RESUMEN
Manipulating thermal properties of materials can be interpreted as the control of how vibrations of atoms (known as phonons) scatter in a crystal lattice. Compared to a perfect crystal, crystalline solids with defects are expected to have shorter phonon mean free paths caused by point defect scattering, leading to lower lattice thermal conductivities than those without defects. While this is true in many cases, alloying can increase the phonon mean free path in the Cd-doped AgSnSbSe3 system to increase the lattice thermal conductivity from 0.65 to 1.05 W m-1 K-1 by replacing 18% of the Sb sites with Cd. It is found that the presence of lone pair electrons leads to the off-centering of cations from the centrosymmetric position of a cubic lattice. X-ray pair distribution function analysis reveals that this structural distortion is relieved when the electronic configuration of the dopant element cannot produce lone pair electrons. Furthermore, a decrease in the Grüneisen parameter with doping is experimentally confirmed, establishing a relationship between the stereochemical activity of lone pair electrons and the lattice anharmonicity. The observed "harmonic" behavior with doping suggests that lone pair electrons must be preserved to effectively suppress phonon transport in these systems.
RESUMEN
Topological electronic transition is the very promising strategy for achieving high band degeneracy (NV) and for optimizing thermoelectric performance. Herein, this work verifies in p-type Mg3Sb2- xBix that topological electronic transition could be the key mechanism responsible for elevating the NV of valence band edge from 1 to 6, leading to much improved thermoelectric performance. Through comprehensive spectroscopy characterizations and theoretical calculations of electronic structures, the topological electronic transition from trivial semiconductor is unambiguously demonstrated to topological semimetal of Mg3Sb2- xBix with increasing the Bi content, due to the strong spin-orbit coupling of Bi and the band inversion. The distinct evolution of Fermi surface configuration and the multivalley valence band edge with NV of 6 are discovered in the Bi-rich compositions, while a peculiar two-step band inversion is revealed for the first time in the end compound Mg3Bi2. As a result, the optimal p-type Mg3Sb0.5Bi1.5 simultaneously obtains a positive bandgap and high NV of 6, and thus acquires the largest thermoelectric power factor of 3.54 and 6.93 µW cm-1 K-2 at 300 and 575 K, respectively, outperforming the values in other compositions. This work provides important guidance on improving thermoelectric performance of p-type Mg3Sb2- xBix utilizing the topological electronic transition.
RESUMEN
Some of the best thermoelectric (TE) materials to date are also topological insulators (TIs). While many studies have investigated the effects of topologically-protected TI surface states on TE properties, the conditions needed to realize such effects are quite different from typical operating conditions of TE devices for, e.g., power generation and room-temperature Peltier cooling. As a result, it is still unclear what properties of TIs, especially those related to the bulk band structure, are beneficial for TE performance, if any. Here, we perform high-throughput transport calculations using density functional theory to reveal that, within the same structure type, TIs tend to outperform normal insulators as TEs when properly optimized. The calculations also indicate that the TE performance is higher for TIs with strongly inverted bands. To explain these observations, we develop models based on Boltzmann transport theory which show that warping driven by band inversion, a key characteristic of TIs, is responsible for the high TE performance of TIs. We find that warping benefits the TE performance because of reduced transport mass and effectively higher valley degeneracy. Our results show that the band inversion strength is a critical property of a TI dictating the TE performance, and we suggest potential strategies to tune the inversion strength and enhance the TE performance in TIs, such as alloying and strain engineering. The study marks TIs as serious candidates for TE applications owing to band inversion-driven warping.
