Second-harmonic generation in atomically thin Formula Presented and its possible origin from charge density wave transitions

Optical second-harmonic generation (SHG) can only occur in noncentrosymmetric crystals in the leading electric-dipole approximation. Transition metal dichalco genides with the 1T octahedral coordination is centrosymmetric, hence precluding SHG. Here we report the surprising observation of SHG in atomically thin 1T−TiSe2, a prototypical charge density wave (CDW) material. Its intensity peaks in the trilayer, reaching 2% of that in monolayer MoS2, a two-dimensional crystal featuring pronounced nonlinear optical effect. The SHG signal exhibits a sixfold polarization dependence characteristic of a lattice with threefold rotational symmetry. It monotonically decreases with increasing temperature and persists at room temperature. Raman spectroscopy demonstrates that the CDW order is robust in atomically thin samples, with the transition temperature slightly lower than in the bulk. The SHG can be explained by the lattice distortion associated with the CDW as well as its fluctuation above the transition temperature. These results challenge the exciton insulator scenario and the chiral nature of the CDW, but support the band Jahn-Teller mechanism. Our work demonstrates SHG as a sensitive probe of the stacking order of the CDW in 1T−TiSe2 and enriches the material base for nonlinear optical effects.