Directional Anisotropy of the Vibrational Modes in 2D-Layered Perovskites

[Image: see text] The vibrational modes in organic/inorganic layered perovskites are of fundamental importance for their optoelectronic properties. The hierarchical architecture of the Ruddlesden–Popper phase of these materials allows for distinct directionality of the vibrational modes with respect to the main axes of the pseudocubic lattice in the octahedral plane. Here, we study the directionality of the fundamental phonon modes in single exfoliated Ruddlesden–Popper perovskite flakes with polarized Raman spectroscopy at ultralow frequencies. A wealth of Raman bands is distinguished in the range from 15 to 150 cm(–1) (2–15 meV), whose features depend on the organic cation species, on temperature, and on the direction of the linear polarization of the incident light. By controlling the angle of the linear polarization of the excitation laser with respect to the in-plane axes of the octahedral layer, we gain detailed information on the symmetry of the vibrational modes. The choice of two different organic moieties, phenethylammonium (PEA) and butylammonium (BA), allows us to discern the influence of the linker molecules, evidencing strong anisotropy of the vibrations for the (PEA)(2)PbBr(4) samples. Temperature-dependent Raman measurements reveal that the broad phonon bands observed at room temperature consist of a series of sharp modes and that such mode splitting strongly differs for the different organic moieties and vibrational bands. Softer molecules such as BA result in lower vibrational frequencies and splitting into fewer modes, while more rigid molecules such as PEA lead to higher frequency oscillations and larger number of Raman peaks at low temperature. Interestingly, in distinct bands the number of peaks in the Raman bands is doubled for the rigid PEA compared to the soft BA linkers. Our work shows that the coupling to specific vibrational modes can be controlled by the incident light polarization and choice of the organic moiety, which could be exploited for tailoring exciton–phonon interaction, and for optical switching of the optoelectronic properties of such 2D layered materials.