Thermoelectric technology enables the harvest of waste heat and its direct conversion into electricity. The conversion efficiency is determined by the materials figure of merit Here we show a maximum of ~2.8 ± 0.5 at 773 kelvin in n-type tin selenide (SnSe) crystals out of plane. The thermal conductivity in layered SnSe crystals is the lowest in the out-of-plane direction [two-dimensional (2D) phonon transport]. We doped SnSe with bromine to make n-type SnSe crystals with the overlapping interlayer charge density (3D charge transport). A continuous phase transition increases the symmetry and diverges two converged conduction bands. These two factors improve carrier mobility, while preserving a large Seebeck coefficient. Our findings can be applied in 2D layered materials and provide a new strategy to enhance out-of-plane electrical transport properties without degrading thermal properties.

Due to point defect phonon scattering, formation of solid solutions has long been considered as an effective approach for enhancing thermoelectric performance through reducing the lattice thermal conductivity. The scattering of phonons by point defects mainly comes from the mass and strain fluctuations between the guest and the host atoms. Both the fluctuations can be maximized by point defects of interstitial atoms and/or vacancies in a crystal. Here, a demonstration of phonon scattering by interstitial Cu atoms is shown, leading to an extremely low lattice thermal conductivity of 0.5 W m−1 K−1 in SnTe‐Cu2Te solid solutions. This is the lowest lattice thermal conductivity reported in SnTe‐based materials so far, which is actually approaching the amorphous limit of SnTe. As a result, a peak thermoelectric figure of merit, zT, higher than 1 is achieved in Sn0.94Cu0.12Te at 850 K, without relying on other approaches for electrical performance enhancements. The strategy used here is believed to be equally applicable in thermoelectrics with interstitial point defects.

In order to locate the optimal carrier concentrations for peaking the thermoelectric performance in p‐type group IV monotellurides, existing efforts focus on aliovalent doping, either to increase (in PbTe) or to decrease (in SnTe and GeTe) the hole concentration. The limited solubility of aliovalent dopants usually introduces insufficient phonon scattering for thermoelectric performance maximization. With a decrease in the size of cation, the concentration of holes, induced by cation vacancies in intrinsic compounds, increases rapidly from ≈1018 cm−3 in PbTe to ≈1020 cm−3 in SnTe and then to ≈1021 cm−3 in GeTe. This motivates a strategy here for reducing the carrier concentration in GeTe, by increasing the mean size of cations and vice‐versa decreasing the average size of anions through isovalent substitutions for increased formation energy of cation vacancy. A combination of the simultaneously resulting strong phonon scattering due to the high solubility of isovalent impurities, an ultrahigh thermoelectric figure of merit, zT of 2.2 is achieved in GeTe–PbSe alloys. This corresponds to a 300% enhancement in average zT as compared to pristine GeTe. This work not only demonstrates GeTe as a promising thermoelectric material but also paves the way for enhancing the thermoelectric performance in similar materials.