Low Electron Scattering Potentials in High Performance Mg2Si0.45Sn0.55 Based Thermoelectric Solid Solutions with Band Convergence

Understanding the electron and phonon transport characteristics is crucial for designing and developing high performance thermoelectric materials. Weak scattering effects on charge carriers, characterized by deformation potential and alloy scattering potential, are favorable for thermoelectric solid solutions to enable high carrier mobility and thereby promising thermoelectric performance. Mg₂(Si,Sn) solid solutions have attracted much attention due to their low cost and environmental compatibility. Usually, their high thermoelectric performance with ZT ～ 1 is ascribed to the band convergence and reduced lattice thermal conductivity caused by alloying. In this work, both a low deformation potential Ξ = 13 eV and a low alloy scattering potential U = 0.7 eV are found for the thermoelectric alloys by characterizing and modeling of thermoelectric transport properties. The band convergence is also verified by the increased density‐of‐states effective mass. It is proposed that, in addition to band convergence and reduced lattice thermal conductivity, the low deformation potential and alloy scattering potential are additional intrinsic features that contribute to the high thermoelectric performance of the solid solutions.     

Bringing Conducting Polymers to High Order: Toward Conductivities beyond 105 S cm−1 and Thermoelectric Power Factors of 2 mW m−1 K−2

Here, an effective design strategy of polymer thermoelectric materials based on structural control in doped polymer semiconductors is presented. The strategy is illustrated for two archetypical polythiophenes, e.g., poly(2,5‐bis(3‐dodecyl‐2‐thienyl)thieno[3,2‐b]thiophene) (C₁₂‐PBTTT) and regioregular poly(3‐hexylthiophene) (P3HT). FeCl₃ doping of aligned films results in charge conductivities up to 2 × 10⁵ S cm^?1 and metallic‐like thermopowers similar to iodine‐doped polyacetylene. The films are almost optically transparent and show strongly polarized near‐infrared polaronic bands (dichroic ratio >10). The comparative study of structure–property correlations in P3HT and C₁₂‐PBTTT identifies three conditions to obtain conductivities beyond 10⁵ S cm^?1: i) achieve high in‐plane orientation of conjugated polymers with high persistence length; ii) ensure uniform chain oxidation of the polymer backbones by regular intercalation of dopant molecules in the polymer structure without disrupting alignment of π‐stacked layers; and iii) maintain a percolating nanomorphology along the chain direction. The highly anisotropic conducting polymer films are ideal model systems to investigate the correlations between thermopower S and charge conductivity σ. A scaling law S ∝ σ^?1/4 prevails along the chain direction, but a different S ∝ ?ln(σ) relation is observed perpendicular to the chains, suggesting different charge transport mechanisms. The simultaneous increase of charge conductivity and thermopower along the chain direction results in a substantial improvement of thermoelectric power factors up to 2 mW m^?1 K^?2 in C₁₂‐PBTTT.     

Engineering the Thermoelectric Transport in Half‐Heusler Materials through a Bottom‐Up Nanostructure Synthesis

Half‐Heusler (HH) alloys are among the best promising thermoelectric (TE) materials applicable for the middle‐to‐high temperature power generation. Despite of the large thermoelectric power factor and decent figure‐of‐merit ZT (≈1), their broad applications and enhancement on TE performance are limited by the high intrinsic lattice thermal conductivity (κ_L) due to insufficiencies of phonon scattering mechanisms, and the fewer powerful strategies associated with the microstructural engineering for HH materials. This study reports a bottom‐up nanostructure synthesis approach for these HH materials based on the displacement reaction between metal chlorides/bromides and magnesium (or lithium), followed by vacuum‐assisted spark plasma sintering process. The samples are featured with dense dislocation arrays at the grain boundaries, leading to a minimum κ_L of ≈1 W m^?1 K^?1 at 900 K and one of the highest ZT (≈1) and predicted η (≈11%) for n‐type Hf_0.25Zr_0.75NiSn_0.97Sb_0.03. Further manipulation on the dislocation defects at the grain boundaries of p‐type Nb_0.8Ti_0.2FeSb leads to enhanced maximum power factor of 47 × 10^?4 W m^?1 K^?2 and the predicted η of ≈7.5%. Moreover, vanadium substitution in FeNb_0.56V_0.24Ti_0.2Sb significantly promotes the η to ≈11%. This strategy can be extended to a broad range of advanced alloys and compounds for improved properties.     

