oOo \ Refractive Index Dispersion of Gallium Lanthanum Sulfide and Oxysulfide Glasses Hiroyuki Yayama, Shigeru Fujino, Kenji Morinaga Department of Materials Science and Technology, Graduate School of Engineering Sciences, Kyushu University, Kasuga, Fukuoka 816, Japan Hiromichi Takebet, Daniel W. Hewak, David N. Payne ae Research Centre, University of Southampton, Highfield, Southampton SO17 1B, ‘TCorresponding author Hiromichi Takebe Currently at Onto etronics Research Centre, University of Southampton, Highfield, Southampton SO17 1B, iy Tel +44-1703-593954, Fax +44-1703-593149, E-mail ht@orc.soton.ac.uk Permanent address Department of Materials Science and Technology, Graduate School of Engineering Sciences, Kyushu University, Kasuga, Fukuoka 816, Japan Tel +81-92-583-7529, Fax +81-92-75-2318, E-mail takeigz@mbox.nc.kyushu-u.ac,jpAbstract Refractive indexes were measured for Ga2S3-La2S3 and Ga2S3-La203 glasses in the range of 0.48 and 1.71 jim using the minimum deviation method. Data is analyze¢ by the Wemple equation based on the single oscillator model. These glasses have relatively large average bandgaps Eo, and electronic oscillator strengths Ea, in comparison with other chalcogenide glasses. Possible origins of these features are discussed. 1. Introduction Gallium lanthanum sulfide (GLS) glass is one of leading candidates for 1.3 um optical fibre amplifiers (1], infrared lasers [2, 3], acousto-optic modulators [4], and optical switching devices [5]. It possesses high quantum efficiencies of the forced electric dipole transitions, resulting from high radiative rate and low non-radiative multiphonon decay rate. These desirable properties follow from its high refractive indexes over 2.4 [6] and a low maximum phonon energy of ~ 425 cm! [1]. GLS glass is of particular interest for practical devices because of its relatively low toxicity, thermal stability and ability to draw into fibre, as well as its superior optical properties. The high refractive index with a wide optically transparent range of 0.5 and 10 jum [4] also results in high third-order optical nonlinearity due to the electronic origin for ultra-fast optical switching [5]. The purpose of this study is to measure accurate refractive indexes of GLS-based glasses in the UV and near- infrared region, which are useful data to characterize optical materials, and to discuss their dispersion characteristics in comparison with other chalcogenide, oxide and fluoride glasses for optic applications. 2. Experimental Procedure Glass samples with molar compositions of 70Ga2S3+30La2S3 (GLS) and 70Ga2S3+30La203 (GLSO) were prepared by melt-quenching the mixed powders in a vitreous carbon crucible. Starting materials of Ga2S3, La2S3 and La2Os were provided by Merck Ltd; Ga2S3 and La2S3 starting powders typically contains less than 0.1 and 1% oxides, respectively. Density was 2determined by the Archimedes method using kerosene as an immersion liquid. The refractive index was measured with a precision spectrometer (Model GMR-1, Kalnew, Nagano, Japan) at 23°C in the wavelength range of 0.4800 and 1.7101 ym using Hg, Cd, Ha and He lamps as spectral sources. Measured refractive indexes were analyzed by using the Wemple equation based on the single electronic oscillator model in the region from UV to near infrared as [9] ExEo OA Eee a where n is the refractive index, E is the photon energy, Eo is the average electronic energy gap, Ea is the electronic oscillator strength. High refractive index is derived from large Eo and/or Ea, according to eq. (1). Since there are some electronic oscillators relating to cations, sulfur and oxygen ions in the UV region, the material parameters Eo and Ed give average features of the oscillators. Eq. (1) is modified to a convenient form to fit the data as 1. _& ot = Ea” Bees ie Eoand Ea were obtained from the slope and intercept of the relationship between 1/ (n? -1) and E2. ‘The straight lines were fitted to the refractive index data points at 10 and 15 different wavelengths for the GLS and GLSO respective glasses. 