CA2306267A1 - Stable cladding glasses for sulphide fibres - Google Patents
Stable cladding glasses for sulphide fibres Download PDFInfo
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- CA2306267A1 CA2306267A1 CA002306267A CA2306267A CA2306267A1 CA 2306267 A1 CA2306267 A1 CA 2306267A1 CA 002306267 A CA002306267 A CA 002306267A CA 2306267 A CA2306267 A CA 2306267A CA 2306267 A1 CA2306267 A1 CA 2306267A1
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- 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
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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
- C03C13/041—Non-oxide glass compositions
- C03C13/043—Chalcogenide glass compositions
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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
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Abstract
A stable cladding glass (12) for use in optical fibers (10). The invention is based upon the discovery that the addition of silicon or phosphorus in small amounts to GeAs sulfide glasses results in improved thermal stability and a lower refractive index.
Description
STABLE CLADDING GLASSES FOR SULPHIDE FIBRES
Field of the Invention This invention relates generally to glasses for use in optical fibers, and more specifically to cladding glasses which exhibit improved thermal stability and a low refractive index.
Background of the Invention U.S. Patent 5,389,584, NGa-and/or In-Containing AsGe Sulphide Glasses" describes the addition of either Ga or In to GeAs Sulphide glasses, which when doped with a suitable rare earth metal, can be used for the fabrication of efficient amplifier, laser and/or upconverter devices. In the particular application of 1300 nm optical amplification, such glasses are excellent hosts for Pr, and are characterized by a high quantum efficiency for the desired 'G4 >'Hs emission. These glasses also have sufficient thermal stability to be drawn into fibre, and are therefore suitable for use as the core glass of an optical waveguide to amplify 1300 run signals.
In order to fabricate such a sulphide glass waveguide, it is necessary to clad the core glass with another chemically and physically compatible glass that has a lower refractive index. In the basic GeGaAsS or GeInAsS systems, lower index glasses can be obtained by reducing the As content, andlor increasing the - Ge content, respectively, relative to that of a given core glass. However, such compositional changes typically degrade the thermal stability of these materials, e.g. as measured by the temperature interval TX T8, resulting in an increased tendency towards crystallization. It can therefore be seen that there is a need for a method to both lower the refractive index and maintain or improve the thermal stability of such sulphide glasses so as to be able to z fabricate a waveguide with suitable light-guiding properties. The present invention is based on the discovery that the addition of silicon or phosphorus to GeAs sulphide glasses provides a means to achieving the above goals.
Summary of the Invention In one embodiment of the present invention, the glass composition consists principally of Ge, As and S, t Ga and/or In, with small but necessary additions of Si. Other metals, including Ca, Sr, Ba, Ag, Tl, Cd, Sn, Hg, Pb, Y, La and other rare-earth metals from the lanthanide series and Sb, as well as optional anionic components such as Se, Te and the halogens F, Cl, Br and I, can be added to optimize various other physical properties such as thermal expansion, viscosity, etc., but are not essential constituents. In a second embodiment of the present invention, the addition of phosphorus to GeAs sulphide glasses can be used instead of silicon to accomplish the same objectives. Glasses of these compositions provide for a cladding glass which exhibits improved thermal stability and a lower refractive index relative to that of a GeGaAsS or GeInAsS core.
Brief Description of the Drawings For a fuller understanding of the nature and objects of the invention, reference should be made to the following detailed description of a preferred mode of practicing the invention, read in connection with the accompanying drawings, in which:
FIG. 1 is a perspective view of a segment of an optical fiber made of a glass composition of the present invention.
FIG. 2 is a cross sectional view of the fiber of Fig. 1 taken along line 2-2.
FIG. 3 is a plot of the refractive index based on the concentration of Si (as expressed in terms of atomic %) in a GeAs sulfide glass.
FIG. 4 is a plot of the thermal stability of GeAs sulfide glasses with varying concentrations of Si as expressed in atomic %.
FIG. 5 is a plot of the refractive index based on the concentration of P as expressed in terms of atomic ~ in a GeAs sulfide glass.
Detailed Description of the Invention Fig. 1 illustrates a segment of an optical fiber 10 suitable for use in an amplifier, laser andlor upconverter device. The fiber comprises an inner glass core 14 which is clad with an outer glass cladding 12 which is a chemically and physically S compatible glass that has a lower refractive index than core glass 14 (see Fig. 2).
The present invention, in one embodiment, is based on the discovery that the incorporation of Si in a GeAs sulphide glass results in a progressive decrease of the refractive index, as illustrated in Fig. 3 of the drawings.
The data in Fig. 1 show that substitution of 2.5% At% of Si for Ge lowers the refractive index by about 0.025 for glasses with the (Ge, Si)uAs,oSbs stoichiometry. Therefore, if glasses Nos. '7 and 1 were utilized as core and cladding glasses, respectively, the numerical aperture (NA) of the resultant waveguide would be about 0.35, which is sufficiently high for an efficient amplifier fibre.
