EP1240113A2 - Procede de fabrication de fibres vitroceramiques nanocristallines - Google Patents

Procede de fabrication de fibres vitroceramiques nanocristallines

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Publication number
EP1240113A2
EP1240113A2 EP00991848A EP00991848A EP1240113A2 EP 1240113 A2 EP1240113 A2 EP 1240113A2 EP 00991848 A EP00991848 A EP 00991848A EP 00991848 A EP00991848 A EP 00991848A EP 1240113 A2 EP1240113 A2 EP 1240113A2
Authority
EP
European Patent Office
Prior art keywords
glass
cladding
core
fiber
ceramic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00991848A
Other languages
German (de)
English (en)
Inventor
George Beall
Linda Pinckney
William D. Vockroth
Ji Wang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Corning Inc
Original Assignee
Corning Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Corning Inc filed Critical Corning Inc
Publication of EP1240113A2 publication Critical patent/EP1240113A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • G02B6/0229—Optical fibres with cladding with or without a coating characterised by nanostructures, i.e. structures of size less than 100 nm, e.g. quantum dots
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
    • C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
    • 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
    • C03B37/01205—Manufacture of preforms for drawing fibres or filaments starting from tubes, rods, fibres or filaments
    • C03B37/01211—Manufacture of preforms for drawing fibres or filaments starting from tubes, rods, fibres or filaments by inserting one or more rods or tubes into a tube
    • 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
    • C03B37/02—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor
    • C03B37/025—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor from reheated softened tubes, rods, fibres or filaments, e.g. drawing fibres from preforms
    • C03B37/027—Fibres composed of different sorts of glass, e.g. glass optical fibres
    • 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
    • C03C13/006—Glass-ceramics fibres
    • 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
    • C03C13/045—Silica-containing oxide 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
    • C03C13/00—Fibre or filament compositions
    • C03C13/04—Fibre optics, e.g. core and clad fibre compositions
    • C03C13/045—Silica-containing oxide glass compositions
    • C03C13/046—Multicomponent glass compositions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
    • C09K11/646—Silicates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
    • C09K11/68—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals containing chromium, molybdenum or tungsten
    • C09K11/685—Aluminates; Silicates
    • 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
    • C03B2201/08—Doped silica-based glasses doped with boron or fluorine or other refractive index decreasing dopant
    • C03B2201/10—Doped silica-based glasses doped with boron or fluorine or other refractive index decreasing dopant doped with boron
    • 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
    • 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
    • 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
    • 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
    • C03B2201/40—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with transition metals other than rare earth metals, e.g. Zr, Nb, Ta or Zn
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2203/00—Fibre product details, e.g. structure, shape
    • C03B2203/10—Internal structure or shape details
    • C03B2203/22—Radial profile of refractive index, composition or softening point
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2205/00—Fibre drawing or extruding details
    • C03B2205/56—Annealing or re-heating the drawn fibre prior to coating
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2205/00—Fibre drawing or extruding details
    • C03B2205/60—Optical fibre draw furnaces
    • C03B2205/72—Controlling or measuring the draw furnace temperature