Three‐Stage Inter‐Orthorhombic Evolution and High Thermoelectric Performance in Ag‐Doped Nanolaminar SnSe Polycrystals

The ultrahigh thermoelectric performance of SnSe‐based single crystals has attracted considerable interest in their polycrystalline counterparts. However, the temperature‐dependent structural transition in SnSe‐based thermoelectric materials and its relationship with their thermoelectric performance are not fully investigated and understood. In this work, nanolaminar SnSe polycrystals are prepared and characterized in situ using neutron and synchrotron powder diffraction measurements at various temperatures. Rietveld refinement results indicate that there is a complete inter‐orthorhombic evolution from Pnma to Cmcm by a series of layer slips and stretches along the a‐ and b‐axes over a 200 K temperature range. This phase transition leads to drastic enhancement of the carrier concentration and phonon scattering above 600 K. Moreover, the unique nanolaminar structure effectively enhances the carrier mobility of SnSe. Their grain and layer boundaries further improve the phonon scattering. These favorable factors result in a high ZT of 1.0 at 773 K for pristine SnSe polycrystals. The thermoelectric performances of polycrystalline SnSe are further improved by p‐type and n‐type dopants (i.e., doped with Ag and SnCl₂, respectively), and new records of ZT are achieved in Ag_0.015Sn_0.985Se (ZT of 1.3 at 773 K) and SnSe_0.985Cl_0.015 (ZT of 1.1 at 773 K) polycrystals.     

Synergistical Enhancement of Thermoelectric Properties in n‐Type Bi2O2Se by Carrier Engineering and Hierarchical Microstructure

Oxygen‐containing compounds are promising thermoelectric (TE) materials for their chemical and thermal stability. As compared with the high‐performance p‐type counterparts (e.g., ZT ≈1.5 for BiCuSeO), the enhancement of the TE performance of n‐type oxygen‐containing materials remains challenging due to their mediocre electrical conductivity and high thermal conductivity. Here, n‐type layered Bi₂O₂Se is reported as a potential TE material, of which the thermal conductivity and electrical transport properties can be effectively tuned via carrier engineering and hierarchical microstructure. By selective modification of insulating [Bi₂O₂]²⁺ layers with Ta dopant, carrier concentration can be increased by four orders of magnitude (from 10¹⁵ to 10¹⁹ cm^?3) while relatively high carrier mobility can be maintained, thus greatly enhancing the power factors (≈451.5 µW K^?2 m^?1). Meanwhile, the hierarchical microstructure can be induced by Ta doping, and the phonon scattering can be strengthened by atomic point defects, nanodots of 5–10 nm and grains of sub‐micrometer level, which progressively suppresses the lattice thermal conductivity. Accordingly, the ZT value of Bi_1.90Ta_0.10O₂Se reaches 0.36 at 773 K, a ≈350% improvement in comparison with that of the pristine Bi₂O₂Se. The average ZT value of 0.30 from 500 to 823 K is outstanding among n‐type oxygen‐containing TE materials. This work provides a desirable way for enhancing the ZT values in oxygen‐containing compounds.     

Highly Passivated n‐Type Colloidal Quantum Dots for Solution‐Processed Thermoelectric Generators with Large Output Voltage

Colloidal quantum dots (CQDs) are attractive materials for thermoelectric applications due to their simple and low‐cost processing; advantageously, they also offer low thermal conductivity and high Seebeck coefficient. To date, the majority of CQD thermoelectric films reported upon have been p‐type, while only a few reports are available on n‐type films. High‐performing n‐ and p‐type films are essential for thermoelectric generators (TEGs) with large output voltage and power. Here, high‐thermoelectric‐performance n‐type CQD films are reported and showcased in high‐performance all‐CQD TEGs. By engineering the electronic coupling in the films, a thorough removal of insulating ligands is achieved and this is combined with excellent surface trap passivation. This enables a high thermoelectric power factor of 24 µW m^?1 K^?2, superior to previously reported n‐type lead chalcogenide CQD films operating near room temperature (<1 µW m^?1 K^?2). As a result, an all‐CQD film TEG with a large output voltage of 0.25 V and a power density of 0.63 W m^?2 at ?T = 50 K is demonstrated, which represents an over fourfold enhancement to previously reported p‐type only CQD TEGs.     

Low‐Temperature‐Processed Colloidal Quantum Dots as Building Blocks for Thermoelectrics

Colloidal quantum dots (CQDs) are demonstrated to be promising materials to realize high‐performance thermoelectrics owing to their low thermal conductivity. The most studied CQD films, however, are using long ligands that require high processing and operation temperature (>400 °C) to achieve optimum thermoelectric performance. Here the thermoelectric properties of CQD films cross‐linked using short ligands that allow strong inter‐QD coupling are reported. Using the ligands, p‐type thermoelectric solids are demonstrated with a high Seebeck coefficient and power factor of 400 μV K^?1 and 30 µW m^?1 K^?2, respectively, leading to maximum ZT of 0.02 at a lower measurement temperature (<400 K) and lower processing temperature (<300 °C). These ligands further reduce the annealing temperature to 175 °C, significantly increasing the Seebeck coefficient of the CQD films to 580 μV K^?1. This high Seebeck coefficient with a superior ZT near room temperature compared to previously reported high temperature‐annealed CQD films is ascribed to the smaller grain size, which enables the retainment of quantum confinement and significantly increases the hole effective mass in the films. This study provides a pathway to approach quantum confinement for achieving a high Seebeck coefficient yet strong inter‐QD coupling, which offers a step toward low‐temperature‐processed high‐performance thermoelectric generators.