Past exam of the MPhil in micro- and nanotechnology enterprise course of the University of Cambridge / 2020 / Paper 1 / Section A(iii) / 7

The Seebeck effect produces an open-circuit voltage when a material has a temperature gradient: $S=-dV/dT$ for the stated sign convention. A circuit containing dissimilar thermoelectric legs converts this into useful voltage and current. The intrinsic thermoelectric figure of merit isHere $\sigma$ is electrical conductivity and $\kappa ={\kappa }_e+{\kappa }_L$ total thermal conductivity. $Z$ has units ${\mathrm{K}}^{-1}$; $ZT$ is dimensionless. A large Seebeck coefficient and electrical conductivity, together with low thermal conductivity, favour efficient conversion.

At low carrier concentration, $|S|$ can be large but electrical conductivity is too small. Increasing the carrier concentration usually increases $\sigma =ne\mu$, while $|S|$ decreases. Electronic thermal conductivity rises approximately as ${\kappa }_e=L\sigma T$ by the Wiedemann-Franz law; lattice conduction supplies an additional background. Thus neither an insulator nor an ordinary metal usually maximizes $Z$.

Heavily doped semiconductors and semimetals often give the useful compromise, near a maximum of $S^2\sigma /\kappa$ as doping is varied. The optimum is material- and temperature-dependent; there is no universal optimal concentration.

Tune doping to the optimum carrier concentration; a rise in conductivity is useful only if it outweighs the accompanying loss of thermopower and extra electronic heat conduction. Band convergence, favourable density of states and energy-dependent transport can improve the power factor $S^2\sigma$, provided mobility is retained.

Reduce lattice thermal conductivity through alloy disorder, heavy or complex unit cells, grain boundaries and nanoscale inclusions that scatter phonons. Aim to scatter heat-carrying phonons much more strongly than charge carriers; indiscriminate disorder can reduce both thermal and electrical conductivity. Nanostructuring and interfaces can therefore help, but an improvement must be demonstrated in total $ZT$ at the operating temperature, not inferred from lower $\kappa$ alone.^[ref]