RESUMO
Over the last years, several different pathways have been suggested for producing perovskite thin films for solar cell applications. While the merit of these methods with respect to the solar cell efficiency have been shown, the actual composition of the resulting thin films is often not investigated. Here, we show that methylammonium lead iodide films produced using lead acetate as a lead source can have up to 15 % dimethylammonium incorporated into their crystal structure, even though this ion is often consider to be too large for incorporation. The origin of this ion lies in the precursor solution, where it is formed in a reaction that is facilitated by the basic character of the acetate ions. We further show that these dimethylammonium ions are incorporated in a random fashion throughout the crystal structure, owing to the lack of observable ordered domains.
RESUMO
Poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) is frequently used as hole transport layer in planar p-i-n perovskite solar cells. Here we show that processing of a metal halide perovskite layer on top of PEDOT:PSS via spin coating of a precursor solution chemically reduces the oxidation state of PEDOT:PSS. This reduction leads to a lowering of the work function of the PEDOT:PSS and the perovskite layer on top of it. As a consequence, the solar cells display inferior performance with a reduced open-circuit voltage and a reduced short-circuit current density, which increases sublinearly with light intensity. The reduced PEDOT:PSS can be re-oxidized by thermal annealing of the PEDOT:PSS/perovskite layer stack in the presence of oxygen. As a consequence, thermal annealing of the perovskite layer in air provides solar cells with increased open-circuit voltage, short-circuit current density and high efficiency.
RESUMO
Moisture, in the form of ambient humidity, has a significant impact on methylammonium lead halide perovskite films. In particular, due to the hygroscopic nature of the methylammonium component, moisture plays a significant role during film formation. This issue has so far not been well understood and neither has the impact of moisture on the physical properties of resultant films. Herein, we carry out a comprehensive and well-controlled study of the effect of moisture exposure on methylammonium lead halide perovskite film formation and properties. We find that films formed in higher humidity atmospheres have a less continuous morphology but significantly improved photoluminescence, and that film formation is faster. In photovoltaic devices, we find that exposure to moisture, either in the precursor solution or in the atmosphere during formation, results in significantly improved open-circuit voltages and hence overall device performance. We then find that by post-treating dry films with moisture exposure, we can enhance photovoltaic performance and photoluminescence in a similar way. The enhanced photoluminescence and open-circuit voltage imply that the material quality is improved in films that have been exposed to moisture. We determine that this improvement stems from a reduction in trap density in the films, which we postulate to be due to the partial solvation of the methylammonium component and "self-healing" of the perovskite lattice. This work highlights the importance of controlled moisture exposure when fabricating high-performance perovskite devices and provides guidelines for the optimum environment for fabrication. Moreover, we note that often an unintentional water exposure is likely responsible for the high performance of solar cells produced in some laboratories, whereas careful synthesis and fabrication in a dry environment will lead to lower-performing devices.