CN110204197A - In infrared erbium ion-doped perfluoro-compound glass - Google Patents
In infrared erbium ion-doped perfluoro-compound glass Download PDFInfo
- Publication number
- CN110204197A CN110204197A CN201910457375.3A CN201910457375A CN110204197A CN 110204197 A CN110204197 A CN 110204197A CN 201910457375 A CN201910457375 A CN 201910457375A CN 110204197 A CN110204197 A CN 110204197A
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- Prior art keywords
- infrared
- perfluoro
- glass
- doped
- compound glass
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- 239000011521 glass Substances 0.000 title claims abstract description 34
- 229910052691 Erbium Inorganic materials 0.000 title claims abstract description 11
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000009477 glass transition Effects 0.000 claims 1
- 238000007578 melt-quenching technique Methods 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 239000005383 fluoride glass Substances 0.000 description 16
- 239000000835 fiber Substances 0.000 description 7
- 239000013307 optical fiber Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 239000000075 oxide glass Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910003439 heavy metal oxide Inorganic materials 0.000 description 2
- -1 sulphur Compound Chemical class 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910016495 ErF3 Inorganic materials 0.000 description 1
- 229910004504 HfF4 Inorganic materials 0.000 description 1
- 229910002319 LaF3 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910007998 ZrF4 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000007507 annealing of glass Methods 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000005387 chalcogenide glass Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000087 laser glass Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- SYHGEUNFJIGTRX-UHFFFAOYSA-N methylenedioxypyrovalerone Chemical compound C=1C=C2OCOC2=CC=1C(=O)C(CCC)N1CCCC1 SYHGEUNFJIGTRX-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 1
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
- C03C13/00—Fibre or filament compositions
- C03C13/04—Fibre optics, e.g. core and clad fibre compositions
- C03C13/041—Non-oxide glass compositions
- C03C13/042—Fluoride glass compositions
-
- 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
- C03C3/32—Non-oxide glass compositions, e.g. binary or ternary halides, sulfides or nitrides of germanium, selenium or tellurium
- C03C3/325—Fluoride glasses
-
- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/10—Compositions for glass with special properties for infrared transmitting glass
Landscapes
- 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)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Glass Compositions (AREA)
Abstract
The present invention provides erbium ion-doped perfluoro-compound glass infrared in a kind of high stability, the molar percentage compositing ranges of the glass are as follows: 27ZrF4-25HfF4- (20-z) BaF2-0.75SrF2-0.25CaF2-4LaF3-3AlF3- (20-x-y) NaF-xLiF-yKF-zErF3 (mol%).Wherein 2≤x≤7；3.5≤y≤6.7；0.5≤z≤6.Using melt quenching method, it is prepared for infrared erbium ion-doped perfluoro-compound glass in high stability.Glass of the invention is greatly improved by ion modification, the stability of glass, high in visible light and infrared band transmitance, and fluorescence lifetime is significantly enhanced.
Description
Technical field:
The present invention relates to technical field of glass materials, and in particular to infrared erbium ion-doped perfluoro-compound glass in one kind.
Background technique:
According to the demand of national defense safety etc., the optical fiber laser of infrared band is paid high attention in 3~5 μm, at
For photoelectronic warfare core.Currently, the gain media of mid-infrared fiber laser is divided into three categories: heavy metal oxide glass, sulphur
Compound glass and heavy metal fluoride glass.Wherein, heavy metal oxide glass chemical stability is good, nonlinear refractive index is high,
But its phonon energy is big, can not penetrate in middle infrared band, so not being suitable for the gain media of mid-infrared fiber laser.
The infrared penetrating region of chalcogenide glass is wide, optical gap is wide, energy absorption caused by free electron transition is few, and loss is low, but its
Easily fusing, damage threshold are smaller at high temperature.And heavy metal fluoride glass is infrared wide through range, rare earth ion dissolution rate
Height, low (the about 400cm of phonon energy-1), the radiationless transition of active ions can be reduced.It theoretically has extremely low damage
Consumption (10-3dB/km).It is much better than oxide optical fiber and sulphur system optical fiber, becomes the core base material of infrared laser.
Fluoride glass fiber is most expected to the core base material as mid-infrared fiber laser, and fluoride glass without
It is suspected to be the core of fluoride glass fiber.Currently, the active loss of fluoride glass fiber is 0.05dB/m, much higher than theoretical damage
Consumption (10-3DB/km), this is because fluoride glass there are still many insufficient places: fluoride glass stability is poor, easily occur
The phenomenon that uneven area and crystallization, to increase the scattering loss of glass.In addition the lower fusion temperature of fluoride glass makes
It is difficult with the effective welding of quartz transport optical fiber, this make fluoride glass fiber in terms of practical performance far below be expected.Cause
This, it is imperative to prepare infrared fluoride glass in high stability.