Tables 1 and 2 report a group of glass compositions expressed in terms of atomic percent (At% ) , illustrating the subject inventive glasses. Because the glasses were prepared in the laboratory, the glasses were typically prepared by melting mixtures of the respective elements, although in some cases a given metal was hatched as a sulfide. As can be appreciated, however, that practice is not necessary. The actual batch ingredients can be any materials which, upon melting together with the other batch components, are converted into the desired sulfide in the proper proportions.
The batch constituents were weighed, loaded and sealed into silica ampoules which had been evacuated to about 10-5 to 10-6 Torr. The ampoules were placed into a furnace designed to impart a rocking motion to the batch during melting. After melting the batch for about 1-3 days at 850°-950° C., the melts were quenched to form homogeneous glass rods having diameters of about 7-10 mm and lengths of about 60-70 mm, which rods were annealed at about 325 °-425 °C.
Table 1 also records the glass transition temperature (Tg), the temperature at the onset of crystallization (Tx), and the difference between those measurements (TX - Tg), which quantity is commonly used to gauge the thermal stability of a glass, as well as the refractive index at the sodium D
WO 99/23517 PCTIUS98I22'739 line (nD).
It will be appreciated that the above-described procedures represent laboratory practice only. That is, the batches for the inventive glasses can be melted in large commercial glass melting units and the resulting melts formed into desired glass shapes utilizing commercial glass forming techniques and equipment. It is only necessary that the batch materials be heated to a sufficiently high temperature for an adequate period of time to secure a homogeneous melt, and that melt thereafter cooled and simultaneously shaped into a body of a desired configuration at a sufficiently rapid rate to avoid the development of devitrification.
Examples of Si-containing glasses of the present invention that are useful for the purpose of cladding a core consisting of GeGaAsS or GeInAsS
glass are tabulated below in Table 1 in At%, along with an example of a representative GeGaAsS core glass (Example 7).
Table 1 Glass 1 2 3 4 5 6 7 Ge 22.5 20 17.5 25.3 22.5 19.7 25.0 Si 2.5 5 7.5 2.8 5.6 8.4 -As 10 10 10 6.3 6.3 6.3 9.8 S 65 65 65 65.6 65.6 65.6 65.0 Ga - __ __ __ __ __ 0.2 Tg 312 348 339 364 368 361 -Tx > 650 -630 585 640 625 630 -TX Tg > 335 --280 246 275 255 270 -np 2.283 2.265 - 2.264 2.252 2.241 2.308 In order to achieve corelcladding structures with a comparable NA in the basic GeGaAsS or GeInAsS systems, the thermal stability (TX TB) of typical cladding glasses is on the order of 230-250°C. However, the Tx Tg of Si-5 substituted glasses can be maintained at a value in excess of 250°C
over a wide range of compositions, and in some cases can be in excess of that of the base GeAs sulphide glass, as illustrated in Fig. 2 of the drawings.
The composition of the Si containing cladding glasses comprise the following approximate ranges in terms of mole percent on the sulfide basis (see Tabie 2): 50-95 % GeS2, 2-40% AsZS3, 0.1-30% SiS2, 0-20% Ga2S3 and /or InZS3, 0-10 % MSX, where M is selected from Ca, Sr, Ba, Ag, Tl, Cd, Hg, Sn, Pb, Y, La and other rare-earth metals of the lanthanide series, or Sb, 0-5 % of the corresponding metal selenide andlor telluride, 0-20 % of the corresponding metal halide, and wherein the sulfur and/or selenium and/or tellurium content can vary between 85-125 % of the stoichiometric value.
