After rapid progress over the past five years, organic-inorganic perovskite solar cells (PSCs) currently exhibit photoconversion efficiencies comparable to the best commercially available photovoltaic technologies. However, instabilities in the materials and devices, primarily due to reactions with water, have kept PSCs from entering the marketplace. Here, we use laser beam induced current (LBIC) imaging to investigate the spatial and temporal evolution of the quantum efficiency of perovskite solar cells under controlled humidity conditions. Several interesting mechanistic aspects are revealed as the degradation proceeds along a four-stage process. Three of the four stages can be reversed, while the fourth stage leads to irreversible decomposition of the photoactive perovskite material. A series of reactions in the PbI 2 -CH 3 NH 3 I-H 2 O system explains the interplay between the interactions with water and the overall stability. Understanding of the degradation mechanisms of PSCs on a microscopic level gives insight toward improving the long-term stability.
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A delicate control of the stoichiometry,
crystallographic phase,
and grain structure of the photoactive material is typically required
to fabricate high-performance photovoltaic (PV) devices. Organo-metal
halide perovskite materials, however, exhibit a large degree of tolerance
in synthesis and can be fabricated into high efficiency devices by
a variety of different vacuum and solution-based processes, with a
wide range of precursor ratios. This suggests that the phase field
for the desired material is wider than expected or that high device
efficiency may be achieved with a range of phases. Here, we investigate
the structural and optical properties of the materials formed when
a range of compositions of methylammonium iodide (MAI) and lead iodide
(PbI2) were reacted at temperatures from 40 to 190 °C.
The reactions were performed according to a commonly employed synthetic
approach for high efficiency PV devices, and the data was analyzed
to construct a pseudobinary, temperature-dependent, phase-composition
processing diagram. Escape of MAI vapor at the highest temperatures
(150–190 °C) enabled a PbI2 phase to persist
to very high MAI concentrations, and the processing diagram was not
representative of phase equilibrium in this range. Data from reactions
performed with a fixed vapor pressure of MAI allowed the high temperature
portion of the diagram to be corrected and a near-equilibrium phase
diagram to be proposed. The perovskite phase field is wider than previously
thought under both processing conditions and extended by the existence
of stacked perovskite sheet phases. Several aspects of the diagrams
clarify why the organo-halide perovskite materials are compatible
with solution processing.
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