Arene and functionalized arene based two dimensional organic–inorganic hybrid perovskites for photovoltaic applications

Abstract Recently, two‐dimensional organic–inorganic hybrid perovskites have attracted great attention for their outstanding performances in solar energy conversion devices. By using first principles calculations, we explored the structural, electronic and optical properties of recently synthesized (PEA) 2 PbI 4 and (PEA) 2 SnI 4 organic–inorganic hybrid perovskites to understand the photovoltaic performances of these systems. Our study reveals that both the perovskites are direct band gap semiconductors and possess desirable band gap for solar energy absorption. We have further extended our study to fluoro‐, chloro‐, and bromo‐functionalized phenethylammonium (PEA) cations based [X(X = F, Cl, Br)PEA] 2 A(A = Pb, Sn)I 4 perovskite materials. The halogenated benzene moiety confers an ultrahydrophobic character and protects the perovskites from ambient moisture. The halogen functionalized perovskites remain direct band gap semiconductors and all the perovskites show very strong optical absorption (∼7 × 10 5 cm −1 ) across UV–visible region. We have further calculated the photo‐conversion efficiency (PCE) of both arene and functionalized arene based perovskites. The halogen‐functionalized PEA‐based perovskites also exhibit high PCE as like pristine ones and finally achieve high PCE of up to 24.30%, making them competitive with other previously reported perovskite‐based photovoltaic devices.