Table 2 (Mole %) Glass 1 2 3 4 5 6 7 GeS2 75.0 66.7 58.3 81.0 72.0 63.0 83.3 SiSz 8.3 16.7 25.0 9.0 18.0 27.0 -WO 99/23517 PCTNS9$n2739 Ga2S3 _ _ _ _ _ _ 0.3 As2S3 16.7 16.7 16.7 10.0 10.0 10.0 16.3 prZS3 _ _ _ _ _ _ 0.03 In a second embodiment of the present invention, the glasses consist principally of Ge, As and S, t Ga andlor In, with a small but necessary addition of P. Other metals, including Ca, Sr, Ba, Ag, TI, Cd, Hg, Sn, Pb, Y, La and other rare-earth metals from the lanthanide series and Sb, as well as optional anionic components such as Se, Te and the halogens F, CI, Br and I, can be added to optimize various other physical properties such as thermal expansion, viscosity, etc., but are not essential constituents. Compositions (in atomic %) of suitable P containing glasses that are useful for the purpose of cladding a core consisting of GeGaAsS or GeInAsS glass are given below in Table 3:
Table 3 (Atomic %) Glass 8 9 10 11 12 13 14 Ge 24.4 23.8 23.6 23.3 22.2 19.5 16.9 P 2.4 4.8 5.7 7.0 2.5 4.9 7.2 As 7.3 4.8 3.8 2.3 9.9 9.8 9.6 S 65.9 66.7 67.0 67.4 65.4 65.8 66.3 Glass 15 16 17 18 19 20 21 Ge 23.0 22.1 21.3 22.8 21.9 21.1 23.6 P 4.8 4.8 4.8 5.7 5.7 5.7 2.4 As 5.7 6.7 7.7 4.7 5.7 6.7 7.1 S 66.5 66.4 66.2 66.8 66.7 66.5 66.9 In this embodiment, the incorporation of P in a GeAs sulphide glass results in a progressive decrease of refractive index, and a reduced tendency of GeS2 to crystallize, leading to enhanced thermal stability. Accordingly, when Example 8 is used as cladding for a core glass with the composition of Example ?, the resultant fibre is expected to have a numerical aperture of 0.32 which is more than adequate for a sulphide 1.3 Eun amplifier fibre.
The compositions of these phosphorous containing cladding glasses comprise the following approximate ranges in terms of mole percent on the sulfide basis (see Table 4); 50-95% GeS2, 2-40% As2S3, 0.1-25% P2S5, 0-20%
Ga2S3 andlor In2S3, 0-10% MSx, where M is selected from Ca, Sr, Ba, Ag, Tl, Cd, Hg, Sn, Pb, Y, La and other rare-earth metals of the lanthanide series, or Sb, 0-S % of the corresponding metal selenide and/or telluride, 0-20% of the corresponding metal halide, and wherein the sulfur and/or selenium andlor tellurium content can vary between 85-125 % of the stoichiometric value.
Table 4 (Mole %) Glass 8 9 10 11 12 13 14 GeSz 83.3 83.3 83.3 83.3 78.3 72.7 66.7 PZSs 4.2 8.3 10.0 12.5 4.4 ~ 9.1 14.3 ASzS3 12.5 8.3 6.7 4.2 17.4 18.2 19.1 Tx > 583 > 577 > 557 > 544 > 512 TX Tg > 252 > 240 > 242 > 227 > 232 np 2.286 2.259 2.239 2.314 2.316 2.317 Glass 15 16 17 18 19 20 21 GeS2 81.4 79.3 77.2 81.3 79.3 77.2 83.3 PISS 8.5 8.6 8.8 10.2 10.3 10.5 4.2 AsZS3 10.2 12.1 14.0 8.5 10.3 12.3 12.5 Excess - - - - - - 105 S
np 2.280 2.278 2.298 2.275 2.285 2.289 --Fig. 5 illustrates that the substitution of 2.5 At% P for Ge lowers the refractive index by about 0.022 for glasses with the (Ge,P)uAs,oSbs stoichiometry.
While the present invention has been particularly shown and described with reference to the preferred mode as illustrated in the drawing, it will be understood by one skilled in the art that various changes in detail may be effected therein without departing from the spirit and scope of the invention as defined by the claims.
Field of the Invention This invention relates generally to glasses for use in optical fibers, and more specifically to cladding glasses which exhibit improved thermal stability and a low refractive index.
Background of the Invention U.S. Patent 5,389,584, NGa-and/or In-Containing AsGe Sulphide Glasses" describes the addition of either Ga or In to GeAs Sulphide glasses, which when doped with a suitable rare earth metal, can be used for the fabrication of efficient amplifier, laser and/or upconverter devices. In the particular application of 1300 nm optical amplification, such glasses are excellent hosts for Pr, and are characterized by a high quantum efficiency for the desired 'G4 >'Hs emission. These glasses also have sufficient thermal stability to be drawn into fibre, and are therefore suitable for use as the core glass of an optical waveguide to amplify 1300 run signals.
In order to fabricate such a sulphide glass waveguide, it is necessary to clad the core glass with another chemically and physically compatible glass that has a lower refractive index. In the basic GeGaAsS or GeInAsS systems, lower index glasses can be obtained by reducing the As content, andlor increasing the - Ge content, respectively, relative to that of a given core glass. However, such compositional changes typically degrade the thermal stability of these materials, e.g. as measured by the temperature interval TX T8, resulting in an increased tendency towards crystallization. It can therefore be seen that there is a need for a method to both lower the refractive index and maintain or improve the thermal stability of such sulphide glasses so as to be able to z fabricate a waveguide with suitable light-guiding properties. The present invention is based on the discovery that the addition of silicon or phosphorus to GeAs sulphide glasses provides a means to achieving the above goals.
