Classifications

• • 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
  • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
  • C09K11/7701—Chalogenides
• • 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
  • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
  • C03C14/004—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of particles or flakes
• • 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
  • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
  • C03C14/006—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of microcrystallites, e.g. of optically or electrically active material
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/06—Glass compositions containing silica with more than 90% silica by weight, e.g. quartz
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C4/00—Compositions for glass with special properties
  • C03C4/0071—Compositions for glass with special properties for laserable glass
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C4/00—Compositions for glass with special properties
  • C03C4/10—Compositions for glass with special properties for infrared transmitting glass
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
  • H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
  • H01S3/05—Construction or shape of optical resonators; Accommodation of active medium therein; Shape of active medium
  • H01S3/06—Construction or shape of active medium
  • H01S3/063—Waveguide lasers, i.e. whereby the dimensions of the waveguide are of the order of the light wavelength
  • H01S3/067—Fibre lasers
  • H01S3/06754—Fibre amplifiers
• • 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
  • C03C2201/00—Glass compositions
  • C03C2201/06—Doped silica-based glasses
  • C03C2201/20—Doped silica-based glasses containing non-metals other than boron or halide
• • 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
  • C03C2201/00—Glass compositions
  • C03C2201/06—Doped silica-based glasses
  • C03C2201/30—Doped silica-based glasses containing metals
• • 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
  • C03C2201/00—Glass compositions
  • C03C2201/06—Doped silica-based glasses
  • C03C2201/30—Doped silica-based glasses containing metals
  • C03C2201/34—Doped silica-based glasses containing metals containing rare earth metals
  • C03C2201/3476—Erbium
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
  • H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
  • H01S3/05—Construction or shape of optical resonators; Accommodation of active medium therein; Shape of active medium
  • H01S3/06—Construction or shape of active medium
  • H01S3/063—Waveguide lasers, i.e. whereby the dimensions of the waveguide are of the order of the light wavelength
  • H01S3/067—Fibre lasers
  • H01S3/06708—Constructional details of the fibre, e.g. compositions, cross-section, shape or tapering
  • H01S3/06716—Fibre compositions or doping with active elements
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
  • H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
  • H01S3/14—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range characterised by the material used as the active medium
  • H01S3/16—Solid materials
  • H01S3/169—Nanoparticles, e.g. doped nanoparticles acting as a gain material

