TY - JOUR
T1 - Role of SSe ratio in chemical bonding of As-S-Se glasses investigated by Raman, x-ray photoelectron, and extended x-ray absorption fine structure spectroscopies
AU - Li, Wenyan
AU - Seal, Sudipta
AU - Rivero, Clara
AU - Lopez, Cedric
AU - Richardson, Kathleen
AU - Pope, April
AU - Schulte, Alfons
AU - Myneni, Satish
AU - Jain, Himanshu
AU - Antoine, Keisha
AU - Miller, Alfred C.
N1 - Funding Information:
We would like to thank the National Science Foundation for supporting this work through NSF Grant Nos. DMR-9974129 and DMR-0312081. Our appreciation also extends to the Materials Characterization Facility at the University of Central Florida (UCF), the Physics Department at UCF, Zettlemoyer Center for Surface Studies at Lehigh University, and Stanford Synchrotron Radiation Laboratory for their hospitality and staff support. Table I. Raman data fitting parameters (peak position and peak width both in wave number) and peak assignments. Peak position (Wave number, cm − 1 ) Width (Wave number, cm − 1 ) (Gaussian/Lorentzian) Peak assignment 212 14.5 ∕ 0.007 Interaction of the As Se 3 pyramids 227 19.6 ∕ 10.3 As–Se vibration in As Se 3 pyramidal units 241 16 ∕ 1 As–Se vibration in As Ch 3 units and/or Se–Se chain 257 15.87 ∕ 9 As–Se vibration in As Ch 3 units and/or Se–Se ring fracture 269 18 ∕ 1.5 Interaction of the As Se 3 pyramids 312 24.3 ∕ 5.65 Interaction of the As Se 3 pyramids 340 30 ∕ 10.7 As–S vibration in As Se 3 pyramidal units 362 17 ∕ 9.8 As–S vibration in As Ch 3 units or interaction between As Se 3 and S–S chain ( ∼ 365 ) 380 30 ∕ 7.85 Interaction of the As Se 3 pyramids Table II. XPS data fitting parameters: Δ is the doublet binding energy separation for p or d orbits, DR is the area ratio for the doublets, FWHM is the full width at half maximum of the peaks, and Mix is the Gaussian/Lorentzian mix factor of the peaks. Δ (eV) DR FWHM (eV) Mix As 3 d 0.694 0.71 0.69 0.87 Se 3 d 0.85 0.76 0.75 0.93 Se 3 p 5.72 0.41 1.97 0.6 S 2 p 1.185 0.505 0.77 0.87 Table III. EXAFS data-fitting results: N —neighboring atom number; R —the distance from neighboring atom to the absorbing atom; σ —the standard deviation of the interatomic distance, and Δ E 0 —correction for estimated edge step E 0 . Composition Fitting Shell N R (Å) σ 2 ( Å 2 ) Δ E 0 (eV) As 24 S 38 Se 38 With S As–S 3.1 2.29 0.0035 − 7.4 As 24 S 57 Se 19 With S As–S 3.31 2.3 0.004 − 5.916 As 24 S 19 Se 57 Add Se As–S 1.92 2.32 0.0004 3.679 As–Se 2 2.49 0.011 3.679 FIG. 1. The ternary composition diagram of the As–S–Se system. The compositions on the diagram is as follows (mol %): (1) As 40 S 60 , (2) As 40 S 45 Se 15 , (3) As 40 S 30 Se 30 , (4) As 40 S 15 Se 45 , (5) As 40 Se 60 , (6) As 24 S 76 , (7) As 24 S 57 Se 19 , (8) As 24 S 38 Se 38 , (9) As 24 S 19 Se 57 , and (10) As 24 Se 76 . FIG. 2. Raman spectra and deconvolution of bulk chalcogenide glasses As 40 S 60 − x Se x . FIG. 3. XPS As 3 d spectra and deconvolution of bulk chalcogenide glasses As 40 S 60 − x Se x . FIG. 4. XPS Se 3 d spectra and deconvolution of bulk chalcogenide glasses As 40 S 60 − x Se x . FIG. 5. XPS S 2 p and Se 3 p spectra and deconvolution of bulk chalcogenide glasses As 40 S 60 − x Se x . FIG. 6. Valence bands in As 40 S 60 − x Se x bulk chalcogenide glasses. FIG. 7. Raman spectra and deconvolution of bulk chalcogenide glasses As 24 S 76 − x Se x . FIG. 8. XPS As 3 d spectra and deconvolution of bulk chalcogenide glasses As 24 S 76 − x Se x . FIG. 9. XPS Se 3 d spectra and deconvolution of bulk chalcogenide glasses As 24 S 76 − x Se x . FIG. 10. XPS S 2 p and Se 3 p spectra and deconvolution of bulk chalcogenide glasses As 24 S 76 − x Se x . FIG. 11. Valence bands in As 24 S 76 − x Se x bulk chalcogenide glasses. FIG. 12. (a) Arsenic K -edge EXAFS spectra and (b) the Fourier-transformed arsenic K -edge EXAFS for As 24 S 76 − x Se x . Three sample compositions examined include [Fig. 1 composition number]: (1) As 24 S 19 Se 57 [9], (2) As 24 S 38 Se 38 [8], and (3) As 24 S 57 Se 19 [7].
PY - 2005/9/1
Y1 - 2005/9/1
N2 - Chalcogenide glasses have attracted considerable attention and found various applications due to their infrared transparency and other optical properties. The As-S-Se chalcogenide glass, with its large glass-formation domain and favorable nonlinear property, is a promising candidate system for tailoring important optical properties through modification of glass composition. In this context, a systematic study on ternary As-S-Se glass, chalcogen-rich versus well-studied stochiometric compositions, has been carried out using three different techniques: Raman spectroscopy, x-ray photoelectron spectroscopy, and extended x-ray absorption fine structure spectroscopy. These complementary techniques lead to a consistent understanding of the role of SSe ratio in chalcogen-rich As-S-Se glasses, as compared to stochiometric composition, and to provide insight into the structural units (such as the mixed pyramidal units) and evidence for the existence of homopolar bonds (such as Se-Se, S-S, and Se-S), which are the possible structural origin of the high nonlinearity in these glasses.
AB - Chalcogenide glasses have attracted considerable attention and found various applications due to their infrared transparency and other optical properties. The As-S-Se chalcogenide glass, with its large glass-formation domain and favorable nonlinear property, is a promising candidate system for tailoring important optical properties through modification of glass composition. In this context, a systematic study on ternary As-S-Se glass, chalcogen-rich versus well-studied stochiometric compositions, has been carried out using three different techniques: Raman spectroscopy, x-ray photoelectron spectroscopy, and extended x-ray absorption fine structure spectroscopy. These complementary techniques lead to a consistent understanding of the role of SSe ratio in chalcogen-rich As-S-Se glasses, as compared to stochiometric composition, and to provide insight into the structural units (such as the mixed pyramidal units) and evidence for the existence of homopolar bonds (such as Se-Se, S-S, and Se-S), which are the possible structural origin of the high nonlinearity in these glasses.
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U2 - 10.1063/1.2009815
DO - 10.1063/1.2009815
M3 - Article
AN - SCOPUS:25144468541
SN - 0021-8979
VL - 98
JO - Journal of Applied Physics
JF - Journal of Applied Physics
IS - 5
M1 - 053503
ER -