Titanium Self-Intercalation Induced Formation of Orthogonal (1 × 1) Edge/Surface Reconstruction in 1T-TiSe₂: Atomic Scale Dynamics and Mechanistic Study

Abstract

Edges and surfaces play indispensable roles in affecting the chemical−physical properties of materials, particularly in two-dimensional transition metal dichalcogenides (TMDCs) with reduced dimensionality. Herein, we report a novel edge/ surface structure in multilayer 1T-TiSe 2 , i.e., the orthogonal (1 × 1) reconstruction, induced by the self-intercalation of Ti atoms into interlayer octahedral sites of the host TiSe 2 at elevated temperature. Formation dynamics of the reconstructed edge/ surface are captured at the atomic level by in situ scanning transmission electron microscopy (STEM) and further validated by density functional theory (DFT), which enables the proposal of the nucleation mechanism and two growth routes (zigzag and armchair). Via STEM-electron energy loss spectroscopy (STEM-EELS), a chemical shift of 0.6 eV in Ti L 3,2 is observed in the reconstructed edge/surface, which is attributed to the change of the coordination number and lattice distortion. The present work provides insights to tailor the atomic/electronic structures and properties of 2D TMDC materials.