Definitions

  • a method for making glass ceramic, optoelectronic materials that contain nanocrystals that are doped with at least one kind of optically active metal is provided.
  • optical fiber optic systems have become the standard for long-distance communication. This preponderance stems from several advantages of optical links over the more traditional metallic-based counterparts, including lower loss, higher information capacity, low cost per channel, immunity to crosstalk and electrical interference, and a smaller physical mass.
  • optical fiber systems carry hundreds of terabits per second over distances greater than 1000 km. Even though the capacity of optical fibers is orders of magnitude beyond the capability of metallic links, the demands of global communication are driving the system capacity to double every year. Transition metals have long been used as optically active dopants in crystalline hosts because they fluoresce in the near infrared (1000 - 1500 nm) region, while exhibiting a correspondingly large bandwidth.
  • transition metal dopants Given the useful wavelength range and bandwidth of many transition metal dopants, one can see that their advantageous attributes could be put to good use in telecommunications applications.
  • the crystalline-host transition metal technology of Patent No. 4,987,575, however, is not suited for these applications, since the primary optical communications medium is glass-based optical fiber. While a logical extension would be the inclusion of transition metal dopants into glasses, their performance (particularly their efficiency) has unfortunately been found to degrade in amorphous hosts, where the crystal field strength is much smaller than single-crystal hosts.
  • the transition metal ions instead, merely are suspended in the amorphous body providing or contributing little to the amplification or transmission qualities.
  • Glass ceramics have the advantage described in a United States patent application entitled TRANSITION- METAL GLASS-CERAMIC GAIN MEDIA, filed in the name of George H. Beall, Nicholas F. Borrelli, Linda R. Pinckney, Eric J. Mozdy, on October 11, 2000, which is incorporated by reference in its entirety, herein.
  • the process of internal nucleation forms a glass ceramic, where the crystalline sites are small and uniformly distributed throughout the glass core.
  • the crystals are formed from constituent materials of the original glass melt, not by introducing new materials as disclosed in U.S. Patent No. 5,717,517.
  • the optically active dopants are introduced throughout the entire medium, as compared to only scattered particles.
  • glass-ceramic fibers When making an optical fiber from glass ceramic materials, the nature of a glass-ceramic material generally necessitates drawing the material as a glass fiber and subsequently subjecting the fiber to an appropriate thermal treatment to develop the crystalline phase.
  • the double crucible embodies a central tube for the core glass of a fiber. A larger diameter tube, surrounding the central tube, delivers the cladding glass.
  • the respective glasses are maintained in a molten state in their crucibles, and flow from the tubular outlets to be drawn as a clad fiber.
  • the most critical issue of concern is how to suppress the intense tendency of the compositions to crystallize as the glass is processed when attempting to form a glassy fiber.
  • This phenomenon is due to the fact that the compositions for the precursor glass for a glass-ceramic, particularly the high temperature glass-ceramics useful for present purposes, are purposely designed to crystallize.
  • a critical problem is how to suppress this intense tendency to crystallize, thereby maintaining the fiber as a glass.
  • the present invention is directed to solving.
  • the invention provides a method to minimize cross-diffusion between the core and cladding materials during the optical fiber manufacturing process.
  • the method described in this application is a very different method of fiberizing a glass-ceramic material, which offers certain advantages particularly with respect to the cladding, described below, and is the preferred fiberization method for certain glass ceramic compositions.
  • the present invention resides in a method to produce clad optical fiber and other materials for optoelectronic applications, including lasers and amplifiers, without having to suffer unnecessarily, when forming and drawing optical fiber, contamination of the fiber core by the cladding material. More particularly, the invention provides a unique method for making an optoelectronic material by modifying the "rod-in-tube" process to produce a clad optical fiber. Diffusion of contaminant elements into the precursor glass compositions for the glass-ceramic fiber core is kept to a minimum. Maintaining the purity of the core and its transparency to light is useful and favored in optoelectronic applications.
  • the method can best be described as a "viscous-liquid-in-tube" process, wherein precursor glass compositions for making glass-ceramic materials that contain nanocrystals doped with optically active ions are employed with a more refractory or temperature resistant cladding material.
  • a precursor glass composition is first prepared and formed into a cane.
  • a chemically inert cladding material comprising, for example, modified silica is formed into a tube that is fitted around the glass cane.
  • a glass fiber is drawn from the combined precursor-glass-cane-in- tube at a temperature slightly above the liquidus of the fiber-core glass composition, and subsequently at least a portion of the drawn clad glass fiber is heat treated to develop nanocrystals within the core composition, thereby forming a glass ceramic.
  • FIG. 1B Differential thermal analysis (DTA) curves indicating the respective areas of formative regions of glass-ceramic fiber fiberization used in creating the present invention, a "viscous" liquid-in-tube process.