3. Results Prepared samples were homogeneous and transparent with dark-brown in color for the GLS glass and with pale-yellow for the GLSO glass. Densities of the GLS and GLSO glasses were 4.03 and 4.26 g/cm?, respectively. Table 1 summarizes measured refractive indexes of the GLS and GLSO glasses in the region from 0.48 to 1.71 um. The error for refractive indexes caused by the inhomogeneity of the samples did not exceed + 2.0 x 10-3, These data were used to plot the valuesof I/ (n2-1) as a function of E2, as shown in Fig.1; the material parameters Eo and Ea of the GLS and GLSO glasses were determined from the straight lines. Similar analysis was performed using refractive indexes of sulfide (8, 9] and oxide [11] glasses for comparison. Table 2 summarizes the representative refractive indexes and the materials parameters Eoand Ed of the GLS, GLSO, sulfide [8, 9], selenide [10}, oxide [11] and fluoride [12] glasses. The refractive indexes na of the GLS and GLSO glasses are much higher than those of GesoS70, SiO2 and 20BaO*80TeO2 glasses and No of ZBLAN glass. The GLS and GLSO glasses have comparable nd values of heavy metal gallate glasses, 40Tl20*40Bi203+20Ga203 and 40PbO*40Bi203+20Ga203, respectively. The GLSO glass have a smaller nd than the GLS glass due to the substitution of S for O. Table 2 also shows a tendency of refractive index dispersion that higher refractive index is related to smaller Eo and it results in higher dispersion all through the glass systems. However, note that the GLS and GLSO glasses have relatively-large Eo in spite of their high refractive indexes over 2.3. This feature is related to high Ea values in comparison with the other glasses. In the following section, reasons for the high Ea in the GLS glass is discussed. 4. Discussion According to the Wemple equation shown as eq. (1), refractive index increases with decreasing average electronic band gap Eo and/or increasing electronic oscillator strength Ea. A general tendency in all the glass systems: chalcogenide, oxide and fluoride glasses is that high refractive index corresponds to a small Eo. In our previous study of multi-component oxide glasses ou by using the single-oscillator Drude- Voight equation, refractive index na was mainly affected by the effective resonance wavelength Ao all through oxide glasses. Since there is a relationship of Eo =hc/Ao, where h is the Plank constant, c is the light velocity, the previous tendency of nd in oxide glasses agrees with the present result in the various glass systems. As a typical example, thallium bismuth gallate (TBG) glass 40T120°40Bi203*20Ga20s has one of the highest nd (= 2.49214) in oxide glasses; its high na is related to a small Eo (larger Ao [11]) due to the longer resonance wavelengths of the electronic transitions of Ti+ and Bi3+ ions [13]. 4The GLS glass with a molar composition of 70Ga2S3+30La2S3 has a similar na (= 2.493) of the TBG glass, although the GLS glass has a larger Eo value of 5.9, compared with that of the TBG glass (Eo = 4.9). Therefore, the high na of the GLS glass fesults in the high Ed in the chalcogenide, oxide and fluoride glasses, as listed in Table 2. The electronic oscillator strength Ea has a relation with the Drude-Voight parameters N, f, 20 Ea = he2/nme x Nfho, Oy where ¢ is the electron charge, m is the mass of the electron, N is the number of molecules in a unit Volume of glass, fis the effective oscillator strength. Since the GLS glass should have a relatively- small Ao (large Eo), as a result, the large Ed is related to large Nf. There are some electronic oscillators due to Ga**, La**, S% ions in the GLS glass and the parameters N and f gives an average feature of these oscillators according to the single-oscillator model. Since S2- ions have a ‘much higher electronic polarizability than Ga** and La3+ ions and O2-ions [14], the high Ea of the GLS glass may be related to the large number of S?