0000000000087827
AUTHOR
Christophe P. Heinrich
Local Bonding Influence on the Band Edge and Band Gap Formation in Quaternary Chalcopyrites
Quaternary chalcopyrites have shown to exhibit tunable band gaps with changing anion composition. Inspired by these observations, the underlying structural and electronic considerations are investigated using a combination of experimentally obtained structural data, molecular orbital considerations, and density functional theory. Within the solid solution Cu2ZnGeS4-x Se x , the anion bond alteration parameter changes, showing larger bond lengths for metal-selenium than for metal-sulfur bonds. The changing bonding interaction directly influences the valence and conduction band edges, which result from antibonding Cu-anion and Ge-anion interactions, respectively. The knowledge of the underlyi…
Effect of Isovalent Substitution on the Thermoelectric Properties of the Cu2ZnGeSe4–xSx Series of Solid Solutions
Knowledge of structure–property relationships is a key feature of materials design. The control of thermal transport has proven to be crucial for the optimization of thermoelectric materials. We report the synthesis, chemical characterization, thermoelectric transport properties, and thermal transport calculations of the complete solid solution series Cu_2ZnGeSe_(4–x)S_x (x = 0–4). Throughout the substitution series a continuous Vegard-like behavior of the lattice parameters, bond distances, optical band gap energies, and sound velocities are found, which enables the tuning of these properties adjusting the initial composition. Refinements of the special chalcogen positions revealed a chang…
Phonon Scattering through a Local Anisotropic Structural Disorder in the Thermoelectric Solid Solution Cu_2Zn_(1−x)Fe_xGeSe_4
Inspired by the promising thermoelectric properties of chalcopyrite-like quaternary chalcogenides, here we describe the synthesis and characterization of the solid solution Cu(2)Zn(1-x)Fe(x)GeSe(4). Upon substitution of Zn with the isoelectronic Fe, no charge carriers are introduced in these intrinsic semiconductors. However, a change in lattice parameters, expressed in an elongation of the c/a lattice parameter ratio with minimal change in unit cell volume, reveals the existence of a three-stage cation restructuring process of Cu, Zn, and Fe. The resulting local anisotropic structural disorder leads to phonon scattering not normally observed, resulting in an effective approach to reduce th…
Tetragonal tungsten bronzes Nb8−xW9+xO47−δ: optimization strategies and transport properties of a new n-type thermoelectric oxide
Engineering of nanoscaled structures may help controlling the electrical and thermal transport in solids, in particular for thermoelectric applications that require the combination of low thermal conductivity and low electrical resistivity. The tetragonal tungsten bronzes Nb8−xW9+xO47 (TTB) allow a continuous variation of the charge carrier concentration while fulfilling at the same time the concept of a “phonon-glass electron-crystal” through a layered nanostructure defined by intrinsic crystallographic shear planes. The thermoelectric properties of the tetragonal tungsten bronzes Nb8−xW9+xO47−δ (0 < x < 2) were studied in the temperature range from 373 to 973 K. Structural defects and the…
Influence of a nano phase segregation on the thermoelectric properties of the p-type doped stannite compound Cu(2+x)Zn(1-x)GeSe4.
Engineering nanostructure in bulk thermoelectric materials has recently been established as an effective approach to scatter phonons, reducing the phonon mean free path, without simultaneously decreasing the electron mean free path for an improvement of the performance of thermoelectric materials. Herein the synthesis, phase stability, and thermoelectric properties of the solid solutions Cu_(2+x)Zn_(1–x)GeSe_4 (x = 0–0.1) are reported. The substitution of Zn^(2+) with Cu^+ introduces holes as charge carriers in the system and results in an enhancement of the thermoelectric efficiency. Nano-sized impurities formed via phase segregation at higher dopant contents have been identified and are l…
On the True Indium Content of In-Filled Skutterudites
The incongruently melting single-filled skutterudite InxCo4Sb12 is known as a promising bulk thermoelectric material. However, the products of current bulk syntheses contain always impurities of InSb, Sb, CoSb, or CoSb2, which prevent an unbiased determination of its thermoelectric properties. We report a new two-step synthesis of high-purity InxCo4Sb12 with nominal compositions x = 0.12, 0.15, 0.18, and 0.20 that separates the kieftite (CoSb3) formation from the topotactic filler insertion. This approach allows conducting the reactions at lower temperatures with shorter reaction times and circumventing the formation of impurity phases. The synthesis can be extended to other filled skutteru…
Bond strength dependent superionic phase transformation in the solid solution series Cu2ZnGeSe4−xSx
Recently, copper selenides have shown to be promising thermoelectric materials due to their possible superionic character resulting from mobile copper cations. Inspired by this recent development in the class of quaternary copper selenides we have focused on the structure-to-property relationships in the solid solution series Cu2ZnGeSe4−xSx. The material exhibits an insulator-to-metal transition at higher temperatures, with a transition temperature dependent on the sulfur content. However, the lattice parameters show linear thermal expansion at elevated temperatures only and therefore no indication of a structural phase transformation. 63Cu nuclear magnetic resonance shows clear indications…
Using crystallographic shear to reduce lattice thermal conductivity: high temperature thermoelectric characterization of the spark plasma sintered Magnéli phases WO2.90 and WO2.722.
Engineering of nanoscale structures is a requisite for controlling the electrical and thermal transport in solids, in particular for thermoelectric applications that require a conflicting combination of low thermal conductivity and low electrical resistivity. We report the thermoelectric properties of spark plasma sintered Magnéli phases WO2.90 and WO2.722. The crystallographic shear planes, which are a typical feature of the crystal structures of Magnéli-type metal oxides, lead to a remarkably low thermal conductivity for WO2.90. The figures of merit (ZT = 0.13 at 1100 K for WO2.90 and 0.07 at 1100 K for WO2.722) are relatively high for tungsten-oxygen compounds and metal oxides in general…