Localized holes and delocalized electrons in photoexcited inorganic perovskites: Watching each atomic actor by picosecond X-ray absorption spectroscopy

We report on an element-selective study of the fate of charge carriers in photoexcited inorganic CsPbBr3 and CsPb(ClBr)3 perovskite nanocrystals (NCs) in toluene solutions using time-resolved X-ray absorption spectroscopy with 80 ps time resolution. Probing the Br K-edge, the Pb L3-edge and the Cs L2-edge, we find that holes in the valence band are localized at Br atoms, forming small polarons, while electrons appear as delocalized in the conduction band. No signature of either electronic or structural changes are observed at the Cs L2-edge. The results at the Br and Pb edges suggest the existence of a weakly localized exciton, while the absence of signatures at the Cs edge indicates that the Cs+ cation plays no role in the charge transport, at least beyond 80 ps. These results can explain the rather modest charge carrier mobilities in these materials.Comment: 19 pages, 3 figure

Atomic-Level Description of Thermal Fluctuations in Inorganic Lead Halide Perovskites

A comprehensive microscopic description of thermally induced distortions in lead halide perovskites is crucial for their realistic applications, yet still unclear. Here, we quantify the effects of thermal activation in CsPbBr3 nanocrystals across length scales with atomic-level precision, and we provide a framework for the description of phase transitions therein, beyond the simplistic picture of unit-cell symmetry increase upon heating. The temperature increase significantly enhances the short-range structural distortions of the lead halide framework as a consequence of the phonon anharmonicity, which causes the excess free energy surface to change as a function of temperature. As a result, phase transitions can be rationalized via the soft-mode model, which also describes displacive thermal phase transitions in oxide perovskites. Our findings allow to reconcile temperature-dependent modifications of physical properties, such as changes in the optical band gap, that are incompatible with the perovskite time- and space-average structures

Establishing nonlinearity thresholds with ultraintense X-ray pulses

X-ray techniques have evolved over decades to become highly refined tools for a broad range of investigations. Importantly, these approaches rely on X-ray measurements that depend linearly on the number of incident X-ray photons. The advent of X-ray free electron lasers (XFELs) is opening the ability to reach extremely high photon numbers within ultrashort X-ray pulse durations and is leading to a paradigm shift in our ability to explore nonlinear X-ray signals. However, the enormous increase in X-ray peak power is a double-edged sword with new and exciting methods being developed but at the same time well-established techniques proving unreliable. Consequently, accurate knowledge about the threshold for nonlinear X-ray signals is essential. Herein we report an X-ray spectroscopic study that reveals important details on the thresholds for nonlinear X-ray interactions. By varying both the incident X-ray intensity and photon energy, we establish the regimes at which the simplest nonlinear process, two-photon X-ray absorption (TPA), can be observed. From these measurements we can extract the probability of this process as a function of photon energy and confirm both the nature and sub-femtosecond lifetime of the virtual intermediate electronic state

Quantifying Photoinduced Polaronic Distortions in Inorganic Lead Halide Perovskites Nanocrystals

The development of next generation perovskite-based optoelectronic devices relies critically on the understanding of the interaction between charge carriers and the polar lattice in out-of-equilibrium conditions. While it has become increasingly evident for CsPbBr3 perovskites that the Pb-Br framework flexibility plays a key role in their light-activated functionality, the corresponding local structural rearrangement has not yet been unambiguously identified. In this work, we demonstrate that the photoinduced lattice changes in the system are due to a specific polaronic distortion, associated with the activation of a longitudinal optical phonon mode at 18 meV by electron-phonon coupling, and we quantify the associated structural changes with atomic-level precision. Key to this achievement is the combination of time-resolved and temperature-dependent studies at Br K-edge and Pb L3-edge X-ray absorption with refined ab-initio simulations, which fully account for the screened core-hole final state effects on the X-ray absorption spectra. From the temporal kinetics, we show that carrier recombination reversibly unlocks the structural deformation at both Br and Pb sites. The comparison with the temperature-dependent XAS results rules out thermal effects as the primary source of distortion of the Pb-Br bonding motif during photoexcitation. Our work provides a comprehensive description of the CsPbBr3 perovskites photophysics, offering novel insights on the light-induced response of the system and its exceptional optoelectronic properties.Comment: Main: 27 pages, 4 figures SI: 16 pages, 8 figure

