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A review of the application of 2D isotropic-anisotropic correlation NMR spectroscopy in structural studies of chalcogenide glasses

The application of solid-state high-resolution NMR spectroscopy in the structural investigation of chalcogenide glasses in Ge/As/P/Si-X (X = S, Se,Te) systems has remained challenging even for the spin-1/2 nuclides ( 29 Si, 31 P, 77 Se, 125 Te), owing to their low natural abundance (except for 31 P), slow spin-lattice relaxation rate and large CSA and chemical shift distribution induced line broadening effects. However, most of these deleterious effects can be successfully overcome in two-dimensional (2D) isotropic-anisotropic correlation NMR experiments, especially when performed at high magnetic field and in conjunction with the Car-Purcell-Meiboom-Gill (CPMG) echo train acquisition. Here, we present a short introduction to the basic principles of such experiments and review their applications over the last decade in deciphering various short- and intermediate- range structural characteristics of chalcogenide glasses in S-Se, Se-Te, Ge-Se, As-Se and Si-Se systems as well as in investigating the molecular dynamics in a P-Se supercooled liquid. We anticipate possible future applications of these 2D isotropic-anisotropic correlation NMR experiments, particularly in conjunction with density functional theory-based calculations of NMR chemical shift tensor parameters and additional signal enhancement schemes, in addressing complex structural correlations and distributions in chalcogenide glasses.

2D NMR↗

Materials Data on GeSe2 by Materials Project

GeSe2 crystallizes in the tetragonal I-42d space group. The structure is three-dimensional. Ge4+ is bonded to four equivalent Se2- atoms to form corner-sharing GeSe4 tetrahedra. All Ge–Se bond lengths are 2.40 Å. Se2- is bonded in a water-like geometry to two equivalent Ge4+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on GeSe by Materials Project

GeSe is Halite, Rock Salt structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Ge2+ is bonded to six equivalent Se2- atoms to form a mixture of corner and edge-sharing GeSe6 octahedra. The corner-sharing octahedral tilt angles are 0°. All Ge–Se bond lengths are 2.83 Å. Se2- is bonded to six equivalent Ge2+ atoms to form a mixture of corner and edge-sharing SeGe6 octahedra. The corner-sharing octahedral tilt angles are 0°.

36 MATERIALS SCIENCE↗

Materials Data on Ge4Se9 by Materials Project

Ge4Se9 crystallizes in the orthorhombic Pca2_1 space group. The structure is two-dimensional and consists of two Ge4Se9 sheets oriented in the (0, 1, 0) direction. there are four inequivalent Ge3+ sites. In the first Ge3+ site, Ge3+ is bonded to four Se+1.33- atoms to form corner-sharing GeSe4 tetrahedra. There are a spread of Ge–Se bond distances ranging from 2.38–2.40 Å. In the second Ge3+ site, Ge3+ is bonded to four Se+1.33- atoms to form corner-sharing GeSe4 tetrahedra. There are two shorter (2.39 Å) and two longer (2.41 Å) Ge–Se bond lengths. In the third Ge3+ site, Ge3+ is bonded to four Se+1.33- atoms to form corner-sharing GeSe4 tetrahedra. There are a spread of Ge–Se bond distances ranging from 2.40–2.42 Å. In the fourth Ge3+ site, Ge3+ is bonded to four Se+1.33- atoms to form corner-sharing GeSe4 tetrahedra. There are a spread of Ge–Se bond distances ranging from 2.40–2.42 Å. There are nine inequivalent Se+1.33- sites. In the first Se+1.33- site, Se+1.33- is bonded in an L-shaped geometry to two Ge3+ atoms. In the second Se+1.33- site, Se+1.33- is bonded in a water-like geometry to two Ge3+ atoms. In the third Se+1.33- site, Se+1.33- is bonded in a water-like geometry to two Ge3+ atoms. In the fourth Se+1.33- site, Se+1.33- is bonded in an L-shaped geometry to two Ge3+ atoms. In the fifth Se+1.33- site, Se+1.33- is bonded in a water-like geometry to two Ge3+ atoms. In the sixth Se+1.33- site, Se+1.33- is bonded in a distorted single-bond geometry to one Ge3+ atom. In the seventh Se+1.33- site, Se+1.33- is bonded in a water-like geometry to two Ge3+ atoms. In the eighth Se+1.33- site, Se+1.33- is bonded in a water-like geometry to two Ge3+ atoms. In the ninth Se+1.33- site, Se+1.33- is bonded in a distorted single-bond geometry to one Ge3+ atom.

36 MATERIALS SCIENCE↗

Materials Data on GeSe by Materials Project

GeSe crystallizes in the orthorhombic Pnma space group. The structure is two-dimensional and consists of two GeSe sheets oriented in the (0, 0, 1) direction. Ge2+ is bonded in a 3-coordinate geometry to three equivalent Se2- atoms. There are one shorter (2.59 Å) and two longer (2.61 Å) Ge–Se bond lengths. Se2- is bonded in a distorted trigonal non-coplanar geometry to three equivalent Ge2+ atoms.

36 MATERIALS SCIENCE↗