Multivalency-induced structural variations of 2D selenium nanosheets: facile solution-phase synthesis and optical...

The structural stability of two-dimensional (2D) phases derived from bulk selenium (Se) is intrinsically rooted in the multivalent nature of the material. The emergence of 2D Se, as its morphology evolves from 1D to 2D, was initially inspired by theoretical predictions of various quasi-stable structural phases of 2D Se. Here, we report a facile liquid-phase synthesis of free-standing few-layer selenium nanosheets (SeNS) employing a simple magnetic stirring of their bulk counterpart in N-methyl pyrrolidone (NMP). The synthesized SeNS possess lateral dimensions ranging from several hundreds of nanometers to a few microns, with a minimum thickness of ∼1 nm. High-resolution transmission electron microscopy reveals the existence of α- and β-selenene. Fourier transform infrared analysis suggests that the inherent surface/edge functionalization of 2D SeNS by NMP enhances their dispersion stability. The UV-vis-NIR absorption spectrum of SeNS exhibits a shoulder peak at 330 nm, attributed to surface/edge functionalization, and multiple peaks across the vis-NIR region, stemming from size quantization effects. The functionalized selenium nanosheets generate photoluminescence that spans the blue-green range, while the size quantization of SeNS leads to green-orange luminescence. The non-linear optical studies following Z-scan experiments with an open aperture revealed reverse saturable absorption (RSA) and strong optical limiting in 2D SeNS under 532 nm, 10 ns laser pulses. Notably, a transition from RSA to saturable absorption (SA) has also been observed in samples stirred over an extended period. In this perspective, the results illustrate the first experimental realization of free-standing multivalent 2D selenium in allotropic forms with unique optical properties.