embodiment 15 mother glasses excite lower three peak wavelength ~ 1040 at 445nm pump light, 1163 and the fluorescence lifetime of 1470nm position;
Embodiment
Below in conjunction with embodiment and accompanying drawing, the invention will be further described.
Lower list 1, table 2 and table 3 have been listed the molar percentage composition of 27 embodiment of praseodymium ion doping alkali-free borophosphate base broadband infrared luminescence glass of the present invention and the parameter of corresponding glass preparation altogether.
The composition (mol%) of table 1 praseodymium ion doping alkali-free borophosphate base broadband infrared luminescence glass embodiment 1-9
The composition (mol%) of table 2 praseodymium ion doping alkali-free borophosphate base broadband infrared luminescence glass embodiment 10-18
The composition (mol%) of table 3 praseodymium ion doping alkali-free borophosphate base broadband infrared luminescence glass embodiment 19-27
The preparation method of embodiment 1-27 is as follows:
In embodiment 1-27, P
2o
5, B
2o
3, Al
2o
3respectively by NH
4h
2pO
4, H
3bO
3,, Al (OH)
3introduce, other raw materials all select corresponding oxide compound to introduce.Then the pure raw material of selection analysis, respectively according to table 1, table 2, in corundum mortar, fully ground and mixed is even respectively respectively to take 50g frit with embodiment 1-27 proportioning (mol%) in table 3, put into corundum crucible and fully ground and mixed is even again after pre-burning at 800 ~ 1000 ℃, every pot of frit is placed in respectively to 1450～1600 ℃ of High Temperature Furnaces Heating Apparatuss to be founded, all be incubated 90 ~ 120 minutes, glass metal is cast on the steel plate grinding tool that is preheating in advance certain temperature, after glass ware forming, by glass sample in 590～620 ℃ annealing 4-6 hour, then with stove, be cooled to room temperature.Sanding and polishing becomes the glass sample that 1mm is thick.Sample is at 445nm, 588nm, 805nm, 972nm, can be observed obvious absorption peak near 1499nm and 1906nm, and can excite lower generation to be positioned at the near-infrared fluorescent transmitting across 830～1700nm at 445nm pump light, have compared with hyperfluorescenceZeng Yongminggaoyingguang, corresponding fluorescence lifetime is also longer.Typically test result is as shown in Figure 1, 2, 3:
Fig. 1 is the fluorescence emission spectrograms of embodiment 15 mother glasses under 445nm pump light excites, and solid line is test spectral, and dotted line 1-3 is Gauss's swarming;
Fig. 2 is the absorption spectrum of embodiment 15 samples, and sample is at 445nm, 588nm, and 805nm, 972nm, near absorption peak 1499nm and 1906nm marks;
Fig. 3 is that embodiment 15 mother glasses excite lower three peak wavelength ~ 1040 at 445nm pump light, 1163 and the fluorescence lifetime of 1470nm position;
Glass preparation technique of the present invention is simple, has the ultra broadband near-infrared fluorescent emission characteristic that 830～1700nm is stronger, improves the stability of glass, has strengthened the luminous intensity of praseodymium ion, more advantageously meets the needs of drawing optical fibers.
Claims (2)
1. mix a praseodymium borophosphate base broadband infrared luminescence glass, it is characterized in that each composition of this glass and molar percentage thereof are as follows:
2. the preparation method who mixes praseodymium borophosphate base broadband infrared luminescence glass claimed in claim 1, is characterized in that the concrete steps of the method are as follows:
1. according to each of selected glass, form and molar percentage weighs the raw material of certain total amount, and will to adopt primary ammonium phosphate be P
2o
5introducing raw material, in corundum mortar, fully ground and mixed is even;
2. pre-burning: fully pre-burning at 800～1000 ℃, to discharge moisture and the composition in raw material completely, after treating the abundant pre-burning of frit, again grind and fully mix;
3. found: by the uniform raw material of abundant ground and mixed, found 90-120min in 1450～1600 ℃, frit melts completely, and homogenizing is clarified as glass metal;
4. cast: glass metal is cast on the steel plate mould that is preheating in advance 350 ℃;
5. annealing: after glass ware forming, this glass sample, in 590～620 ℃ of annealing 4-6 hour, is then cooled to room temperature with stove.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210167643.6A CN102674688B (en) | 2012-05-25 | 2012-05-25 | Praseodymium-doped borophosphate base near-infrared ultra wide band luminescent glass and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210167643.6A CN102674688B (en) | 2012-05-25 | 2012-05-25 | Praseodymium-doped borophosphate base near-infrared ultra wide band luminescent glass and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102674688A CN102674688A (en) | 2012-09-19 |
| CN102674688B true CN102674688B (en) | 2014-04-09 |
Family
ID=46807325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210167643.6A Expired - Fee Related CN102674688B (en) | 2012-05-25 | 2012-05-25 | Praseodymium-doped borophosphate base near-infrared ultra wide band luminescent glass and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102674688B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113387564B (en) * | 2020-03-13 | 2022-04-05 | 包头稀土研究院 | Praseodymium and erbium doped luminescent glass and preparation method thereof |
