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A thermoelectric generator maintains hot and cold junctions of two materials with different Seebeck coefficients. Mobile charge carriers redistribute in the temperature gradient, producing an open-circuit voltage of magnitude $|V|=|S_p-S_n|\Delta T$ for constant coefficients. A load permits electric current; pairs of p-type and n-type legs are commonly connected electrically in series and thermally in parallel. Maintaining the output requires continuous heat transfer from the hot reservoir and rejection of heat to the cold reservoir. The thermoelectric figure of merit $ZT=S^2\sigma T/\kappa$ expresses the favorable combination of large Seebeck coefficient, large electrical conductivity and small thermal conductivity. Contact losses, Joule heating and parasitic heat leaks reduce practical efficiency.

A pyroelectric generator instead exploits a change of spontaneous electric polarization with temperature. If the relevant component of the pyroelectric coefficient is $p=d{P}_s/dT$, an electrode of area $A$ receives a short-circuit electric current approximately $I=pAdT/dt$. A heating stroke and a cooling stroke produce opposite charge changes. Rectification or a synchronized electrical cycle can transfer energy to storage. A spatial temperature difference drives the thermoelectric device; a temporal temperature change drives the pyroelectric device. Uniform, constant temperature gives no continuing current from pyroelectricity even if the material is hot. Reported nanowire generators deliberately use changing temperature, rather than infer continuous generation from a static hot specimen.^[ref]

Both approaches can be compact, silent and free of macroscopic moving parts. The thermoelectric generator gives continuous output under a sustained gradient, but needs two effective thermal contacts and sufficient heat flow; very small $\Delta T$ gives a small voltage and thermal contacts can consume much of the available gradient. Thin films exhibiting pyroelectricity can respond to intermittent heating without a permanently maintained hot/cold separation across their thickness, but require repeated thermal cycling, low electrical leakage and suitable charge extraction. Their thermal time constant limits useful cycling frequency, and sensible heating/cooling can dominate the heat budget. A steady hot pipe with an available cold sink favors a thermoelectric generator; periodic radiative heating can favor a pyroelectric generator. Neither converts equilibrium thermal motion at a single fixed temperature into sustained useful work.

A thermoelectric generator uses the Seebeck effect and needs a spatial temperature gradient: a couple develops $V\simeq (S_p-S_n)\Delta T$ between hot and cold junctions. It can deliver continuous power under a steady thermal gradient and has no moving parts, but requires sustained heat flow and adequate hot- and cold-side thermal contacts. Thermal conduction, internal electrical resistance and the material's thermoelectric figure of merit limit conversion.

A pyroelectric generator responds to a time-dependent spontaneous electric polarization. Under approximately uniform heating or cooling, $I=pAdT/dt$ when the electrical boundary condition allows charge flow. It can harvest temporal thermal fluctuations without a persistent spatial gradient. However, at a constant uniform temperature its ordinary pyroelectric current stops; practical extraction needs cycling, low-leakage electronics and a suitable load. A large open-circuit voltage is not evidence of a large available average power. Temperature-driven nanowire measurements provide a primary experimental example of this distinction.^[ref]

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.

For one homogeneous thermoelectric material, the dimensional thermoelectric figure of merit isThe dimensionless quantity is $ZT$. The Seebeck coefficient $S$ measures the open-circuit voltage response to a temperature difference and reflects the energy asymmetry of charge-carrier transport. The electrical conductivity $\sigma$ depends on carrier density and mobility and sets electrical loss; $\rho =1/\sigma$. The thermal conductivity is $\kappa ={\kappa }_e+{\kappa }_l$, with contributions from carriers and phonons, and represents unwanted heat leakage.

Increasing carrier concentration usually raises $\sigma$ while reducing $|S|$ once transport becomes strongly degenerate. The electronic part of $\kappa$ also tends to rise, approximately through the Wiedemann-Franz law where applicable. This competition produces an intermediate optimum, commonly in heavily doped semiconductors, rather than in a very resistive insulator or an ordinary high-carrier-density metal. The optimum depends on band structure and scattering; the schematic is not a universal measured concentration curve.