2D Ferroelectric Ruddlesden-Popper Perovskites: an Emerging Fully Electronically Controllable Shift Current and Persistent Spin Helix

Abstract

Two-dimensional (2D) hybrid organic--inorganic perovskites (HOIPs) are promising candidates for next-generation optoelectronic and spintronic applications. This work systematically investigates the relationship between structural distortions and functional responses in three $C_{2v}$-symmetric Ruddlesden--Popper (RP) ferroelectric perovskites, $(4,4\text{-DFPD})_{2}\mathrm{PbI}_{4}$, $(\mathrm{DFCHA})_{2}\mathrm{PbI}_{4}$, and PEPI, using first-principles calculations combined with irreducible representation decomposition and wave-vector point-group symmetry (WPGS) analysis. The results reveal that the lead--iodide framework yields shift-current (SC) magnitudes comparable to, and in specific cases even an order of magnitude larger than, those of traditional ferroelectric oxides, with PEPI reaching a maximum of $69.16\ \mu\mathrm{A}/\mathrm{V}^{2}$. The SC magnitude correlates positively with the octahedral distortion index ($D_i$), while a competition mechanism is identified between covalent bond strength and structural asymmetry, where increased average bond lengths can offset the enhancement induced by $D_i$. Regarding spintronics, $C_{2v}$ symmetry-protected persistent spin textures (PST) are identified. A transition to $C_2$-protected quasi-PST occurs in monoclinic $(4,4\text{-DFHHA})_{2}\mathrm{PbI}_{4}$, leading to a persistent spin helix (PSH) with long-distance spin transport. The synergy among ferroelectricity, SC, and PST enables nonvolatile electrical control of both photocurrent direction and spin configurations. This work provides evaluation criteria and practical guidance for designing high-performance integrated spintronic--photovoltaic devices.