  • DTA Differential thermal analysis
  • Figure 2 A cross-sectional view of a clad optical fiber in accordance with the present invention.
  • the invention involves using the thermal properties of materials in a way to produce transparent glass-ceramic fiber cores in combination with a durable cladding.
  • Figures 1A and IB illustrate the thermodynamic principles involved in the invention.
  • the present inventive process occurs at a higher temperature.
  • the glass composition of the core tends to devitrify, often forming crystals too large to permit effective light transmission. It is, therefore, desirable to avoid any uncontrolled crystallization in the glass fiber as it is being drawn and clad.
  • the glass composition of the core should remain glassy at this stage of production.
  • the draw should be carried-out at a temperature just above the liquidus temperature (T-) of the candidate glass-ceramic material that will be used as the core of a fiber.
  • T- liquidus temperature
  • the outer cladding material may become too soft and compositional species may become mobile.
  • too much chemical reaction occurs between the core and clad compositions.
  • a material for cladding that can withstand higher temperatures and that is unlikely to chemically react or diffuse with the core glass composition is used to surround the fiber core before drawing begins.
  • the new method entails essentially a shifting of the respective temperature dynamics for the core and cladding materials.
  • the temperature is slightly above the liquidus temperature (Ti) of the glass in the core, while simultaneously remaining below the kinetically-controlled crystallization temperature (T x ) of the much more viscous cladding glass.
  • This process can also be described as a conceptual hybrid between the rod-in-tube and the double crucible methods.
  • FIG. 2 is a cross-sectional view of a clad fiber in accordance with the present invention.
  • a clad fiber is designated by the numeral 10.
  • Clad fiber 10 comprises a core fiber 12 having a cladding layer 14 deposited on the surface of fiber
  • the fiber core 12 is made from a high temperature glass-ceramic material having a liquidus-viscosity in the range of approximately from 100-200-2500 poises. Although the viscosity of the glass core composition at liquidus temperature may be low by conventional glass standards, the core material nevertheless has a sufficiently high viscosity at the liquidus temperature to minimize diffusion of component elements. Glass ceramic compositions that can work well with the inventive method of making fiber typically have a softening point above about 900° C.
  • glass compositions include a substantially transparent, alpha- and beta-willemite glass-ceramic, which may be doped with transition-metals to impart optical activity, as disclosed in a United States patent application entitled GLASS-CERAMICS BASED ON ALPHA- AND BETA-WILLEMITE, filed in the name of Linda R.
  • These glass ceramic compositions are characterized in that the defining crystal phase(s) is nanocrystalline in nature, that is, the crystals can range from being not larger than about 50 nm in diameter, to 25 nm to, 10 nm or even as small as 5 nm. Further, these compositions are doped with at least one kind of optically active ion. Optically active ions for example may be chosen from either the transition metals or the lanthanide elements. Transition-metal doped nanocrystalline glass-ceramics are a unique class of novel laser and optical amplifying material used for optoelectronic applications.
  • transition metal dopants can include titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), cobalt (Co), nickel (Ni), copper (Cu), or even iron (Fe).
  • Glass ceramic materials doped with transition metal ions preserve not only their typical broad-emission characteristics, but also tend to show high, crystal-like quantum yield as compared to similarly-doped amorphous, pure glass hosts. Thus, they provide the advantages of a pure crystal in terms of spectroscopic characteristics. At the same time, they provide the advantages of a glass insofar as material processing is concerned.
  • lanthanide elements for example, erbium (Er), thulium (Tm), neodymium (Nd), praseodymium (Pr), or ytterbium (Yb), dysprosium (Dy), holmium (Ho) are doped into the glass-ceramic.
  • lanthanide elements for example, erbium (Er), thulium (Tm), neodymium (Nd), praseodymium (Pr), or ytterbium (Yb), dysprosium (Dy), holmium (Ho) are doped into the glass-ceramic.
  • a small amount of alkali or halogen ions in the core material may be lost and this may be easily compensated by adding a little extra amount of the volatile components in the starting batches of the core glass composition.
  • a common practice in optical fiber production is to apply a cladding layer to the optical fiber core.
  • This cladding layer surrounds the fiber as shown by cladding layer 14 in Figure 2.
  • This cladding layer serves to maintain an optical signal within the fiber core, since it is lower in refractive index than the core.
  • the cladding should provide a close match in coefficient of thermal expansion (CTE) with the core.
  • CTE coefficient of thermal expansion
  • the CTE of the cladding will be slightly lower than that of the core to thereby induce a small compressive stress and lend a source of mechanical strength.
  • the cladding material should exhibit relatively high viscosity and the absence of significant amounts of mobile species R + , R 2+ in the cladding, so as to minimize diffusion rates of the elements in the core material. This characteristic reduces the amount of cross diffusion between the core and cladding materials. Yet, the cladding should be soft enough and drawable before the core material becomes too molten, soft, or volatile.