Summary of the Invention In one embodiment of the present invention, the glass composition consists principally of Ge, As and S, t Ga and/or In, with small but necessary additions of Si. Other metals, including Ca, Sr, Ba, Ag, Tl, Cd, Sn, Hg, Pb, Y, La and other rare-earth metals from the lanthanide series and Sb, as well as optional anionic components such as Se, Te and the halogens F, Cl, Br and I, can be added to optimize various other physical properties such as thermal expansion, viscosity, etc., but are not essential constituents. In a second embodiment of the present invention, the addition of phosphorus to GeAs sulphide glasses can be used instead of silicon to accomplish the same objectives. Glasses of these compositions provide for a cladding glass which exhibits improved thermal stability and a lower refractive index relative to that of a GeGaAsS or GeInAsS core.
Brief Description of the Drawings For a fuller understanding of the nature and objects of the invention, reference should be made to the following detailed description of a preferred mode of practicing the invention, read in connection with the accompanying drawings, in which:
FIG. 1 is a perspective view of a segment of an optical fiber made of a glass composition of the present invention.
FIG. 2 is a cross sectional view of the fiber of Fig. 1 taken along line 2-2.
FIG. 3 is a plot of the refractive index based on the concentration of Si (as expressed in terms of atomic %) in a GeAs sulfide glass.
FIG. 4 is a plot of the thermal stability of GeAs sulfide glasses with varying concentrations of Si as expressed in atomic %.
FIG. 5 is a plot of the refractive index based on the concentration of P as expressed in terms of atomic ~ in a GeAs sulfide glass.
Detailed Description of the Invention Fig. 1 illustrates a segment of an optical fiber 10 suitable for use in an amplifier, laser andlor upconverter device. The fiber comprises an inner glass core 14 which is clad with an outer glass cladding 12 which is a chemically and physically S compatible glass that has a lower refractive index than core glass 14 (see Fig. 2).
The present invention, in one embodiment, is based on the discovery that the incorporation of Si in a GeAs sulphide glass results in a progressive decrease of the refractive index, as illustrated in Fig. 3 of the drawings.
The data in Fig. 1 show that substitution of 2.5% At% of Si for Ge lowers the refractive index by about 0.025 for glasses with the (Ge, Si)uAs,oSbs stoichiometry. Therefore, if glasses Nos. '7 and 1 were utilized as core and cladding glasses, respectively, the numerical aperture (NA) of the resultant waveguide would be about 0.35, which is sufficiently high for an efficient amplifier fibre.
Tables 1 and 2 report a group of glass compositions expressed in terms of atomic percent (At% ) , illustrating the subject inventive glasses. Because the glasses were prepared in the laboratory, the glasses were typically prepared by melting mixtures of the respective elements, although in some cases a given metal was hatched as a sulfide. As can be appreciated, however, that practice is not necessary. The actual batch ingredients can be any materials which, upon melting together with the other batch components, are converted into the desired sulfide in the proper proportions.
The batch constituents were weighed, loaded and sealed into silica ampoules which had been evacuated to about 10-5 to 10-6 Torr. The ampoules were placed into a furnace designed to impart a rocking motion to the batch during melting. After melting the batch for about 1-3 days at 850°-950° C., the melts were quenched to form homogeneous glass rods having diameters of about 7-10 mm and lengths of about 60-70 mm, which rods were annealed at about 325 °-425 °C.
Table 1 also records the glass transition temperature (Tg), the temperature at the onset of crystallization (Tx), and the difference between those measurements (TX - Tg), which quantity is commonly used to gauge the thermal stability of a glass, as well as the refractive index at the sodium D
WO 99/23517 PCTIUS98I22'739 line (nD).
It will be appreciated that the above-described procedures represent laboratory practice only. That is, the batches for the inventive glasses can be melted in large commercial glass melting units and the resulting melts formed into desired glass shapes utilizing commercial glass forming techniques and equipment. It is only necessary that the batch materials be heated to a sufficiently high temperature for an adequate period of time to secure a homogeneous melt, and that melt thereafter cooled and simultaneously shaped into a body of a desired configuration at a sufficiently rapid rate to avoid the development of devitrification.
Examples of Si-containing glasses of the present invention that are useful for the purpose of cladding a core consisting of GeGaAsS or GeInAsS
glass are tabulated below in Table 1 in At%, along with an example of a representative GeGaAsS core glass (Example 7).
