Disorder in GeSe2 small crystals and medium-range structure in amorphous GeSe2

The Raman scattering spectra of various forms of GeSe₂, such as amorphous films, single crystals, and small crystals prepared by a gas-evaporation deposition technique, are investigated with an excitation photon energy ranging from 2.1 to 2.8 eV. In the spectra of the crystals, there are two Raman bands, originating from two types of breathing vibrations of the GeSe_4/2 tetrahedra: one is spread over the corner-sharing tetrahedra and the other is quasi-localized on the edge-sharing tetrahedra. In addition to the resonant Raman scattering related to the edge-sharing tetrahedra through the exciton transition observed with 2.71 eV excitation in the single crystals, a new resonant spectrum is found only in the small crystals with 2.54 eV excitation. With increasing disorder in the crystals, the intensity ratio between the two breathing vibration bands increases in the off-resonant excitation region. The Raman spectra in the amorphous states are ascribed to the breathing vibrations of GeSe_4/2 tetrahedra which form a medium-range structure topologically similar to that of crystalline fragments.