Molecular structure of Se-rich amorphous films

Structure and its transformation are examined for amorphous Se-rich As_xSe_1-x (0 ≤ x ≤ 0.2) alloys by employment of diffraction and non-diffraction structural probes. It is shown that the molecular structure of amorphous Se (a-Se) on the scale of short-range order is close to that of crystalline phase, while medium-range order differs from the structure of most inorganic glasses and may be placed between three-dimensional network glasses and polymeric ones. Further experiments show the existence of successive phases in laser-induced glass-crystalline transition with pronounced threshold behavior. Below the energy density threshold, E_th, only small changes in the local structure of the system can be detected. Above E_th, the changes were attributed to crystallization transformation. The corresponding Raman spectra reveal transformation of the system from amorphous into the crystalline phase under laser irradiation. In the binary As_xSe_1-x glass system, a change of structural regime takes place near the composition x ≈ 0.04. The presence of this topological threshold is established by direct and indirect evidence, such as peculiarities in the composition dependence of the basic parameters for electron diffraction and Raman vibration modes. The peculiarities are caused by the transition from a chain-ring-like structure to preferentially a chain-like structure. Experiments described in this section have shown that Raman technique is a particularly sensitive method to determine the presence of microcrystal's in the glassy matrix. Room-temperature polarized Raman scattering spectra of model glass have been collected. Low-frequency peaks were observed in the spectra. A model is proposed for explanation of their appearance. It is shown clearly that the low-frequency Raman spectra allow determining the conditions at the boundaries, sizes as well as concentration of micro-heterogeneities in non-crystalline materials. It was established earlier that for all amorphous (glassy) materials a low-frequency peak, observed in the corresponding spectral region of Raman scattering and called boson peak, is inherent. This peak is absent in crystals of the same chemical composition and is associated with space correlations on the scale of medium-range order R_c ≈ 10 Å. On the contrary, less known is that a boson peak can give important information about the presence of microcrystalline inclusions and heterogeneities in the low-frequency Raman spectra of glasses irrespective to their chemical composition.