0000000000319613
AUTHOR
Tristan Day
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…
INFLUENCE OF THE CHEMICAL POTENTIAL ON THE CARRIER EFFECTIVE MASS IN THE THERMOELECTRIC SOLID SOLUTION Cu2Zn1-xFexGeSe4
In this paper, we describe the synthesis and characterization of the solid solution Cu 2 Zn 1-x Fe x GeSe 4. Electronic transport data have been analyzed using a single parabolic band model and have been compared to Cu 2+x Zn 1-x GeSe 4. The effective mass of these undoped, intrinsically hole conducting materials increases linearly with increasing carrier concentration, showing a non-parabolic transport behavior within the valence band.
Thermoelectric Transport in Cu7PSe6 with High Copper Ionic Mobility
Building on the good thermoelectric performances of binary superionic compounds like Cu2Se, Ag2Se and Cu2S, a better and more detailed understanding of phonon-liquid electron-crystal (PLEC) thermoelectric materials is desirable. In this work we present the thermoelectric transport properties of the compound Cu7PSe6 as the first representative of the class of argyrodite-type ion conducting thermoelectrics. With a huge variety of possible compositions and high ionic conductivity even at room temperature, the argyrodites represent a very good model system to study structure-property relationships for PLEC thermoelectric materials. We particularly highlight the extraordinary low thermal conduct…
Influence of Compensating Defect Formation on the Doping Efficiency and Thermoelectric Properties of Cu2-ySe1–xBrx
The superionic conductor Cu_(2−δ)Se has been shown to be a promising thermoelectric at higher temperatures because of very low lattice thermal conductivities, attributed to the liquid-like mobility of copper ions in the superionic phase. In this work, we present the potential of copper selenide to achieve a high figure of merit at room temperature, if the intrinsically high hole carrier concentration can be reduced. Using bromine as a dopant, we show that reducing the charge carrier concentration in Cu_(2−δ)Se is in fact possible. Furthermore, we provide profound insight into the complex defect chemistry of bromine doped Cu_(2−δ)Se via various analytical methods and investigate the conseque…
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…