Quasi-1D TiS₃ Nanoribbons: Mechanical Exfoliation and Thickness-Dependent Raman Spectroscopy

Quasi-one-dimensional (quasi-1D) materials enjoy growing interest due to their unusual physical properties and promise for miniature electronic devices. However, the mechanical exfoliation of quasi-1D materials into thin flakes and nanoribbons received considerably less attention from researchers than the exfoliation of conventional layered crystals. In this study, we investigated the micromechanical exfoliation of representative quasi-1D crystals, TiS₃ whiskers, and demonstrate that they typically split into narrow nanoribbons with very smooth, straight edges and clear signatures of 1D TiS₃ chains. Theoretical calculations show that the energies required for breaking weak interactions between the two-dimensional (2D) layers and between 1D chains within the layers are comparable and, in turn, are considerably lower than those required for breaking the covalent bonds within the chains. We also emulated macroscopic exfoliation experiments on the nanoscale by applying a local shear force to TiS₃ crystals in different crystallographic directions using a tip of an atomic force microscopy (AFM) probe. In the AFM experiments, it was possible to slide the 2D TiS₃ layers relative to each other as well as to remove selected 1D chains from the layers. We systematically studied the exfoliated TiS₃ crystals by Raman spectroscopy and identified the Raman peaks whose spectral positions were most dependent on the crystals' thickness. These results could be used to distinguish between TiS₃ crystals with thickness ranging from one to about seven monolayers. The conclusions established in this study for the exfoliated TiS₃ crystals can be extended to a variety of transition metal trichalcogenide materials as well as other quasi-1D crystals. The possibility of exfoliation of TiS₃ into narrow (few-nm wide) crystals with smooth edges could be important for the future realization of miniature device channels with reduced edge scattering of charge carriers.