CN102086089A - Method for manufacturing rare-earth-doped fiber precast rod - Google Patents
Method for manufacturing rare-earth-doped fiber precast rod Download PDFInfo
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- CN102086089A CN102086089A CN 201010605713 CN201010605713A CN102086089A CN 102086089 A CN102086089 A CN 102086089A CN 201010605713 CN201010605713 CN 201010605713 CN 201010605713 A CN201010605713 A CN 201010605713A CN 102086089 A CN102086089 A CN 102086089A
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- Prior art keywords
- cigarette ash
- rare earth
- sandwich layer
- loose cigarette
- doped fiber
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
- C03B37/01—Manufacture of glass fibres or filaments
- C03B37/012—Manufacture of preforms for drawing fibres or filaments
- C03B37/014—Manufacture of preforms for drawing fibres or filaments made entirely or partially by chemical means, e.g. vapour phase deposition of bulk porous glass either by outside vapour deposition [OVD], or by outside vapour phase oxidation [OVPO] or by vapour axial deposition [VAD]
- C03B37/018—Manufacture of preforms for drawing fibres or filaments made entirely or partially by chemical means, e.g. vapour phase deposition of bulk porous glass either by outside vapour deposition [OVD], or by outside vapour phase oxidation [OVPO] or by vapour axial deposition [VAD] by glass deposition on a glass substrate, e.g. by inside-, modified-, plasma-, or plasma modified- chemical vapour deposition [ICVD, MCVD, PCVD, PMCVD], i.e. by thin layer coating on the inside or outside of a glass tube or on a glass rod
- C03B37/01807—Reactant delivery systems, e.g. reactant deposition burners
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
- C03B37/01—Manufacture of glass fibres or filaments
- C03B37/012—Manufacture of preforms for drawing fibres or filaments
- C03B37/014—Manufacture of preforms for drawing fibres or filaments made entirely or partially by chemical means, e.g. vapour phase deposition of bulk porous glass either by outside vapour deposition [OVD], or by outside vapour phase oxidation [OVPO] or by vapour axial deposition [VAD]
- C03B37/018—Manufacture of preforms for drawing fibres or filaments made entirely or partially by chemical means, e.g. vapour phase deposition of bulk porous glass either by outside vapour deposition [OVD], or by outside vapour phase oxidation [OVPO] or by vapour axial deposition [VAD] by glass deposition on a glass substrate, e.g. by inside-, modified-, plasma-, or plasma modified- chemical vapour deposition [ICVD, MCVD, PCVD, PMCVD], i.e. by thin layer coating on the inside or outside of a glass tube or on a glass rod
- C03B37/01807—Reactant delivery systems, e.g. reactant deposition burners
- C03B37/01838—Reactant delivery systems, e.g. reactant deposition burners for delivering and depositing additional reactants as liquids or solutions, e.g. for solution doping of the deposited glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/20—Doped silica-based glasses doped with non-metals other than boron or fluorine
- C03B2201/28—Doped silica-based glasses doped with non-metals other than boron or fluorine doped with phosphorus
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
- C03B2201/31—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with germanium
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
- C03B2201/34—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with rare earth metals, i.e. with Sc, Y or lanthanides, e.g. for laser-amplifiers
- C03B2201/36—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with rare earth metals, i.e. with Sc, Y or lanthanides, e.g. for laser-amplifiers doped with rare earth metals and aluminium, e.g. Er-Al co-doped
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacture, Treatment Of Glass Fibers (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses a method for manufacturing a rare-earth-doped fiber precast rod. The method comprises the following steps of: depositing a loose cigarette ash core layer on the inner surface of a quartz deposition pipe at a deposition temperature; then, soaking the loose cigarette ash core layer in a rare-earth-contained solution so that rare-earth elements in the solution are absorbed in holes of the loose cigarette ash core layer; then, arranging the deposition pipe in a sintering furnace and drying the loose cigarette ash core layer with inert gases; sintering the loose cigarette ash core layer at a low temperature into a glass layer; and finally, melting and concentrating the deposition pipe into a solid precast rod. The invention can effectively control the volatilization of P2O5, GeO2 and rare-earth elements of the loose cigarette ash core layer in the drying and sintering processes so that the high-concentration rare-earth elements can be doped in the precast rod core layer and can be more uniformly distributed on the precast rod core layer in the radial direction. Optical fiber drawn by the rare-earth-doped fiber precast rod which is manufactured in the invention can be used for manufacturing fiber amplifiers, fiber lasers and fiber sensors.