Summary of the invention:
To solve the above-mentioned problems, the present invention is intended to provide infrared erbium ion-doped perfluoro-compound glass in one kind, thus
Improve fluoride glass stability.
In order to achieve the above object, the component of fluoride glass of the invention is as follows: 27ZrF4-25HfF4-(20-z)
BaF2-0.75SrF2-0.25CaF2-4LaF3-3AlF3-(20-x-y)NaF-xLiF-yKF-zErF3(mol%).Wherein 2≤x≤
7；3.5≤y≤6.7；0.5≤z≤6.
Further, the perfluoro-compound stability, glass is greatly improved, Δ T >=88 DEG C.
Further, average linear transmitance >=90% of the perfluoro-compound glass at 0.4-7.0 μm
Further, infrared cutoff side >=8.0 μm at 50% transmitance of perfluoro-compound glass, ultraviolet cut-on side≤
0.21μm。
Further, the fluorescence lifetime of the perfluoro-compound glass significantly increases, its fluorescence lifetime >=3ms at 2.7 μm,
Its fluorescence lifetime >=16.5ms at 1.5 μm.
The technical effect of invention:
The stability of existing fluoride glass is poor, and Δ T is generally at 80 DEG C or so, the present invention and existing fluoride
Glass phase ratio, stability are greatly improved (Δ T >=88 DEG C).
Existing fluoride glass limited in infrared transmission by component it is very big, especially if mixed with oxide,
The phonon energy of oxide is very high, so oxide glass is very low in infrared region transmitance.And the material that the present invention uses is
Perfluoro-compound has largely expanded glass in the application of infrared regime.Perfluoro-compound glass of the present invention is at 0.4-7.0 μm
Average linear transmitance >=90%, and infrared cutoff side >=8.0 μm at 50% transmitance, ultraviolet cut-on side≤0.21 μ
m.It can satisfy the application demand of ultra wide wave band glass optical fiber.
Detailed description of the invention:
Fig. 1 is that the DTA of glass of the present invention schemes
Fig. 2 is the infrared through figure of glass of the present invention
Fig. 3 is the ultraviolet cut-on edge graph of glass of the present invention
Fig. 4 is the fluorescence lifetime figure of glass of the present invention
Specific embodiment:
Below with reference to embodiment, the invention will be further described, but should not limit the scope of the present invention with this.
Embodiment 1:
Prepared glass matrix group is divided into (molar percentage):
27ZrF4-25HfF4-19.5BaF2-0.75SrF2-0.25CaF2-4LaF3-3AlF3-14.5NaF-2LiF-
3.5KF-0.5ErF3(mol%).
Firstly, using analytically pure ZrF4、HfF4、BaF2、SrF2、CaF2、LaF3、AlF3、NaF、LiF、KF、ErF3As
Raw material weighs raw material according to calculation, raw material is uniformly mixed in crucible, is placed in 850 DEG C of high temperature furnaces and reacts 30min.
It is placed in 250 DEG C or so of annealing furnace immediately after and handles 3h to remove stress existing for inside glass, glass annealing later is cold
But to room temperature.The glass of firing is subjected to cutting and polishing, sheet glass is made, is used for subsequent test.
Using II TG/DTA of EXSTAR S, 7300 apparatus measures DTA, wherein heating rate is 10 K/min.With
70 Fourier infrared spectrograph of VERTEX tests infrared transmission.With Perkin-Elmer Lambda 750UV/VIS/NIR light
Spectrometer has surveyed the UV transmission of sample.The fluorescence lifetime of sample has been surveyed under the excitation of 980nm light with 920 spectrometer of FLSP.
Remaining each instance parameter is as follows:
| Embodiment | x | y | z | ΔT(℃) | Infrared cutoff side (μm) | Fluorescence lifetime (ms) |
| 1 | 2 | 3.5 | 0.5 | 88.05 | 8.1 | 1.66 |
| 2 | 3 | 3.5 | 1 | 89.96 | 8.1 | 1.64 |
| 3 | 3 | 5 | 3 | 92.30 | 8.0 | 1.65 |
| 4 | 5 | 5 | 5 | 91.93 | 8.0 | 1.69 |
| 5 | 5 | 6.7 | 5 | 90.77 | 8.0 | 1.71 |
| 6 | 7 | 6.7 | 6 | 88.57 | 8.0 | 1.68 |
Claims (5)
1. infrared erbium ion-doped perfluoro-compound glass in one kind, it is characterised in that the molar percentage of its component are as follows: 27ZrF4-
25HfF4-(20-z)BaF2-0.75SrF2-0.25CaF2-4LaF3-3AlF3-(20-x-y)NaF-xLiF-yKF-zErF3
(mol%), wherein 2≤x≤7；3.5≤y≤6.7；0.5≤z≤6.
