Publication date: 15th December 2025
Control over conductivity and carrier type defines semiconductors. A general approach to increase carrier concentrations is electrical doping, where a host atom is substituted for a higher (lower) valence dopant atom, releasing a free hole (electron). Indeed, high performance commercial semiconductors based on first-generation semiconductors are often heavily doped (dopant levels ~ 10^13-10^20 cm-3). However, controlled doping of third-generation PSCs remains under-developed, most likely because traditional exogeneous methods for doping would likely cause severe damage to the relatively soft perovskite structure. On the other hand, Sn-Pb perovskites are known to undergo strong p-doping, with hole doping levels as high as 10^19 cm-3. Such high dopant densities are generally not sought after due to the greater potential for photogenerated charges to recombine before they can be extracted. Given that Sn-only and Sn-Pb perovskites hold promise for single-junction and all-perovskite tandem solar cells, it is necessary to understand the underpinning structure-function relationships to control (and perhaps even harness) doping. In this talk, I will summarize our recent work exploring photophysical heterogeneity and its drivers in narrow bandgap perovskite films. First, we have demonstrated an optical technique for estimating the dopant density, which we use to characterize dopant densities between 10^14 and 10^19 cm-3 in narrow-bandgap halide perovskites. Second, we have deployed this technique on the microscale on several Sn-Pb compositions to produce dopant density maps, which we correlate with various imaging modes to identify correlations between electronic, compositional, and structural heterogeneity. Third, we combine photoluminescence mapping with atomic force microscopy to identify localized reduction from NaBH4 aggregates in tin halide perovskites. Together, these results demonstrate the promise of multi-modal microscopy for further developing narrow-bandgap perovskites for single- and multi-junction photovoltaics and beyond.
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