CN103043904B - Ytterbium doped fluorphosphate glass with long fluorescent life and preparation method of glass - Google Patents
Ytterbium doped fluorphosphate glass with long fluorescent life and preparation method of glass Download PDFInfo
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- CN103043904B CN103043904B CN201310005385.6A CN201310005385A CN103043904B CN 103043904 B CN103043904 B CN 103043904B CN 201310005385 A CN201310005385 A CN 201310005385A CN 103043904 B CN103043904 B CN 103043904B
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Abstract
The invention discloses ytterbium doped fluorphosphate glass with a long fluorescent life and a preparation method of the glass. The glass comprises the following components by mole percentage: 10-20mol% of P2O5, 25-35mol% of AlF3, 20-35mol% of CaF2, 10-15mol% of RF and 7-25mol% of R'F2, wherein a sum of the percentage of the components is 100mol%; additional 3wt% of Yb2O3 is doped according to a weight ratio; R is Li<+>, Na<+> or K<+>; and R' is Mg<2+>, Sr<2+>, Ba<2+> or Zn<2+>. The preparation method of the glass comprises the following steps that raw materials are weighed according to the formula in a glove box, mixed uniformly, and added to a graphite crucible; carbon tetrachloride is added to the crucible, and heated to 900-1100 DEG C by a high frequency furnace and kept for 45min; finally, the high frequency furnace is turned off; the temperature falls to a room temperature rapidly; and the glass is taken out and placed in a muffle furnace for annealing. The glass has better gain performance; the fluorescent life reaches as high as 2.25ms; an emission cross section is 0.8pm<2>; a gain coefficient is 1.8ms*pm<2>; and a hydroxy absorption coefficient alphaOH is less than 0.3cm<-1>.
Description
Technical field
The present invention relates to laser glass material, particularly a kind of long fluorescence lifetime ytterbium-doped phosphate glass and preparation method thereof.
Background technology
Owing to having long fluorescence lifetime, high emission efficiency and strong emissive porwer, ytterbium doping laser glass is considered to a kind of optical fiber laser substrate material of being potential.In the laser glass of ytterbium ion doping, fluorphosphate glass owing to having low phonon energy, low nonlinearity specific refractory power, ultraviolet is near infrared wide through scope, the high-dissolvability of ytterbium ion, and the performance such as good thermostability and chemical stability, shown good application potential.
The eigenvibration peak of free hydroxyl is at 2500cm
-1and 3600cm
-1near, this vibration band, much larger than the maximum phonon energy of glass matrix, therefore only needs two hydroxyls to cause Yb
3+ion
2f
5/2→
2f
7/2transition, this process is more much bigger than the multi-phonon relaxation probability of glass matrix self, and the simultaneously high hydroxyl concentration absorption that near-infrared band can be caused strong, reduces the transmitance of near-infrared band.Containing a large amount of F in fluorphosphate glass
-ion, they have good dehydration, but compared with other glass matrixs, remaining hydroxyl ion is more difficult to removing, and the fluorphosphate glass of low hydroxyl concentration is widely used, particularly as infrared window material and long lifetime gain material.Therefore the hydroxyl concentration reduced in glass will make fluorphosphate glass be more suitable for commercial applications further.
Traditional processing method is difficult to obtain hydroxyl group absorption factor alpha
oHbe less than 0.5cm
-1gain glass, therefore, adopt new technique prepare low hydroxyl concentration high gain glass become more meaningful.
Summary of the invention
The object of this invention is to provide a kind of gain factor comparatively large, long fluorescence lifetime ytterbium-doped phosphate glass of low hydroxyl concentration and preparation method thereof.
Long fluorescence lifetime ytterbium-doped phosphate glass of the present invention, its molar percentage consists of:
P
2O
5：10 – 20 mol%，
AlF
3：25 - 35 mol%，
CaF
2：20 - 35 mol %，
RF：10 - 15 mol %，
R’F
2：7 - 25 mol%，
Said components and be 100 mol %, Yb
2o
33wt% is mixed according to outside weight ratio,
Wherein R is Li
+, Na
+or K
+, R ' is Mg
2+, Sr
2+, Ba
2+or Zn
2+.
Above-mentioned component Raw purity is all 4 N.
