title: 125Te NMR chemical-shift trends in PbTe-GeTe and PbTe-SnTe alloys.
abstract: Complex tellurides, such as doped PbTe, GeTe, and their alloys, are among the best thermoelectric materials. Knowledge of the change in (125)Te NMR chemical shift due to bonding to dopant or "solute" atoms is useful for determination of phase composition, peak assignment, and analysis of local bonding. We have measured the (125)Te NMR chemical shifts in PbTe-based alloys, Pb1-xGexTe and Pb1-xSnxTe, which have a rocksalt-like structure, and analyzed their trends. For low x, several peaks are resolved in the 22-kHz MAS (125)Te NMR spectra. A simple linear trend in chemical shifts with the number of Pb neighbors is observed. No evidence of a proposed ferroelectric displacement of Ge atoms in a cubic PbTe matrix is detected at low Ge concentrations. The observed chemical shift trends are compared with the results of DFT calculations, which confirm the linear dependence on the composition of the first-neighbor shell. The data enable determination of the composition of various phases in multiphase telluride materials. They also provide estimates of the (125)Te chemical shifts of GeTe and SnTe (+970 and +400±150 ppm, respectively, from PbTe), which are otherwise difficult to access due to Knight shifts of many hundreds of ppm in neat GeTe and SnTe.
authors.affiliation: Division of Materials Sciences and Engineering, Ames Laboratory U.S. DOE, Ames, IA 50011, USA; Department of Chemistry, Iowa State University, Ames, IA 50011, USA.
authors.forename: B
authors.initials: B
authors.lastname: Njegic
authors.forename: E M
authors.initials: EM
authors.lastname: Levin
authors.forename: K
authors.initials: K
authors.lastname: Schmidt-Rohr
keywords: (125)Te NMR; (125)Te chemical shift calculation; GeTe; Pb(1−x)Ge(x)Te; Pb(1−x)Sn(x)Te; PbTe; Plane-wave DFT; SnTe