Description
Technical field
The present invention relates to the manufacture method of preform, particularly relate to manufacture method as the preform of a kind of sandwich layer doped with rare-earth elements of fiber amplifier, optical fiber laser and Fibre Optical Sensor.
Background technology
The rare-earth doped optical fibre that doped with rare-earth elements obtains in the silica fibre can be used for making fiber amplifier, optical fiber laser and Fibre Optical Sensor.With the erbium-doped fiber is erbium-doped fiber amplifier (the erbium doped fiber amplifier of gain media, EDFA), not only solved the restriction of decay to optical-fiber network transfer rate and distance, and started the wavelength-division multiplex technique of 1.55 mu m wavebands, thereby ultra-high speed, vast capacity, over distance wavelength-division multiplex, dense wave division multipurpose, full light transmission, soliton transmission etc. will be become a reality.And with the Yb dosed optical fiber be gain media optical fiber laser especially with its good beam quality, compact construction, be easy to plurality of advantages such as integrated, be widely used in fields such as industry, medical treatment, military affairs, and be expected to replace most of traditional superpower laser.In addition, rare-earth doped optical fibre can also be used to make Fibre Optical Sensor.
Optical fiber is drawn by prefabricated rods and forms.Gas phase deposition technology is generally adopted in the manufacturing of preform at present, comprise axial vapor deposition method (vapor axial deposition, VAD), outside vapour deposition process (outside vapor deposition, OVD), modified chemical vapor deposition process (MCVD) (modified chemical vapor deposition, MCVD) and plasma chemical vapor deposition (plasma chemical vapor deposition, PCVD).Make the required raw material of prefabricated rods at normal temperatures normally gas (as O
2, Cl
2Deng) or liquid with higher vapor pressure (as SiCl
4, GeCl
4Deng).And when making the required rare earth dopant (being generally rare earth halide) of rare-earth doped optical fibre and only being heated to 500～1000 ℃, could guarantee enough vapour pressures, make its can with other popular response thing gas participation vapor deposition reaction.Therefore adopt conventional prefabricated rods manufacturing technology to be difficult to realize rear-earth-doped.The method that is used to make the rare-earth doped optical fibre prefabricated rods in the prior art comprise gas phase doping method, solute doping method, the direct sedimentation of nanoparticle (Direct Nanoparticle Deposition, DND), sol-gel method and solution atomization method.Wherein most widely used is the solute doping method.J. E. Townsend etc. is at " Solution-doping technique for fabrication of rare-earth-doped fibers ", Electronic letters, 1987,23 (7), the 329-331 page or leaf has been described and has been adopted the MCVD binding soln to soak the method for making rear-earth-doped prefabricated rods: (a) contain SiO with ordinary method formation of deposits in quartzy deposited tube 12
2-P
2O
5The optical fiber inner cladding 13 of-F, wherein P
2O
5Can reduce glass viscosity, make molten contracting be more prone to P
2O
5Doping improved quartzy specific refractory power, mix F and can reduce specific refractory power, thereby make the specific refractory power of inner cladding and the refractive index match of quartzy deposited tube.Oxyhydrogen flame blowtorch 11 is used for heating deposition pipe 12.(b) reduce the loose cigarette ash sandwich layer 14 of temperature deposition, shown in Figure 1A of the present invention.(c) take off deposited tube 12, in the solution 10 that contains rare earth element, soaked about one hour, shown in Figure 1B of the present invention.(d) after soaking well, clean loose cigarette ash sandwich layer 14 with acetone, and reinstall on the lathe.(e) be warming up to 600 ℃ and feed Cl simultaneously
2Dehydrate.(f) the loose cigarette ash sandwich layer 14 of sintering is a transparent glass layer, shown in Fig. 1 C of the present invention.(g) shorten solid prefabricated rods into the deposited tube 12 that dehydrates is at high temperature molten.Fig. 2 A of the present invention and Fig. 2 B show before deposited tube 12 and loose cigarette ash sandwich layer 14 molten the contracting respectively and the cross sectional representation after molten the contracting.
