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Nitrogen: A promising doping strategy for high-performance ovonic threshold switching selectors

The Ovonic Threshold Switching (OTS) selector serves as an essential component in the development of three-dimensional high-density memory integration technology. Nevertheless, the state-of-the-art high-performance OTS materials usually contain toxic elements such as arsenic (As), posing significant risks to both environmental and human health. Nitrogen (N), which belongs to the same group as arsenic (As), has emerged as a highly promising alternative for As doping. However, the underlying mechanisms that govern N-based OTS materials have not yet been extensively investigated. In this study, we delve into the effects of N doping on the structural, bonding, and electronic properties of amorphous GeSe (a-GeNSe) by ab initio molecular dynamics simulations to bridge the knowledge gap. Our findings indicate that upon N doping in a-GeSe, the formation of robust Ge-N bonds, along with N-centered tetrahedral and triangular structures, resulting in the sluggish atomic movement that enhances the thermal stability and endurance of a-GeNSe. The OTS characteristics are significantly influenced by the material’s electronic band structure, and thus the relatively slow performance drift can be attributed to the stabilization of mid-gap states, a result of N doping which effectively slows down the aging process of chalcogenide glass. Moreover, the increased mobility gap in a-GeNSe raises the threshold voltage (V th ), making it more compatible with commercially available phase-change memory materials. Furthermore, our findings reveal the extensive impact of the N element on a typical OTS material and offer valuable perspectives for alternative doping strategies that could potentially supplant As practices.

36 MATERIALS SCIENCE↗

Materials Data on Ge3N4 by Materials Project

Ge3N4 crystallizes in the hexagonal P6_3/m space group. The structure is three-dimensional. Ge4+ is bonded to four N3- atoms to form corner-sharing GeN4 tetrahedra. There is three shorter (1.85 Å) and one longer (1.86 Å) Ge–N bond length. There are two inequivalent N3- sites. In the first N3- site, N3- is bonded in a trigonal planar geometry to three equivalent Ge4+ atoms. In the second N3- site, N3- is bonded in a trigonal planar geometry to three equivalent Ge4+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on Ge3N4 by Materials Project

Ge3N4 is Hausmannite structured and crystallizes in the cubic Fd-3m space group. The structure is three-dimensional. there are two inequivalent Ge4+ sites. In the first Ge4+ site, Ge4+ is bonded to six equivalent N3- atoms to form GeN6 octahedra that share corners with six equivalent GeN4 tetrahedra and edges with six equivalent GeN6 octahedra. All Ge–N bond lengths are 2.01 Å. In the second Ge4+ site, Ge4+ is bonded to four equivalent N3- atoms to form corner-sharing GeN4 tetrahedra. The corner-sharing octahedral tilt angles are 57°. All Ge–N bond lengths are 1.92 Å. N3- is bonded to four Ge4+ atoms to form a mixture of distorted corner and edge-sharing NGe4 trigonal pyramids.

36 MATERIALS SCIENCE↗

Materials Data on Ge3N4 by Materials Project

Ge3N4 crystallizes in the cubic I-43d space group. The structure is three-dimensional. Ge4+ is bonded to four equivalent N3- atoms to form corner-sharing GeN4 tetrahedra. All Ge–N bond lengths are 1.86 Å. N3- is bonded in a trigonal planar geometry to three equivalent Ge4+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on Ge3N4 by Materials Project

Ge3N4 crystallizes in the trigonal P31c space group. The structure is three-dimensional. there are two inequivalent Ge4+ sites. In the first Ge4+ site, Ge4+ is bonded to four N3- atoms to form corner-sharing GeN4 tetrahedra. There are a spread of Ge–N bond distances ranging from 1.84–1.86 Å. In the second Ge4+ site, Ge4+ is bonded to four N3- atoms to form corner-sharing GeN4 tetrahedra. There is two shorter (1.85 Å) and two longer (1.86 Å) Ge–N bond length. There are four inequivalent N3- sites. In the first N3- site, N3- is bonded in a trigonal planar geometry to three Ge4+ atoms. In the second N3- site, N3- is bonded in a trigonal planar geometry to three Ge4+ atoms. In the third N3- site, N3- is bonded in a trigonal planar geometry to three equivalent Ge4+ atoms. In the fourth N3- site, N3- is bonded in a trigonal planar geometry to three equivalent Ge4+ atoms.

36 MATERIALS SCIENCE↗