Moisture-Driven
Formation and Growth of Quasi-2‑D
Organolead Halide Perovskite Crystallites
Posted on 2020-06-16 - 20:29
Ruddlesden–Popper
phase quasi-2-D organolead halide perovskites
like n-butylammonium methylammonium lead iodide (nBA-MAPI) exhibit improved moisture stability over typical
3-D perovskite materials, making them exciting for use in a variety
of applications such as photovoltaic (PV) devices. This improved stability
is the result of a unique disproportionation-based degradation mechanism
that protects the bulk of the nBA-MAPI from extensive
damage through the formation of a protective, low-n surface layer. In addition to this surface layer, nBA-MAPI films also exhibit the dynamic growth of micrometer-scale
crystallites and cracks at the surface of the film, unique and potentially
important byproducts of quasi-2-D perovskite disproportionation. Here,
we present a detailed study of these crystallites using several analytical
techniques including photoluminescence spectroscopy (PL), confocal
fluorescence microscopy (CFM), atomic force microscopy (AFM) combined
with time-of-flight-secondary ion mass spectrometry (ToF-SIMS), and
others in an effort to better understand the relationship between
material disproportionation and crystallite growth. Our results show
that the crystallites form after exposure to humid air and confirm
that they are composed of low-n phases of nBA-MAPI. The crystallites are found to extend into the
interior of the film and exhibit continued growth while exposed to
moisture over 72 h. This growth is accompanied by both a decrease
in the bulk 2-D phase and an increase in a 3-D-like phase in the surface
PL spectra, indicating that the crystallites are likely a product
of moisture-driven disproportionation. Importantly, similar crystallites
are also observed to form within model PV devices, indicating that
such processes must be accounted for when designing future devices
containing materials like nBA-MAPI.
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Wygant, Bryan
R.; Geberth, Geoff T.; Ye, Alexandre Z.; Dolocan, Andrei; Cotton, Daniel E.; Roberts, Sean T.; et al. (2020). Moisture-Driven
Formation and Growth of Quasi-2‑D
Organolead Halide Perovskite Crystallites. ACS Publications. Collection. https://doi.org/10.1021/acsaem.0c00423