The cluster phenomenon takes place in rare earth element easily in quartz substrate, limited the doping content of rare earth element.Mix Al in the silica fibre sandwich layer
2O
3The cluster effect that can effectively suppress rare earth element improves the solubleness of rare earth element in quartz.While Al
2O
3Can reduce the volatilization of rare earth element.Yet Al
2O
3Doping content in quartz is subjected to the restriction of himself solubleness, works as Al
2O
3Concentration when surpassing 4mol%, will cause phase-splitting and crystallization.Know, mix P in the quartz
2O
5Can stop Al
2O
3Crystallization.P
2O
5To mix be at SiCl during by loose cigarette ash sandwich layer deposition
4Add POCl in the air-flow
3Gas is realized.High density P
2O
5Mix and not only can guarantee high-concentration dopant Al
2O
3Can not produce phase-splitting and crystallization, but also improve the doping content of rare earth element, and can improve the performance of rare earth element.
On the other hand, doped with Ge O in the fiber core layer
2, behind ultraviolet radiation, can cause the variation of defective in the optical fiber, thereby cause change of refractive.Utilize this principle, germnium doped fiber can form fiber grating through periodically producing index modulation.The photosensitivity of germnium doped fiber depends on the concentration of germanium in the optical fiber, and the concentration of germanium is high more, at high temperature decomposites more GeO, and the photosensitivity of optical fiber is just strong more.
Prior art adopts MCVD binding soln doping method manufacturing sandwich layer to contain P
2O
5Perhaps GeO
2The rare earth doped fiber prefabricated rods, can produce following problem: after (1) solution soaking is finished, deposited tube is reinstalled on the MCVD lathe P of loose cigarette ash sandwich layer internal surface in dry, the agglomerating process
2O
5Perhaps GeO
2Can produce volatilization, thereby cause the component of prefabricated rods sandwich layer to change, influence the final use properties of optical fiber.(2) P
2O
5And GeO
2The doping quartz can improve specific refractory power, POCl when depositing by controlling loose cigarette ash sandwich layer
3, GeCl
4With SiCl
4Gas flow ratio can control the parameter of optical fiber such as numerical value aperture (numerical aperture, NA), and P
2O
5, GeO
2Volatilization cause the control of optical fiber parameter become the difficulty.(3) field intensity of transmission light is approximated to Gaussian distribution in the optical fiber, and light intensity is in axis place maximum, and successively decreases to the periphery.Therefore the radial distribution of rare earth element in fiber core layer needs strict control, thereby makes its efficient reach maximization.Yet in drying, the sintering process, rare earth element can be along with P
2O
5Perhaps GeO
2Volatilization and run off, the distribution that finally causes rare earth element radially to be gone up at the preform sandwich layer is the central concave shape.
Summary of the invention
The technical assignment of the technical problem to be solved in the present invention and proposition is to overcome prior art to adopt MCVD binding soln doping method manufacturing sandwich layer to contain P
2O
5Perhaps GeO
2The existing loose cigarette ash sandwich layer that contains rare earth element of rare earth doped fiber prefabricated rods P in dry, sintering process
2O
5, GeO
2The volatilization problem, and by P
2O
5, GeO
2Volatilization and the optical fiber parameter that causes changes and rare earth element in distribution center's depression problem that the preform sandwich layer is radially gone up, a kind of method of making the rare earth doped fiber prefabricated rods is provided.
Purpose of the present invention is achieved through the following technical solutions: a kind of method of making the rare earth doped fiber prefabricated rods is characterized in that may further comprise the steps:
The loose cigarette ash sandwich layer of internal surface deposition at quartzy deposited tube;
In containing the solution of rare earth element, soak described loose cigarette ash sandwich layer, the rare earth element in the solution is adsorbed in the hole of loose cigarette ash sandwich layer;
In sintering oven, use rare gas element and the described loose cigarette ash sandwich layer of dry chlorine;
The described loose cigarette ash sandwich layer of sintering is a glass coating;
Molten described quartzy deposited tube and the glass coating of contracting is solid preform.
As the optimization technique means, adopt the MCVD method to deposit described loose cigarette ash sandwich layer.
