Recently single crystals of layered SnSe have created a paramount importance in thermoelectrics owing to their ultralow lattice thermal conductivity and high thermoelectric figure of merit (zT). However, nanocrystalline or polycrystalline SnSe offers a wide range of thermoelectric applications for the ease of its synthesis and machinability. Here, we demonstrate high zT of ∼2.1 at 873 K in two-dimensional nanoplates of Ge-doped SnSe synthesized by a simple hydrothermal route followed by spark plasma sintering (SPS). Anisotropic measurements also show a high zT of ∼1.75 at 873 K parallel to the SPS pressing direction. Ge doping (3 mol %) in SnSe nanoplates significantly enhances the p-type carrier concentration, which results in high electrical conductivity and power factor of ∼5.10 μW/cm K 2 at 873 K. High lattice anharmonicity, nanoscale grain boundaries, and Ge precipitates in the SnSe matrix synergistically give rise to the ultralow lattice thermal conductivity of ∼0.18 W/mK at 873 K.

The present review provides an in-depth insight into the structure–property relationship focusing on the electronic and phonon transport properties of various 2D layered state-of-the-art thermoelectric materials.

SnSe, an environmentally friendly layered chalcogenide, has fostered immense attention in the thermoelectric community with its high thermoelectric figure of merit in single crystals. Although the stride toward developing superior p-type SnSe as a thermoelectric material is progressing rapidly, synthesis of n-type SnSe is somewhat overlooked. Here, we report the solution-phase synthesis and thermoelectric transport properties of twodimensional (2D) ultrathin (1.2−3 nm thick) few-layer nanosheets (2−4 layers) of n-type SnSe. The n-type nature of the nanosheets initially originates from chlorination of the material during the synthesis. We could increase the carrier concentration of n-type SnSe significantly from 3.08 × 10 17 to 1.97 × 10 18 cm −3 via further Bi doping, which results in an increase of electrical conductivity and power factor. Furthermore, Bi-doped nanosheets exhibit ultralow lattice thermal conductivity (∼0.3 W/mK) throughout the temperature range of 300−720 K, which can be ascribed to the effective phonon scattering by an interface of SnSe layers, nanoscale grain boundaries, and point defects.

Single crystals of SnSe have gained considerable attention in thermoelectrics due to their unprecedented thermoelectric performance. However, polycrystalline SnSe is more favorable for practical applications due to its facile chemical synthesis procedure, processability, and scalability. Though the thermoelectric figure of merit (zT) of p‐type bulk SnSe polycrystals has reached >2.5, zT of n‐type counterpart is still lower and lies around ≈1.5. Herein, record high zT of 2.0 in n‐type polycrystalline SnSe0.92 + x mol% MoCl5 (x = 0–3) samples is reported, when measured parallel to the spark plasma sintering pressing direction due to the simultaneous optimization of n‐type carrier concentration and enhanced phonon scattering by incorporating modular nano‐heterostructures in SnSe matrix. Modular nanostructures of layered intergrowth [(SnSe)1.05]m(MoSe2)n like compounds embedded in SnSe matrix scatters the phonons significantly leading to an ultra‐low lattice thermal conductivity (κlat) of ≈0.26 W m−1 K−1 at 798 K in SnSe0.92 + 3 mol% MoCl5. The 2D layered modular intergrowth compound resembles the nano‐heterostructure and their periodicity of 1.2–2.6 nm in the SnSe matrix matches the phonon mean free path of SnSe, thereby blocking the heat carrying phonons, which result in low κlat and ultra‐high thermoelectric performance in n‐type SnSe.

Two-dimensional layered tin selenide (SnSe) has attracted immense interest in thermoelectrics due to its ultralow lattice thermal conductivity and high thermoelectric performance. To date, the majority of thermoelectric studies of SnSe have been based on single crystals. However, because synthesizing SnSe single crystals is an expensive, time-consuming process that requires high temperatures and because SnSe single crystals have relatively weaker mechanical stability, they are not favorable for scaling up synthesis, commercialization, or practical applications. As a result, research on nanocrystalline SnSe that can be produced in large quantities by simple and low-temperature solution-phase synthesis is needed. In this Perspective, we discuss the progress in thermoelectric properties of SnSe with a particular emphasis on nanocrystalline SnSe, which is grown in solution. We first describe the state-of-the-art high-performance single crystal and polycrystals of SnSe and their importance and drawbacks and discuss how nanocrystalline SnSe can solve some of these challenges. We illustrate different solution-phase synthesis procedures to produce various SnSe nanostructures and discuss their thermoelectric properties. We also highlight a unique solution-phase synthesis technique to prepare CdSe-coated SnSe nanocomposites and its unprecedented thermoelectric figure of merit (ZT) of 2.2 at 786 K, as reported in this issue of ACS Nano. In general, solution synthesis showed excellent control over nanoscale grain growth, and nanocrystalline SnSe shows ultralow thermal conductivity due to strong phonon scattering by the nanoscale grain boundaries. Finally, we offer insight into the opportunities and challenges associated with nanocrystalline SnSe synthesized by the solution route and its future in thermoelectric energy conversion.