Probing Local Heterogeneity in the Optoelectronic Properties of Organic-Inorganic Perovskites Using Fluorescence Microscopy

Probing Local Heterogeneity in the Optoelectronic Properties of Organic-Inorganic Perovskites Using Fluorescence Microscopy Dane W. De Quilettes Chair of the Supervisory Committee: Professor David S. Ginger Department of Chemistry Unregulated emission of carbon dioxide and greenhouse gases into our atmosphere has led to an increase in the average global surface air temperature, to a disruption of weather patterns, and to the acidification of oceans all of which threaten the continued prosperity of our race and our planet. The transition to renewable sources of energy is therefore one of, if not the most, important challenge that the 21 century faces. Solar energy is predicted to play a major role in global energy production in the coming century, as the amount of energy hitting the earth’s surface is far greater than the energy demands of industrialized human activity. Many current photovoltaic technologies show promise in contributing to a large fraction of global energy production, but in order to reach terawatt-scale production the photovoltaic modules will need to be scalable, cheap, and efficient. Perovskite-based photovoltaics hold exceptional potential in contributing to solar energy production. Thus far, the unprecedented rise in power conversion efficiencies over the past few years can be primarily attributed to improvements in film processing and device engineering. Although effective, the fundamental photophysical processes that govern charge generation, transport, recombination, and collection in these materials is still in its infancy. Historically in semiconductor technologies, this understanding has been essential in the rational design of optimized materials. This knowledge appears to be even more critical as perovskite thin films are polycrystalline on the microscale, which suggests that the local structure may determine the optoelectronic quality and device performance on a similar length scale. Prior to these studies, much of the field had focused on bulk spectroscopic measurements to characterize the semiconducting properties of hybrid perovskite thin films. From our contributions as well as many others, microscopy has now given us a window into how this bulk behavior is composed of an ensemble of spatially varying structure and composition, which controls carrier transport and dynamics on the way to carrier extraction and power generation. This understanding has led to some exciting new discoveries on the rational design of materials and is leveraged to deploy chemical passivation techniques to improve the optoelectronic quality of the material, with the ultimate goal of improving photovoltaic power conversion efficiency. Reducing non-radiative recombination in semiconducting materials is a prerequisite for achieving the highest performance in a host of light-emitting and photovoltaic applications. In the first study described herein, we used confocal fluorescence microscopy correlated with scanning electron microscopy to spatially resolve the photoluminescence (PL) decay dynamics from films of nonstoichiometric organicinorganic perovskites, CH3NH3PbI3(Cl). The PL intensities and lifetimes varied between different grains in the same film, even for films that exhibited long bulk lifetimes. The grain boundaries were dimmer and exhibited faster non-radiative decay. Energydispersive x-ray spectroscopy showed a positive correlation between chlorine concentration and regions of brighter PL, while PL imaging revealed that chemical treatment with pyridine could activate previously dark grains. Next, to better elucidate the sources of these loss pathways, we performed a systematic study using confocal and widefield fluorescence microscopy to deconvolve the contributions from diffusion and non-radiative recombination which lead to the observed image heterogeneity. We showed that, in addition to local variations in non-radiative loss, carriers diffuse anisotropically due to heterogeneous intergrain connectivity. In addition to non-radiative recombination impeding material performance, we also showed that the materials exhibit a range of complex dynamic phenomena under illumination. We used a unique combination of confocal PL microscopy and chemical imaging to correlate the local changes in photophysics with composition in CH3NH3PbI3 films under illumination. We demonstrated that the photo-induced “brightening” of the perovskite PL can be attributed to an order-of-magnitude reduction in trap state density. By imaging the same regions with time-of-flight secondary-ion-mass spectrometry (ToFSIMS), we correlated this photobrightening with a net migration of iodine. This work provides visual evidence for photo-induced halide migration in triiodide perovskites and reveals the complex interplay between charge carrier populations, electronic traps, and mobile halides, which collectively impact optoelectronic performance. Next, we studied the effects of a series of post-deposition ligand treatments on the PL of polycrystalline methylammonium lead triiodide perovskite thin films. We showed that a variety of Lewis bases can improve the bulk PL quantum efficiency (PLQE) and extend the average PL lifetime <τ>, with large enhancements concentrated at grain boundaries. Notably, we demonstrated thin film PLQE as high as 35 ± 1% and <τ> as long as 8.82 ± 0.03 μs, at solar equivalent carrier densities using tri-n-octylphosphine oxide (TOPO) treated films. Using glow discharge optical emission spectroscopy (GDOES) and nuclear magnetic resonance (NMR) spectroscopy, we showed that the ligands are incorporated primarily at the film surface and are acting as electron donors. These results indicate it is possible to obtain thin film PL lifetime and PLQE values that are comparable to those from single crystals by control over surface chemistry. Finally, we further characterized these TOPO treated films to show, with respect to material bandgap, these passivated films could demonstrate quasi-Fermi level splittings comparable to the highest performing GaAs solar cells, reaching 96% of the ShockleyQueisser limit. Importantly, we reported internal photoluminescence quantum efficiency values of 92% under one sun illumination intensity, which are the highest values achieved to date. These results suggest that the material optoelectronic quality has been nearly optimized and further increases in voltage and device efficiency will be obtained by integrating these types of surface passivation schemes into charge carrier selective interfaces.