Unique Structural Features of NbS₃ Ribbon Whiskers

The X-ray diffraction analysis of NbS₃ ribbon whiskers has revealed three structural features: (i) a fine-crystalline structure throughout the entire volume with the preferred orientation along the [001] direction perpendicular to the long b axis of the whisker, (ii) the combination of crystalline macroblocks with a length up to 0.5 mm with small crystallites of various orientations, and (iii) the combination of crystalline macroblocks with the left-hand twisting of planes around the b axis with a pitch angle of 1.25° per every 0.2 mm and with the return to the initial orientation in the next block. Structural features (ii) and (iii) of NbS₃ whiskers have not yet been observed, and inorganic crystals with such properties are absent to the best of our knowledge. All crystallites have a unit cell with almost right angles and approximately the same lattice constant c (18.130 Å), whereas the lattice constants a and b are noticeably different in a single sample. All crystallites can be referred to phase IV rather than to phase I, as expected. The right angle between the a and c axes can be explained by the twinning of phase I along the c axis. Differences in the lattice constants in macroblocks indicate large stresses in structures. Such stresses near twins (and/or stacking faults) can significantly affect the free electron density and play a key role in the formation of charge density waves in various phases of NbS₃.