We reported the thermoelectric properties of the sintered type-II clathrate K8Ba16Ga40Sn96 in a previous paper [S. Koda et al., J. Appl. Phys. 116, 023710 (2014)]. The clathrate had a high dimensionless figure of merit ZT, namely, 0.93. In this study, we optimized the carrier concentration n by modifying the chemical compositions of (K, Ba)24(Ga, Sn)136 samples, and heat treated the sintered samples. The carrier mobilities μ were improved because of the reduction in potential barrier scattering at grain boundaries. The room-temperature (RT) n values varied from 7.7 × 1017 to 3.7 × 1019 cm−3; the maximum RT μ value was 170 cm2V−1s−1. Consequently, we obtained a high ZT value of 1.19 at 630 K for n = 2.5 × 1019 cm−3. This material therefore has good thermoelectric properties.

Periodically structured nanomaterials such as superlattices have a wide range of applications. Many electronic devices have been fabricated from these materials. The formation of spontaneous layer structures using epitaxial growth has also been reported for many compound semiconductors but for very few ceramics. We demonstrate that strontium titanate (Sr-Ti-O) thin films having an A-site excess composition in the perovskite structure deposited by pulsed laser deposition under a magnetic field show a spontaneously formed superlattice structure. The spontaneous superlattice formation mechanism has been proven to exhibit spinodal decomposition. Preparation of a part of the phase diagram for Sr-Ti-O thin films is reported for the first time. Although SrTiO 3 bulk is quantum paraelectric, previous reports have described that strained SrTiO 3 thin films show room-temperature ferroelectricity, especially along the in-plane direction. However, induced ferroelectricity along the out-of-plane direction has been reported in films with a limited thickness of less than 10 ml. The results show that the Sr-Ti-O thin films with spontaneously formed superlattice structures exhibit room-temperature ferroelectricity even when 300 nm thick. The induced ferroelectricity is brought about by the strain along the out-of-plane direction and is explained based on thermodynamic considerations.

This clathrate had a maximum dimensionless figure-of-merit, ZT, of 0.93 at 637 K, which was slightly higher than that of 0.83 for the sintered type-VIII clathrate Ba8Ga16Sn30. We investigated the high-temperature thermoelectric properties, transport properties, electronic structures, and thermal stabilities of the clathrates. The type-II clathrate was found to be superior to the type-VIII clathrate as a thermoelectric material; it had a high thermal stability and melting point, 859 K, high mobility, 141 cm2V−1s−1 at 300 K, because of its low inertial mass, and low high-temperature lattice thermal conductivity, approximately 4 mW cm−1K−1, resulting from a larger unit cell and weaker bipolar thermal conduction. We discuss these properties in terms of the electronic structure and the differences between the two types of clathrate.

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