As the optimization technique means, described deposition is that the mixed gas with oxygen, silicon tetrachloride and impurity gas feeds and makes mixed gas generation chemical reaction form soot deposits by heating (as by the heating of oxyhydrogen flame blowtorch, also can be that other heating unit such as resistance furnace heat) in the described quartzy deposited tube to form described loose cigarette ash sandwich layer to the deposited tube internal surface; Described impurity gas is germanium tetrachloride or phosphorus oxychloride or the combination of the two.When implementing described sintering with the mixed gas of described impurity gas and oxygen, helium by described loose cigarette ash sandwich layer.
As the optimization technique means, described sedimentary temperature is 1200-1700 ℃.
As the optimization technique means, contain muriate or nitrate and a kind of co-dopant of at least a rare earth element in the described solution, described rare earth element ordination number is 57-71, described co-dopant is aluminum chloride or aluminum nitrate.
As the optimization technique means, described sintering carries out in sintering oven.
As the optimization technique means, described exsiccant temperature is 600-1300 ℃, and be 0.5-2 hour time of drying.
As the optimization technique means, described rare gas element when dry is a nitrogen.
As the optimization technique means, described agglomerating temperature is 1500-1600 ℃.
As the optimization technique means, the solvent of described solution is water or ethanol.
As the optimization technique means, the time that described loose cigarette ash sandwich layer soaks in solution is preferably 1 hour for being at least 0.5 hour.
The invention has the beneficial effects as follows: the sintering method of prior art is because torch flame temperature height causes P in the loose cigarette ash sandwich layer
2O
5, GeO
2Volatilization.Heating region generally only is about 2cm simultaneously, and the fluctuation of torch flame temperature and the fluctuation in the axial direction of deposited tube wall thickness all can cause the inhomogeneous of loose cigarette ash sandwich layer Heating temperature, thereby causes the axial ununiformity of prefabricated rods sandwich layer component and specific refractory power.By adopting the loose cigarette ash sandwich layer of sintering oven low-temperature sintering, make heat can be distributed in loose cigarette ash sandwich layer inside more equably, reduced the fluctuation of prefabricated rods sandwich layer component.The method according to this invention can effectively be controlled loose cigarette ash sandwich layer P in drying, sintering process
2O
5, GeO
2Volatilization, thereby the control of optical fiber parameter such as NA is more prone to, the further rare earth element that the prefabricated rods sandwich layer can doped with high concentration, the distribution that rare earth element is radially gone up at the prefabricated rods sandwich layer is more even.
Description of drawings
Figure 1A is the synoptic diagram of the loose cigarette ash sandwich layer of existing method deposition.
Figure 1B is existing method is soaked loose cigarette ash sandwich layer in solution a synoptic diagram.
Fig. 1 C is that the loose cigarette ash sandwich layer of existing method sintering is the synoptic diagram of transparent glass layer.
Fig. 2 A is the cross sectional representation of molten contract preceding deposited tube and loose cigarette ash sandwich layer.
Fig. 2 B is for melting the cross sectional representation of the deposited tube after contracting and the cigarette ash sandwich layer that loosens.
Fig. 3 A is the synoptic diagram of the loose cigarette ash sandwich layer of the inventive method deposition.
Fig. 3 B is the inventive method is soaked loose cigarette ash sandwich layer in solution a synoptic diagram.
Fig. 3 C is that the inventive method is dry in sintering oven, the synoptic diagram of the loose cigarette ash sandwich layer of sintering.
Number in the figure explanation: 11-blowtorch, 12-deposited tube, 13-inner cladding, the 14-cigarette ash sandwich layer that loosens, the 15-furnace core tube, the 16-heating member, 17-draws bar, 18-air feed port, 19-venting port.
Embodiment
The present invention will be further described below in conjunction with Figure of description.
The method of manufacturing rare earth doped fiber prefabricated rods of the present invention may further comprise the steps:
At first quartzy deposited tube 12 is polished (as the thermal-flame polishing), in order to eliminate cut impurity, surface irregularity and the collapsed cell on deposited tube 12 surfaces.
