RESUMO
CsPb2Br5 belongs to all inorganic perovskite-related quasi-two-dimensional materials that have attracted considerable attention due to their potential for optoelectronic applications. In this study, we solve numerous controversies on the physical properties of this material. We show that optical absorption in the visible spectrum and green photoluminescence are due to microcrystallites of the three-dimensional CsPbBr3 perovskite settled on the CsPb2Br5 plates and that carefully cleaned crystal plates are devoid of these features. The high-pressure structural and spectroscopic experiments, performed on the single crystals free of CsPbBr3 impurities, evidenced that the layered tetragonal structure of CsPb2Br5 is stable at least up to 6 GPa. The absorption edge is located in the ultraviolet at around 350 nm and continuously red shifts under pressure. Moderate band gap narrowing is well correlated to the pressure-induced changes in the crystal structure. Although the compressibility of CsPb2Br5 is much higher than for CsPbBr3, the response in optical properties is weaker because the Pb-Br layers responsible for the optical absorption are much less affected by hydrostatic pressure than those built of Cs+ cations. Our study clarifies the confusing data in the literature on the optical properties and thermodynamic stability of CsPb2Br5.
RESUMO
Improvement in the performance of perovskite solar cells (PSC) and dye-sensitized solar cells (DSSC) upon modifications of mesoporous titania layers has been studied. For PSC with triple cation perovskite (FA0.76 MA0.19 Cs0.05 Pb (I0.81 Br0.19)3) about 40% higher photocurrent (up to â¼24 mA cm-2) was found for more homogenous, made of larger particles (30 nm) and thinner (150-200 nm) titania layer. For DSSC (both with liquid cobalt-based electrolyte as well as with solid state hole transporter - spiro-OMeTAD), a greater dye loading, rise in photovoltage, and the enhancement in relative photocurrent were observed for the cells prepared from the diluted titania paste (2 : 1 w/w ratio) with respect to those prepared from undiluted one. The impact of these improvements in titania layers on charge transfer dynamics in the complete solar cells as well as in pristine TiO2 layers was investigated by femtosecond transient absorption. Shorter photocarriers lifetime in perovskite material observed in better PSC, indicated that faster electron transfer at the titania interface was responsible for the higher photocurrent. Moreover, the photoinduced changes close to TiO2 interface were revealed in better PSC, which may indicate that in the efficient devices halide segregation takes place in perovskite material. In liquid DSSC, the fast component of unwanted recombination was slower in the samples with the diluted titania paste than in those made with undiluted ones. In solid state DSSC, hole injection from MK2 dye to spiro-OMeTAD takes place on the very fast ps time scale (comparable to that of electron injection) and the evidence of better penetration of spiro-OMeTAD into thinner and more porous titania layers was provided.
RESUMO
The properties of efficient solar cells fabricated with triple-cation perovskite placed between a mesoporous titania layer and a spiro-OMeTAD layer are studied by using devices either prepared under water-free drybox conditions or fabricated under ambient room humidity. The morphological studies indicate that the content of unreacted PbI2 phase in the perovskite structure is much higher near the interface with titania than near the interface with spiro-OMeTAD. The stationary emission spectra and transient bleach peaks of perovskites show additional long-wavelength features close to the titania side. Time-resolved techniques ranging from femtoseconds to seconds reveal further differences in charge dynamics at both interfaces. The population decay is significantly faster at the titania side than at the spiro-OMeTAD side for the cells prepared under ambient conditions. An increased hole injection rate correlates with higher photocurrent seen in the devices prepared under drybox conditions. The charge recombination loss on the millisecond time scale is found to be slower at the interface with titania than at the interface with spiro-OMeTAD. The ideality factor of the cells is found to increase with increasing DMSO content in the precursor solution, indicating a change in recombination mechanism from bulk to surface recombination. We also found that the charge dynamics are not uniform within the whole perovskite layer. This feature has significant implications for understanding the operation and optimizing the performance of solar devices based on mixed cation perovskites.
