Optical Effect Modulation in Polarized Raman Spectroscopy of Transparent Layered α‐MoO₃

Abstract Optical anisotropy, which is quantified by birefringence (Δ n ) and linear dichroism (Δ k ), can significantly modulate the angle‐resolved polarized Raman spectroscopy (ARPRS) response of anisotropic layered materials (ALMs) by external interference. This work studies the separate modulation of birefringence on the ARPRS response and the intrinsic response by selecting transparent birefringent crystal α‐MoO 3 as an excellent platform. It is found that there are several anomalous ARPRS responses in α‐MoO 3 that cannot be reproduced by the real Raman tensor widely used in non‐absorbing materials; however, they can be well explained by considering the birefringence‐induced Raman selection rules. Moreover, the systematic thickness‐dependent study indicates that birefringence modulates the ARPRS response to render an interference pattern; however, the amplitude of modulation is considerably lower than that by linear dichroism as occurred in black phosphorous. This weak modulation brings convenience to the crystal orientation determination of transparent ALMs. Combining the atomic vibrational pattern and bond polarizability model, the intrinsic ARPRS response of α‐MoO 3 is analyzed, giving the physical origins of the Raman anisotropy. This study employs α‐MoO 3 as an example, although it is generally applicable to all transparent birefringent ALMs.