Then contain SiO in deposited tube 12 internal surfaces deposition
2-P
2O
5The inner cladding 13 of-F, deposition method can be used existing method.P wherein
2O
5Can reduce glass viscosity, make molten contracting be more prone to P
2O
5Doping improved quartzy specific refractory power, mix F and can reduce specific refractory power, thereby make the specific refractory power of inner cladding 13 and the refractive index match of quartzy deposited tube 12.In the deposition process, the accurate control that feeds the flow of deposited tube 12 unstripped gases can (deposit used raw material SiCl by entering foamed pot
4, GeCl
4Be liquid under the normal temperature, SiCl
457.65 ℃ of boiling points, GeCl
4Therefore 84 ℃ of boiling points need carrier gas such as oxygen to take it out of feeding deposited tube by foamed pot; MCVD all adopts these means) carrier gas flux or directly the pilot-gas flow realize.Deposited tube 12 and flow through oxyhydrogen flame blowtorch 11 heating of gas by deposited tube 12 outsides in the pipe, for deposited tube 12 and interior gas thermally equivalent thereof, deposited tube should rotate along its axis in deposition process, and the tube wall of deposited tube and the distance of blowtorch just can be consistent, thereby are heated evenly.The temperature of deposited tube 12 is measured by infrared thermometer.Temperature controlling is based on computer and MFC(mass flowmeter) to the adjusting of gas flow.When reactant gases enters the hot-zone that produces because of oxyhydrogen flame blowtorch 11 heating deposition pipes through the process that the end (inlet end) of deposited tube 12 enters by deposited tube 12, reach the needed temperature of reaction and will form glass particle.These glass particles flow with the other end (exit end) of heated air to deposited tube 12, when reaching the cold zone of deposited tube 12, because the thermograde that the footpath makes progress, thereby cause that glass particle deposits to the tube wall thermophoresis.Not sedimentary glass particle then flows in the loose body particle collector with waste gas.Blowtorch 11 moves (being that the direction that moves of oxyhydrogen flame blowtorch 11 is identical with flowing to of reactant gases) from the inlet end of deposited tube 12 to exit end in deposition process, when blowtorch 11 arrives deposited tubes 12 terminal, will rapid return to the gas inlet end of deposited tube 12.Along with moving of blowtorch 12, sinter particle into very thin glass coating from the heat of blowtorch 11.Thereby depositing temperature should enough highly make the deposited particles vitrifying saturating, exceeds but should keep not making deposited tube 12 to deform.Blowtorch 11 periodically moves around, and formation in layer contains the inner cladding 13 of specific components in deposited tube 12, and inner cladding 13 effect is to prevent that impurity in the deposited tube 12 is (as OH
-) be diffused into sedimentary subsequently loose cigarette ash sandwich layer 14.
Reduce temperature subsequently, as the loose cigarette ash sandwich layer 14 of Fig. 3 A deposition.Depositing temperature should be not too high, sinters glass coating into to avoid loose cigarette ash sandwich layer 14, causes sandwich layer 14 porositys low excessively, can't adsorb the enough solution that contains rare earth element 10.Depositing temperature should be not low excessively yet simultaneously, has enough intensity to guarantee loose cigarette ash sandwich layer 14, prevents that loose cigarette ash sandwich layer 14 comes off in the solution soaking process.Therefore, depositing temperature is a key parameter of making the rare earth doped fiber prefabricated rods, and depositing temperature scope of the present invention is 1200-1700 ℃ (when specifically implementing, this temperature is corresponding with the component of loose cigarette ash sandwich layer, different component depositing temperature differences).For doping content that improves rare earth element or the photosensitivity that increases optical fiber, need in loose cigarette ash sandwich layer, mix POCl
3Gas or GeCl
4Gas forms P
2O
5Or GeO
2Mix.P
2O
5Or GeO
2SiCl when adulterated concentration deposits by the loose cigarette ash sandwich layer 14 of MFC control
4Gas flow and POCl
3Gas flow or GeCl
4The ratio of gas flow realizes.Preparation high-concentration dopant P
2O
5Loose cigarette ash sandwich layer 14 time, needing to adopt oppositely, deposition prevent the excessive sintering of deposition process to loose cigarette ash sandwich layer 14.Oppositely deposition is that the direction that moves of oxyhydrogen flame blowtorch 11 is opposite with the flow direction of reactant gases.
