CN101481213B - 2 mu m high-phosphorus-content fluorophosphate laser glass and preparation method thereof - Google Patents
2 mu m high-phosphorus-content fluorophosphate laser glass and preparation method thereof Download PDFInfo
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- CN101481213B CN101481213B CN2009100466119A CN200910046611A CN101481213B CN 101481213 B CN101481213 B CN 101481213B CN 2009100466119 A CN2009100466119 A CN 2009100466119A CN 200910046611 A CN200910046611 A CN 200910046611A CN 101481213 B CN101481213 B CN 101481213B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000087 laser glass Substances 0.000 title claims abstract description 15
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 title claims abstract 5
- 239000011521 glass Substances 0.000 claims abstract description 44
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 17
- 239000011574 phosphorus Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 8
- -1 rare earth ions Chemical class 0.000 claims abstract description 5
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 4
- 229910016036 BaF 2 Inorganic materials 0.000 claims abstract description 3
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 3
- 229910017768 LaF 3 Inorganic materials 0.000 claims abstract description 3
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims abstract 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims 1
- 230000009477 glass transition Effects 0.000 claims 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims 1
- 239000006060 molten glass Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 239000013307 optical fiber Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 238000005086 pumping Methods 0.000 abstract description 2
- 239000003365 glass fiber Substances 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000002189 fluorescence spectrum Methods 0.000 description 7
- 238000000137 annealing Methods 0.000 description 6
- 238000005352 clarification Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000005383 fluoride glass Substances 0.000 description 4
- 238000004455 differential thermal analysis Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000005371 ZBLAN Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000382 optic material Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000005365 phosphate glass Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种2μm高磷含量的氟磷酸盐激光玻璃及其制备方法，该玻璃的摩尔百分比组成范围为：Al(PO3)3：18～22％，BaF2：45～50％，MgF2：10～15％，LiF：8～13％，LaF3：0～6％，RF3(R为稀土元素Yb，Er，Tm，Ho)：4～10％。使用熔融法制备该氟磷酸盐激光玻璃，得到的玻璃透明，无析晶，物理化学性质优良，稳定性参数ΔT≥100℃。在980nm或者800nm波长的激光二极管泵浦下可以获得很强的2μm荧光，适用于2μm发光的掺稀土离子的特种玻璃及光纤材料的制备及应用。
A 2μm high-phosphorus content fluorophosphate laser glass and a preparation method thereof, wherein the molar percentage composition range of the glass is: Al(PO 3 ) 3 : 18-22%, BaF 2 : 45-50%, MgF 2 : 10-15%, LiF: 8-13%, LaF 3 : 0-6%, RF 3 (R is a rare earth element Yb, Er, Tm, Ho): 4-10%. The fluorophosphate laser glass is prepared by a melting method, and the obtained glass is transparent, has no crystallization, has excellent physical and chemical properties, and has a stability parameter ΔT≥100°C. Strong 2μm fluorescence can be obtained under the pumping of a laser diode with a wavelength of 980nm or 800nm, and is suitable for the preparation and application of special glass and optical fiber materials doped with rare earth ions for 2μm light emission.
Description
Technical field
The present invention relates to fluorphosphate glass, fluophosphate laser glass of particularly a kind of 2 μ m highs content of phosphorus and preparation method thereof.
Background technology
In recent years, the solid statelaser of rear-earth-doped 2 μ m output has caused people's attention because of its extensive use.Because 1.93 μ m absorption peaks of 2 μ m laser and water are very near, and are shallow to the absorption penetration depth of biological tissue, are a kind of ideal medical lasers; In addition, 2 μ m laser have atmospheric extinction than low, to characteristics such as eye-safes, can be used for long range detection such as coherent Doppler wind-observation radar; Moreover 2 μ m laser apparatus are the optimum pumping sources that obtain 3～5 μ m optical parametric oscillators, have determined its effect militarily.Therefore no matter military or civilian, the development of 2 μ m laser apparatus all has urgent demand and important meaning.
The output of 2 μ m laser at first obtains by the holmium doped crystal.1865, U.S. Johnson reported first mixing Ho
3+The YGA crystal in obtain the output of 2.09 μ m.At present abroad a lot of to the research that obtains 2 μ m output by rear-earth-doped crystal, and that the Ho:YGA laser apparatus has been applied to is clinical medical.But shortcomings such as large-size crystals is difficult to prepare, rear-earth-doped concentration is little have limited its application.And rear-earth-doped glass optical fiber can be avoided these shortcomings of crystalline well.1998, Britain University of Southampton was first at Tm
3+Obtained 2 μ m output in the adulterated silica fibre; In the same year, Japanese NEC Corporation has realized Ho
3+: the 2 μ m output of ZBLAN optical fiber; 2003, French reyn university excited Tm
3+Adulterated ZBLAN fluoride glass has obtained the output of 1.8 μ m.Yet the phonon energy height of silica glass matrix, the rare earth ion fluorescence lifetime in silica glass is short, is difficult to realize narrow pulsewidth Q impulse output; Although and the phonon energy of fluoride glass is low, the relatively poor and harsh preparation condition of its chemical stability and physical strength has also limited its application in 2 μ m outputs.