The preparation method of long fluorescence lifetime ytterbium-doped phosphate glass, step is as follows:
First, under argon shield, in glove box, take raw material 35g by formula, join in the plumbago crucible of 50ml after fully mixing, and in crucible, add tetracol phenixin powder is completely soaked; Then, the plumbago crucible of adding a cover is placed in quartz cover and passes into argon shield, be heated to 900 ~ 1100 degree with high frequency furnace, insulation 45min; Finally, close high frequency furnace, pass into argon gas and lower the temperature rapidly, make quartz cover be down to room temperature rapidly with air gun simultaneously; Take out glass and be placed in retort furnace, be warming up to glass transformation temperature annex with stove and be incubated 4 hours, be then annealed to room temperature with the cooling rate of 10 DEG C/h.
beneficial effect:ytterbium-doped phosphate glass of the present invention, alkaline-earth metal fluoride (CaF
2, BaF
2) and AlF
3content is higher, has suitable specific refractory power and lower nonlinear refractive index, adds appropriate bases metal fluoride and is conducive to improving the formation range of glass system and reduces glass melting temperature, reduce the volatile quantity of fluorochemical.This ytterbium-doped phosphate glass has long fluorescence lifetime, and the advantages such as high gain coefficient and low hydroxyl concentration are the perfect medium materials realizing superpower high gain.
Accompanying drawing explanation
Fig. 1 is absorption cross section and the stimulated emission cross section figure of embodiment 2,
Fig. 2 is the fluorescence lifetime extinction curve of embodiment 2.
Fig. 3 is the infrared H103 resin of embodiment 2.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1 ~ 8 design of components and performance perameter such as table 1(unit are mol%, Yb
2o
3doping is 3wt%):
| Component | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| P 2O 5 | 17 | 17 | 17 | 17 | 17 | 17 | 17 | 17 |
| AlF 3 | 28.5 | 28.5 | 28.5 | 28.5 | 28.5 | 28.5 | 28.5 | 28.5 |
| LiF | 14 | |||||||
| NaF | 14 | 14 | 14 | 14 | 14 | 14 | ||
| KF | 14 | |||||||
| MgF 2 | 12.5 | |||||||
| CaF 2 | 28 | 28 | 28 | 28 | 28 | 28 | 23 | 18 |
| SrF 2 | 12.5 | |||||||
| BaF 2 | 12.5 | 12.5 | 12.5 | 17.5 | 22.5 | |||
| ZnF 2 | 12.5 | |||||||
| Emission cross section pm 2 | 0.82 | 0.80 | 0.73 | 0.80 | 0.82 | 0.78 | 0.86 | 0.79 |
| Life-span ms | 2.08 | 2.25 | 2.03 | 2.17 | 1.85 | 1.86 | 1.65 | 1.66 |
| Gain | 1.70 | 1.8 | 1.48 | 1.74 | 1.52 | 1.45 | 1.42 | 1.31 |
Embodiment 1 ~ 8 adopts identical preparation method, and concrete steps are as follows:
First; in glove box, raw material 35g is taken by formula under argon shield; join after fully mixing in the plumbago crucible of 50ml; in crucible, add tetracol phenixin makes powder be completely soaked; then the plumbago crucible of adding a cover is placed in the logical argon shield of quartz cover; be heated to 900 ~ 1100 DEG C of insulation 45min with high frequency furnace, closedown high frequency furnace passes into argon gas and lowers the temperature rapidly, makes quartz cover be down to room temperature rapidly with air gun simultaneously.Take out glass and be placed in retort furnace, be warming up to glass transformation temperature annex with stove and be incubated 4 hours, be then annealed to room temperature with the cooling rate of 10 DEG C/h.
As shown in Table 1, all embodiments all have higher fluorescence lifetime, and wherein the fluorescence lifetime of embodiment 2, embodiment 4 is greater than 2.1ms; The emission cross section of all embodiments is all greater than 0.7pm
2, wherein embodiment 7 has maximum stimulated emission cross section 0.86pm
2.Long fluorescence lifetime is except relevant with glass ingredient, also relevant with the hydroxyl concentration of glass matrix, and all glass tests are infrared all has extremely low hydroxyl group absorption peak through discovery, and Fig. 3 gives the infrared H103 resin of embodiment 2, hydroxyl group absorption factor alpha
oHbe less than 0.3 cm
-1.
