In situ high-pressure X-ray diffraction study of densification of a molecular chalcogenide glass

Structural mechanisms of densification of a molecular chalcogenide glass of composition Ge2.5As51.25S46.25 have been studied in situ at pressures ranging from 1 atm to 11 GPa at ambient temperature as well as ex situ on a sample quenched from 12 GPa and ambient temperature using high-energy X-ray diffraction. The X-ray structure factors display a reduction in height of the first sharp diffraction peak and a growth of the principal diffraction peak with a concomitant shift to higher Q-values with increasing pressure. At low pressures of at least up to 5 GPa the densification of the structure primarily involves an increase in the packing of the As4S3 molecules. At higher pressures the As4S3 molecules break up and reconnect to form a high-density network with increased extended-range ordering at the highest pressure of 11 GPa indicating a structural transition. This high-density network structure relaxes only slightly on decompression indicating that the pressure-induced structural changes are quenchable.