Definitions

• An optical guide comprising nanoparticles and a method of manufacturing a preform for forming such an optical guide.
• the present invention relates to an optical guide, and in particular an optical fiber, amplifying telecommunications signals and a method of manufacturing a preform intended to form such an optical fiber.
• an optical fiber comprising an amplifying medium for regenerating the optical signal received by this fiber and retransmitting the regenerated optical signal with increased intensity.
• an amplifying fiber comprises: a core formed of a transparent material incorporating at least one doping element such as rare earth ions such as erbium (Er) which carry out the amplification of the optical signal, and
• a sheath surrounding the heart which aims to maintain the optical signal mainly in the heart.
• the MCVD process involves high temperatures which are incompatible with the high volatility of many elements and / or the low stability of the complexes formed with these elements.
• multicomponent oxide glass or MOG for “Multicomponent Oxide Gloss” in English
• MOG Multicomponent Oxide Gloss
• the MOG process uses a conventional sythesis glass by mixing in crucible and a heat treatment at high temperature which in particular have the disadvantage of requiring complex fiber techniques and expensive.
• the optical fibers obtained according to this MOG method have an attenuation rate of the upper optical signal or false attenuation of a fiber obtained using the MCVD process, taking into account the impurities introduced during the crucible synthesis. , and welding problems with transmission fibers that are manufactured using an MCVD process,
• An amplifying fiber is described for example in US-2003/0, 175,003 which teaches the use of nanoparticles, less than 20 nm in size, containing chemical elements in the vicinity of the doping element to improve amplification of the signal, these elements being referred to hereafter as improvement elements.
• This document also describes the organometallic synthesis of these nanoparticles and their implantation in the core of the fiber via an MCVD process.
• the present invention includes the finding that there is a need for an amplifying fiber manufacturing process for introducing enhancement elements in the vicinity of the doping element to maintain physical properties close to those of a silica fiber. standard and thus facilitate the welding between the standard fiber and the amplifying fiber thus manufactured.
• the object of the present invention is an optical fiber comprising an amplifying medium provided with a core (22) formed of a transparent material and nanoparticles (24) comprising a doping element and at least one element improving the use of this material.
• dopant, and an outer sheath (26) surrounding the core characterized in that the doping element is erbium (Er) and in that the enhancement element is selected from antimony (Sb), bismuth (Bi) and a combination of antimony (Sb) and bismuth (Bi).
• An optical fiber according to the present invention uses novel types of nanoparticles comprising antimony and / or bismuth. This benefits properties of improving bismuth and / or antimony when these elements are in the vicinity of erbium.
• the relatively large size of these nanoparticles allows the incorporation and the maintaining the latter in its fiber even lawsque high temperatures are implemented to manufacture i ⁇ guide, for example during a MCVD process.
• the doping element and / or the enhancement element is present in the oxide form.
• the risks of alteration of the nanoparticle by an oxidation of its elements are limited.
• the guide comprises aluminum in the heart, close to the nanoparticles, this arrangement improving the properties of nanoparticles.
• the invention also relates to a method of manufacturing a preform intended to generate a free optical system comprising a core, formed of a transparent matrix and nanoparticles comprising a doping element and at least one element improving the use of this doping element, and an outer sheath surrounding the heart, characterized in that:
• the nanoparticles are synthesized by an operation for precipitating at least one salt in solution containing the enhancement element and / or the doping element, and then
• the nanoparticles formed in the core of the preform are introduced by a porous impregnation operation or a modified vapor phase chemical deposition (MCVD).
• nanoparticles of various compositions which are more resistant to incorporation into a glass matrix, since the doping elements and the improvement elements form nanoparticles of structures and relatively large size, between 1 and 500 nm, and preferably greater than 20 nm, so less volatile and less sensitive to temperature than if these elements were introduced by other methods.
• the doping and / or improvement elements are in the form of oxides so that they are less sensitive to the high temperatures resulting from the steps specific to the MCVD process, implemented subsequently to produce a preform and transform it into fiber comprising these nanoparticles.
• the precipitation of the nanoparticles is obtained under conditions of mild chemistry, and in particular at ambient pressure.
• the experimental means required by the process are inexpensive.
• the precipitation is carried out in a controlled pH solution, for example as a function of the saturation thresholds of the various elements involved.
• the invention also relates to an optical fiber comprising a core, formed of a transparent matrix and nanoparticles comprising a doping element and an element improving the use of this dopant, as well as an outer sheath surrounding the core, obtained by fiber drawing from a preform manufactured by the one produced according to one of the previous embodiments.
• FIGS. 1a and 1b are diagrams representative of the gain generated by fibers comprising antimony or bismuth
• FIG. 2 represents an amplifying fiber according to the invention
• FIGS. 3a, 3b and 3c are structural diagrams of different glasses obtained by various methods.
• FIG. 4 is a representative graph of the gain generated by an amplifying fiber according to the invention.
• the glasses comprising bismuth or antimony have particularly advantageous characteristics described below with the aid of FIGS. 1 a and 1 b which represent the amplification gains of materials comprising erbium as doping element and antimony (Figure 1a) or bismuth [Figure 1b) as an element of improvement.
• FIGS. 1 a and 1 b represent the gain (axis of the ordinates) of the amplifier of the material considered as a function of the wavelength of the amplified signal (abscissa axis 12) for fibers comprising antimony (curve 14, FIG. 1 a) or bismuth (curve 16, FIG. 1b), these gains being compared with those of a known fiber comprising alumina as a dopant (curve 18).
• antimony (Sb) or bismuth (Bi) have respective properties of interest for the treatment of an optical signal, namely widening the gain curve (Sb) of the amplifying medium or the flattening of this curve (Bi).
