  Nanobelts, nanoribbons and other quasi-one-dimensional nanostructures formed
from layered, so-called, van der Waals semiconductors have garnered much
attention due to their high-performance, tunable optoelectronic properties. For
layered alloys made from the gallium monochalcogenides GaS, GaSe, and GaTe,
near-continuous tuning of the energy bandgap across the full composition range
has been achieved in GaSe1-xSx and GaSe1-xTex alloys. Gold-catalyzed
vapor-liquid-solid (VLS) growth of these alloys yields predominantly nanobelts,
nanoribbons and other nanostructures for which the fast crystal growth front
consists of layer edges in contact with the catalyst. We demonstrate that in
the S-rich, GaS1-xTex system, unlike GaSe1-xSx and GaSe1-xTex, the Au-catalyzed
VLS process yields van der Waals nanowires for which the fast growth direction
is normal to the layers. The high mismatch between S and Te leads to
extraordinary bowing of the GaS1-xTex alloy's energy bandgap, decreasing by at
least 0.6 eV for x as small as 0.03. Calculations using density functional
theory confirm the significant decrease in bandgap in S-rich GaS1-xTex. The
nanowires can exceed fifty micrometers in length, consisting of tens of
thousands of van der Waals-bonded layers with triangular or hexagonal
cross-sections of uniform dimensions along the length of the nanowire. We
propose that the low solubility of Te in GaS results in an enhancement in Te
coverage around the Au catalyst-nanowire interface, confining the catalyst to
the chalcogen-terminated basal plane (rather than the edges) and thereby
enabling layer-by-layer, c-axis growth.