2. infrared erbium ion-doped perfluoro-compound glass according to claim 1, which is characterized in that thermal stability Δ T
>=88 DEG C, Δ T=Tx-Tg, wherein Tx is starting crystallization temperature, and Tg is glass transition temperature.
3. infrared erbium ion-doped perfluoro-compound glass according to claim 1, which is characterized in that the perfluor of 1mm thickness
Compound glass is in 25 DEG C of 0.4-7.0 μm of average linear transmitance >=90% at room temperature.
4. infrared erbium ion-doped perfluoro-compound glass according to claim 1, it is characterised in that perfluoro-compound glass
Infrared cutoff side >=8.0 μm at 50% transmitance, ultraviolet cut-on side≤0.21 μm.
5. infrared erbium ion-doped perfluoro-compound glass according to claim 1, it is characterised in that perfluoro-compound glass
Fluorescence lifetime >=3ms at 2.7 μm, fluorescence lifetime >=16.5ms at 1.5 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910457375.3A CN110204197A (en) | 2019-05-29 | 2019-05-29 | In infrared erbium ion-doped perfluoro-compound glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910457375.3A CN110204197A (en) | 2019-05-29 | 2019-05-29 | In infrared erbium ion-doped perfluoro-compound glass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110204197A true CN110204197A (en) | 2019-09-06 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910457375.3A Pending CN110204197A (en) | 2019-05-29 | 2019-05-29 | In infrared erbium ion-doped perfluoro-compound glass |
Country Status (1)
| Country | Link |
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| CN (1) | CN110204197A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111995255A (en) * | 2020-08-26 | 2020-11-27 | 中国科学院上海光学精密机械研究所 | Low thermal expansion perfluorinated glass ceramic and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02145457A (en) * | 1988-11-25 | 1990-06-04 | Sumitomo Electric Ind Ltd | Fluoride glass optical fiber |
| JPH08245236A (en) * | 1995-03-10 | 1996-09-24 | Nippon Telegr & Teleph Corp <Ntt> | Optical fiber for optical amplification, optical amplifying method and device using the same |
| CN105392746A (en) * | 2013-07-19 | 2016-03-09 | 中央硝子株式会社 | Phosphor-dispersed glass and method for producing same |
-
2019
- 2019-05-29 CN CN201910457375.3A patent/CN110204197A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02145457A (en) * | 1988-11-25 | 1990-06-04 | Sumitomo Electric Ind Ltd | Fluoride glass optical fiber |
| JPH08245236A (en) * | 1995-03-10 | 1996-09-24 | Nippon Telegr & Teleph Corp <Ntt> | Optical fiber for optical amplification, optical amplifying method and device using the same |
| CN105392746A (en) * | 2013-07-19 | 2016-03-09 | 中央硝子株式会社 | Phosphor-dispersed glass and method for producing same |
Non-Patent Citations (3)
| Title |
|---|
| C.H. KAM 等: "Near infrared to red and yellow to blue upconversion emission from Pr3+：ZrF4-BaF2-LaF3-YF3-AlF3-NaF glasses", 《JOURNAL OF QUANTITATIVE SPECTROSCOPY &RADIATIVE TRANSFER》 * |
| W.C. HASZ 等: "Comparison of physical properties of ZrF4- and HfF4-based melts and glasses", 《JOURNAL OF NON-CRYSTALLINE SOLIDS》 * |
| 沈德元 等: "《中红外激光器》", 31 December 2005, 国防工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111995255A (en) * | 2020-08-26 | 2020-11-27 | 中国科学院上海光学精密机械研究所 | Low thermal expansion perfluorinated glass ceramic and preparation method thereof |
| CN111995255B (en) * | 2020-08-26 | 2022-10-11 | 中国科学院上海光学精密机械研究所 | Low thermal expansion perfluorinated glass ceramic and preparation method thereof |
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Effective date of registration: 20200520 Address after: No. 328, Daqiao South Road, Chunjiang street, Fuyang District, Hangzhou City, Zhejiang Province Applicant after: Hangzhou Institute of Optics and precision machinery Address before: 201800 Qinghe Road 390, Shanghai, Jiading District Applicant before: SHANGHAI INSTITUTE OF OPTICS AND FINE MECHANICS CHINESE ACADEMY OF SCIENCES |
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Application publication date: 20190906 |