STEM in situ thermal wave observations for investigating thermal diffusivity in nanoscale materials and devices.

Practical techniques to identify heat routes at the nanoscale are required for the thermal control of microelectronic, thermoelectric, and photonic devices. Nanoscale thermometry using various approaches has been extensively investigated, yet a reliable method has not been finalized. We developed an original technique using thermal waves induced by a pulsed convergent electron beam in a scanning transmission electron microscopy (STEM) mode at room temperature. By quantifying the relative phase delay at each irradiated position, we demonstrate the heat transport within various samples with a spatial resolution of ~10 nm and a temperature resolution of 0.01 K. Phonon-surface scatterings were quantitatively confirmed due to the suppression of thermal diffusivity. The phonon-grain boundary scatterings and ballistic phonon transport near the pulsed convergent electron beam were also visualized.

Phonon Scattering and Suppression of Bipolar Effect in MgO/VO2 Nanoparticle Dispersed p-Type Bi0.5Sb1.5Te3 Composites.

Bismuth-Telluride-based compounds are unique materials for thermoelectric cooling applications. Because Bi2Te3 is a narrow gap semiconductor, the bipolar diffusion effect is a critical issue to enhance thermoelectric performance. Here, we report the significant reduction of thermal conductivity by decreasing lattice and bipolar thermal conductivity in extrinsic phase mixing of MgO and VO2 nanoparticles in Bi0.5Sb1.5Te3 (BST) bulk matrix. When we separate the thermal conductivity by electronic κel, lattice κlat, and bipolar κbi thermal conductivities, all the contributions in thermal conductivities are decreased with increasing the concentration of oxide particle distribution, indicating the effective phonon scattering with an asymmetric scattering of carriers. The reduction of thermal conductivity affects the improvement of the ZT values. Even though significant carrier filtering effect is not observed in the oxide bulk composites due to micro-meter size agglomeration of particles, the interface between oxide and bulk matrix scatters carriers giving rise to the increase of the Seebeck coefficient and electrical resistivity. Therefore, we suggest the extrinsic phase mixing of nanoparticles decreases lattice and bipolar thermal conductivity, resulting in the enhancement of thermoelectric performance over a wide temperature range.

Thermoelectric Properties and Low-Energy Carrier Filtering by Mo Microparticle Dispersion in an n-Type (CuI)0.003Bi2(Te,Se)3 Bulk Matrix.

We investigate the thermoelectric properties of (CuI)0.003Bi2Te2.7Se0.3/Mo (Mo: 0.0, 0.9, 1.3, 1.8, 3.1, and 4.3 vol %) composites, which were synthesized by extrinsic phase mixing with hot press sintering. From X-ray diffraction (XRD) and energy-dispersive X-ray spectroscopy (EDX) measurements, we confirm that micro-sized Mo particles are dispersed homogeneously in the (CuI)0.003Bi2Te2.7Se0.3 matrix without doping. While the electrical resistivity of Mo-dispersed (CuI)0.003Bi2Te2.7Se0.3 composites is not changed significantly, the Seebeck coefficient is significantly increased. Because the work function (5.3 eV) of the (CuI)0.003Bi2Te2.7Se0.3 compounds, measured by ultraviolet photoelectron spectroscopy (UPS), is larger than that of Mo particles (4.95 eV), we expect the potential barrier near the interfaces between the BTS matrix and Mo particles. The band bending effect and potential barrier can give rise to the low-energy carrier filtering. For a low concentration dispersion of Mo particles (<2 vol %), a decrease of Hall carrier concentration, an increase of Hall mobility, a decrease of effective mass, and an increase of Seebeck coefficient also support the formation of low-energy carrier filtering. The Mo dispersion does not affect the decrease in the lattice thermal conductivity but enhances the power factor significantly, leading to the high ZT value above 1.0 at room temperature, which is a high level in n-type thermoelectric room-temperature applications.

