ABSTRACT
We report on the inelastic response of the homologous compounds (PbSe)5(Bi2Se3)3m for m = 1, 2 and 3 followed in a broad temperature range (50-500 K) using high-resolution powder inelastic neutron scattering experiments. These results are complemented by low-temperature measurements of the specific heat (2-300 K). The evolution of the anisotropic crystal structure of these compounds with varying m, built from alternate Pb-Se and mBi-Se layers, only weakly influences the generalized phonon density of states. In all the three compounds, intense inelastic signals, likely mainly associated with the dynamics of the Pb atoms, are observed in the 4.5-6 meV low-energy range. The response of these low-energy modes to temperature variations indicates a conventional quasi-harmonic behavior over the whole temperature range investigated. The modes located above 8 meV show a minor temperature effect regardless of the value of m. The low-energy excess of vibrational modes manifests itself in the low-temperature specific heat as a pronounced peak in the Cp(T)/T3 data near 10 K. The lack of significant anharmonicity beyond that associated with the thermal expansion of the lattice suggests that the inherent disorder in the monoclinic unit cell and scattering at interlayer interfaces are the most important ingredients that limit the heat transport in this series of compounds.
ABSTRACT
The crystal structure and transport properties (2-723 K) of the homologous compound Pb5Bi6Se14 with partial substitution of Te for Se are studied by means of powder X-ray diffraction, scanning electron microscopy, electrical resistivity, thermopower, thermal conductivity and Hall effect measurements. Polycrystalline samples of Pb5Bi6Se14-xTex (0 ≤ x ≤ 1.0) were prepared by a two-step synthesis method based on the pseudo-binary PbSe-Bi2Se3 phase diagram combined with Te substitution in the PbSe precursor. The successful insertion of Te into the crystal structure of Pb5Bi6Se14 was confirmed by powder X-ray diffraction and scanning electron microscopy. Transport property measurements indicate an increase in the heavily doped character of the transport with increasing the Te concentration. The extremely low lattice thermal conductivity values (0.3-0.4 W m-1 K-1 at 723 K) that approach the glassy limit at high temperatures are nearly independent of the chemical composition suggesting no influence on point-defect scattering mechanisms in the substituted compounds. Despite the inherent complexity of this system, the evolution of the electronic properties with x is well described by a simple single-parabolic band model. Because the increase in the power factor with increasing x is compensated by the concomitant increase in the electronic thermal conductivity, this substitution does not yield enhanced ZT values with respect to the pristine compound with a similar peak ZT value of 0.5 achieved at 723 K. Nevertheless, the simple synthetic method used in this study to insert a doping element opens new avenues for controlling the transport properties of the homologous series (PbSe)5(Bi2Se3)3m (m = 1, 2 and 3).
ABSTRACT
We report on a detailed investigation of the crystal structure and transport properties in a broad temperature range (2-723 K) of the homologous compounds (PbSe)5(Bi2Se3)3m for m = 2, 3. Single-crystal X-ray diffraction data indicate that the m = 2, 3 compounds crystallize in the monoclinic space groups C2/m (No. 12) and P21/m (No. 11), respectively. In agreement with diffraction data, high-resolution transmission electron microscopy analyses carried out on single crystals show that the three-dimensional crystal structures are built from alternating Pb-Se and m Bi-Se layers stacked along the a axis in both compounds. Scanning electron microcopy and electron-probe microanalyses reveal deviations from the nominal stoichiometry, suggesting a domain of existence in the pseudo binary phase diagram at 873 K. The complex atomic-scale structures of these compounds lead to very low lattice thermal conductivities κL that approach the glassy limit at high temperatures. A comparison of the κL values across this series unveiled an unexpected increase with increasing m from m = 1 to m = 3, in contrast to the expectation that increasing the structural complexity should tend to lower the thermal transport. This result points to a decisive role played by the Pb-Se/Bi-Se interfaces in limiting κL in this series. Both compounds behave as heavily doped n-type semiconductors with relatively low electrical resistivity and thermopower values. As a result, moderate peak ZT values of 0.25 and 0.20 at 700 K were achieved in the m = 2, 3 compounds, respectively. The inherent poor ability of these structures to conduct heat suggests that these homologous compounds may show interesting thermoelectric properties when properly optimized by extrinsic dopants.