Thermoelectric power and its correlation with conductivity in NbS3 whiskers

We report studies of the Seebeck coefficient $S$ of the quasi-one-dimensional compound $\mathrm{Nb}{\mathrm{S}}₃$, together with the temperature dependence of its specific conductivity ${\ensuremath{\sigma}}_{\mathrm{s}}$ and heat capacity ${c}_p$. The monoclinic phase $(\mathrm{Nb}{\mathrm{S}}₃$-II) is studied over the temperature range $T=80--400$ K, which covers two charge density wave (CDW) transitions at ${T}_{\mathrm{P}1}=360$ K (CDW-1) and ${T}_{\mathrm{P}2}=150$ K (CDW-2). The $S(T)$ curves show features in the vicinities of both CDW transitions and appear to be correlated with the value of ${\ensuremath{\sigma}}_{\mathrm{s}}(300\phantom{\rule{0.28em}{0ex}}\mathrm{K})$: The increase of $S$ below ${T}_{\mathrm{P}1}$ in the high-Ohmic samples reveals a complete dielectrization of the electronic spectrum, while in the low-Ohmic samples $S$ decreases below ${T}_{\mathrm{P}1}$ and even becomes negative below ${T}_{\mathrm{P}2}$. The magnitude of $S$ in low-Ohmic samples at $T<{T}_{\mathrm{P}2}$ is well below ${k}_{\mathrm{B}}/e\ensuremath{\approx}86\phantom{\rule{0.28em}{0ex}}\ensuremath{\mu}\mathrm{V}/\mathrm{K},{k}_B$ being the Boltzmann constant and $e$ the elementary charge, which is surprisingly low for a usual CDW semiconducting state. Our results suggest that at ${T}_{\mathrm{P}1}$ the main electronic band with $p$-type carriers becomes gapped, while some $n$-type carriers can remain in a separate band with low density of states. These carriers, whose concentration is defined by the compositional doping, are gapped at ${T}_{\mathrm{P}2}$. We also report $S$ for the triclinic dielectric phase of $\mathrm{Nb}{\mathrm{S}}₃\phantom{\rule{4pt}{0ex}}(\mathrm{Nb}{\mathrm{S}}₃\text{\ensuremath{-}}\mathrm{I})$. Its low absolute value, $\ensuremath{\sim}{k}_{\mathrm{B}}/e$, and the anomalous temperature dependence demonstrate that $\mathrm{Nb}{\mathrm{S}}₃\text{\ensuremath{-}}\mathrm{I}$ is neither a semiconductor nor a CDW conductor in the usual sense.