Effects of Cd Diffusion and Doping in High-Performance Perovskite Solar Cells Using CdS as Electron Transport Layer

Perovskite solar cells with stabilized power conversion efficiency exceeding 15% have been achieved, using a methylammonium lead iodide (MAPbI₃) absorber and CdS as the electron transport layer. X-ray photoelectron spectroscopy reveals a small presence of Cd at the surface of most perovskite films fabricated on CdS. Perovskite films were deliberately doped with Cd to understand the possible impacts of Cd diffusion into the perovskite absorber layer. Doping substantially increases the grain size of the perovskite films but also reduces device performance through the formation of an electrical barrier, as inferred by the S-shape of their <i>J</i>–<i>V</i> curves. Time-resolved photoluminescence measurements of the doped films do not indicate substantial nonradiative recombination due to bulk defects, but a secondary phase is evident in these films, which experiments have revealed to be the organic–inorganic hybrid material methylammonium cadmium iodide, (CH₃NH₃)₂CdI₄. It is further demonstrated that this compound can form via the reaction of CdS with methylammonium iodide and may form as a competing phase during deposition of the perovskite. Buildup of this insulating compound may act as an electrical barrier at perovskite interfaces, accounting for the drop in device performance

Examining the Effects of Homochirality for Electron Transfer in Protein Assemblies

Protein voltammetry studies of cytochrome c, immobilized on chiral tripeptide monolayer films, reveal the importance of the electron spin and the film’s homochirality on electron transfer kinetics. Magnetic film electrodes are used to examine how an asymmetry in the standard heterogeneous electron transfer rate constant arises from changes in the electron spin direction and the enantiomer composition of the tripeptide monolayer; rate constant asymmetries as large as 60% are observed. These findings are rationalized in terms of the chiral induced spin selectivity effect and spin-dependent changes in electronic coupling. Lastly, marked differences in the average rate constant are shown between homochiral ensembles, in which the peptide and protein possess the same enantiomeric form, compared to heterochiral ensembles, where the handedness of the peptide layer is opposite to that of the protein or itself comprises heterochiral building blocks. These data demonstrate a compelling rationale for why nature is homochiral; namely, spin alignment in homochiral systems enables more efficient energy transduction