CN103043904A - 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
- Publication number
- CN103043904A CN103043904A CN2013100053856A CN201310005385A CN103043904A CN 103043904 A CN103043904 A CN 103043904A CN 2013100053856 A CN2013100053856 A CN 2013100053856A CN 201310005385 A CN201310005385 A CN 201310005385A CN 103043904 A CN103043904 A CN 103043904A
- Authority
- CN
- China
- Prior art keywords
- glass
- mol
- preparation
- high frequency
- ytterbium
- 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.)
- Granted
Links
Images
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 the laser glass material, particularly a kind of long fluorescence lifetime ytterbium-doped phosphate glass and preparation method thereof.
Background technology
Since have long fluorescence lifetime, high emission efficiency and strong emissive porwer, and 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 is owing to have low phonon energy, low nonlinearity specific refractory power, ultraviolet is to the near infrared wide scope that sees through, the high-dissolvability of ytterbium ion, and the performances such as good thermostability and chemical stability have shown good application potential.
The eigenvibration peak of free hydroxyl is at 2500cm
-1And 3600cm
-1Near, therefore this vibration band only needs two hydroxyls will cause Yb much larger than the maximum phonon energy of glass matrix
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 high hydroxyl concentration can cause the strong absorption of near-infrared band simultaneously, reduces the transmitance of near-infrared band.Contain a large amount of F in the fluorphosphate glass
-Ion, they have good dehydration, but compare with other glass matrixs, and remaining hydroxyl ion more is difficult to remove, 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 that further reduces in the glass will make fluorphosphate glass be more suitable for commercial applications.
Traditional processing method is difficult to obtain the hydroxyl absorption coefficient
OHLess than 0.5cm
-1Gain glass, therefore, adopt more meaningful that the low hydroxyl concentration high gain glass of new technique preparation becomes.
?
Summary of the invention
It is larger to the purpose of this invention is to provide a kind of gain factor, 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
3Mix 3wt% outward according to 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 all is 4 N.
The preparation method of long fluorescence lifetime ytterbium-doped phosphate glass, step is as follows:
At first, under argon shield, in glove box, take by weighing raw material 35g by prescription, join after fully mixing in the plumbago crucible of 50ml, and add tetracol phenixin in the crucible powder is soaked fully; Then, place the plumbago crucible of adding a cover quartz cover to pass into argon shield, be heated to 900 ~ 1100 degree with high frequency furnace, insulation 45min; At last, close high frequency furnace, pass into argon gas and lower the temperature rapidly, make quartz cover be down to rapidly room temperature with air gun simultaneously; Take out glass and place retort furnace, be warming up to glass transformation temperature annex insulation 4 hours with stove, then be annealed to room temperature with 10 ℃/hour cooling rate.
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 the appropriate bases metal fluoride and is conducive to improve the formation range of glass system and reduces glass melting temperature, reduces the volatile quantity of fluorochemical.This ytterbium-doped phosphate glass has long fluorescence lifetime, and high gain coefficient and the low advantages such as hydroxyl concentration are the perfect medium materials of realizing the superpower high gain.
?
Description of drawings
Fig. 1 is absorption crosssection 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 curve that sees through of embodiment 2.
?
Embodiment
The invention will be further described below in conjunction with specific embodiment.
Embodiment 1 ~ 8 design of components and performance perameter are mol% such as table 1(unit, 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:
At first; under argon shield, in glove box, take by weighing raw material 35g by prescription; join after fully mixing in the plumbago crucible of 50ml; adding tetracol phenixin in the crucible is soaked powder fully; then place the plumbago crucible of adding a cover quartz cover to lead to argon shield; be heated to 900 ~ 1100 ℃ of insulation 45min with high frequency furnace, close high frequency furnace and pass into argon gas and lower the temperature rapidly, make quartz cover be down to rapidly room temperature with air gun simultaneously.Take out glass and place retort furnace, be warming up to glass transformation temperature annex insulation 4 hours with stove, then be annealed to room temperature with 10 ℃/hour cooling rate.
As shown in Table 1, all embodiment 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 embodiment is all greater than 0.7pm
2, wherein embodiment 7 has maximum stimulated emission cross section 0.86pm
2Long fluorescence lifetime is except relevant with glass ingredient, and is also relevant with the hydroxyl concentration of glass matrix, and all infrared seeing through of glass test find all to have extremely low hydroxyl absorption peak, and Fig. 3 has provided infrared curve, the hydroxyl absorption coefficient of seeing through of embodiment 2
OHLess than 0.3 cm
-1
Claims (2)
1. one kind 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
3Mix 3wt% outward according to weight ratio,
Wherein R is Li
+, Na
+Or K
+, R ' is Mg
2+, Sr
2+, Ba
2+Or Zn
2+
2. the preparation method of a long fluorescence lifetime ytterbium-doped phosphate glass as claimed in claim 1 is characterized in that preparation process is as follows:
At first, under argon shield, in glove box, take by weighing raw material 35g by prescription, join after fully mixing in the plumbago crucible of 50ml, and add tetracol phenixin in the crucible powder is soaked fully; Then, place the plumbago crucible of adding a cover quartz cover to pass into argon shield, be heated to 900 ~ 1100 degree with high frequency furnace, insulation 45min; At last, close high frequency furnace, pass into argon gas and lower the temperature rapidly, make quartz cover be down to rapidly room temperature with air gun simultaneously; Take out glass and place retort furnace, be warming up to glass transformation temperature annex insulation 4 hours with stove, then be annealed to room temperature with 10 ℃/hour cooling rate.
