Anton Kovalsky

Femtosecond Time-Resolved Transient Absorption Spectroscopy of CH3NH3PbI3 Perovskite Films: Evidence for Passivation Effect of PbI2

CH3NH3PbI3 perovskite layered films deposited on substrates with and without a titania support structure have been prepared and studied using time-resolved femtosecond transient absorption (fs-TA) spectroscopy in the visible light range (450-800 nm). The electron injection dynamics from the photoexcited perovskite layers to the neighboring film structures could be directly monitored via the transient bleaching dynamics of the perovskite at ∼750 nm and thus systematically studied as a function of the layer-by-layer architecture. In addition, for the first time we could spectrally distinguish transient bleaching at ∼750 nm from laser-induced fluorescence that occurs red-shifted at ∼780 nm. We show that an additional bleach feature at ∼510 nm appears when PbI2 is present in the perovskite film. The amplitudes of the PbI2 and perovskite TA peaks were compared to estimate relative amounts of PbI2 in the samples. Kinetic analysis reveals that perovskite films with less PbI2 show faster relaxation rates than those containing more PbI2. These fast dynamics are attributed to charge carrier trapping at perovskite grain boundaries, and the slower dynamics in samples containing PbI2 are due to a passivation effect, in line with other recently reported work.

Complete Conversion of PbI2 to Methyl Ammonium PbI3 Improves Perovskite Solar Cell Efficiency

One major disadvantage to the two-step deposition method of perovskite films is the incomplete conversion from PbI2 to perovskite resulting in the presence of a thick PbI2 layer, which hinders charge carrier transportation. In this study, a quaternary ammonium salt has been used to manipulate the crystallization of PbI2 in the first deposition step, which leads to facile incorporation of the methylammonium iodide into the Pb-I lattice and promotes the conversion of PbI2 to perovskite leading to improved device performance.

Complete Conversion of PbI₂ to MAPbI₃ Improves Perovskite Solar Cell Efficiency

One major disadvantage to the two-step deposition method of perovskite films is the incomplete conversion from PbI2 to perovskite resulting in the presence of a thick PbI2 layer, which hinders charge carrier transportation. In this study, a quaternary ammonium salt has been used to manipulate the crystallization of PbI2 in the first deposition step, which leads to facile incorporation of the methylammonium iodide into the Pb-I lattice and promotes the conversion of PbI2 to perovskite leading to improved device performance.

Combination of optical and electrical loss analyses for a Si-phthalocyanine dye-sensitized solar cell

In order to promote the development of solar cells with varying types of sensitizers including dyes and quantum dots, it is crucial to establish a general experimental analysis that accounts for all important optical and electrical losses resulting from interfacial phenomena. All of these varying types of solar cells share common features where a mesoporous scaffold is used as a sensitizer loading support as well as an electron transport material, which may result in light scattering. The loss of efficiency at interfaces of the sensitizer, the mesoporous TiO2 nanoparticle films, the FTO conductive layer, and the supportive glass substrate should be considered in addition to the photoinduced electron transport properties within a cell. On the basis of optical parameters, one can obtain the internal quantum efficiency (IQE) of a solar cell, an important parameter that cannot be directly measured but must be derived from several key experiments. By integrating an optical loss model with an electrical loss model, many solar cell parameters could be characterized from electro-optical observables including reflectance, transmittance, and absorptance of the dye sensitizer, the electron injection efficiency, and the charge collection efficiency. In this work, an integrated electro-optical approach has been applied to SiPc (Pc 61) dye-sensitized solar cells for evaluating the parameters affecting the overall power conversion efficiency. The absorptance results of the Pc 61 dye-sensitized solar cell provide evidence that the adsorbed Pc 61 forms noninjection layers on TiO2 surfaces when the dye immersion time exceeds 120 min, resulting in shading light from the active layer rather than an increase in photoelectric current efficiency.

Optoelectronic Dichotomy of Mixed Halide CH3NH3Pb(Br1–xClx)3 Single Crystals: Surface versus Bulk Photoluminescence

In this work, the spatially dependent recombination kinetics of mixed-halide hybrid perovskite CH3NH3Pb(Br1- xCl x)3 (0 ≤ x ≤ 0.19) single crystals are investigated using time-resolved photoluminescence spectroscopy with one- and two-photon femtosecond laser excitation. The introduction of chloride by substituting a fraction of the bromide leads to a decreased lattice constant compared to pure bromide perovskite ( x = 0) and a higher concentration of surface defects. The measured kinetics under one-photon excitation (1PE) shows that increasing the chloride addition quenches the photoluminescence (PL) lifetimes, due to substitution-induced surface defects. In stark contrast, upon 2PE, the PL lifetimes measured deeper in the bulk become longer with increasing chloride addition, until the halide substitution reaches the critical concentration of ∼19%. At x = 19% Cl concentration, a significant reversal of this behavior is observed indicating a change in crystal structure beyond the continuous trends observed at lower percentages of halide substitution ( x ≤ 11%). The observed opposing trends, based on 1PE versus 2PE, highlight a dichotomy between extrinsic (surface) and intrinsic (bulk) effects of chloride substitution on the carrier dynamics in lead bromide perovskites. We discuss the physical relation between halide exchange and bulk carrier lifetimes in CH3NH3PbBr3 in terms of the Rashba effect. We propose that the latter is suppressed at the surface due to disorder in the alignment of the MA and that it increases in the bulk with Cl concentration because of the reduction in lattice parameters, which compresses the space available for the MA orientational degrees of freedom.