Hierarchical Phonon Scattering from Nano to Macro Scale in Ag-Nano/TiO2-Micro Particle-Decorated p-type Bismuth Telluride Bulk Composites.

We study the thermoelectric properties of a p-type Bi0.4Sb1.6Te3.4 (BST) composite with Ag nanoparticle-decorated TiO2 microparticles (US-Ag/TiO2). The dispersion of US-Ag/TiO2 particles, synthesized by an ultrasonication (US) method, into the matrix effectively decreases lattice and bipolar thermal conductivity, attributed to the scattering centers formed at nano and micro scales. The electron backscattering diffraction (EBSD) measurements revealed smaller grain sizes within the BST composite when paired with the US-Ag/TiO2 particle dispersion. These reduced grain sizes, alongside nanoparticle-decorated microparticles dispersed throughout the matrix, scatter phonons effectively from long- to short-wavelength phonons and subsequently decrease lattice thermal conductivity. While the power factors of the composites are reduced, significant suppression of lattice and bipolar thermal conductivity has led to an increase in the maximum zT value (1.4 at 325 K) for a 0.9 wt % US-Ag/TiO2 particle dispersion within the BST matrix. This particle dispersion in the BST composite consistently demonstrates a high zT value across an extensive temperature spectrum, leading to an exceptionally high average zTavg value (1.38 up to 400 K), which is superior to the other values from reported BST composites. Thus, this research indicates that the dispersion of nanoparticle-decorated microparticles within a thermoelectric material matrix can significantly improve thermoelectric performance, which has promising implications for practical applications in thermoelectric cooling and sustainable and economical energy harvesting technologies.

Synergistic Enhancement of Thermoelectric Performances by Cl-Doping and Pb-Excess in (Pb,Sn)Se Topological Crystal Insulator.

We investigated the thermoelectric properties of the Pb0.75Sn0.25Se and Pb0.79Sn0.25Se1-xClx (x = 0.0, 0.2, 0.3, 0.5, 1.0, 2.0 mol.%) compounds, synthesized by hot-press sintering. The electrical transport properties showed that low concentration doping of Cl (below 0.3 mol.%) in the Pb-excess (Pb,Sn)Se samples increased the carrier concentration and the Hall mobility by the increase of carriers' mean free path. The effective mass of the carrier was also enhanced from the measurements of the Seebeck coefficient. The enhanced effective masses of the carrier by the Cl-doping can be understood by the enhanced electron-phonon interaction, caused by the crystalline mirror symmetry breaking. The significantly decreased lattice thermal conductivities showed that the crystalline mirror symmetry breaking decreased the lattice thermal conductivity of the Pb-excess (Pb,Sn)Se. By the Cl-doping and the Pb-excess's synergistic effect, which can suppress the bipolar effect, the zT values of x = 0.2 and 0.3 mol.% reached 0.8 at 773 K. Therefore, we suggest that Pb-excess and the crystalline mirror symmetry breaking by Cl-doping are effective for high thermoelectric performance in the (Pb,Sn)Se.

Catalytic effect of laser-combined atmospheric pressure plasma in lowering the reduction temperature of hematite.

Atmospheric pressure plasma (APP) generates highly reactive species that are useful for surface activation. We demonstrate a fast regeneration of iron oxides, that are popular catalysts in various industrial processes, using microwave-driven argon APP under ambient conditions. The surface treatment of hematite powder by the APP with a small portion of hydrogen (0.5 vol%) lowers the oxide's reduction temperature. A near-infrared laser is used for localized heating to control the surface temperature. Controlled experiments without plasma confirm the catalytic effect of the plasma. Raman, XRD, SEM, and XPS analyses show that the plasma treatment changed the chemical state of the hematite to that of magnetite without sintering.

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.

Phonon-induced diamagnetic force and its effect on the lattice thermal conductivity.

Phonons are displacements of atoms around their rest positions in a crystalline solid. They carry sound and heat, but are not classically associated with magnetism. Here, we show that phonons are, in fact, sensitive to magnetic fields, even in diamagnetic materials. We do so by demonstrating experimentally that acoustic phonons in a diamagnetic semiconductor (InSb) scatter more strongly from one another when a magnetic field is applied. We attribute this observation to the magnetic-field sensitivity of the anharmonicity of the interatomic bonds that govern the probability of phonon-phonon interactions. The displacements of atoms locally affect the orbital motion of valence band electrons, which, in the presence of an external magnetic field, spatially modulates the orbital diamagnetism around the displaced atoms. The spatial gradient in magnetic moment results in an anharmonic magnetic force exerted on the displaced atom. The process is modelled by ab initio calculations that, without the use of a single adjustable parameter, reproduce the observed 12% decrease in the lattice thermal conductivity under a 7 T magnetic field at a temperature of 5.2 K.