Fluorphosphate glass is a kind of comparatively ideal substrate material, it combines the advantage of fluoride glass and phosphate glass, glass ingredient adjustability has in a big way been brought the adjustability of a series of optical properties, lower nonlinear refractive index and higher stimulated emission cross section make it be expected to become the superpower laser laser glass, and it has the fluorescence linewidth of broad and higher rare earth ion solubleness simultaneously.On preparation technology, it is than the easier preparation of fluoride glass in addition, and technology is ripe more, and this drawing for high quality, low loss fiber provides guarantee.But, at present both at home and abroad the research that realizes 2 mu m luminous fluorphosphate glasses also seldom is seen in report.
Summary of the invention
Fluophosphate laser glass that provides a kind of 2 μ m highs content of phosphorus and preparation method thereof is provided the technical problem to be solved in the present invention, this glass has good thermostability, can obtain 2 very strong μ m fluorescence down the laser diode-pumped of 980nm or 800nm wavelength.
The concrete technical solution of the present invention is as follows:
A kind of fluorphosphate glass of 2 μ m highs content of phosphorus is characterized in that its molar percentage consists of:
Form mol%
Al(PO
3)
3 18～22％，
BaF
2 45～50％，
MgF
2 10～15％，
LiF 8～13％，
LaF
3 0～6％，
RF
3, (R is rare earth element y b, Er, and Tm, Ho) 4～10%,
Rare earth ion doped mode has: Tm singly mixes, Yb-Tm two mixes, Er-Tm twoly mixes, Yb-Ho twoly mixes, Er-Ho twoly mixes, Tm-Ho twoly mixes, Yb-Tm-Ho three mixes, Er-Tm-Ho three mixes, Yb-Er-Tm three mixes or Yb-Er-Ho three mixes.
The concrete preparation process of the fluophosphate laser glass of the present invention's 2 μ m highs content of phosphorus is as follows:
Selected and according to the molar percentage that above-mentioned glass is formed, calculate corresponding each weight percent of forming, take by weighing each raw material and mix; Compound is put into platinum crucible melt in 1020～1100 ℃ globars electric furnace, the clarification of fusing back is 10～15 minutes fully, glass metal is cast in the mould of preheating; Glass is moved into rapidly has been warming up to glass transformation temperature (T
g) in the following 10 ℃ retort furnace, be incubated 3～4 hours, reduce to room temperature with 10 ℃/hour speed again, glass sample is taken out in the cooling back fully.
The fluorphosphate glass of high content of phosphorus of the present invention has glass transparent, no crystallization, excellent in physical and chemical performance, stability parameter Δ T 〉=100 ℃.Down 2 very strong μ m fluorescence be can obtain the laser diode-pumped of 980nm or 800nm wavelength, the 2 mu m luminous rare-earth-ion-doped special glasss and the preparation and the application of fiber optic materials are applicable to.
Description of drawings
Fig. 1 is the embodiment of the invention 1
#The differential thermal curve of the fluophosphate laser glass of high content of phosphorus.
Fig. 2 is the embodiment of the invention 1
#The fluorescence spectrum of the fluophosphate laser glass of high content of phosphorus under 800nm wavelength laser diode-pumped.
Fig. 3 is the embodiment of the invention 2
#The fluorescence spectrum of the fluophosphate laser glass of high content of phosphorus under 980nm wavelength laser diode-pumped.
Embodiment
Following the invention will be further described with accompanying drawing in conjunction with the embodiments, but should not limit protection scope of the present invention with this.
10 specific embodiments of the fluorphosphate glass of high content of phosphorus of the present invention, as shown in table 1:
Table 1: the glass formula of concrete 10 embodiment
Embodiment 1
#:
Form as in the table 11
#Shown in, concrete preparation process is as follows:
Selected and according in the table 11
#The molar percentage that glass is formed calculates corresponding each weight percent of forming, takes by weighing each raw material and mixes; Compound is put into platinum crucible melt in 1050 ℃ globars electric furnace, the clarification of fusing back is 10～15 minutes fully, glass metal is cast in the mould of preheating; Glass is moved into rapidly in the retort furnace that has been warming up to 435 ℃, is incubated 3～4 hours, reduce to room temperature with 10 ℃/hour speed again, glass sample is taken out in the cooling back fully.
