Prof Laura Herz FRS

Abstract:

Mixed-halide perovskites offer ideal bandgaps for tandem solar cells, but photoinduced halide segregation compromises photovoltaic device performance. This study explores the influence of a hole-transport layer, necessary for a full device, by monitoring halide segregation through in situ, concurrent X-ray diffraction and photoluminescence measurements to disentangle compositional and optoelectronic changes. This work demonstrates that top coating FA0.83Cs0.17Pb(Br0.4I0.6)3 perovskite films with a poly(triaryl)amine (PTAA) hole-extraction layer surprisingly leads to suppression of halide segregation because photogenerated charge carriers are rapidly trapped at interfacial defects that do not drive halide segregation. However, the generation of iodide-enriched regions near the perovskite/PTAA interface enhances hole back-transfer from the PTAA layer through improved energy level offsets, increasing radiative recombination losses. It is further found that while passivation with a piperidinium salt slows halide segregation in perovskite films, the addition of a PTAA top-coating accelerates such effects, elucidating the specific nature of trap types that are able to drive the halide segregation process. This work highlights the importance of selective passivation techniques for achieving efficient and stable wide-bandgap perovskite photovoltaic devices.

Abstract:

The use of layered, 2D perovskites can improve the stability of metal halide perovskite thin films and devices. However, the charge carrier transport properties in layered perovskites are still not fully understood. Here, the sum of the electron and hole mobilities (Σμ) in thin films of the 2D perovskite PEA2PbI4, through transient electronically contacted nanosecond-to-millisecond photoconductivity measurements, which are sensitive to long-time, long-range (micrometer length scale) transport processes is investigated. After careful analysis, accounting for both early-time recombination and the evolution of the exciton-to-free-carrier population, a long-range mobility of 8.0 +/− 0.6 cm2 (V s)–1, which is ten times greater than the long-range mobility of a comparable 3D material FA0.9Cs0.1PbI3 is determined. These values are compared to ultra-fast transient time-resolved THz photoconductivity measurements, which are sensitive to early-time, shorter-range (tens of nm length scale) mobilities. Mobilities of 8 and 45 cm2 (V s)–1 in the case of the PEA2PbI4 and FA0.9Cs0.1PbI3, respectively, are obtained. This previously unreported concurrence between the long-range and short-range mobility in a 2D material indicates that the polycrystalline thin films already have single-crystal-like qualities. Hence, their fundamental charge carrier transport properties should aid device performance.