Raman scattering in the IVB transition-metal trichalcogenides: ZrS3, ZrSe3, ZrTe3and HfSe3

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Abstract
Phonons in the quasi-one-dimensional compounds ZrS3, ZrSe3, ZrTe3 and HfSe3 have been investigated by Raman spectroscopy. Most of the structures observed have been assigned to Raman active zone centre phonons. Although twelve such k=0 optical phonons are theoretically predicted, some of them are still missing; particularly, the authors failed to excite most of the Bg modes (which involve atomic motions along the b axis of the crystal) even with different laser frequencies. The more complete Ag spectra are characterised by two sets of three major lines, well separated in frequency except for ZrTe3. The low-frequency set is attributed to scattering by rigid chain modes while the upper-frequency set is assigned to intrachain modes. The close relationship between analogous spectra from the different compounds suggests the establishment of one-to-one correspondence between the phonons and their wavenumbers by simple scaling relations. The Ag spectra from HfSe3 exhibit a strong dependence upon laser frequency in the range 1.83-2.73 eV.

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