NMR study of Ba8Cu5SixGe41−x clathrate semiconductors

Literature Information

Publication Date 2015-06-01
DOI 10.1039/C5CP02575C
Impact Factor 3.676
Authors

Ali A. Sirusi, Xinlin Yan, Silke Paschen


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Abstract

We have performed 63Cu, 65Cu, and 137Ba NMR on Ba8Cu5SixGe41−x, a series of intermetallic clathrates known for their potential as thermoelectric materials, in order to investigate the electronic behavior of the samples. The spectra and spin–lattice relaxation times were measured at 77 K and 290 K for the entire composition range 0 ≤ x ≤ 41. Magnetic and quadrupole shifts and relaxation rates of the Cu NMR data were extracted, and thereby carrier-induced metallic contributions identified. The observed shifts change in a nonlinear way with increasing Si substitution: from x = 0 to about 20 the shifts are essentially constant, while approaching x = 41 they increase rapidly. At the same time, Ba NMR data indicate greater Ba-site participation in the conduction band in Ba8Cu5Si41 than in Ba8Cu5Ge41. The results indicate surprisingly little change in electronic features vs. Si content for most of the composition range, while Ba8Cu5Si41 exhibits enhanced hybridization and a more metallic framework than Ba8Cu5Ge41.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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