CN106094100A - Europium ion-doped fused quartz fluorescence optical fiber and preparation method thereof - Google Patents
Europium ion-doped fused quartz fluorescence optical fiber and preparation method thereof Download PDFInfo
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- CN106094100A CN106094100A CN201610532500.9A CN201610532500A CN106094100A CN 106094100 A CN106094100 A CN 106094100A CN 201610532500 A CN201610532500 A CN 201610532500A CN 106094100 A CN106094100 A CN 106094100A
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/02—Optical fibres with cladding with or without a coating
- G02B6/02395—Glass optical fibre with a protective coating, e.g. two layer polymer coating deposited directly on a silica cladding surface during fibre manufacture
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- 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
- C03C13/048—Silica-free oxide glass compositions
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- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
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Abstract
The present invention relates to a kind of europium ion-doped fused quartz fluorescence optical fiber and preparation method thereof.In fibre core silica matrix, the particular fiber prefabricated rods doped with trivalent europium element uses MCVD(Modified Chemical Vapor Deposition) technique, preparation, then by drawing optical fibers technique, it is specific europium ion-doped fused quartz fluorescence optical fiber that preform is drawn, and in its fibre core, the doping content of trivalent europium ion is about 2wt% 0.01wt%.Under the effect of exciting light, Eu in this europium ion-doped fused quartz fluorescence optical fiber3+Ion is excited, and produces5D0→7Fn(n=0,1,2,3) transition, sends fluorescence.The strongest fluorescence is positioned at 618nm, for positive trivalent europium ion5D0→7F2Super quick transition.Due to the impact in amorphous state fused quartz complexity change crystal ligand field, the spectral line of this super quick transition has the biggest width, and halfwidth is 13nm.This europium ion-doped optical fiber can have important application in the active optical fiber apparatus such as optical fiber laser, fiber amplifier.
Description
Technical field
The present invention relates to a kind of europium ion-doped fused quartz fluorescence optical fiber and preparation method thereof, specifically a kind of europium ion is mixed
Miscellaneous fused quartz fluorescence optical fiber and preparation method thereof, this optical fiber can emission center wavelength be 618nm's under the effect of exciting light
There is the fluorescence of wider wave-length coverage.
Technical background
As signal transmission medium, fiber amplifier, the optical gain medium of optical fiber laser in communication, to optical fiber system
Make Quality Research optical with optical fiber to be constantly subjected to pay high attention to.1961, American Optical Corporation was public
The Snitzer of department etc. propose optical fiber laser, the conception of amplifier；1966, high Kun proposed optical fiber and is applicable to the communications field, promoted
Enter the great development of human communication cause, and obtain the Nobel Prize of 2009 for this.Hereafter, optical fiber is led in photoelectron technology
Territory and the research of the communications field and application boundless are developed.As the weight constituting the optics such as fiber amplifier, optical fiber laser
Wanting optics ingredient, the development of the special optical fiber with special nature has great importance with exploitation.
The various element that adulterates in a fiber always changes the important means of optical fiber optical property.At present, important in optical fiber
Doped chemical typically have erbium (Er), neodymium (Nd), praseodymium (Pr), holmium (Ho), ytterbium (Yb), thulium (Tm) etc..After these elements that adulterate
The optical property of optical fiber infrared wave band, obtained in-depth study, and fiber amplifier in fiber optic communication field, light
Fibre laser is used widely；And to having the special optical fiber of visible light wave range, fiber amplifier, optical fiber laser research
Less.But special optical fiber, fiber amplifier, optical fiber laser the most also have the heaviest in the optical property of visible light wave range
The researching value wanted and using value.Research developing new special doped fiber and special optical property thereof have important meaning
Justice.
Summary of the invention
The deficiency existed for prior art, it is an object of the invention to provide a kind of europium ion-doped fused quartz fluorescence light
Fine and preparation method thereof, this optical fiber is a kind of can be inspired the europium ion-doped fused quartz that centre wavelength is 618nm fluorescence
Fluorescence optical fiber.
