Solid-State Electrochemical Thermal Transistors with Strontium Cobaltite-Strontium Ferrite Solid Solutions as the Active Layers.

Thermal transistors have potential as thermal management devices because they can electrically control the thermal conductivity (κ) of the active layer. Recently, we realized solid-state electrochemical thermal transistors by utilizing the electrochemical redox reaction of SrCoOy (2 ≤ y ≤ 3). However, the guiding principle to improve the on/off κ ratio has yet to be clarified because the κ modulation mechanism is unclear. This study systematically modulates κ of SrCo1-xFexOy (0 ≤ x ≤ 1, 2 ≤ y ≤ 3) solid solutions used as the active layers in solid-state electrochemical thermal transistors. When y = 3, the lattice κ of SrCo1-xFexOy is ∼2.8 W m-1 K-1 and insensitive to x. When x = 0 and y = 3, κ increases to ∼3.8 W m-1 K-1 due to the contribution of the electron κ. When y = 2, κ slightly depends on the ordered atomic arrangement. Materials that are high electrical conductors with highly ordered lattices when the transistor is on but are electrical insulators with disordered lattices when the transistor is off should be well-suited for the active layers of solid-state electrochemical thermal transistors.

Ba1/3CoO2: A Thermoelectric Oxide Showing a Reliable ZT of ∼0.55 at 600 °C in Air.

Thermoelectric energy conversion technology has attracted attention as an energy harvesting technology that converts waste heat into electricity by means of the Seebeck effect. Oxide-based thermoelectric materials that show a high figure of merit are promising because of their good chemical and thermal stability as well as their harmless nature compared to chalcogenide-based state-of-the-art thermoelectric materials. Although several high-ZT thermoelectric oxides (ZT > 1) have been reported thus far, the reliability is low due to a lack of careful observation of their stability at elevated temperatures. Here, we show a reliable high-ZT thermoelectric oxide, Ba1/3CoO2. We fabricated Ba1/3CoO2 epitaxial films by the reactive solid-phase epitaxy method (Na3/4CoO2) followed by ion exchange (Na+ → Ba2+) treatment and performed thermal annealing of the film at high temperatures and structural and electrical measurements. The crystal structure and electrical resistivity of the Ba1/3CoO2 epitaxial films were found to be maintained up to 600 °C. The power factor gradually increased to ∼1.2 mW m-1 K-2 and the thermal conductivity gradually decreased to ∼1.9 W m-1 K-1 with increasing temperature up to 600 °C. Consequently, the ZT reached ∼0.55 at 600 °C in air.

Modulation of electrical and thermal transports through lattice distortion in BaTi1-xNbxO3solid solutions.

The electron and heat transports in solids are through the movement of carrier electrons and quantized lattice vibrations (phonons), which are sensitive to the lattice distortion and ionized impurities, and are essential aspects for the development of novel thermoelectric materials. In this study, we systematically investigated the modulations of electrical and thermal conductivities of BaTi1-xNbxO3solid solution (BTNO, 0 ≤ x ≤ 1) epitaxial films. At room temperature, BaTiO3belongs to tetragonal perovskite and exhibits electron conduction through doubly degenerated Ti 3d-t2gorbitals upon doping, while BaNbO3belongs to cubic perovskite and exhibits metallic electron conduction through partially filled triply degenerate Nb 4d-t2gorbitals. By controlling the Ti/Nb ratio, we found a dual modulation effect on both the lattice structures and conduction band, which affects the electrical and thermal conductivities. Similar to the SrTi1-xNbxO3solid solution (STNO, 0 ≤ x ≤ 1) system, a phase transition was detected atx âˆ¼ 0.5, at which both the electron and heat transports exhibit abrupt changes. Unlike the transition in STNO, which was attributed to a polaronic phase transition, the transition in BTNO was due to contributions from both the lattice distortion and polaron effect. By controlling the lattice distortion, conduction band, and polaronic phase transitions, the electrical and thermal conductivity of BTNO epitaxial films are modulated within a much greater range than those of the STNO epitaxial films. Due to the double contribution of electron carriers and phonon to thermal conductivity (κ), the maximumκmodulation ratio of BTNO epitaxial films was ∼6.9. Our research provides an effective route to design electrical/thermal management materials.

Anisotropic Electrical Conductivity of Oxygen-Deficient Tungsten Oxide Films with Epitaxially Stabilized 1D Atomic Defect Tunnels.

Materials having an anisotropic crystal structure often exhibit anisotropy in the electrical conductivity. Compared to complex transition-metal oxides (TMOs), simple TMOs rarely show large anisotropic electrical conductivity due to their simple crystal structure. Here, we focus on the anisotropy in the electrical conductivity of a simple TMO, oxygen-deficient tungsten oxide (WOx) with an anisotropic crystal structure. We fabricated several WOx films by the pulsed laser deposition technique on the lattice-matched (110)-oriented LaAlO3 substrate under a controlled oxygen atmosphere. The crystallographic analyses of the WOx films revealed that highly dense atomic defect tunnels were aligned one-dimensionally (1D) along [001] LaAlO3. The electrical conductivity along the 1D atomic defect tunnels was ∼5 times larger than that across the tunnels. The present approach, introduction of 1D atomic defect tunnels, might be useful to design simple TMOs exhibiting anisotropic electrical conductivity.

Thermopower Modulation Clarification of the Operating Mechanism in Wide Bandgap BaSnO3 -SrSnO3 Solid-Solution Based Thin Film Transistors.

The transparent oxide semiconductor (TOS) with large bandgap (Eg ≈ 4 eV) based thin-film transistors (TFTs) showing both high carrier mobility and UV-visible transparency has attracted increasing attention as a promising component for next generation optoelectronics. Among TOSs, BaSnO3 -SrSnO3 solid-solutions (Eg = 3.5-4.2 eV) are good candidates because the single crystal shows very high mobility. However, the TFT performance has not been optimized due to the lack of fundamental knowledge especially the effective thickness (teff ) and the carrier effective mass (m*). Here, it is demonstrated that the electric field thermopower (S) modulation method addresses this problem by combining with the standard volume carrier concentration (n3D ) dependence of S measurements. By comparing the electric field accumulated sheet carrier concentration (n2D ) and n3D at same S, it is clarified that the teff (n2D /n3D ) of the conducting channel becomes thicker with increasing Sr concentration, whereas the m* becomes lighter. The former would be due to the increase of Eg and latter would be due to the enhancement of overlap population of neighboring Sn 5s orbitals. The present analyses technique is useful to experimentally clarify the teff and m*, and essentially important to realize advanced TOS-based TFTs showing both high optical transparency and high mobility.