| CN112062474B (en) * | 2020-09-17 | 2022-01-25 | 昆明理工大学 | Preparation method and application of near-infrared perovskite quantum dot glass |
| CN116217071A (en) * | 2023-02-21 | 2023-06-06 | 云南大学 | Rare earth ion doped borosilicate laser glass and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294768A (en) * | 1999-02-26 | 2001-05-09 | 住友电气工业株式会社 | Optical fiber for optical amplifying and production method therefor |
| CN1397833A (en) * | 2002-08-15 | 2003-02-19 | 上海交通大学 | Multi-band rare-earth doped optical fibre amplifier |
| US6911160B2 (en) * | 2002-03-21 | 2005-06-28 | Kigre, Inc. | Phosphate glass for use in the manufacture of ultra-short length lasers and amplifiers |
| CN201576109U (en) * | 2009-11-04 | 2010-09-08 | 北京交通大学 | Multi rare-earth ion-doped multicore double-clad optical fiber |
| CN102211871A (en) * | 2011-04-01 | 2011-10-12 | 中国科学院上海光学精密机械研究所 | Ytterbium-bismuth co-doped base-free borophosphate optical glass and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3005074B2 (en) * | 1991-07-02 | 2000-01-31 | 住友電気工業株式会社 | Fiber amplifier, fiber laser, waveguide device amplifier, and waveguide device laser |
-
2012
- 2012-05-25 CN CN201210167643.6A patent/CN102674688B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294768A (en) * | 1999-02-26 | 2001-05-09 | 住友电气工业株式会社 | Optical fiber for optical amplifying and production method therefor |
| US6911160B2 (en) * | 2002-03-21 | 2005-06-28 | Kigre, Inc. | Phosphate glass for use in the manufacture of ultra-short length lasers and amplifiers |
| CN1397833A (en) * | 2002-08-15 | 2003-02-19 | 上海交通大学 | Multi-band rare-earth doped optical fibre amplifier |
| CN201576109U (en) * | 2009-11-04 | 2010-09-08 | 北京交通大学 | Multi rare-earth ion-doped multicore double-clad optical fiber |
| CN102211871A (en) * | 2011-04-01 | 2011-10-12 | 中国科学院上海光学精密机械研究所 | Ytterbium-bismuth co-doped base-free borophosphate optical glass and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 1.3μm波段掺镨光纤放大器;梁晓炜 等;《内江科技》;20090930(第9期);第74页，第144页 * |
| JP平5-13865A 1993.01.22 |
| 梁晓炜 等.1.3μm波段掺镨光纤放大器.《内江科技》.2009,(第9期),第74页，第144页. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102674688A (en) | 2012-09-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101117271B (en) | Ytterbium-bismuth co-doped phosphonate based optical glass and method for making same | |
| Adam | Lanthanides in non-oxide glasses | |
| CN102659313B (en) | Near-infrared broadband luminescence erbium and thulium-co-doped bismuthate laser glass and preparation method thereof | |
| Elisa et al. | Optical and structural characterization of samarium and europium-doped phosphate glasses | |
| Li et al. | Broadband near-infrared emission in Pr3+–Er3+ codoped phosphate glasses for optical amplifiers | |
| CN110407462B (en) | Rare earth doped silicate glass and preparation method and application thereof | |
| CN100513339C (en) | Rare earth doped gallium germanium bismuth lead luminous glass material and its preparation method and uses | |
| CN102211873A (en) | 3mu m luminous rare-earth ion-doped fluogermanate laser glass and preparation method thereof | |
| CN102674688B (en) | Praseodymium-doped borophosphate base near-infrared ultra wide band luminescent glass and preparation method thereof | |
| Lakshminarayana et al. | Fluorescence features of Tm3+-doped multicomponent borosilicate and borotellurite glasses for blue laser and S-band optical amplifier applications | |
| Zhang et al. | Fabrication and emission properties of Er3+/Yb3+ codoped tellurite glass fiber for broadband optical amplification | |
| CN101168473B (en) | Ytterbium-nickel codoping transparent silicate micro-crystal glass and preparation method thereof | |
| Almukhtar et al. | Wideband optical fiber amplifier with short length of enhanced erbium–zirconia–yttria–aluminum co-doped fiber | |
| CN101870557A (en) | Preparation method of germanium tellurite glass optical prefabricated rod output by green ray | |
| CN1269755C (en) | Bismuth blended germanium base optical glass | |
| CN109354402B (en) | Ytterbium and erbium co-doped phosphate glass and preparation method and application thereof | |
| CN102211871B (en) | Ytterbium-bismuth co-doped base-free borophosphate optical glass and preparation method thereof | |
| Yang et al. | Energy transfer and frequency upconversion in Yb3+, Er3+ co-doped sodium–lead–germanate glasses | |
| CN102276147B (en) | Bismuth-doped silicophosphate-based optical glass and preparation method thereof | |
| CN102603190A (en) | Rare-earth-doped chalcogenide (halogen) thin film material, preparation method and application | |
| CN102515513A (en) | Er<3+> and Ce<3+> codoped bismuth titanium tellurite glass and its preparation method | |
| CN1363848A (en) | Wide wavelength optical waveguide amplifier and manufacture thereof | |
| US6797657B2 (en) | Tm-doped fluorophosphate glasses for 14xx amplifiers and lasers | |
| CN103359940A (en) | Red light laser glass and preparation method thereof | |
| CN108147659A (en) | A kind of fiber amplifier is co-doped with bismuthates laser glass and preparation method thereof with erbium cerium |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140409 Termination date: 20160525 |