Surface sulphination of germanium oxide based materials

Laëtitia Petit (1) , Kathleen Richardson (1) , B. Campbell (2) , Glenn Orveillon (2) , Thierry Cardinal (2) , François Guillen (2) , Christine Labrugère (2) , Philippe Vinatier (2) , Michel Couzi (3) , W. Li (4) , S. Seal (4)

1 CREOL - The College of Optics and Photonics [Orlando]
2 ICMCB - Institut de Chimie de la Matière Condensée de Bordeaux
3 LPCM - Laboratoire de Physico-Chimie Moléculaire
4 AMPAC, Department of Mechanical

The effect of oxygen substitution for sulphur has been investigated in germanium and boron based glasses con-taining heavy metal oxides (Sb2O3). After heat treat-ment under H2S flow, the colour of the glass (powder and bulk) changes from colourless to yellowish indica-tive of anion exchange. The oxygen substitution for sul-phur has been confirmed by the presence of a new Raman band located at 340 cm-1 corresponding to a Ge–S and Sb–S bond vibration. The influence of the borate addition has been studied. XPS measurements have shown (i) the oxidation of Sb3+ to Sb5+ during the melting which increases with an increase of boron content and (ii) the reduction of Sb5+ to Sb3+ during the sulphination, resulting in the departure of more than one oxygen anion upon replacement by one sulphur and in the absence of weight gain. It has been clearly dem-onstrated that sulphination near the oxide glass tran-sition temperature can lead to the formation of oxysulphide glass materials.

Mots clés: Glass transition temperature; Heat treatment; Redox reaction; Glasses; Physical properties; Sulphination; Antimony boron germanate; Oxysulfide

Domaines: Matériaux

Laëtitia Petit, Kathleen Richardson, B. Campbell, Glenn Orveillon, Thierry Cardinal, et al.. Surface sulphination of germanium oxide based materials. Physics and Chemistry of Glasses - European Journal of Glass Science and Technology Part B, 2004, 45 (6), pp.315-321. ⟨hal-00157926⟩