Table 1 Glass 1 2 3 4 5 6 7 Ge 22.5 20 17.5 25.3 22.5 19.7 25.0 Si 2.5 5 7.5 2.8 5.6 8.4 -As 10 10 10 6.3 6.3 6.3 9.8 S 65 65 65 65.6 65.6 65.6 65.0 Ga - __ __ __ __ __ 0.2 Tg 312 348 339 364 368 361 -Tx > 650 -630 585 640 625 630 -TX Tg > 335 --280 246 275 255 270 -np 2.283 2.265 - 2.264 2.252 2.241 2.308 In order to achieve corelcladding structures with a comparable NA in the basic GeGaAsS or GeInAsS systems, the thermal stability (TX TB) of typical cladding glasses is on the order of 230-250°C. However, the Tx Tg of Si-5 substituted glasses can be maintained at a value in excess of 250°C
over a wide range of compositions, and in some cases can be in excess of that of the base GeAs sulphide glass, as illustrated in Fig. 2 of the drawings.
The composition of the Si containing cladding glasses comprise the following approximate ranges in terms of mole percent on the sulfide basis (see Tabie 2): 50-95 % GeS2, 2-40% AsZS3, 0.1-30% SiS2, 0-20% Ga2S3 and /or InZS3, 0-10 % MSX, where M is selected from Ca, Sr, Ba, Ag, Tl, Cd, Hg, Sn, Pb, Y, La and other rare-earth metals of the lanthanide series, or Sb, 0-5 % of the corresponding metal selenide andlor telluride, 0-20 % of the corresponding metal halide, and wherein the sulfur and/or selenium and/or tellurium content can vary between 85-125 % of the stoichiometric value.
Table 2 (Mole %) Glass 1 2 3 4 5 6 7 GeS2 75.0 66.7 58.3 81.0 72.0 63.0 83.3 SiSz 8.3 16.7 25.0 9.0 18.0 27.0 -WO 99/23517 PCTNS9$n2739 Ga2S3 _ _ _ _ _ _ 0.3 As2S3 16.7 16.7 16.7 10.0 10.0 10.0 16.3 prZS3 _ _ _ _ _ _ 0.03 In a second embodiment of the present invention, the glasses consist principally of Ge, As and S, t Ga andlor In, with a small but necessary addition of P. Other metals, including Ca, Sr, Ba, Ag, TI, Cd, Hg, Sn, Pb, Y, La and other rare-earth metals from the lanthanide series and Sb, as well as optional anionic components such as Se, Te and the halogens F, CI, Br and I, can be added to optimize various other physical properties such as thermal expansion, viscosity, etc., but are not essential constituents. Compositions (in atomic %) of suitable P containing glasses that are useful for the purpose of cladding a core consisting of GeGaAsS or GeInAsS glass are given below in Table 3:
Table 3 (Atomic %) Glass 8 9 10 11 12 13 14 Ge 24.4 23.8 23.6 23.3 22.2 19.5 16.9 P 2.4 4.8 5.7 7.0 2.5 4.9 7.2 As 7.3 4.8 3.8 2.3 9.9 9.8 9.6 S 65.9 66.7 67.0 67.4 65.4 65.8 66.3 Glass 15 16 17 18 19 20 21 Ge 23.0 22.1 21.3 22.8 21.9 21.1 23.6 P 4.8 4.8 4.8 5.7 5.7 5.7 2.4 As 5.7 6.7 7.7 4.7 5.7 6.7 7.1 S 66.5 66.4 66.2 66.8 66.7 66.5 66.9 In this embodiment, the incorporation of P in a GeAs sulphide glass results in a progressive decrease of refractive index, and a reduced tendency of GeS2 to crystallize, leading to enhanced thermal stability. Accordingly, when Example 8 is used as cladding for a core glass with the composition of Example ?, the resultant fibre is expected to have a numerical aperture of 0.32 which is more than adequate for a sulphide 1.3 Eun amplifier fibre.
The compositions of these phosphorous containing cladding glasses comprise the following approximate ranges in terms of mole percent on the sulfide basis (see Table 4); 50-95% GeS2, 2-40% As2S3, 0.1-25% P2S5, 0-20%
Ga2S3 andlor In2S3, 0-10% MSx, where M is selected from Ca, Sr, Ba, Ag, Tl, Cd, Hg, Sn, Pb, Y, La and other rare-earth metals of the lanthanide series, or Sb, 0-S % of the corresponding metal selenide and/or telluride, 0-20% of the corresponding metal halide, and wherein the sulfur and/or selenium andlor tellurium content can vary between 85-125 % of the stoichiometric value.