  • the cladding must be sufficiently viscous at the drawing temperature to permit it to be drawn, while the core glass should remain compositionally stable, that is, have a sufficiently low vapor pressure to avoid appreciable volatility.
  • the ratio of the viscosity of the cladding to the viscosity of the core is about three orders of magnitude, (cladding: core ⁇ 10 6 : 10 3 ), so as to minimize diffusion.
  • the liquid core material should remain as a viscous liquid, having as low a vapor pressure as possible.
  • the cladding should be chemically inert with respect to the glass of the core. That is, the cladding material reacts only minimally, if at all, with the viscous-liquid core.
  • a cladding material that satisfies these two concerns can comprise a composition of predominantly silica modified with additives.
  • Suitable additives for modifying silica include oxides of boron (B), germanium (Ge), phosphorous (P), aluminum (Al), gallium (Ga), tantalum (Ta), titanium (Ti) and antimony (Sb). These oxide additives are oxides known as conditional glass-forming oxides with silica, and any one of which may be used singly or in combination with another.
  • the B, Ge and P oxides are preferred, with the B and Ge being slightly favored.
  • Phosphorous is more effective in decreasing the softening point, but its double bond may leave bigger voids in the glass structure. These voids may permit entry of alkali ions, thereby lessening the chemically inert properties of the cladding.
  • alkali metal and alkaline earth metal oxides are avoided to the extent feasible. These compounds tend to reduce chemical inertness and tend to unduly lower the glass softening point.
  • the softening points of these materials can be varied greatly ranging from about 1200 °C to as high as that of pure silica, depending on the requirements of the compositional nature of the core material.
  • a high softening temperature provides, according to an embodiment of the inventive method, a drawing temperature that is slightly above the liquidus temperature of the core composition.
  • high temperature glass-ceramics may have coefficients of thermal expansion in the range of about 10-90x 10 '7 /°C, but more often within the range of 20-70x10 "7 /°C, or 30-60x10 "7 /°C.
  • the cladding material used will then preferably have a somewhat lower CTE than that of the core glass.
  • the cladding then can have a CTE in the range of about 5-70x10 " 7 /°C, or in the range of 15-60xlO "7 /°C but more likely within 15-25x10 '7 /°C.
  • the differential between coefficients of thermal expansion provides compressive stress that helps strengthen the clad fiber.
  • the fiber produced is compatible with silica-based fiber technology and is easily fusion spliced, since the cladding contains high amounts of silica.
  • a clad glass fiber is first produced by drawing a cane from the precursor glass and cladding it with a cladding of modified silica, as described above.
  • the modified silica tube is preferably fabricated by an outside chemical vapor deposition (CVD) process such as OVD or VAD, but traditional fusion or flame process may be employed as well.
  • CVD produced modified silica cladding tends not to contain monovalent or divalent ions.
  • Cladding may be attached to the core in a mechanical process by placing the core within the cladding.
  • the drawing process occurs at a temperature that is above liquidus for the core, and below crystallization for the cladding.
  • the clad glass fiber is drawn and then subjected to an appropriate thermal treatment to crystallize either during the drawing process or, more commonly, in a subsequent step.
  • our invention is in part a method for making an optoelectronic material.
  • the method comprises several steps: a) preparing a glass composition to yield a precursor glass for a nanocrystalline glass ceramic doped with at least one kind of optically active ion; b) forming the precursor glass into a glass cane; c) incorporating the glass cane with a chemically inert cladding material, preferably made from modified silica; d) making an optical component, such as a fiber, from the combined glass cane and cladding at a temperature slightly above the liquidus temperature of the relatively more fluid, precursor glass, and below the kinetic crystallization temperature of the viscous cladding (glass) material; e) heat treating at least a portion of the optical component to develop nanocrystals within the precursor glass.
  • the optically active dopant is selected from transition metals and lanthanides.
  • the nanocrystals formed in the glass ceramic are not larger than about 50 nm, and may be as small as 5 nm, in size.
  • the cladding glass is sufficiently viscous at the drawing temperature to permit it to be drawn at a temperature where the core glass is chemically stable even though more fluid than the cladding.
  • the cladding-glass batch is made as a tube formed by a chemical vapor deposition process.
  • the cladding glass is adapted to provide a glass containing essentially silica modified by at least one modifying oxide selected from the group composed of B, Ge, P, G, Al, Ta, Ti, or Sb oxides.
  • the cladding glass, thus modified has a softening point of at least 900 to 1000 °C, alternatively 1200 °C, or even as high as pure fused silica (1640-1650 °C).
  • the optical fiber produced according to the method comprises a nanocrystalline glass-ceramic fiber core surrounded by a cladding, such that chemical migration of component elements between the core and cladding glasses are minimized by controlling compositional and thermal parameters of the fiberization process and the core and cladding materials. Further, the migration of component elements is reduced such that the refractive interface between the core and cladding does not adversely affect transmission and waveguiding in the core.
  • the fiber core has a coefficient of thermal expansion in the range of about 10-90 x 10 "7 /°C
  • the cladding material has a coefficient of thermal expansion in the range of about 5-70 x ⁇ o- 7 /°c

