RESUMO
Inorganic and organic lead halide perovskite materials attract great interest in the scientific community because of their potential for low-cost, high efficiency solar cells. In this report we add a new property of these materials, namely their photochemical activity in the visible light range. Both inorganic (CsPbBr3) and organic (CH3NH3PbBr3-MAPbBr3) perovskite thin films were demonstrated to promote photo-dissociation of adsorbed ethyl chloride (EC), employing 532 nm pulsed laser irradiation under ultra-high vacuum (UHV) conditions. From the post-irradiation temperature programmed desorption (TPD) analysis, the yield of photoproduct formation was found to be up to two orders of magnitude higher than for UV light-excited EC molecules on metallic and oxide surfaces. Photo-reactivity on top of the CsPbBr3 surface is almost an order of magnitude more efficient than on the CH3NH3PbBr3 surface, apparently due to the lower density of defect and surface states. A direct correlation was found between electron-induced luminescence and photoluminescence intensities and the photoreactivity cross-sections. We conclude that both the intense luminescence and the well-known photovoltaic properties associated with these halide perovskite materials are consistent with the efficiency of photo-reactivity in the visible range, reported here for the first time.
RESUMO
Using several metals with different work functions as solar cell back contact we identify majority carrier type inversion in methylammonium lead bromide (MAPbBr3, without intentional doping) as the basis for the formation of a p-n junction. MAPbBr3 films deposited on TiO2 are slightly n-type, whereas in a full device they are strongly p-type. The charge transfer between the metal electrode and the halide perovskite (HaP) film is shown to determine the dominant charge carrier type of the HaP and, thus, also of the final cells. Usage of Pt, Au and Pb as metal electrodes shows the effects of metal work function on minority carrier diffusion length and majority carrier concentration in the HaP, as well as on built-in voltage, band bending, and open circuit voltage (VOC) within a solar cell. VOC > 1.5 V is demonstrated. The higher the metal WF, the higher the carrier concentration induced in the HaP, as indicated by a narrower space charge region and a smaller minority carrier diffusion length. From the analysis of bias-dependent electron beam-induced currents, the HaP carrier concentrations are estimated to be â¼ 1 × 1017 cm-3 with Au and 2-3 × 1018 cm-3 with Pt. A model in which type-inversion stretches across the entire film width implies formation of the p-n junction away from the interface, near the back-contact metal electrode. This work highlights the importance of the contact metal on device performance in that contact engineering can also serve to control the carrier concentration in HaP.
RESUMO
The origin of the low densities of electrically active defects in Pb halide perovskite (HaP), a crucial factor for their use in photovoltaics, light emission, and radiation detection, remains a matter of discussion, in part because of the difficulty in determining these densities. Here, we present a powerful approach to assess the defect densities, based on electric field mapping in working HaP-based solar cells. The minority carrier diffusion lengths were deduced from the electric field profile, measured by electron beam-induced current (EBIC). The EBIC method was used earlier to get the first direct evidence for the n-i-p junction structure, at the heart of efficient HaP-based PV cells, and later by us and others for further HaP studies. This manuscript includes EBIC results on illuminated cell cross sections (in operando) at several light intensities to compare optoelectronic characteristics of different cells made by different groups in several laboratories. We then apply a simple, effective single-level defect model that allows deriving the densities (Nr) of the defect acting as recombination center. We find Nr ≈ 1 × 1013 cm-3 for mixed A cation lead bromide-based HaP films and â¼1 × 1014 cm-3 for MAPbBr3(Cl). As EBIC photocurrents are similar at the grain bulk and boundaries, we suggest that the defects are at the interfaces with selective contacts rather than in the HaP film. These results are relevant for photovoltaic devices as the EBIC responses distinguish clearly between high- and low-efficiency devices. The most efficient devices have n-i-p structures with a close-to-intrinsic HaP film, and the selective contacts then dictate the electric field strength throughout the HaP absorber.
RESUMO
The presence of excess lead iodide in halide perovskites has been key for surpassing 20% photon-to-power conversion efficiency. To achieve even higher power conversion efficiencies, it is important to understand the role of remnant lead iodide in these perovskites. To that end, we explored the mechanism facilitating this effect by identifying the impact of excess lead iodide within the perovskite film on charge diffusion length, using electron-beam-induced current measurements, and on film formation properties, from grazing-incidence wide-angle X-ray scattering and high-resolution transmission electron microscopy. Based on our results, we propose that excess lead iodide in the perovskite precursors can reduce the halide vacancy concentration and lead to formation of azimuthal angle-oriented cubic α-perovskite crystals in-between 0° and 90°. We further identify a higher perovskite carrier concentration inside the nanostructured titanium dioxide layer than in the capping layer. These effects are consistent with enhanced lead iodide-rich perovskite solar cell performance and illustrate the role of lead iodide.