-ions in a unit volume with a large oscillator strength. Wemple and Didomenico {7, 15] showed an empirical rule of Eain crystalline materials as Ea=BxNex ZaxNe, @ where B = 0.37 + 0.04 eV in covalent materials (e.g., C, GaP, ZnS) and B = 0.26 + 0.03 eV in the more ionic materials (e.g., NaCl, Al20s), Ne is the anion coordination number of the cation, Zais the formal chemical valency of the anion and Neis the total number of valency electrons of the anion. Itis postulated that the following sum rule for Ea exists in the GLS glass, Ea (GLS glass) = 0.7 x Ea (GazS3) + 0.3 x Ea (LanSs). 6) The EXAFS study of gallium lanthanum sulfide 8lasses [16] revealed that the sulfur coordination number of Ga} and La3+ ions are 4 and 7.5, respectively, and La - § bonds has an ionic character. 5Tf one calculates the Ea values of Ga2Ss and LazSs by using eq, (4) and by considering the result of the EXAFS study [16] and Ga-S covalent bonding character in terms of electronegativity [17], obtained Ea are 0.37 x 4 x 2.x 8 = 23.7 (eV) for GaaSs and 0.26 x'7.5 x 2 x 8 = 31.2 (eV) for La2Ss. Note that a high sulfur coordination number of La>* ions gives a high Ea value of LaxSs, Calculated Ea value of the GLS glass using eq. (5) is 25.9 is comparable with the value Ea (= 26.7) oblained from refractive index dispersion data. Consequently, the large Ea value of the GLS glass is mainly due to the high sulfur coordination number (-7.5) of La ions. Ea of GLSO glass is also supposedly to concern with a high O?-ion coordination number of La3+ ions (- 7) [18]. The sulfur ion has a larger electronic polarizability, compared with cations including high polarizable ions with non-noble gas structure, ¢.g., Pb2*, Bi?* and other glass forming anions, ¢.¢,, OF (14). Our discussion reveals that the GLS glass has high refractive indexes ~ 2.5 due to the incorporation of LaaS3 with a high sulfur coordination number. This feature of the GLS glass is also likely to cause high third-order optical nonlinearity due to the electronic origin [5] in sulfide glasses. 5. Conclusions Accurate refractive indexes of the gallium lanthanum sulfide and oxysulfide glasses were measured in the wavelength range of 0.48 and 1.71 jm. These glass have high refractive indexes, for instance, na = 2.493 for the sulfide glass and né= 2.311 for the oxysulfide glass with relatively-low dispersion characteristics in chalcogenide glasses. 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Brasted, Comprehensive Inorganic Chemistry (D. Van Nostand Company, Inc., NJ, 1965) vol. 4, p. 170.Figure caption Figure 1 Relationship between 1/(n? -1) and E? for Wemple analysis.Table 1 Measured refractive indexes of gallium lanthanuin sulfide and oxysulfide glasses in the region of 0.48 and 1.71 ym.‘ Wavelength Refractive index (um) 70Ga2S3+30La2$370GarS3+30La203 0.48000 2316 0.49160 2.367 0.49219 2.366 0.50157 2.360 0.50858 2.353 0.54610 2.330 0.57897 2315 0.58756 2311 0.64385 2292 0.65627 2.289 0.66784 2.286 0.70652 2277 1.01398 2241 1.36731 2.226 1.71010 2.219Table 2 Refractive indexes and material parameters of chalcogenide, oxysulfide, oxide and fluoride glasses. * Material Refractive index E 0(eV) Ea(eV) Reference 70Ga2S330La2S3 5.9 26.7 this stay 70Ga2S330La203 64 24.6 this study GesoS70 58 18.2 (8) AswSeo 47 228 (9) GersSe7s 2378 45 209 [10] Ge2aSbi2Seso 2.628** 41 242 fo} SiO2 (Coming 7940) 1.45849* 124 13.6 [I] 20Ba0-80TeO2 210053 = 6.7205 fl] 40PbO*40Bi20320Ga203 _2.34640* 540 217 (1) 40TLO+40Bi203-20Ga03 2.49214" 4.9208 [1] ZBLAN 1.480*** 13.0 15.1 12) * He - d line: 0.5876 pm 3 *** Na - D line: 0.589 um0.30 ™ 70Ga2Sx30La2Ss 5 70Ga2Ss°30La203 Figure 1