Priority Applications (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 |
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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103043904A true CN103043904A (en) | 2013-04-17 |
| CN103043904B CN103043904B (en) | 2015-02-11 |
Family
ID=48056793
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| 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 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103043904B (en) |
Cited By (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 (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4120814A (en) * | 1977-02-28 | 1978-10-17 | Hoya Corporation | Fluorophosphate-base laser glasses |
| JPS5645849A (en) * | 1979-09-21 | 1981-04-25 | Hoya Corp | Fluorophosphate visible laser glass |
| 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 |
-
2013
- 2013-01-08 CN CN201310005385.6A patent/CN103043904B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4120814A (en) * | 1977-02-28 | 1978-10-17 | Hoya Corporation | Fluorophosphate-base laser glasses |
| JPS5645849A (en) * | 1979-09-21 | 1981-04-25 | Hoya Corp | Fluorophosphate visible laser glass |
| 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 |
Cited By (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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103043904B (en) | 2015-02-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102659313B (en) | Near-infrared broadband luminescence erbium and thulium-co-doped bismuthate laser glass and preparation method thereof | |
| Qi et al. | Highly Er3+ doped fluorotellurite glass for 1.5 µm broadband amplification and 2.7 µm microchip laser applications | |
| CN109704569B (en) | ZBYA fluoride glass and preparation method thereof | |
| CN111377609B (en) | Preparation method of transparent glass with mid-infrared 3.9 mu m luminescence characteristic at room temperature | |
| CN112010557A (en) | Transparent glass with middle infrared 3.5 mu m luminescence characteristic and preparation method thereof | |
| CN103241948B (en) | Method for preparing oxygen fluorine chlorine tellurate glass with intermediate infrared fluorescence output at 4 mu m | |
| CN103011593A (en) | Erbium neodymium ion co-doped tellurium fluoride glass for emitting 2.7 microns of intermediate infrared light | |
| CN102211873A (en) | 3mu m luminous rare-earth ion-doped fluogermanate laser glass and preparation method thereof | |
| CN103043904B (en) | Ytterbium doped fluorphosphate glass with long fluorescent life and preparation method of glass | |
| CN109252219B (en) | Ytterbium, holmium and dysprosium tri-doped lead fluoride mid-infrared laser crystal and preparation method thereof | |
| CN104743885A (en) | Rare earth-doped oxyfluoride germanate microcrystalline glass and preparation method thereof | |
| CN106186679A (en) | Er ions mid-infrared luminescence fluorine chlorine phosphorus glass and preparation method thereof | |
| CN101618946B (en) | Yb<3+>-doped oxyfluoride transparent microcrystal glass material and preparation method thereof | |
| CN103183472B (en) | Erbium and terbium co-doped fluoride halide phosphate laser glass as well as preparation method and application thereof | |
| CN110510875A (en) | The method for improving rare earth ion doped 2 mu m waveband fluorescent emission of germanate glass | |
| CN105271727A (en) | Erbium-doped mid-infrared luminescent zirconium fluoride zinc-based glass and preparation method thereof | |
| CN112062467B (en) | Rare earth ion doped Er 3+ Preparation method of zirconium magnesium borate glass | |
| CN105347674A (en) | Phosphate neodymium glass with high thermal conductivity | |
| CN108892375A (en) | A kind of SiGe silicate glass and preparation method thereof | |
| CN103359940A (en) | Red light laser glass and preparation method thereof | |
| CN112876069A (en) | Ho3+/Eu3+Co-doped fluorine indium glass capable of generating 3.9 mu m mid-infrared band fluorescence | |
| CN103663963A (en) | Intermediate infrared laser glass and preparation method thereof | |
| CN103288350B (en) | P2O5-BaO-K2O-NaF-Eu<3+>:GGG systemic glass ceramic and preparation method thereof | |
| CN106746621B (en) | erbium-ytterbium co-doped lead-free fluorine germanate glass of high-temperature optical sensing material and preparation method thereof | |
| CN103043903A (en) | Ytterbium-doped fluorphosphate glass with large emission section and preparation method of ytterbium-doped fluorphosphate glass |
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 | ||
| EE01 | Entry into force of recordation of patent licensing contract |
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 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model | ||
| EC01 | Cancellation of recordation of patent licensing contract | ||
| EC01 | Cancellation of recordation of patent licensing contract |
Assignee: Jiangsu Nanyou IOT Technology Park Ltd. Assignor: Nanjing Post & Telecommunication Univ. Contract record no.: 2016320000211 Date of cancellation: 20180116 |
|
| 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: 20150211 Termination date: 20180108 |