RESUMO
Direct comparison between perovskite-structured hybrid organic-inorganic methylammonium lead bromide (MAPbBr3) and all-inorganic cesium lead bromide (CsPbBr3), allows identifying possible fundamental differences in their structural, thermal and electronic characteristics. Both materials possess a similar direct optical band gap, but CsPbBr3 demonstrates a higher thermal stability than MAPbBr3. In order to compare device properties, we fabricated solar cells, with similarly synthesized MAPbBr3 or CsPbBr3, over mesoporous titania scaffolds. Both cell types demonstrated comparable photovoltaic performances under AM1.5 illumination, reaching power conversion efficiencies of â¼6% with a poly aryl amine-based derivative as hole transport material. Further analysis shows that Cs-based devices are as efficient as, and more stable than methylammonium-based ones, after aging (storing the cells for 2 weeks in a dry (relative humidity 15-20%) air atmosphere in the dark) for 2 weeks, under constant illumination (at maximum power), and under electron beam irradiation.
RESUMO
We report valence and conduction band densities of states measured via ultraviolet and inverse photoemission spectroscopies on three metal halide perovskites, specifically methylammonium lead iodide and bromide and cesium lead bromide (MAPbI3, MAPbBr3, CsPbBr3), grown at two different institutions on different substrates. These are compared with theoretical densities of states (DOS) calculated via density functional theory. The qualitative agreement achieved between experiment and theory leads to the identification of valence and conduction band spectral features, and allows a precise determination of the position of the band edges, ionization energy and electron affinity of the materials. The comparison reveals an unusually low DOS at the valence band maximum (VBM) of these compounds, which confirms and generalizes previous predictions of strong band dispersion and low DOS at the MAPbI3 VBM. This low DOS calls for special attention when using electron spectroscopy to determine the frontier electronic states of lead halide perovskites.
RESUMO
Hybrid organic-inorganic lead halide perovskite photovoltaic cells have already surpassed 20% conversion efficiency in the few years that they have been seriously studied. However, many fundamental questions still remain unanswered as to why they are so good. One of these is "Is the organic cation really necessary to obtain high quality cells?" In this study, we show that an all-inorganic version of the lead bromide perovskite material works equally well as the organic one, in particular generating the high open circuit voltages that are an important feature of these cells.
RESUMO
High band gap, high open-circuit voltage solar cells with methylammonium lead tribromide (MAPbBr3) perovskite absorbers are of interest for spectral splitting and photoelectrochemical applications, because of their good performance and ease of processing. The physical origin of high performance in these and similar perovskite-based devices remains only partially understood. Using cross-sectional electron-beam-induced current (EBIC) measurements, we find an increase in carrier diffusion length in MAPbBr3(Cl)-based solar cells upon low intensity (a few percent of 1 sun intensity) blue laser illumination. Comparing dark and illuminated conditions, the minority carrier (electron) diffusion length increases about 3.5 times from Ln = 100 ± 50 nm to 360 ± 22 nm. The EBIC cross section profile indicates a p-n structure between the n-FTO/TiO2 and p-perovskite, rather than the p-i-n structure, reported for the iodide derivative. On the basis of the variation in space-charge region width with varying bias, measured by EBIC and capacitance-voltage measurements, we estimate the net-doping concentration in MAPbBr3(Cl) to be 3-6 × 10(17) cm(-3).
RESUMO
Low-cost solar cells with high VOC, relatively small (EG - qVOC), and high qVOC/EG ratio, where EG is the absorber band gap, are long sought after, especially for use in tandem cells or other systems with spectral splitting. We report a significant improvement in CH3NH3PbBr3-based cells, using CH3NH3PbBr3-xClx, with EG = 2.3 eV, as the absorber in a mesoporous p-i-n device configuration. By p-doping an organic hole transport material with a deep HOMO level and wide band gap to reduce recombination, the cell's VOC increased to 1.5 V, a 0.2 V increase from our earlier results with the pristine Br analogue with an identical band gap. At the same time, in the most efficient devices, the current density increased from â¼1 to â¼4 mA/cm(2).