The deposited tube 12 that will contain loose cigarette ash sandwich layer 14 then is immersed in (referring to Fig. 3 B) in the solution 10 that contains rare earth element.Contain muriate or nitrate and a kind of co-dopant of at least a rare earth element in the solution, the rare earth element ordination number is 57-71, and co-dopant is aluminum chloride or aluminum nitrate.Wherein the solvent of solution is water or ethanol.The concentration of rare earth chloride or nitrate is 0.001-0.1 mol/L, and the concentration of aluminum chloride or aluminum nitrate is 0-1.25 mol/L.The time of soaking is answered sufficiently long, so that contain in the hole that the solution of rare earth element can fully enter loose cigarette ash sandwich layer 14.Soak time was at least 0.5 hour, was preferably 1 hour.
After immersion is finished, discharge rest solution.Shown in Fig. 3 C deposited tube 12 is installed on the anchor clamps that draw bar 17, bar 17 is drawn in slow decline enters in the sintering oven deposited tube 12.Sintering oven is by heating member 16(resistance furnace or other heating unit) heating furnace core tube 15, heating zone length 400mm(± 25 ℃), deposited tube 12 is positioned at heating zone central authorities.Gas enters sintering oven from air feed port 18, flows through loose cigarette ash sandwich layer 14 from the deposited tube lower port, flows out from sintering oven venting port 19 through deposited tube 12 upper port.Drawing bar 17 speed of rotation is 3-10rpm.At first feed inert nitrogen gas and purge, elevated temperature is to 600-1300 ℃ then, and aerating oxygen, chlorine and helium dehydrate, to remove the OH in the loose cigarette ash sandwich layer
-Its reaction equation is:
2Cl
2?+?2H
2O?=?O
2?+?4HCl
2Si-OH?+?2Cl
2?=?2Si-Cl?+?O
2?+?2HCl
The main effect of He is auxiliary dehydration, atomic volume is little, diffusivity is high, the characteristics of stable performance because He has, penetrate into inside and can the performance of prefabricated rods not exerted an influence so it is easy to hole by loose cigarette ash sandwich layer 14, helium is brought Cl on the one hand into
2, O
2, make it fully to contact with loose cigarette ash sandwich layer 14, on the other hand, the waste gas and the moisture of dehydration reaction is brought out; O
2Effect be in order to prevent doped element (for example Ge, P) and Cl
2Halogenating reaction taking place volatilize away, causes Ge, P to run off.Be 0.5-2 hour time of drying.In the exsiccant process, rare earth chloride generally is converted into oxide compound under lower temperature.Adopt alap oxidizing temperature can reduce the volatilization of rare earth element.
After the drying and dehydrating, feed He, O
2Carry out sintering, the agglomerating temperature range is 1500-1600 ℃.The mixed gas of the contained impurity gas of oxygen, helium and deposition sandwich layer is by described loose cigarette ash sandwich layer 14 in the sintering step.Because 14 P that mixed in loose cigarette ash sandwich layer
2O
5, then when sintering, feed POCl
3Flow through sandwich layer 14 and generate P with oxygen reaction
2O
5The volatilization of compensation P.
After sintering is finished, deposited tube 12 is promoted to the cooling of sintering oven outside, the cross section that attaches the deposited tube that inner cladding 13, loose cigarette ash sandwich layer 14 are arranged this moment is shown in Fig. 2 A.At last deposited tube 12 is reinstalled on the MCVD lathe, (2200-2300 ℃) melts the transparent solid glass rods that shorten into shown in Fig. 2 B with inner cladding 13, loose cigarette ash sandwich layer 14 with deposited tube 12 under the high temperature.
