Transition metal d-band occupancy in skutterudites studied by electron energy-loss spectroscopy

The transition-metal 3d occupancy of a series of thermoelectric skutterudites is investigated using electron energy-loss spectroscopy. We find that bonding causes an emptying of the 3d states in the binary skutterudites CoP3, CoAs3, CoSb3, and NiP3, while compared to the pure Fe the 3d occupancy in LaFe4P12 is significantly increased, consistent with the idea that each interstitial La atom (rattler) donates three electrons to compensate for missing valence electron of Fe as compared to Co. These experimental results are in agreement with previous models suggesting a predominantly covalent bonding between transition metal and pnictogen atoms in skutterudites, and provide evidence of charge transfer from La to the Fe-P complex in LaFe4P12

Composition and the thermoelectric performance of β-Zn_4Sb_3

β-Zn_4Sb_3 is a promising thermoelectric material due to the abundance of zinc and antimony and reports of high efficiency in bulk samples. This work establishes the high temperature properties of β-Zn_4Sb_3 across the phase stability window. By controlling the stoichiometry, the Hall carrier concentration can be tuned from 6–9 × 10^(19) cm^(−3) without requiring extrinsic dopants. The trend in Seebeck coefficient on carrier concentration is rationalized with a single, parabolic band model. Extremely low lattice thermal conductivity (0.4–0.6 W m^(−1) K^(−1)) coupled with a moderate effective mass (1.2 m_e) and mobility leads to a large figure of merit (zT of 0.8 by 550 K). The single parabolic band model is used to obtain the carrier concentration dependence of the figure of merit and an optimum carrier concentration near 5 × 10^(19) cm^(−3) is predicted

Reduction of lattice thermal conductivity from planar faults in the layered Zintl compound SrZnSb_2

The layered Zintl compound SrZnSb_2 is investigated using transmission electron microscopy (TEM) to understand the low lattice thermal conductivity. The material displays out-of-phase boundaries with a spacing from 100 down to 2 nm. Density functional theory calculations confirm that the TEM-derived defect structure is energetically reasonable. The impact of these defects on phonon scattering is analyzed within the Debye–Callaway model, which reveals a significant reduction in the acoustic phonon mean free path. This enhancement in phonon scattering leads to an ~30% reduction in lattice thermal conductivity at 300 K

Determination of the local concentrations of Mn interstitials and antisite defects in GaMnAs

We present a method for the determination of the local concentrations of interstitial and substitutional Mn atoms and As antisite defects in GaMnAs. The method relies on the sensitivity of the structure factors of weak reflections to the concentrations and locations of these minority constituents. High spatial resolution is obtained by combining structure factor measurement and X-ray analysis in a transmission electron microscope. We demonstrate the prevalence of interstitials with As nearest neighbors in as-grown layers.Comment: 10 pages, 4 figure

Nanoscale inclusions in the phonon glass thermoelectric material

We have investigated the thermoelectric material Zn 4 Sb 3 using transmission electron microscopy (TEM). Nanoscale inclusions with a diameter of about 10 nm were observed, constituting on the order of 1% by volume of the material. Studies using energy filtered imaging, electron diffraction, and high-angle annular dark-field STEM indicate that the inclusions consist of Zn. These inclusions are expected to scatter the medium and long-wavelength phonons effectively, thus contributing to phonon glass behavior which results in the exceptionally low thermal conductivity for this thermoelectric material