Extrinsic Doping and Compensating Defects in The 2D Hybrid Perovskite PEA₂PbI₄

2D hybrid organic-inorganic perovskites (HOIPs) are exciting materials for optoelectronic device applications due to their high degree of chemical and structural tunability. The ability to electronically dope these materials via incorporation of extrinsic dopants is essential for control over carrier concentrations. Conversely, the presence of intrinsic defects can negatively impact electronic doping efficiencies. Here, we present a systematic study of intrinsic point defects and extrinsic dopants (eg. Bi, Sn [<i>PRX Energy</i>, <b>2, 023010 </b>(2023)]), both in isolation and as combined defects, in phenylethylammonium lead iodide (PEA₂PbI₄). Using spin-orbit coupled hybrid density functional theory (DFT) and supercell models up to 3,383 atoms in size, we pinpoint the expected positions of dopant-derived electronic levels in the bandgap. Complementary experimental findings reinforce hypotheses of compensation mechanisms and limiting factors derived from DFT.