Structure of GexGa8Se92-x Glasses Studied by High-resolution X-ray Photoelectron Spectroscopy
XU Siwei1,*, WANG Rongping2, WANG Xunsi2
1 Hunan Key Laboratory of Photoelectric Information Integration and Optical Manufacturing Technology, College of Mathematics and Physics, Hunan University of Arts and Science, Changde 415000, Hunan, China 2 Zhejiang Key Laboratory of Photoelectric Materials and Devices, The Research Institute of Advanced Technologies, Ningbo University, Ningbo 315211,Zhejiang, China
Abstract: Chalcogenide glass Ge-Ga-Se has become an important matrix material for active photonic devices such as fiber lasers, optical amplifiers and planar waveguides due to its remarkable properties. Therefore, understanding the structure of Ge-Ga-Se glass in the systematic way is essential for the design of optimal optical glasses. However, the information provided by Raman scattering, infrared spectroscopy, and nuclear magnetic resonance for the study of Ge-Ga-Se glasses structure is incomplete to varying degrees. Therefore, in the work, we prepared a group of GexGa8Se92-x chalcogenide glasses (x=16%, 20%, 24%, 26.67%, 29.6%, 32% and 36%), and measured their structural by high-resolution X-ray photoelectron spectroscopy, in order to understand the evolution of the glass structure with chemical composition. From the Ge, Ga and Se 3d XPS spectra, it can be found that Ge and Ga atoms mainly exhibit 4-fold coordination in Ge-Ga-Se glass, and Ga atoms preferentially form a 4-fold coordination structure before Ge atoms. However, the Se atoms of GexGa8Se92-x glass are 2-fold coordinated regardless of whether the glass is Se-rich or Se-poor. As the Ge-Ga-Se chalcogenide glass composition changes from Se-rich to Se-poor, it can be found that the integrated area of Se-Se-Se and Se-Se-Ge/Ga doublet decreases with increasing Ge concentration, and is completely suppressed in the Ge26.67Ga8Se65.33 and Ge32Ga8Se60 glasses. The GeSe4 and GaSe4 tetrahedral structural units in Se-rich chalcogenide glasses were gradually destroyed and evolved into defect states, especially in the glasses containing high concentrations of Ge or Ga atoms. It is shown that the Ga atoms are more evenly distributed in the Se-rich compared with those in the Se-poor Ge-Ga-Se glass, so it is more suitable as hosts for the doping of rare earth ions.
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2025, Vol. 39 