Embodiment 1
Quartzy deposited tube 12 carries out high temperature (1800-2100 ℃) flame polish, eliminates cut impurity, surface irregularity and the collapsed cell on deposited tube 12 surfaces.Contain SiO for 10 layers in deposited tube 12 internal surfaces deposition under 1870 ℃ (general in 1800-2000 ℃ temperature range all can)
2-P
2O
5To be blowtorch 11 move 10 times and carry out deposition 10 times to exit end from the inlet end of deposited tube 12 for 10 layers of described depositions of the inner cladding 13(of-F, actual formed 10 layers of inner cladding 13 boundlessness on the transverse section, show as successive one deck, the deposition that following examples are addressed is same notion for 10 layers).Reduce depositing temperature to 1280 ℃, feed SiCl
4 And GeCl
4The gas aggradation cigarette ash sandwich layer 14 that loosens.The deposited tube 12 that will contain loose cigarette ash sandwich layer 14 is immersed in the ErCl that contains 0.01 mol/L
36H
2O, the YbCl of 0.05 mol/L
36H
2The AlCl of O and 0.3 mol/L
36H
2In the aqueous solution 10 of O about 1 hour.Subsequently, discharge excessive solution, deposited tube 12 is put into sintering oven, feed nitrogen and blow 30min, then progressively elevated temperature to 600-1300 ℃ of (the dry needs between a heating zone, in this temperature range all are drying processs), aerating oxygen, chlorine and helium dehydrate, and be 1.5 hours time of drying.After the drying and dehydrating, feed He, O
2Loose cigarette ash sandwich layer 14 is carried out sintering, and the agglomerating temperature is 1500 ℃.Feed GeCl in the sintering process
4Gas stream is crossed loose cigarette ash sandwich layer 14.At last deposited tube 12 is reinstalled on the MCVD lathe, shorten transparent solid glass rod into deposited tube 12 is molten under 2200 ℃ (in temperature ranges of 2000-2300 ℃ all can).(electron probe microanalysis, EPMA) test obtains GeO to present embodiment preform sandwich layer through electronic probe
2Concentration is 10wt%, Yb
2O
3Concentration be 1 wt%, Er
2O
3Concentration be 0.2 wt%, be drawn into optical fiber after, its numerical aperture is 0.12, naked fine diameter is 125 μ m, core diameter is 10 μ m, can be used for making Erbium-Doped Fiber Amplifier.
Embodiment 2
Quartzy deposited tube 12 carries out the thermal-flame polishing, eliminates cut impurity, surface irregularity and the collapsed cell on deposited tube 12 surfaces.Contain SiO for 10 layers in deposited tube 12 internal surfaces deposition under 1870 ℃
2-P
2O
5The inner cladding 13 of-F.1550 ℃ are adopted oppositely deposition down, feed SiCl
4 And POCl
3The gas aggradation cigarette ash sandwich layer 14 that loosens.The deposited tube 12 that will contain loose cigarette ash sandwich layer 14 is immersed in the YbCl that contains 0.07 mol/L
36H
2The AlCl of O and 0.5 mol/L
36H
2In the aqueous solution 10 of O about 1.5 hours.Subsequently, discharge excessive solution, deposited tube 12 is put into sintering oven, feed nitrogen and blow 30min, progressively elevated temperature is to 600-1300 ℃ then, and aerating oxygen, chlorine and helium dehydrate, and be 2 hours time of drying.After the drying and dehydrating, feed He, O
2Loose cigarette ash sandwich layer 14 is carried out sintering, and the agglomerating temperature is 1550 ℃.Feed POCl in the sintering process
3Gas stream is crossed loose cigarette ash sandwich layer 14.At last deposited tube 12 is reinstalled on the MCVD lathe, shorten transparent solid glass rod into deposited tube 12 is molten under 2200 ℃.Present embodiment preform sandwich layer obtains P through electron probe test
2O
5Concentration is 15wt%, Yb
2O
3Concentration be 3 wt%, be drawn into optical fiber after, its numerical aperture is 0.15, naked fine diameter is 125 μ m, core diameter is 11 μ m, can be used for making ytterbium-doping optical fiber laser.
