Longitudinal Piezoelectricity and Polarization-Insensitive Oxidation in Janus vdWs Nb3SeI7

Small. 2024 Nov 3:e2408628. doi: 10.1002/smll.202408628. Online ahead of print.

Abstract

As a newly discovered Janus van der Waals (vdW) material, semiconducting Nb3SeI7 offers several notable advantages, including spontaneous out-of-plane polarization, facile exfoliation to the monolayer limit, and significant out-of-plane emission dipole in second harmonic generation. These properties make it a promising candidate for piezoelectric and piezophototronic applications in highly efficient energy conversion. However, Nb3SeI7 is prone to oxidation when exposed to oxygen, which can severely limit the exploration and utilization of these intriguing physical properties. Therefore, understanding the oxidation mechanism of pristine Nb3SeI7 and its correlation with electrical polarization-an area that remains largely unexplored-is highly significant. In this study, the out-of-plane piezoelectricity of Nb3SeI7 is experimentally demonstrated, with a piezoelectric coefficient (|d33 eff|) of 0.76 nm V-1. Furthermore, by combining near ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS), Time-of-Flight secondary ion mass spectrometry (ToF-SIMS), and Density functional theory (DFT) calculations, it is revealed that the oxidation of Nb3SeI7 is self-limiting and independent of its electrical polarization, owing to the similar defect formation energies of Se and I atoms. This self-limiting and polarization-insensitive oxidation provides valuable insights into the stabilization mechanisms and expands the potential applications of out-of-plane piezoelectricity and other intriguing physical properties in Janus vdW Nb3SeI7.

Keywords: Janus structure; Nb3SeI7; piezoelectricity; self‐limiting oxidation; strain.