The object of the present invention is achieved like this: a kind of europium ion-doped fused quartz fluorescence optical fiber, at fused quartz optical fiber
Mixed with the material containing trivalent europium element in fibre core, the doping content of trivalent europium ion is about 2wt% ~ 0.01wt%.This fluorescence optical fiber
The fluorescence that centre wavelength is 618nm can be launched, due in the special ligand field of fused quartz substrate under the effect of exciting light
Under effect, the fluorescence of stimulated emission has wider wave-length coverage.Described europium ion-doped fused quartz fluorescence optical fiber is mixed
Miscellaneous trivalent europium elemental substance can select borontrifluoride europium (EuF3) or europiumsesquioxide (Eu2O3) etc..
Described europium ion-doped fused quartz fluorescence optical fiber base substance is configured to fused quartz.Light in this fused quartz substrate
The fine clad doped germanium dioxide composition having specific trace, fibre core is doped with the germanium dioxide of specific trace and trivalent europium ion merit
Can property element.The purpose of the Ge element of fibre core and clad doped different certain content is regulation fibre core and the refractive index of covering, from
And realize optimum optical fiber light-guiding effect and with the mating of other optical fiber；In fibre core, the doping of trivalent europium ion is this fluorescence light
The source of fine fluorescent characteristic.
The preparation method of described europium ion-doped fused quartz fluorescence optical fiber is: utilize MCVD(Modified Chemical
Vapor Deposition) technique, adulterate in the fibre core of optical fiber EuF3Or other materials containing trivalent europium element are (such as: Eu2O3
Deng), produce the fibre core fluorescence optical fiber doped with the trivalent europium ion of the various different sizes of 2wt% ~ 0.01wt% concentration.Gao Pin
The MCVD preparation method of matter preform is as shown in Figure 1.MCVD system is by batch can, graphite furnace, gas circuit, control system, machinery
The part composition such as system, exhaust treatment system.The preparation process of preform can be divided into: chemical deposition process, sedimentary
During Vitrification in vitro, prefabricated rods receive real process.In chemical deposition process, in batch can A, B, C, it is loaded with highly purified trivalent respectively
Europium ion compound (such as EuF3Powder), SiCl4Liquid, GeSi4Liquid.Batch can connects specific gas circuit, is connected with both as anti-
Answering thing again as the high pure oxygen of carrier gas, throughput is controlled, thus ensures that the quantity that its reactant carried participates in reacting can
Control.Being heated by europium ion compound in batch can A in advance, make to be in evaporating state, the high pure oxygen injected in batch can A carries evaporation
Ion is in the quartz ampoule that gas circuit input is pure；Meanwhile, the SiCl in batch can B, C4With GeSi4Also being carried importing by high pure oxygen should
In quartz ampoule.Quartz ampoule is in graphite furnace high-temperature region, and high temperature makes each reacting gas importing in quartz ampoule that multiple chemistry occur
Reaction, according to technological requirement, controlled depositing high purity SiO2And the material such as europium ion compound.The chlorine etc. simultaneously produced
Tail gas is drained by exhaust treatment system.Eventually pass deposition structure sheaf vitrification, prefabricated rods is received the technological processes such as reality and is completed
The preparation of one preform.In preform preparation process, control the deposit thickness of sandwich layer and covering and shape with
And control the content of germanium dioxide mixed for regulation sandwich layer and cladding index, eventually pass wire drawing, fiber can be prepared
Core and the various geometry of covering and the europium ion-doped fused quartz fluorescence optical fiber of various guided mode.That is: this europium ion is mixed
Miscellaneous fused quartz fluorescence optical fiber can be fabricated to common single cladded-fiber and have many cladding lights of variously-shaped covering and fibre core
Fibre, and for the guide-lighting single mode of specific wavelength or multimode fibre.
