Emission Dipole and Pressure‐Driven Tunability of Second Harmonic Generation in vdWs Ferroelectric NbOI2

2D in‐plane ferroelectric NbOI2 exhibits strong second harmonic generation (SHG) and ultrahigh effective susceptibility. To push forward their applications in nonlinear photonics and optoelectronics, it is highly desirable to understand the emission dipole orientation and tunability of SHG, which is not achieved. Here, by integrating tight focusing from parabolic mirror with back focal plane (BFP) imaging technique, for the first time it is demonstrated that SHG emission of NbOI2 presents purely in‐plane dipole orientation in consistent with numerical simulations, suggesting the in‐plane components of the SHG susceptibility tensor in NbOI2 dominate the emission. Moreover, with the aid of ab‐initio calculations, it is found that the hydrostatic pressure can dramatically change the structure and resultant SHG intensity of NbOI2. Explicitly, SHG intensity endures a slight increase due to the distortion of octahedral at low pressure pressure, and then monotonously decreases due to the improvement of structural symmetry with further increasing pressure, and drastically quenching resulting from the ferroelectric to paraelectric phase transition. This work unambiguously demonstrates the dipole emission behavior of SHG and the relationship between structural evolution and SHG intensity, which provides an avenue for tunable nonlinear optics and optoelectronics.