Waveguide structure

Abstract: This invention is directed broadly to transparent glasses exhibiting excellent transmission far into the infrared region of the electromagnetic radiation spectrum, those glasses consisting essentially, expressed in terms of mole percent, of 40-80% Ga 2 S 3 , 0-35% RS x , wherein R is at least one network forming cation selected from the group consisting of aluminum, antimony, arsenic, germanium, and indium, 1-50% Ln 2 S 3 , wherein Ln is at least one cation selected from the group consisting of a rare earth metal cation and yttrium, 1-45% MS x , wherein M is at least one modifying metal cation selected from the group consisting of barium, cadmium, calcium, lead, lithium, mercury, potassium, silver, sodium, strontium, thallium, and tin, and 0-10% total chloride and/or fluoride. Glass compositions consisting essentially, expressed in terms of mole percent, of 5-30% Ga 2 S 3 , 0-10% R 2 S 3 , wherein R is at least one network forming cation selected from the group consisting of aluminum, antimony, arsenic, and indium, 55-94.5% GeS 2 , 0.5-25% MS x , wherein M is at least one modifying metal cation selected from the group consisting of barium, cadmium, calcium, lead, lithium, potassium, silver, sodium, strontium, tin, yttrium, and a rare earth metal of the lanthanide series, 0-10% total selenide, 0-25% total chloride and/or fluoride, and wherein the sulfur and/or selenium content can vary between 85-125% of the stoichiometric value when doped with Pr demonstrate exceptionally high values of τ.

