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Electronic and Vibrational Properties of TiS <sub/>2</sub> , ZrS <sub/>2</sub> , and HfS <sub/>2</sub> : Periodic Trends Studied by Dispersion-Corrected Hybrid Density Functional Methods
摘要： The electronic and vibrational properties of TiS2, ZrS2, and HfS2 have been studied using dispersion corrected hybrid density functional methods. The periodic trends in electronic band structures, electronic transport coefficients, IR and Raman spectra, and phonon dispersion relations were investigated. Comparison to the available experimental data shows that the applied DFT methodology is suitable for the investigation of the layered transition metal dichalcogenide materials with weak interlayer Van der Waals interactions. The choice of damping function in the D3 dispersion correction proved to have surprisingly large effect. Systematic investigation of the periodic trends within group 4 disulfides reveals that TiS2 shows many differences to ZrS2 and HfS2 due to the more covalent M–S bonding in TiS2. ZrS2 and HfS2 mainly show differences for properties where the atomic mass plays a role. All three compounds show similar Seebeck coefficients, but clear differences in the relative electrical conductivity of cross- and in-plane directions. The transport and vibrational properties of thin TiS2 single crystals were also investigated experimentally.
关键词： ZrS2,HfS2,dispersion corrected hybrid density functional methods,thermoelectric properties,periodic trends,vibrational properties,electronic properties,TiS2
更新于2025-09-23 15:21:01
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Defects controlled doping and electrical transport in TiS <sub/>2</sub> single crystals
摘要： TiS2 has been intensively studied as an electrode material and a thermoelectric material for energy storage and conversion applications due to its high electrical conductivity. Understanding the influence of defects on electrical transport is of importance not only to resolve the long-standing question concerning the nature of TiS2, but also for the rational design of TiS2 based devices for energy scavenging applications. In this study, we integrate photoemission spectroscopy, Raman spectroscopy, and electrical transport measurements to determine the chemical compositions dominated by defects and their influence on the doping and electrical properties. Our results demonstrate that TiS2 is a heavily self-doped semiconductor with the Fermi level close to the conduction band, which serves as the conclusive experimental evidence regarding the semiconducting nature of TiS2. The doping effect is sensitive to the (subtle) changes in the chemical composition. The electron donation from the Ti interstitials (Tii) to the TiS2 host explains the high carrier concentration. The Ti Frenkel pair (TiF) acting as the acceptor is responsible for the decrease in the electron carrier concentration and electrical conductivity. High conductivity maintains upon partial oxidization, indicating the oxidization-tolerance in terms of the electronic structure. Our results provide valuable insight into the evolution of electronic properties modulated by defects that reveal unambiguously the self-doped semiconducting nature of TiS2 and chemical- and environment-tolerance of TiS2 as an advanced energy scavenging material.
关键词： TiS2,doping,defects,electrical transport,energy storage,energy conversion,photoemission spectroscopy,thermoelectric material,Raman spectroscopy
更新于2025-09-19 17:13:59