Table 4 (Mole %) Glass 8 9 10 11 12 13 14 GeSz 83.3 83.3 83.3 83.3 78.3 72.7 66.7 PZSs 4.2 8.3 10.0 12.5 4.4 ~ 9.1 14.3 ASzS3 12.5 8.3 6.7 4.2 17.4 18.2 19.1 Tx > 583 > 577 > 557 > 544 > 512 TX Tg > 252 > 240 > 242 > 227 > 232 np 2.286 2.259 2.239 2.314 2.316 2.317 Glass 15 16 17 18 19 20 21 GeS2 81.4 79.3 77.2 81.3 79.3 77.2 83.3 PISS 8.5 8.6 8.8 10.2 10.3 10.5 4.2 AsZS3 10.2 12.1 14.0 8.5 10.3 12.3 12.5 Excess - - - - - - 105 S
np 2.280 2.278 2.298 2.275 2.285 2.289 --Fig. 5 illustrates that the substitution of 2.5 At% P for Ge lowers the refractive index by about 0.022 for glasses with the (Ge,P)uAs,oSbs stoichiometry.
While the present invention has been particularly shown and described with reference to the preferred mode as illustrated in the drawing, it will be understood by one skilled in the art that various changes in detail may be effected therein without departing from the spirit and scope of the invention as defined by the claims.
Claims (31)
1. An optical fiber which exhibits improved thermal stability and enhanced light guiding properties comprising;
(a) a core which is made of a glass selected from the group consisting of GeGaAsS and GeInAsS; and (b) a glass cladding surrounding said core, said cladding being made of a GeAs sulphide glass which contains Si in an amount sufficient to lower the refractive index of said GeAs sulphide glass and improve its thermal stability.
(a) a core which is made of a glass selected from the group consisting of GeGaAsS and GeInAsS; and (b) a glass cladding surrounding said core, said cladding being made of a GeAs sulphide glass which contains Si in an amount sufficient to lower the refractive index of said GeAs sulphide glass and improve its thermal stability.
2. The optical fiber of claim 1 in which the Si is present in a concentration of from about 0.1 to 30 % SiS2.
3. The optical fiber of claim 1 in which the glass cladding comprises the following composition in mole percent:
GeS2 50-95%
AS2S3 2-40%
SiS2 0.1-30%
GeS2 50-95%
AS2S3 2-40%
SiS2 0.1-30%
4. An optical fiber which exhibits improved thermal stability and enhanced light guiding properties comprising;
(a) an inner core which is made of an AsGe sulfide glass; and (b) a glass cladding surrounding said core, said cladding being made of a GeAs sulphide glass which contains Si in an amount sufficient to lower the refractive index of said GeAs sulphide glass, and improve its thermal stability.
(a) an inner core which is made of an AsGe sulfide glass; and (b) a glass cladding surrounding said core, said cladding being made of a GeAs sulphide glass which contains Si in an amount sufficient to lower the refractive index of said GeAs sulphide glass, and improve its thermal stability.
5. The optical fiber of claim 4 in which the Si is present in a concentration of from about 0.1 to 30% SiS2.
6. The optical fiber of claim 4 in which the glass cladding comprises the following composition in mole percent:
GeS2 50-95%
As2S3 2-40%
SiS2 0.1-30%
GeS2 50-95%
As2S3 2-40%
SiS2 0.1-30%
7. An optical fiber which exhibits improved thermal stability and enhanced light guiding properties comprising;
(a) an inner glass core which is doped with a suitable rare earth element and which is made of a glass selected from the group consisting of GeGaAsS and GeInAsS; and (b) a transparent glass cladding surrounding said core, said cladding being made of a GeAs sulphide glass which contains Si in an amount sufficient to lower the refractive index of said GeAs sulphide glass and improve its thermal stability.
(a) an inner glass core which is doped with a suitable rare earth element and which is made of a glass selected from the group consisting of GeGaAsS and GeInAsS; and (b) a transparent glass cladding surrounding said core, said cladding being made of a GeAs sulphide glass which contains Si in an amount sufficient to lower the refractive index of said GeAs sulphide glass and improve its thermal stability.
8. The optical fiber of claim 7 in which the Si is present in a concentration of up to about 30 mole percent SiS2.
9. The optical fiber of claim 7 in which the glass cladding comprises the following composition in mole percent:
GeS 50-95%
AS2S3 2-4.0%
SiS2 0.1-30%
GeS 50-95%
AS2S3 2-4.0%
SiS2 0.1-30%
10. The fiber of claim 7 in which the rare earth dopant is Pr.
11. A glass composition which is suitable for use as a stable cladding for an optical fiber which comprises a GeAs sulfide glass which contains Si in an amount sufficient to lower the refractive index of the glass and improve its thermal stability.
12. The composition of claim 11 in which the Si is present in a concentration of up to about 30 mole percent of SiS2 of the total glass composition.
13. The composition of claim 11 in which the glass composition contains Ga and/or In in a concentration of up to about 20 mole percent of Ga2S3 and/or In2S3.
14. A stable glass composition suitable for use in cladding optical fibers comprising in mole percent:
GeS2 50-95%
As2S3 2-40%
SiS2 0.1-30%
Ga2S3 0-20%
In2S3 0-20%
MSx 0-10%
where M is selected from Ca, Sr, Ba, Ag, Tl, Cd, Hg, Pb, Y, La and other rare earth metals of the lanthanide series, or Sb.