This europium ion-doped fused quartz fluorescence optical fiber, under the effect of exciting light is injected in the external world, mixes Eu in europium optical fiber3+Ion
It is excited, produces5D0→7Fn(n=0,1,2,3) transition, sends fluorescence.Such as accompanying drawing 5 and accompanying drawing 6, swash at different wave length exciting light
Giving, the emission spectra of the europium ion-doped optical fiber of this example shows: its5D0→7F2The fluorescence quantum yield that energy level transition produces is
Height, centre wavelength is about 618nm.Owing to fused quartz is amorphous substance, microstructure is netted aperiodic structure, and this makes
There is the silica part of complicated change structure to europium ion5D0→7F2The operative condition of super quick transition is the most single, so
When exciting of particular excitation light, the spectral line that this transition produces has the biggest width.
The present invention compared with prior art, has and the most obviously highlights substantive distinguishing features and remarkable advantage:
(1) doped with trivalent europium ion during in the present invention, europium ion-doped optical fiber is characterized by fused quartz fiber core, at molten stone
Under the effect in the special ligand field of English substrate, trivalent europium ion5D0→7FnIn a series of fluorescent transitions 5D0→7F2Energy level transition has
Having higher transition probability, under the effect of extraneous exciting light, this optical fiber can launch the fluorescence of 618nm specific wavelength；And
And due to the amorphous character of fused quartz microstructure so that the microcosmic ligand field of effect trivalent europium ion has certain change
Scope, causes when exciting of particular excitation light, the fluorescence wider width of trivalent europium ion stimulated emission.
(2) it is the coupling needs realizing all-fiber devices, in the manufacturing process of optical fiber, fibre core and surrounding layer size is entered
Row designs targetedly, and by the content of the doped chemical such as europium ion, germanium ion in fibre core is optimized；Make this
Europium ion-doped fused quartz fluorescence optical fiber not only has high fluorescent yield but also can be with conventional single mode, multimode fibre coupling.Tool
Body has following technique to realize: in preform preparation process, controls deposit thickness and shape and the control of sandwich layer and covering
The content of the germanium dioxide being made as regulating sandwich layer and cladding index and mix, through wire drawing, i.e. can prepare fibre core and bag
The various geometry of layer and the europium ion-doped fused quartz fluorescence optical fiber of various guided mode.It is to say, this europium ion is mixed
Miscellaneous fused quartz fluorescence optical fiber can be fabricated to common single cladded-fiber and have many cladding lights of variously-shaped covering and fibre core
Fibre, and for the guide-lighting single mode of specific wavelength or multimode fibre.
(3) in the present invention, europium ion-doped optical fiber is with fused quartz as fibre core with the substrate of covering, so this special optical fiber tool
There is the highest heat resistanceheat resistant damage threshold.
Accompanying drawing explanation
Fig. 1 is the MCVD preparation method schematic diagram of europium ion-doped fused quartz fluorescence optical fiber prefabricated rods
Fig. 2 is the refractive index distribution curve of example europium ion-doped fused quartz fluorescence optical fiber.
Fig. 3 is the absorption line of example europium ion-doped fused quartz fluorescence optical fiber.
Fig. 4 is the exciting light with 532nm laser as injection fibre, the fluorescence of this europium ion-doped fused quartz fluorescence optical fiber with
The luminous contrast photo of common SM28 optical fiber.
Fig. 5 is the exciting light with 532nm laser as injection fibre, and the fluorescence of this europium ion-doped fused quartz fluorescence optical fiber is sent out
Penetrate spectrum.
Fig. 6 is the exciting light with 445nm laser as injection fibre, and the fluorescence of this europium ion-doped fused quartz fluorescence optical fiber is sent out
Penetrate spectrum.
Detailed description of the invention
It is as follows that the preferred embodiments of the present invention combine detailed description:
Embodiment one: this europium ion-doped fused quartz fluorescence optical fiber uses the MCVD optical fiber prefabricating bar system preparation shown in Fig. 1 to mix
The preform of miscellaneous europium, uses graphite furnace wire drawing to become 9/125 europium ion-doped fused quartz fluorescence optical fiber.Described europium from
Son doping fused quartz fluorescence optical fiber, it is characterised in that: this fibre cladding is the fused quartz material doped with germanium dioxide composition, fine
Core is doping functional material in doped with the fused quartz substrate of germanium dioxide composition: borontrifluoride europium.Utilize scanning electron microscopy
It is as shown in the table that the component distributing of each element at its fibre core measured by mirror (SEM).
