125Te NMR for structural investigations in phase change materials: Optimization of experimental conditions coupled to NMR shift prediction

Juliette Lizion (1) , Andrea Piarristeguy (1) , Robert Laskowski (2) , Peter Blaha (3) , Raphael Escalier (1) , Michel Ménétrier (4) , Annie Pradel (1) , Gilles Silly (1)

1 ICGM - Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier
2 A*STAR - Institute of High Performance Computing
3 TU Wien - Vienna University of Technology = Technische Universität Wien
4 ICMCB - Institut de Chimie de la Matière Condensée de Bordeaux

Phase Change Materials as those of the Ge-Sb-Te ternary system are of great interest for technological applications. Properties of these compounds are strongly related to presence of vacancies and structural investigations remain challenging. In this paper we evidence that 125 Te NMR in natural abundance and using commercial systems at intermediate field (14.1T) together with NMR parameters prediction can contribute to improve understanding of electronic structure of such systems. GeTe is a typical phase change material, whose structure contains germanium vacancies, even in its stoichiometric form, giving it metallic properties. Here, we use nominal Ge50Te50 and Ge48Te52 crystalline samples as an example to optimize the WURST-CPMG technique, a powerful technique to record wide NMR spectra which has not yet been used on 125 Te. The goal was to minimize the time devoted to experiments as well as maximize the signal-to-noise ratio in order to detect small intensity signals directly linked to vacancies. Virtual Crystal Approximation (VCA) calculations performed with WIEN2K helped to interpret the NMR spectra. For Te-based crystalline conducting samples the best experimental results were obtained using 3.2mm thin wall rotors with diluted samples 40 vol.% GeTe-60 vol.% SiO2. In addition to the WURST-CPMG technique, high resolution spectra using MAS as implemented in the pj-MAT technique allowed us to identify the distributions of 2 chemical shift parameters in the high intensity contribution of the 1D spectra. The NMR spectra recorded on the samples showed that an addition of Tellurium in the stoichiometric Ge50Te50 sample leads to an important broadening of the spectrum together with a shift of the lines. According to VCA calculations it could be attributed to a distribution of concentrations of germanium vacancies in the sample and it would appear that Knight Shift but also Chemical Shift could contribute in similar proportion to the NMR line position when metavalent bonding is invoked.

Mots clés: Solid State NMR; Phase Change Materials; Chemical Shift; Knight Shift; vacancies; WURST-CPMG; pjMAT

Domaines: Science des matériaux [cond-mat.mtrl-sci]

Juliette Lizion, Andrea Piarristeguy, Robert Laskowski, Peter Blaha, Raphael Escalier, et al.. 125Te NMR for structural investigations in phase change materials: Optimization of experimental conditions coupled to NMR shift prediction. Solid State Nuclear Magnetic Resonance, 2021, 115, pp.101751. ⟨10.1016/j.ssnmr.2021.101751⟩. ⟨hal-03318557⟩