GeS2 50-95%
As2S3 2-40%
SiS2 0.1-30%
Ga2S3 0-20%
In2S3 0-20%
MSx 0-10%
where M is selected from Ca, Sr, Ba, Ag, Tl, Cd, Hg, Pb, Y, La and other rare earth metals of the lanthanide series, or Sb.
15. The composition of claim 14 in which any one of the recited sulfides may be replaced with 0-5% of the corresponding metal selenide and/or telluride, and/or 0-20% of the corresponding metal halide, and in which the sulfur and/or selenium and/or tellurium content can vary between 85-125% of the stoichiometric value.
16. An optical fiber which exhibits improved thermal stability and enhanced light guiding properties comprising;
(a) a core which is made of a glass selected from the group consisting of GeGaAsS and GeInAsS; and (b) a glass cladding surrounding said core, said cladding being made of a GeAs sulphide glass which contains P in an amount sufficient lower the refractive index of said GeAs sulphide glass and improve its thermal stability.
(a) a core which is made of a glass selected from the group consisting of GeGaAsS and GeInAsS; and (b) a glass cladding surrounding said core, said cladding being made of a GeAs sulphide glass which contains P in an amount sufficient lower the refractive index of said GeAs sulphide glass and improve its thermal stability.
17. The optical fiber of claim 16 in which the P is present in a concentration of from about 0.1 to 25 mole percent of P2S5.
18. The optical fiber of claim 16 in which the glass cladding comprises the following composition in mole percent:
GeS2 50-95%
As2S3 2-40%
P2S5 0.1-25%
GeS2 50-95%
As2S3 2-40%
P2S5 0.1-25%
19. An optical fiber which exhibits improved thermal stability and enhanced light guiding properties comprising;
(a) an inner core which is made of an AsGe sulfide glass; and (b) a glass cladding surrounding said core, said cladding being made of a GeAs sulphide glass which contains P in an amount sufficient to lower the refractive index of said GeAs sulphide glass, and improve its thermal stability.
(a) an inner core which is made of an AsGe sulfide glass; and (b) a glass cladding surrounding said core, said cladding being made of a GeAs sulphide glass which contains P in an amount sufficient to lower the refractive index of said GeAs sulphide glass, and improve its thermal stability.
20. The optical fiber of claim 19 in which the P is present in a concentration of from about 0.1 to 25 mole percent of P2S5.
21. The optical fiber of claim 19 in which the glass cladding comprises the following composition in mole percent:
GeS2 50-95%
AS2S3 2-40%
P2S5 0.1-25%
GeS2 50-95%
AS2S3 2-40%
P2S5 0.1-25%
22. An optical fiber which exhibits improved thermal stability and enhanced light guiding properties comprising:
(a) an inner glass core which is doped with a suitable rare earth element and which is made of a glass selected from the group consisting of GeGAAsS and GeInAsS; and (b) A transparent glass cladding surrounding said core, said cladding being made of a GeAs sulphide glass which contains P in an amount sufficient to lower the refractive index of said GeAs sulphide glass and improve its thermal stability.
(a) an inner glass core which is doped with a suitable rare earth element and which is made of a glass selected from the group consisting of GeGAAsS and GeInAsS; and (b) A transparent glass cladding surrounding said core, said cladding being made of a GeAs sulphide glass which contains P in an amount sufficient to lower the refractive index of said GeAs sulphide glass and improve its thermal stability.
23. The optical fiber of claim 22 in which the Si is present in a concentration of up to about 25 mole percent P2S5.
24. The optical fiber of claim 22 in which the glass cladding comprises the following composition in mole percent:
GeS2 50-95%
As2S3 2-40%
P2S5 0.1-25%
GeS2 50-95%
As2S3 2-40%
P2S5 0.1-25%
25. The fiber of claim 22 in which the core is doped with Pr.
26. A glass composition which is suitable for use as a stable cladding for an optical fiber which comprises a GeAs sulfide glass which contains P in an amount sufficient to lower the refractive index of the glass and improve its thermal stability.
27. The composition of claim 26 in which the glass composition contains Ga and/or In in a concentration of up to about 20 mole percent of Ga2S3 and/or In2S3.
28. The composition of claim 26 in which P is present in a concentration of up to about 25 mole percent of P2S5 of the total glass composition.
29. A stable glass composition suitable for use in cladding optical fibers comprising in mole percent:
GeS2 50-95%
AS2S3 2-40%
P2S5 0.1-25%
Ga2S3 0-20%
In2S3 0-20%
MS x 0-10%
where M is selected from Si, Ca, Sr, Ba, Ag, Tl, Cd, Hg, Pb, Y, La and other rare earth metals of the lathanide series, or Sb.