Fig. 2, Fig. 3 are refractive index distribution curve and the absorption line of this europium ion-doped fused quartz fluorescence optical fiber respectively.
Together with common SM28 single-mode fiber is fused to this europium ion-doped fused quartz fluorescence optical fiber, inject 532nm's
Green laser.As shown in Fig. 4 digital photograph, directly perceived observation can be judged: optical fiber side effusion light color has significant difference；General
Logical single-mode fiber effusion light is the green of 532nm laser, and the color of europium ion-doped fused quartz fluorescence optical fiber effusion light is
The green secondary colour with 618nm red light of 532nm, is shown as orange.Two kinds of optical fiber escape intensity degree contrast in figure, illustrate europium from
Son doping fused quartz fluorescence optical fiber has extremely strong fluorescence conversion efficiency.This with recorded by experimental apparatus this is europium ion-doped
Fibre optical transmission spectrum result is coincide.
Measuring under the effect of 532nm exciting light, the fluorescence spectrum of europium ion-doped fused quartz fluorescence optical fiber, such as Fig. 5 institute
Show.Can obtain each spectral line data such as following table:
The strongest fluorescence is positioned at 617.60nm, and halfwidth is 12.96nm, derives from positive trivalent europium ion5D0→7F2
Transition.
Measuring under the effect of 445nm exciting light, the fluorescence spectrum of europium ion-doped fused quartz fluorescence optical fiber, such as Fig. 6 institute
Show.Can obtain5D0→7FnThe transition of (n=0,1,2,3) series.Compared with 532nm exciting light, when 445nm excitation
The more spectral details such as it is sharp-pointed that the fluorescent emission spectral line of europium-ion-doped fluorescence optical fiber becomes, the Stark splitting of spectral line are opened up
Existing.
Embodiment two: the present embodiment is essentially identical with embodiment one, and special feature is as follows: be different from embodiment one doping
Fluorescent functional material is borontrifluoride europium, and the fluorescent functional material of the doping of the present embodiment is europiumsesquioxide.Two embodiments glimmering
Light characteristic basic simlarity.
Embodiment three: the preparation method of the above embodiments is as follows: 1) utilize the chemical vapour deposition technique (MCVD) of improvement
Technique, prepares the particular fiber prefabricated rods doped with trivalent europium element in fibre core silica matrix；2) by drawing process,
It is specific europium ion-doped fused quartz fluorescence optical fiber that preform draws, and in its fibre core, the doping content of trivalent europium ion is about
For 2wt% ~ 0.01wt%.
Claims (5)
1. the present invention relates to a kind of europium ion-doped fused quartz fluorescence optical fiber, material is fused quartz, it is characterised in that: described molten stone
Mixed with the material containing trivalent europium element in the fibre core of English optical fiber, the doping content of trivalent europium ion is about 2wt% ~ 0.01wt%, should
Fluorescence optical fiber can emission center wavelength be the fluorescence of 618nm under the effect of exciting light, and this fluorescence results from trivalent europium ion
's 5D0→7F2The super quick transition of energy level, and owing to, under the effect in the special ligand field of fused quartz substrate, the fluorescence of stimulated emission has
There is wider wave-length coverage.
Europium ion-doped fused quartz fluorescence optical fiber the most according to claim 1, it is characterised in that: described containing trivalent europium element
Material is borontrifluoride europium (EuF3) or europiumsesquioxide (Eu2O3) etc..
Europium ion-doped fused quartz fluorescence optical fiber the most according to claim 1, it is characterised in that: this fibre cladding is doping
Have the fused quartz material of germanium dioxide composition, fibre core be adulterate in doped with the fused quartz substrate of germanium dioxide composition functional
Element: trivalent europium ion.
