Stacking Faults Enabled Second Harmonic Generation in Centrosymmetric van der Waals RhI 3 .

Second harmonic generation (SHG) in van der Waals (vdW) materials has garnered significant attention due to its potential for integrated nonlinear optical and optoelectronic applications. Stacking faults in vdW materials are a typical kind of planar defect that introduces a degree of freedom to modulate the crystal symmetry and resultant SHG response. However, the physical origin and tunability of stacking-fault-governed SHG in vdW materials remain unclear. Here, taking the intrinsically centrosymmetric vdW RhI 3 as an example, we theoretically reveal the origin of stacking-fault-governed SHG response, where the SHG response comes from the energetically favorable AC̅ stacking fault of which the electrical transitions along the high-symmetry paths Γ-M and Γ-K in the Brillion zone play the dominant role at 810 nm. Such a stacking-fault-governed SHG response is further confirmed via structural characterizations and SHG measurements. Furthermore, by applying hydrostatic pressure on RhI 3 , the correlation between structural evolution and SHG response is revealed with SHG enhancement up to 6.9 times, where the decreased electronic transition energies and higher momentum matrix elements due to the stronger interlayer interactions upon compression magnify the SHG susceptibility. This study develops a promising foundation for nonlinear nano-optics applications through the strategic design of stacking faults.