GeS2 50-95%
AS2S3 2-40%
P2S5 0.1-25%
Ga2S3 0-20%
In2S3 0-20%
MS x 0-10%
where M is selected from Si, Ca, Sr, Ba, Ag, Tl, Cd, Hg, Pb, Y, La and other rare earth metals of the lathanide series, or Sb.
30. The composition of claim 28 in which any one of the recited sulfides may be replaced with 0-5% of the corresponding metal selenide and/or telluride, and/or 0-20% of the corresponding metal halide, and in which the sulfur and/or selenium and/or tellerium content can vary between 85-125% of the stoichiometric value.
31. A glass composition which is suitable for use as a stable cladding for an optical fiber which comprises a GeAs sulfide glass which contains Si and/or P in an amount sufficient to lower the refractive index of the glass and improve its thermal stability.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US6427397P | 1997-11-04 | 1997-11-04 | |
| US60/064,273 | 1997-11-04 | ||
| PCT/US1998/022739 WO1999023517A1 (en) | 1997-11-04 | 1998-10-27 | Stable cladding glasses for sulphide fibres |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2306267A1 true CA2306267A1 (en) | 1999-05-14 |
Family
ID=22054774
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002306267A Abandoned CA2306267A1 (en) | 1997-11-04 | 1998-10-27 | Stable cladding glasses for sulphide fibres |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1036343A4 (en) |
| JP (1) | JP2001521875A (en) |
| CN (1) | CN1278927A (en) |
| AU (1) | AU1281199A (en) |
| CA (1) | CA2306267A1 (en) |
| WO (1) | WO1999023517A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6505975B2 (en) | 2013-03-15 | 2019-04-24 | スコット コーポレーションＳｃｈｏｔｔ Ｃｏｒｐｏｒａｔｉｏｎ | Optical bonding and formed products using low softening point optical glass for infrared optics |
| CN108585483B (en) * | 2018-06-22 | 2021-04-27 | 武汉理工大学 | Melting process of germanium-based infrared chalcogenide glass |
| CN112955792B (en) * | 2018-12-13 | 2023-05-05 | 住友电气工业株式会社 | Optical fiber |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3370964A (en) * | 1964-03-02 | 1968-02-27 | Texas Instruments Inc | Glasses and method of making same |
| US3655255A (en) * | 1970-07-13 | 1972-04-11 | Bell Telephone Labor Inc | Acoustic-optic ultrasonic devices using germanium containing chalcogenide glasses |
| JPS5935039A (en) * | 1982-08-18 | 1984-02-25 | Nippon Telegr & Teleph Corp <Ntt> | Optical fiber for transmitting infrared ray |
| JPS62252338A (en) * | 1986-04-22 | 1987-11-04 | Hoya Corp | Infrared transmission material |
| GB8624600D0 (en) * | 1986-10-14 | 1986-11-19 | British Telecomm | Coating for optical fibre |
| JPS63218521A (en) * | 1987-03-06 | 1988-09-12 | Hisankabutsu Glass Kenkyu Kaihatsu Kk | Production of chalcogenide glass |
| US5136677A (en) * | 1989-12-21 | 1992-08-04 | Galileo Electro-Optics Corporation | Photorefractive effect in bulk chalcogenide glass and devices made therefrom |
| US5389584A (en) * | 1994-04-11 | 1995-02-14 | Corning Incorporated | Ga- and/or In-containing AsGe sulfide glasses |
| US5757446A (en) * | 1994-10-14 | 1998-05-26 | Energy Conversion Devices, Inc. | Liquid crystal display matrix array employing ovonic threshold switching devices to isolate individual pixels |
| EP0717012B1 (en) * | 1994-11-24 | 1998-06-10 | Hoya Corporation | Laser glasses and laser glass fibers |
-
1998
- 1998-10-27 CA CA002306267A patent/CA2306267A1/en not_active Abandoned
- 1998-10-27 WO PCT/US1998/022739 patent/WO1999023517A1/en not_active Application Discontinuation
- 1998-10-27 JP JP2000519318A patent/JP2001521875A/en active Pending
- 1998-10-27 EP EP98956240A patent/EP1036343A4/en not_active Withdrawn
- 1998-10-27 CN CN 98810950 patent/CN1278927A/en active Pending
- 1998-10-27 AU AU12811/99A patent/AU1281199A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| AU1281199A (en) | 1999-05-24 |
| EP1036343A4 (en) | 2001-08-29 |
| JP2001521875A (en) | 2001-11-13 |
| WO1999023517A1 (en) | 1999-05-14 |
| CN1278927A (en) | 2001-01-03 |
| EP1036343A1 (en) | 2000-09-20 |
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| Date | Code | Title | Description |
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| FZDE | Discontinued |