4. the preparation method of an europium ion-doped fused quartz fluorescence optical fiber according to claim 1, it is characterised in that:
In preform preparation process, the deposit thickness controlling sandwich layer and covering is regulation sandwich layer and covering folding with shape and control
The content of the germanium dioxide penetrating rate and mix, then after wire drawing, can prepare fibre core and the various geometry of covering and
Various guided mode mix europium fluorescence optical fiber, it may be assumed that this is mixed europium fluorescence optical fiber and can be fabricated to common single cladded-fiber and have each
Kind of shape covering and the multi-clad of fibre core, and for the guide-lighting single mode of specific wavelength or multimode fibre.
The preparation method of europium ion-doped fused quartz fluorescence optical fiber the most according to claim 4, it is characterised in that specifically make
Standby operating procedure is as follows:
1) utilize chemical vapour deposition technique (MCVD) technique of improvement, prepare in fibre core silica matrix doped with trivalent europium unit
The particular fiber prefabricated rods of element；
2) by drawing process, it is specific europium ion-doped fused quartz fluorescence optical fiber that preform is drawn, in its fibre core
The doping content of trivalent europium ion is about 2 wt% ~ 0.01wt%.
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| CN201610532500.9A CN106094100A (en) | 2016-07-08 | 2016-07-08 | Europium ion-doped fused quartz fluorescence optical fiber and preparation method thereof |
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| CN201610532500.9A CN106094100A (en) | 2016-07-08 | 2016-07-08 | Europium ion-doped fused quartz fluorescence optical fiber and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108594359A (en) * | 2018-05-09 | 2018-09-28 | 上海大学 | Niobic acid lithium doping silica fibre |
| CN110247291A (en) * | 2019-06-11 | 2019-09-17 | 上海大学 | A kind of PbS annular core fibre and preparation method thereof amplifying OAM light beam |
| CN114690309A (en) * | 2022-02-23 | 2022-07-01 | 上海大学 | Visible light waveband quartz fluorescent optical fiber and preparation method thereof |
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| CN1617001A (en) * | 2003-11-04 | 2005-05-18 | 奥普托内斯特公司 | Method of fabricating optical fiber or optical device doped with reduced metal ion and/or rare earth ion |
| CN102086089A (en) * | 2010-12-27 | 2011-06-08 | 富通集团有限公司 | Method for manufacturing rare-earth-doped fiber precast rod |
| CN102351235A (en) * | 2009-05-08 | 2012-02-15 | 中国科学院上海硅酸盐研究所 | Rare earth complex, rare earth oxide and preparation method thereof |
| CN203558968U (en) * | 2013-07-22 | 2014-04-23 | 中国科学院西安光学精密机械研究所 | Doping device of optical fiber perform |
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2016
- 2016-07-08 CN CN201610532500.9A patent/CN106094100A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1617001A (en) * | 2003-11-04 | 2005-05-18 | 奥普托内斯特公司 | Method of fabricating optical fiber or optical device doped with reduced metal ion and/or rare earth ion |
| CN102351235A (en) * | 2009-05-08 | 2012-02-15 | 中国科学院上海硅酸盐研究所 | Rare earth complex, rare earth oxide and preparation method thereof |
| CN102086089A (en) * | 2010-12-27 | 2011-06-08 | 富通集团有限公司 | Method for manufacturing rare-earth-doped fiber precast rod |
| CN203558968U (en) * | 2013-07-22 | 2014-04-23 | 中国科学院西安光学精密机械研究所 | Doping device of optical fiber perform |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108594359A (en) * | 2018-05-09 | 2018-09-28 | 上海大学 | Niobic acid lithium doping silica fibre |
| CN110247291A (en) * | 2019-06-11 | 2019-09-17 | 上海大学 | A kind of PbS annular core fibre and preparation method thereof amplifying OAM light beam |
| CN110247291B (en) * | 2019-06-11 | 2021-07-20 | 上海大学 | PbS annular core optical fiber for amplifying OAM light beam and preparation method thereof |
| CN114690309A (en) * | 2022-02-23 | 2022-07-01 | 上海大学 | Visible light waveband quartz fluorescent optical fiber and preparation method thereof |
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Application publication date: 20161109 |