Embodiment 3
Quartzy deposited tube 12 carries out the thermal-flame polishing, eliminates cut impurity, surface irregularity and the collapsed cell on deposited tube 12 surfaces.Contain SiO for 10 layers in deposited tube 12 internal surfaces deposition under 1870 ℃
2-P
2O
5The inner cladding 13 of-F.Reduce depositing temperature to 1250 ℃, feed SiCl
4 , GeCl
4And POCl
3The gas aggradation cigarette ash sandwich layer 14 that loosens.The deposited tube 12 that will contain loose cigarette ash sandwich layer 14 is immersed in the TmCl that contains 0.03 mol/L
36H
2The Al(NO of O and 0.3 mol/L
3)
39H
2In the ethanolic soln 10 of O about 1 hour.Subsequently, discharge excessive solution, deposited tube 12 is put into sintering oven, feed nitrogen and blow 30min, progressively elevated temperature is to 600-1300 ℃ then, and aerating oxygen, chlorine and helium dehydrate, and be 1 hour time of drying.After the drying and dehydrating, feed He, O
2Loose cigarette ash sandwich layer 14 is carried out sintering, and the agglomerating temperature is 1600 ℃.Feed GeCl in the sintering process
4And POCl
3Gas stream is crossed loose cigarette ash sandwich layer 14.At last deposited tube 12 is reinstalled on the MCVD lathe, shorten transparent solid glass rod into deposited tube 12 is molten under 2200 ℃.Present embodiment preform sandwich layer obtains GeO through electron probe test
2Concentration is 8wt%, P
2O
5Concentration is 5wt%, Tm
2O
3Concentration be 0.3 wt%, be drawn into optical fiber after, its numerical aperture is 0.16, naked fine diameter is 125 μ m, core diameter is 8 μ m, can be used for making S-band thulium doped fiber amplifier and 2 mum wavelength optical fiber lasers.
The inventive method is not limited to the doping of rare earth element, can also be used for transition metal such as nickel, cobalt, chromium, the doping of metallic element bismuth and semiconductor-quantum-point.
Need to prove, the mode of the foregoing description only limits to describe embodiment, but the present invention is not confined to aforesaid way, and those skilled in the art can modify in not departing from the scope of the present invention in view of the above easily, and therefore scope of the present invention should comprise the disclosed principle and the maximum range of new feature.
Claims (10)
1. method of making the rare earth doped fiber prefabricated rods is characterized in that may further comprise the steps:
The loose cigarette ash sandwich layer of internal surface deposition at quartzy deposited tube;
In containing the solution of rare earth element, soak described loose cigarette ash sandwich layer;
In sintering oven, use rare gas element and the described loose cigarette ash sandwich layer of dry chlorine;
The described loose cigarette ash sandwich layer of sintering is a glass coating;
Molten described quartzy deposited tube and the glass coating of contracting is solid preform.
2. a kind of method of making the rare earth doped fiber prefabricated rods according to claim 1 is characterized in that: adopt the MCVD method to deposit described loose cigarette ash sandwich layer.
3. a kind of method of making the rare earth doped fiber prefabricated rods according to claim 1 is characterized in that: described deposition is that the mixed gas with oxygen, silicon tetrachloride and impurity gas feeds and makes mixed gas generation chemical reaction form soot deposits by heating in the described quartzy deposited tube to form described loose cigarette ash sandwich layer to the deposited tube internal surface; Described impurity gas is germanium tetrachloride or phosphorus oxychloride or the combination of the two.
4. a kind of method of making the rare earth doped fiber prefabricated rods according to claim 3 is characterized in that: when implementing described sintering with the mixed gas of described impurity gas and oxygen, helium by described loose cigarette ash sandwich layer.
5. a kind of method of making the rare earth doped fiber prefabricated rods according to claim 1 is characterized in that: described sedimentary temperature is 1200-1700 ℃.
6. a kind of method of making the rare earth doped fiber prefabricated rods according to claim 1, it is characterized in that: the muriate or nitrate and a kind of co-dopant that contain at least a rare earth element in the described solution, described rare earth element ordination number is 57-71, and described co-dopant is aluminum chloride or aluminum nitrate.
7. a kind of method of making the rare earth doped fiber prefabricated rods according to claim 1, it is characterized in that: described sintering carries out in sintering oven.
8. a kind of method of making the rare earth doped fiber prefabricated rods according to claim 1 is characterized in that: described exsiccant temperature is 600-1300 ℃, and be 0.5-2 hour time of drying.
9. a kind of method of making the rare earth doped fiber prefabricated rods according to claim 1 is characterized in that: described rare gas element when dry is a nitrogen.
10. a kind of method of making the rare earth doped fiber prefabricated rods according to claim 1 is characterized in that: described agglomerating temperature is 1500-1600 ℃.
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| CN 201010605713 CN102086089A (en) | 2010-12-27 | 2010-12-27 | Method for manufacturing rare-earth-doped fiber precast rod |
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| CN 201010605713 CN102086089A (en) | 2010-12-27 | 2010-12-27 | Method for manufacturing rare-earth-doped fiber precast rod |
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Application publication date: 20110608 |