Claims (1)
1. a preparation method for long fluorescence lifetime ytterbium-doped phosphate glass, is characterized in that the molar percentage of this glass consists of:
P
2O
5：10 – 20 mol%，
AlF
3：25 - 35 mol%，
CaF
2：20 - 35 mol %，
RF：10 - 15 mol %，
R’F
2：7 - 25 mol%，
Said components and be 100 mol %, Yb
2o
33wt% is mixed according to outside weight ratio,
Wherein R is Li
+, Na
+or K
+, R ' is Mg
2+, Sr
2+, Ba
2+or Zn
2+;
Preparation process is as follows:
First, under argon shield, in glove box, take raw material 35g by formula, join in the plumbago crucible of 50ml after fully mixing, and in crucible, add tetracol phenixin powder is completely soaked; Then, the plumbago crucible of adding a cover is placed in quartz cover and passes into argon shield, be heated to 900 ~ 1100 degree with high frequency furnace, insulation 45min; Finally, close high frequency furnace, pass into argon gas and lower the temperature rapidly, make quartz cover be down to room temperature rapidly with air gun simultaneously; Take out glass and be placed in retort furnace, be warming up near glass transformation temperature with stove and be incubated 4 hours, be then annealed to room temperature with the cooling rate of 10 DEG C/h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310005385.6A CN103043904B (en) | 2013-01-08 | 2013-01-08 | Ytterbium doped fluorphosphate glass with long fluorescent life and preparation method of glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310005385.6A CN103043904B (en) | 2013-01-08 | 2013-01-08 | Ytterbium doped fluorphosphate glass with long fluorescent life and preparation method of glass |
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| Publication Number | Publication Date |
|---|---|
| CN103043904A CN103043904A (en) | 2013-04-17 |
| CN103043904B true CN103043904B (en) | 2015-02-11 |
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|---|---|---|---|
| CN201310005385.6A Expired - Fee Related CN103043904B (en) | 2013-01-08 | 2013-01-08 | Ytterbium doped fluorphosphate glass with long fluorescent life and preparation method of glass |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103524039A (en) * | 2013-09-27 | 2014-01-22 | 南京邮电大学 | High-ultraviolet-transmittance fluorphosphate glass and preparation method thereof |
| CN106186679A (en) * | 2016-07-06 | 2016-12-07 | 中国计量大学 | Er ions mid-infrared luminescence fluorine chlorine phosphorus glass and preparation method thereof |
| CN110981193A (en) * | 2019-12-04 | 2020-04-10 | 南京邮电大学 | Thulium-holmium co-doped tellurite glass with long fluorescence life and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4120814A (en) * | 1977-02-28 | 1978-10-17 | Hoya Corporation | Fluorophosphate-base laser glasses |
| CN101215073A (en) * | 2008-01-16 | 2008-07-09 | 中南大学 | Technique for reducing hydroxyl group content in glass |
| CN101293737A (en) * | 2008-05-27 | 2008-10-29 | 中国计量学院 | Ytterbium fluorine phosphate doped laser glass with high transmission section and preparation method thereof |
| CN101481212A (en) * | 2009-02-25 | 2009-07-15 | 中国科学院上海光学精密机械研究所 | 2 mu m low phosphorus content fluophosphate laser glass and preparation thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5645849A (en) * | 1979-09-21 | 1981-04-25 | Hoya Corp | Fluorophosphate visible laser glass |
-
2013
- 2013-01-08 CN CN201310005385.6A patent/CN103043904B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4120814A (en) * | 1977-02-28 | 1978-10-17 | Hoya Corporation | Fluorophosphate-base laser glasses |
| CN101215073A (en) * | 2008-01-16 | 2008-07-09 | 中南大学 | Technique for reducing hydroxyl group content in glass |
| CN101293737A (en) * | 2008-05-27 | 2008-10-29 | 中国计量学院 | Ytterbium fluorine phosphate doped laser glass with high transmission section and preparation method thereof |
| CN101481212A (en) * | 2009-02-25 | 2009-07-15 | 中国科学院上海光学精密机械研究所 | 2 mu m low phosphorus content fluophosphate laser glass and preparation thereof |
Non-Patent Citations (1)
| Title |
|---|
| JP昭56-45849A 1981.04.25 * |
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Application publication date: 20130417 Assignee: Jiangsu Nanyou IOT Technology Park Ltd. Assignor: Nanjing Post & Telecommunication Univ. Contract record no.: 2016320000211 Denomination of invention: Ytterbium doped fluorphosphate glass with long fluorescent life and preparation method of glass Granted publication date: 20150211 License type: Common License Record date: 20161114 |
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