• simulations show that the widening of the gain band of an amplifying fiber can be of the order of 15.5% of the width of this band, which can then exceed 38 nm in width, this width being required for some telecommunications applications - 1530 to 1568 nm.
• FIG. 2 represents an amplifying optical fiber 20 according to the invention. It has a core 22 comprising nanoparticles 24 but with a doping element, such as erbium, surrounded by one or more enhancement elements such as bismuth and / or antimony.
• a doping element such as erbium
• enhancement elements such as bismuth and / or antimony.
• the obtained fiber 20 is obtained by fiberizing a preform manufactured using a modified MCVD - chemical vapor deposition process - and allowing the incorporation of these nanoparticles 24 by porous absorption into the heart 22.
• the nanoparticles 24 resist incorporation into a glass, given their relatively large size, generally between 20 and 500 nm.
• some doping / enhancement elements occur in these nanoparticles in the form of connecting oxides so that they are less likely to be destroyed during the preform manufacturing and processing stages. optical fiber.
• nanoparticles 24 may be generated according to a process according to the invention, that is to say using a precipitatin of salts comprising the doping element (s) and / or the dye (s). improvement to be included in the nanoparticles.
• a precipitation makes it possible to obtain antimony nanoparticles, the erbium doping element being incorporated later.
• This procedure uses an aqueous solulion of potassium hexahydroxyantimonate (KSb (OH) 6 which is introduced into water maintained at acidic pH in order to obtain the precipitation of nanoparticles comprising antimony
• the solution is subsequently stirred at room temperature or at 95 ° C. for several days. Nanoparticles comprising antimony are finally obtained after centrifugation of the solution, washing and drying in an oven at 95 ° C.
• these nanoparticles can incorporate erbium by an ion exchange obtained with a solution comprising erClum ErCl3 chloride in an aqueous medium or with erbium acetylacetonate Er (Acac) 3 comprising water and a organic solvent.
• the nanoparticles are then dispersed in a controlled pB aqueous medium and introduced into the core of a preform made using a modified chemical vapor deposition, or MCVD, by impregnating a layer porous glass.
• This preform is then subjected to fiber drawing using a conventional heat treatment.
• nanoparticles comprising bsmuth (Bi) in the vicinity of erbium (Er).
• the precipitation method implemented by the invention does not allow to know precisely the environment of the doping element (erbium in this example) vis-à-vis the enhancement elements contrary to syntheses finer nanoparticles, such as the organometallic synthesis described in the patent application already cited.
• FIGS. 3a, 3b and 3c An explanation relating to the structure of the nanoparticles generated with a process in accordance with the invention is carried out using FIGS. 3a, 3b and 3c in the case of erylum / antimony doping.
• FIG. 3a shows schematically the typical structure of a doped SiO 2 silica glass obtained according to a conventional MCVD method, that is to say in which the dopants are introduced without particular organization in the form of sets. dissolved chloride.
• the doping element (Er) is surrounded by a heterogeneous and disordered matrix of silicon which may comprise the enhancement element (Sb).
• Sb enhancement element
• FIG. 3b shows schematically a glass 105 obtained according to the MOG method already described, this glass being a statistical presence of the improvement element (Sb) in the vicinity of the doping element (erbium). because of the possibility of incorporating it in significant proportion relative to the doping element.
• FIG. 3c shows, schematically, nanoparticles 30 obtained according to the process according to the invention.
• the doping element (Er) and the enhancement element (Sb) have been represented in the form of spheres, but it should be noted that, according to the experimental observations, these elements are present in the nanoparticles in the form of oxides.
• the nanoparticle manufacturing process does not allow a precise control of the structure and the size of these particles. Notwithstanding the diversity of the structures and the sizes of the nanoparticles, their size can be relatively large, generally between 1 and 500 nm.
• Experimental results show that the amplification gain of a fiber generated according to a method according to the invention is very satisfactory as shown below with the aid of FIG. 4 which represents the gain curve (ordinate axis 40). of amplifying an optical signal as a function of the wavelength (abscissa axis 42) of this signal. It appears that a fiber provided with nanoparticles generated according to a process according to the invention (curve 46) can have a gain on a gum wavelength wider than the fiber manufactured by a conventional method and without doping element
• the process according to the present invention is capable of many variants.
• the synthesis of nanoparticles by precipitation makes it possible to generate many types of nanoparticles on the basis of various doping elements, such as erbium, and various improvement elements, such as bismuth or antimony.
• a process according to the invention can be implemented to manufacture nanoparticles using the same element as a doping element and as an improvement element.
• a method according to the invention makes it possible to envisage the synthesis of nanoparticles comprising different doping and / or improvement elements such as: Te, Ta, Zr, V, Pb, Mb, W, In, Go, Sn , Mo, B, As, Ti.
• a fiber according to the invention may comprise, in addition to the nanoparticles, elements such as aluminum which improve the gain of the fiber.
• an amplifying fiber according to the invention can be numerous.
• such a fiber can be implemented as a Raman amplification fiber, as a Raman laser fiber, as a strongly fiber. nonlinear, as saturable absorber fiber and / or as poiarisabie fiber.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
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• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
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• Optics & Photonics (AREA)
• Dispersion Chemistry (AREA)
• Ceramic Engineering (AREA)
• Electromagnetism (AREA)
• Crystallography & Structural Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Plasma & Fusion (AREA)
• Lasers (AREA)
• Manufacture, Treatment Of Glass Fibers (AREA)
• Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)

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• 2005
  • 2005-08-17 FR FR0552520A patent/FR2889876B1/fr not_active Expired - Fee Related
• 2006
  • 2006-08-17 CN CN2006800384151A patent/CN101288212B/zh not_active Expired - Fee Related
  • 2006-08-17 US US12/063,950 patent/US8000577B2/en not_active Expired - Fee Related
  • 2006-08-17 EP EP06808243A patent/EP1917702A2/de not_active Withdrawn
  • 2006-08-17 WO PCT/FR2006/050802 patent/WO2007020362A2/fr active Application Filing
• 2010
  • 2010-08-27 US US12/805,989 patent/US8014647B2/en not_active Expired - Fee Related

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