Possible Charge Density Wave and Enhancement of Thermoelectric Properties at Mild-Temperature Range in n-Type CuI-Doped Bi2Te2.1Se0.9 Compounds.

Bi2Te3-based compounds have long been studied as thermoelectric materials in cooling applications near room temperature. Here, we investigated the thermoelectric properties of CuI-doped Bi2Te2.1Se0.9 compounds. The Cu/I codoping induces the lattice distortion partially in the matrix. We report that the charge density wave caused by the local lattice distortion affects the electrical and thermal transport properties. From the high-temperature specific heat, we found a first-order phase transitions near 490 and 575 K for CuI-doped compounds (CuI)xBi2Te2.1Se0.9 (x = 0.3 and 0.6%), respectively. It is not a structural phase transition, confirming from the high-temperature X-ray diffraction. The temperature-dependent electrical resistivity shows a typical behavior of charge density wave transition, which is consistent with the temperature-dependent Seebeck coefficient and thermal conductivity. The transmission electron microscopy and electron diffraction show a local lattice distortion, driven by the charge density wave transition. The charge density wave formation in the Bi2Te3-based compounds are exceptional because of the possibility of coexistence of charge density wave and topological surface states. From the Kubo formula and Boltzmann transport calculations, the formation of charge density wave enhances the power factor. The lattice modulation and charge density wave decrease lattice thermal conductivity, resulting in the enhancement of thermoelectric performance simultaneously in CuI-doped samples. Consequently, an enhancement of thermoelectric performance ZT over 1.0 is achieved at 448 K in the (CuI)0.003Bi2Te2.1Se0.9 sample. The enhancement of ZT at high temperature gives rise to a superior average ZTavg (1.0) value than those of previously reported ones.

Enhancement of thermoelectric properties over a wide temperature range by lattice disorder and chemical potential tuning in a (CuI) y (Bi2Te3)0.95-x (Bi2Se3) x (Bi2S3)0.05 quaternary system.

Bi2Te3-based compounds have received attention as thermoelectric materials for room-temperature cooling and waste heat recovery applications. With potential application prospects, quaternary compounds of Bi2Te3-Bi2Se3-Bi2S3 composites can be used for mid-temperature power generation under 500 °C. Herein, we investigated the thermoelectric properties of (CuI) y (Bi2Te3)0.95-x (Bi2Se3) x (Bi2S3)0.05 (x = 0.05, 0.2; y = 0.0, 0.003) compounds. Through X-ray diffraction and transmission electron microscopy, we confirmed that the lattice disorder in (Bi2Te3)0.95-x (Bi2Se3) x (Bi2S3)0.05 (x = 0.2) was due to multiple element substitutions. Disorder carrier scattering induced the localized nature of electrical resistivity, as confirmed by variable range hopping at low temperature. The temperature-dependent Seebeck coefficient of (Bi2Te3)0.95-x (Bi2Se3) x (Bi2S3)0.05 showed a carrier-type change from p- to n-type behaviour in the intermediate temperature range (525 K for x = 0.05 and 360 K for x = 0.2). Even though strong carrier localization increased electrical resistivity, resulting in degradation of the power factor and thermoelectric performance, when the chemical potential was increased to the conduction band minimum through CuI co-doping into the (CuI)0.003(Bi2Te3)0.95-x (Bi2Se3) x (Bi2S3)0.05 (x = 0.05, 0.2) compounds, the carriers were delocalized and showed n-type behaviour in the Seebeck coefficient. The temperature-dependent thermal conductivity shows the suppression of bipolar conduction behaviour. The simultaneous effect on carrier optimization through chemical potential tuning and lattice disorder caused a high ZT value of 0.85 at 523 K for CuI-doped (Bi2Te3)0.75(Bi2Se3)0.2(Bi2S3)0.05, which was comparatively high for n-type thermoelectric materials in the mid-temperature range.