In the context of the extensive application prospect of two-dimensional (2D) chalcogenides, we synthesized layered SnSe2+δ bulks with defects employing a hybrid chemical vapor transport-melt approach. Both the Eg and A1g Raman characteristic peaks in SnSe2+δ are dominated by cubic anharmonicity, coupled with nonlinear temperature dependencies below 140 K. Notably, the reduction in phonon energy observed in these vibrational modes can be ascribed to defect-mediated Raman scattering, irrespective of deficient or excess Se defects. However, the lower consistency in the Raman shifts of the in-plane Eg vibrations compared to the out-of-plane A1g modes suggests that the defects predominantly entail the absence of Se atoms and the substitutions of Sn by Se, delineating a continuum of Se-deficient and Se-enriched compositions. Furthermore, Se defects induce the contraction of the indirect bandgaps, facilitating a transition from medium to narrow bandgap semiconductors in SnSe2+δ, which underscores the tunable nature of the bandgaps through the incorporation of Se defects. These discoveries present an avenue for bandgap engineering and foster a deeper comprehension of the phonon and thermal properties of layered chalcogenides for further advanced technologies.
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