Shaowei Song

Tuning the carrier scattering mechanism to effectively improve the thermoelectric properties

A high thermoelectric power factor not only enables a potentially high figure of merit ZT but also leads to a large output power density, and hence it is pivotal to find an effective route to improve the power factor. Previous reports on the manipulation of carrier scattering mechanisms (e.g. ionization scattering) were mainly focused on enhancing the Seebeck coefficient. In contrast, here we demonstrate that by tuning the carrier scattering mechanism in n-type Mg3Sb2-based materials, it is possible to noticeably improve the Hall mobility, from ∼19 to ∼77 cm2 V−1 s−1, and hence substantially increase the power factor by a factor of 3, from ∼5 to ∼15 μW cm−1 K−2. The enhancement in mobility is mainly due to the reason that ionization scattering has been converted into mixed scattering between ionization and acoustic phonon scattering, which less effectively scatters the carriers. The strategy of tuning the carrier scattering mechanism to improve the mobility should be widely applicable to various material systems for achieving better thermoelectric performance.

Manipulation of ionized impurity scattering for achieving high thermoelectric performance in n-type Mg3Sb2-based materials

Significance Higher carrier mobility can contribute to a larger power factor, so it is important to identify effective means for achieving higher carrier mobility. Since carrier mobility is governed by the band structure and the carrier scattering mechanism, its possible enhancement could be obtained by manipulating either or both of these. Here, we report a substantial enhancement in carrier mobility by tuning the carrier scattering mechanism in n-type Mg3Sb2-based materials. The ionized impurity scattering in these materials has been shifted into mixed scattering by acoustic phonons and ionized impurities. Our results clearly demonstrate that the strategy of tuning the carrier scattering mechanism is quite effective for improving the mobility and should also be applicable to other material systems. Achieving higher carrier mobility plays a pivotal role for obtaining potentially high thermoelectric performance. In principle, the carrier mobility is governed by the band structure as well as by the carrier scattering mechanism. Here, we demonstrate that by manipulating the carrier scattering mechanism in n-type Mg3Sb2-based materials, a substantial improvement in carrier mobility, and hence the power factor, can be achieved. In this work, Fe, Co, Hf, and Ta are doped on the Mg site of Mg3.2Sb1.5Bi0.49Te0.01, where the ionized impurity scattering crosses over to mixed ionized impurity and acoustic phonon scattering. A significant improvement in Hall mobility from ∼16 to ∼81 cm2⋅V−1⋅s−1 is obtained, thus leading to a notably enhanced power factor of ∼13 μW⋅cm−1⋅K−2 from ∼5 μW⋅cm−1⋅K−2. A simultaneous reduction in thermal conductivity is also achieved. Collectively, a figure of merit (ZT) of ∼1.7 is obtained at 773 K in Mg3.1Co0.1Sb1.5Bi0.49Te0.01. The concept of manipulating the carrier scattering mechanism to improve the mobility should also be applicable to other material systems.

The significant role of Mg stoichiometry in designing high thermoelectric performance for Mg3(Sb,Bi)2-based n-type Zintls

Complex structures with versatile chemistry provide considerable chemical tunability of the transport properties. Good thermoelectric materials are generally extrinsically doped semiconductors with optimal carrier concentrations, while charged intrinsic defects (e.g., vacancies, interstitials) can also adjust the carriers, even in the compounds with no apparent deviation from a stoichiometric nominal composition. Here we report that in Zintl compounds Mg3+xSb1.5Bi0.5, the carrier concentration can be tuned from p-type to n-type by simply altering the initial Mg concentration. The spherical-aberration-corrected (CS-corrected) high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) and energy-dispersive X-ray spectroscopy (EDX) mapping analysis show that the excess Mg would form a separate Mg-rich phase after Mg vacancies have been essentially compensated. Additionally, a slight Te doping at Bi site on Mg3.025Sb1.5Bi0.5 has enabled good n-type thermoelectric properties, which is comparable to the Te-doped Mg-rich sample. The actual final composition of Mg3.025Sb1.5Bi0.5 analyzed by EPMA is also close to the stoichiometry Mg3Sb1.5Bi0.5, answering the open question whether excess Mg is prerequisite to realize exceptionally high n-type thermoelectric performance by different sample preparation methods. The motivation for this work is first to understand the important role of vacancy and then to guide for discovering more promising n-type Zintl thermoelectric materials.

Study on anisotropy of n-type Mg3Sb2-based thermoelectric materials

The recent discovery of a high thermoelectric figure of merit (ZT) in an n-type Mg3Sb2-based Zintl phase triggered an intense research effort to pursue even higher ZT. Based on our previous report on Mg3.1Nb0.1Sb1.5Bi0.49Te0.01, we report here that partial texturing in the (001) plane is achieved by double hot pressing, which is further confirmed by the rocking curves of the (002) plane. The textured samples of Mg3.1Nb0.1Sb1.5Bi0.49Te0.01 show a much better average performance in the (00l) plane. Hall mobility is significantly improved to ∼105 cm2 V−1 s−1 at room temperature in the (00l) plane due to texturing, resulting in higher electrical conductivity, a higher power factor of ∼18 μW cm−1 K−2 at room temperature, and also higher average ZT. This work shows that texturing is good for higher thermoelectric performance, suggesting that single crystals of n-type Mg3Sb2-based Zintl compounds are worth pursuing.