Description: The present invention relates to a waveguide structure exhibiting a desired numerical aperture. US Patent No 5,240,885 (Aitken et al ) describes the preparation of rare earth metal-doped cadmium halide glasses, which glasses transmit radiation well into the infrared portion of the electromagnetic radiation spectrum due to their low phonon energy. That capability commended their utility for the fabrication of efficient lasers, amplifiers and upconverters when doped with the appropriate rare earth metals. Because metal-sulfur bonds are generally weaker than metal-oxygen bonds, sulfide glasses exhibit much lower phonon energies than oxide glasses and, therefore, transmit radiation much further into the infrared region of the electromagnetic radiation spectrum. Accordingly, sulfide glasses were seen to have the potential of being excellent host materials of rare earth metals for applications such as those listed above requiring efficient radiative emission. Unfortunately, however, many sulfide glasses are black and, consequently, are unsuitable for some of the above applications inasmuch as such a host glass would tend to absorb the pump radiation instead of the rare earth metal dopant. One of the best known sulfide glasses, viz., arsenic sulfide, is transparent to radiation in the long wavelength range of the visible portion of the radiation spectrum as well as far into the infrared region and, hence, would appear to be a suitable host glass for rare earth metals. Nevertheless, rare earth metals have been found to be relatively insoluble in arsenic sulfide glasses, and it has proven to be difficult to dope those glasses with enough rare earth metal for sufficient pump power absorption. Rare earth metals are known to be very soluble in most oxide glasses and their apparent insolubility in arsenic sulfide glasses has been conjectured to be due to the gross structural dissimilarity existing between the latter and oxide glasses. Arsenic sulfide glasses are believed to consist of long chains and layers of covalently bonded pyramidal AsS 3 groups, whereas oxide glasses typically comprise a three-dimensional network of relatively ionically bonded MO 4 tetrahedra, where M is a so-called network-forming metal such as silicon, phosphorus, aluminum, boron, etc. Rare earth metals are readily accommodated in these ionic network structures where they can compensate charge imbalances that arise from the presence of two or more network-forming metals, e.g., aluminum and silicon in aluminosilicate glasses -- energetically similar sites may not exist in the two-dimensional covalent structures typical of arsenic sulfide and related glasses. One system of sulfide glasses which exhibit good transparency in both the visible and infrared portions of the radiation spectrum, and which possess a relatively ionic three-dimensional structure that would be expected to be more accommodating of rare earth metals, comprises gallium sulfide glasses. In contrast to arsenic sulfide glasses, the structure of these glasses is based upon a three-dimensional linkage of corner sharing GaS 4 tetrahedra. Rare earth metals are readily soluble in these glasses. In fact, some of the most stable gallium sulfide glasses contain a rare earth metal as a major constituent. Of general interest are U.S. Patents 4,612,294, 4,704,371 and 4,942,144, and the following Literature Articles: ["Verres Formes Par Les Sulfures L 2 S 3 Des Terres Rares Avec Le Sulfure De Gallium Ga 2 S 3 ", Loireau-Lozac'h et al., Mat. Res. Bull., 11 , 1489-1496 (1976)]. Other academic studies of gallium sulfide-containing glasses have included the following publications: ["Systeme GeS 2 -Ga 2 S 3 Diagramme De Phases Obtention Et Proprietes Des Verres", Loireau-Lozac'h et al , Ann. Chim., 10 , 101-104 (1975)]; ["Etude Du Systeme Ga 2 S 3 -Na 2 S", Palazzi, C. R. Acad. Sc. Paris, 229, Serie II, No 9, 529-532 (1984)]; ["Study on Ge-Ga-x(X=S,Se) Glass Systems", Xilai et al, Collected Papers, XIV Intl. Cong. on glass, 118-127 (1986)]; ["Le Systeme Ga 2 S 3 -Ag 2 S", Guittard et al , Ann. Chim. 8, 215-225 (1983)]; ["An EXAFS Structural Approach of the Lanthanum-Gallium-Sulfur Glasses", Benazeth et al, J. Non-Cryst. Solids, 110, 89-100 (1989)]; ["Glass Formation and Structural Studies of Chalcogenide Glasses in the CdS-Ga 2 S 3 -GeS 2 System", Barnier et al, Materials Science and Engineering, B7, 209-214 (1990)], {"F NMR Study of [(Ga 2 S 3 ) 0.25 (GeS 2 ) 0.75 ] 0.75 (NaF) 0.25 Glass", Baidakov et al , Soviet Journal of Glass Physics and Chemistry, 18, No 4, 322-324 (1992)}; ["Chalcogenide Glasses in Ga 2 S 3 -GeS 2 -MeF n Systems", Orkina et al , Glass Physics and Chemistry, 19, No 3, (1993)]; ["Active Fiber Research Highlights", Snitzer et al , Fiber Optics Materials Research Program, Rutgers University, page 32 (April 13, 1993)] and ["Pr 3+ :La-Ga-S Glass: A Promising Material for 1.3µm Fiber Amplification", Becker et al, Optical Amp. and Their Appl., PD5, 19-23 (1992)]. The above listing of literature references is indicative of the extensive research which has been conducted in recent years in the general field of gallium sulfide-containing glasses. In addition "Proprietes magnetiques de phases amorphes de composition 1,8 Ga 2 S 3 -(LaGd) 2 S 3 ", Wintenberger et al, C R Acad. Sc., Paris t292, Serie II, No 7, 563-566 (1981) describes measurements of the susceptibility and high field magnetisation in the glassy phase 1.8Ga 2 S 3 -Gd 2 S 3 and corresponding glass with the gadolinium largely replaced by lanthanum. The refractive index of lanthanum gallium sulfide glass is about 2.5 and our experiments indicated that the index appears to be rather insensitive to variations in the La:Ga ratio. We have found that the partial replacement of lanthanum with other rare earth metals, in particular gadolinium, can lead to a significant increase in the refractive index. Such replacements can, in principle, allow one to achieve a core/clad structure with a numerical aperture well in excess of 0.4. Accordingly, the present invention provides a waveguide structure exhibiting a desired numerical aperture comprising a core glass demonstrating a high refractive index surrounded by a cladding glass demonstrating a lower refractive index, characterised in that the cladding glass consists of a lanthanum gallium sulfide glass and the core glass consists of a lanthanum gallium sulfide glass wherein gadolinium has replaced a sufficient proportion of the lanthanum to raise the refractive index thereof to a value appropriate to achieve the desired numerical aperture in the waveguide structure. Thus according to the present invention, an effective waveguide structure comprises a core glass demonstrating a high refractive index surrounded by a cladding glass exhibiting a lower refractive index, the difference in those refractive indices being selected to achieve a desired numerical aperture. The cladding glass consists of a lanthanum gallium sulfide glass and the core glass consists of a lanthanum gallium sulfide glass wherein gadolinium has replaced a sufficient proportion of the lanthanum to raise the refractive index to a value appropriate to achieve the desired numerical aperture. Table I records two glass compositions, expressed in terms of mole percent, illustrating lanthanum gallium sulfide glasses with a proportion of the lanthanum replaced with gadolinium. The glasses were doped with Pr 3+ ions to determine the level of τ. Because the glasses were prepared in the laboratory, a sulfide was used for each component. Such is not necessary, however. Thus, sulfur-containing batch materials other than sulfides can be utilized so long as the chosen materials, upon melting together with the other batch ingredients, are converted into the desired sulfide in the proper proportions. The glasses were prepared by compounding the batch constituents, thoroughly mixing the constituents together to aid in securing a homogeneous glass, and then dispensing the batch mixtures into vitreous carbon or alumina crucibles. The crucibles were moved into a furnace operating at about 1000-1100°C, maintained at that temperature for about 15-60 minutes, the melts thereafter poured into steel molds to form discs having a diameter of 4 cm and a thickness of 5 mm, and those discs transferred immediately to an annealer operating at about 500°-550°C. Table I also recites the density (Den.), expressed in terms of g/cm 3 , the transition temperature (T g ) and the temperature of the onset of crystallation (T x ), expressed in terms of °C, the refractive index (n D ), and the τ values, expressed in terms of µsec, of each glass where measured. 1 2 Ga 2 S 3 65.00 65.00 La 2 S 3 24.95 17.45 CaS --- --- BaS --- --- In 2 S 3 --- --- EuS --- --- Gd 2 S 3 10.00 17.50 Pr 2 S 3 0.05 0.05 Den. 4.15 4.22 T g 549 541 T x 658 657 n D --- 2.60 τ 218 212

Claims: A waveguide structure exhibiting a desired numerical aperture comprising a core glass demonstrating a high refractive index surrounded by a cladding glass demonstrating a lower refractive index, characterised in that the cladding glass consists of a lanthanum gallium sulfide glass and the core glass consists of a lanthanum gallium sulfide glass wherein gadolinium has replaced a sufficient proportion of the lanthanum to raise the refractive index thereof to a value appropriate to achieve the desired numerical aperture in the waveguide structure.

Inventors: AITKEN BRUCE GARDINER, NEWHOUSE MARK ANDREW, AITKEN, BRUCE GARDINER, NEWHOUSE, MARK ANDREW
Applicants: CORNING INC, CORNING INCORPORATED
Application year: 1995
Main classification: C03C3
IPC codes: C03C13, C03C3