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Glass Compositions (AREA)
  • Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)
  • Manufacture, Treatment Of Glass Fibers (AREA)

Abstract

L'invention porte sur un procédé de fabrication d'un matériau vitrocéramique, optoélectronique tel qu'une fibre de verre gainée ou autre composant destiné à ête utilisé dans un dispositif optoélectronique. Ce procédé consiste à préparer un lot de compositions de verre afin de produire un verre précurseur pour un vitrocérame nanocristallin dopé avec au moins un type d'ion optiquement actif tel qu'un métal de transition ou un élément des lanthanides ; faire fondre le lot ; former un bâton de verre ; entourer le bâton d'un matériau de gainage chimiquement inerte ayant la forme d'un tube ; étirer une fibre de verre à partir du « bâton dans le tube » en verre précurseur combiné à une température légèrement supérieure à celle de la phase vitreuse de la composition de verre précurseur et traiter thermiquement au moins une partie de la fibre de verre gainée étirée dans des conditions où se développeront des nanocristaux dans la composition du noyau et former ainsi un vitrocérame.
EP00991848A 1999-10-18 2000-10-18 Procede de fabrication de fibres vitroceramiques nanocristallines Withdrawn EP1240113A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US16005299P 1999-10-18 1999-10-18
PCT/US2000/028804 WO2001031367A2 (fr) 1999-10-18 2000-10-18 Procede de fabrication de fibres vitroceramiques nanocristallines
US160052P 2009-03-13

Publications (1)

Publication Number Publication Date
EP1240113A2 true EP1240113A2 (fr) 2002-09-18

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JP (1) JP2003512988A (fr)
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WO2001031367A2 (fr) 2001-05-03
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WO2001031367A3 (fr) 2001-09-13
CN1379740A (zh) 2002-11-13

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