Compared to infrared absorption and Raman spectra,which mayhave provided qualitative evidence for structural changes,theanalysis by high-resolution X-ray photoelectron spectroscopy(XPS)is quantitative,more straightforward,and capable ofprobing the short-range order around each constituentchemical element of the glass networks.In general,the identification procedure is based on the main principle ofXPS dataanalysisthat the position or binding energyof a corelevel XPS peak of a given atom would shift with respect tonormal position as a result of the following: a.changes in its coordination;b.changes in the ionic state;c.substitution of one or more of its neighbors by achemical element with different electronegativities or charge states,etc.1)The resolution as high as 0.05 eV of XPS made it possible to quantitatively deconvolute the core level spectra of a certain element to interpret its surrounding structure environment.In this work,we used high-resolution XPS to understand influence of bismuth on topological self-organization in selenide networks and study network changes of oxy-chalcogenide amorphous films caused by super band-gap light exposure.