RESUMEN
Low-dimensional materials have unique optical, electronic, mechanical, and chemical properties that make them desirable for a wide range of applications. Nano-scaling materials to confine transport in at least one direction is a common method of designing materials with low-dimensional electronic structures. However, bulk materials give rise to low-dimensional electronic structures when bonding is highly anisotropic. Layered Zintl phases are excellent candidates for investigation due to their directional bonding, structural variety, and tunability. However, the complexity of the structure and composition of many layered Zintl phases poses a challenge for producing phase-pure bulk samples to characterize. Eu11Zn4Sn2As12 is a layered Zintl phase of significant complexity that is of interest for its magnetic, electronic, and thermoelectric properties. To prepare phase-pure Eu11-xNaxZn4Sn2As12, a binary EuAs phase was employed as a precursor, along with NaH. Experimental measurements reveal low thermal conductivity and a high Seebeck coefficient, while theoretical electronic structure calculations reveal a transition from a 3D to 2D electronic structure with increasing carrier concentration. Simulated thermoelectric properties also indicate anisotropic transport, and thermoelectric property measurements confirm the nonparabolicity of the relevant bands near the Fermi energy. Thermoelectric efficiency is known to improve as the dimensionality of the electronic structure is decreased, making this a promising material for further optimization and opening the door to further exploitation of layered Zintl phases with low-dimensional electronic structures for thermoelectric applications.
RESUMEN
Thermoelectric (TE) cooling is an environment-friendly alternative to vapor compression cooling. New TE materials with high coefficients of performance are needed to further advance this technology. Narrow-gap semiconductors and semimetals have garnered interest for Peltier cooling, yet large-scale computational searches often rely on material descriptors that do not account for bipolar conduction effects. In this work, we derive three material descriptors to assess the TE performances of narrow-gap semiconductors and semimetals - band gap, n- and p-type TE quality factors, and the asymmetry in transport between the majority and minority carriers. We show that a large asymmetry is critical to achieving high TE performance through minimization of bipolar conduction effects. We validate the predictive power of the descriptors by correctly identifying Mg3Bi2 and Bi2Te3 as high-performing room-temperature TE materials. By applying these descriptors to a broad set of 650 Zintl phases, we identify three candidate room-temperature TE materials, namely SrSb2, Zn3As2, and NaCdSb. The proposed material descriptors will enable fast, targeted searches of narrow-gap semiconductors and semimetals for low-temperature TEs. We further propose a refined TE quality factor, Bbp, which is a composite descriptor of the peak zT in materials exhibiting significant bipolar conduction; Bbp can be used to compare the TE performances of narrow-gap semiconductors.
RESUMEN
Rare-earth chalcogenides Re3-xCh4 (Re = La, Pr, Nd, Ch = S, Se, and Te) have been extensively studied as high-temperature thermoelectric (TE) materials owing to their low lattice thermal conductivity (κL) and tunable electron carrier concentration via cation vacancies. In this work, we introduce Y2Te3, a rare-earth chalcogenide with a rocksalt-like vacancy-ordered structure, as a promising n-type TE material. We computationally evaluate the transport properties, optimized TE performance, and doping characteristics of Y2Te3. Combined with a low κL, multiple low-lying conduction band valleys yield a high n-type TE quality factor. We find that a maximum figure of merit zT > 1 can be achieved when Y2Te3 is optimally doped to an electron concentration of 1-2 × 1020 cm-3. We use defect calculations to show that Y2Te3 is n-type dopable under Y-rich growth conditions, which suppress the formation of acceptor-like cation vacancies. Furthermore, we propose that optimal n-type doping can be achieved with halogens (Cl, Br, and I), with I being the most effective dopant. Our computational results as well as experimental results reported elsewhere motivate further optimization of Y2Te3 as an n-type TE material.
RESUMEN
Cation disordering is commonly found in multinary cubic compounds, but its effect on electronic properties has been neglected because of difficulties in determining the ordered structure and defect energetics. An absence of rational understanding of the point defects present has led to poor reproducibility and uncontrolled conduction type. AgBiSe2 is a representative compound that suffers from poor reproducibility of thermoelectric properties, while the origins of its intrinsic n-type conductivity remain speculative. Here, it is demonstrated that cation disordering is facilitated by BiAg charged antisite defects in cubic AgBiSe2 which also act as a principal donor defect that greatly controls the electronic properties. Using density functional theory calculations and in situ Raman spectroscopy, how saturation annealing with selenium vapor can stabilize p-type conductivity in cubic AgBiSe2 alloyed with SnSe at high temperatures is elucidated. With stable and controlled hole concentration, a peak is observed in the weighted mobility and the density-of-states effective mass in AgBiSnSe3 , implying an increased valley degeneracy in this system. These findings corroborate the importance of considering the defect energetics for exploring the dopability of ternary thermoelectric chalcogenides and engineering electronic bands by controlling self-doping.