Test result to this glass is as follows:
Get a little sample after the annealing, wear into fine powdered, carry out the differential thermal analysis test with agate mortar.The differential thermal curve of the fluophosphate laser glass of high content of phosphorus of the present invention as shown in Figure 1.
The sheet glass that sample after the annealing is processed into 10 * 20 * 1.5 millimeters also polishes, at laser diode-pumped its fluorescence spectrum of test down of 800nm wavelength.The fluorescence spectrum under 800nm wavelength laser diode-pumped of the fluophosphate laser glass of high content of phosphorus of the present invention as shown in Figure 2.
Embodiment 2
#:
Form as in the table 12
#Shown in, concrete preparation process is as follows:
Selected and according in the table 12
#The molar percentage that glass is formed calculates corresponding each weight percent of forming, takes by weighing each raw material and mixes; Compound is put into platinum crucible melt in 1020 ℃ globars electric furnace, the clarification of fusing back is 10～15 minutes fully, glass metal is cast in the mould of preheating; Glass is moved into rapidly in the retort furnace that has been warming up to 430 ℃, is incubated 3～4 hours, reduce to room temperature with 10 ℃/hour speed again, glass sample is taken out in the cooling back fully.
Test result to this glass is as follows:
Get a little sample after the annealing, wear into fine powdered, carry out the differential thermal analysis test with agate mortar.The sheet glass that sample after the annealing is processed into 10 * 20 * 1.5 millimeters also polishes, at laser diode-pumped its fluorescence spectrum of test down of 980nm wavelength.The fluorescence spectrum under 980nm wavelength laser diode-pumped of the fluorphosphate glass of high content of phosphorus of the present invention as shown in Figure 3.
Embodiment 3
#:
Form as in the table 13
#Shown in, concrete preparation process is as follows:
According in the table 13
#The molar percentage that glass is formed calculates corresponding each weight percent of forming, takes by weighing each raw material and mixes; Compound is put into platinum crucible melt in 1080 ℃ globars electric furnace, the clarification of fusing back is 10～15 minutes fully, glass metal is cast in the mould of preheating; Glass is moved into rapidly in the retort furnace that has been warming up to 450 ℃, is incubated 3～4 hours, reduce to room temperature with 10 ℃/hour speed again, glass sample is taken out in the cooling back fully.
Embodiment 4
#:
Form as in the table 14
#Shown in, concrete preparation process is as follows:
According in the table 14
#The molar percentage that glass is formed calculates corresponding each weight percent of forming, takes by weighing each raw material and mixes; Compound is put into platinum crucible melt in 1100 ℃ globars electric furnace, the clarification of fusing back is 10～15 minutes fully, glass metal is cast in the mould of preheating; Glass is moved into rapidly in the retort furnace that has been warming up to 440 ℃, is incubated 3～4 hours, reduce to room temperature with 10 ℃/hour speed again, glass sample is taken out in the cooling back fully.
Test result to this glass is as follows:
Get a little sample after the annealing, wear into fine powdered, carry out the differential thermal analysis test with agate mortar.
The sheet glass that sample after the annealing is processed into 10 * 20 * 1.5 millimeters also polishes, at laser diode-pumped its fluorescence spectrum of test down of 980nm wavelength.
Embodiment 5
#To 10
#
Composition as 5# in the table 1 to shown in the 10#, concrete preparation process such as embodiment 1#.
To embodiment 3#: done corresponding test to 10# glass, obtained embodiment 1
#Similar result.Experiment shows that the fluorphosphate glass of high content of phosphorus of the present invention has glass transparent, no crystallization, excellent in physical and chemical performance, stability parameter Δ T 〉=100 ℃.Down 2 very strong μ m fluorescence be can obtain the laser diode-pumped of 980nm or 800nm wavelength, the 2 mu m luminous rare-earth-ion-doped special glasss and the preparation and the application of fiber optic materials are applicable to.
Claims (2)
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|---|---|---|---|
| CN2009100466119A CN101481213B (en) | 2009-02-25 | 2009-02-25 | 2 mu m high-phosphorus-content fluorophosphate laser glass and preparation method thereof |
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| CN101481213B true CN101481213B (en) | 2011-04-06 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864597A (en) * | 2010-06-07 | 2010-10-20 | 长春理工大学 | Holmium Thulium Double Doped Gadolinium Gallate Laser Crystal |
| CN101870555B (en) * | 2010-06-11 | 2011-12-07 | 陕西科技大学 | Method for preparing high erbium-doped barium-contained phosphate laser glass |
| CN108911502B (en) * | 2018-06-28 | 2021-05-14 | 华南理工大学 | Fluorine-sulfur phosphate laser glass and preparation method and application thereof |
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