Spin-state studies with XES and RIXS: From static to ultrafast

We report on extending hard X-ray emission spectroscopy (XES) along with resonant inelastic X-ray scattering (RIXS) to study ultrafast phenomena in a pump-probe scheme at MHz repetition rates. The investigated systems include low-spin (LS) Fe-II complex compounds, where optical pulses induce a spin-state transition to their (sub)nanosecond-lived high-spin (HS) state. Time-resolved XES clearly reflects the spin-state variations with very high signal-to-noise ratio, in agreement with HS-LS difference spectra measured at thermal spin crossover, and reference HS-LS systems in static experiments, next to multiplet calculations. The 1s2p RIXS, measured at the Fe Is pre-edge region, shows variations after laser excitation, which are consistent with the formation of the HS state. Our results demonstrate that X-ray spectroscopy experiments with overall rather weak signals, such as RIXS, can now be reliably exploited to study chemical and physical transformations on ultrafast time scales. (C) 2012 Elsevier B.V. All rights reserved

X-ray Emission Spectroscopy to Study Ligand Valence Orbitals in Mn Coordination Complexes

We discuss a spectroscopic method to determine the character of chemical bonding and for the identification of metal ligands in coordination and bioinorganic chemistry. It is based on the analysis of satellite lines in X-ray emission spectra that arise from transitions between valence orbitals and the metal ion 1s level (valence-to-core XES). The spectra, in connection with calculations based on density functional theory (DFT), provide information that is complementary to other spectroscopic techniques, in particular X-ray absorption (XANES and EXAFS). The spectral shape is sensitive to protonation of ligands and allows ligands, which differ only slightly in atomic number (e.g., C, N, O...), to be distinguished. A theoretical discussion of the main spectral features is presented in terms of molecular orbitals for a series of Mn model systems: [Mn(H2O)6]2+, [Mn(H2O)5OH]+, [Mn(H2O)5NH2]+, and [Mn(H2O)5NH3]2+. An application of the method, with comparison between theory and experiment, is presented for the solvated Mn2+ ion in water and three Mn coordination complexes, namely [LMn(acac)N3]BPh4, [LMn(B2O3Ph2)(ClO4)], and [LMn(acac)N]BPh4, where L represents 1,4,7-trimethyl-1,4,7-triazacyclononane, acac stands for the 2,4-pentanedionate anion, and B2O3Ph2 represents the 1,3-diphenyl-1,3-dibora-2-oxapropane-1,3-diolato dianion

Local atomic structure around Mn ions in GaN:Mn thin films: Quantitative XANES analysis

GaN:Mn dilute magnetic semiconductors with zinc-blende type of lattice and room temperature ferromagnetism were investigated by the X-ray absorption near edge structure (XANES) with a high accuracy approach of the multidimensional interpolation, which makes it possible to determine the nanoscale local atomic structure around Mn impurities. It is found that Mn atoms are substantially incorporated into the GaN lattice and Jahn-Teller distortion around Mn atom is observed. Our results show that symmetry changes around Mn atom influence on XANES spectrum significantly. Furthermore, the possible impact of local distortions on the magnetic properties is discussed. (C) 2011 Elsevier B.V. All rights reserved

Evidence of octahedral Co-Mo-S sites in hydrodesulfurization catalysts as determined by resonant inelastic X-ray scattering and X-ray absorption spectroscopy

Fundamental understanding of the active sites in CoMo/Al2O3 catalysts is crucial to improve the production of clean transportation fuels by hydrodesulfurization (HDS). In this work, the coordination state and number of active sites (“Co-Mo-S”) in sulfided CoMo/Al2O3 catalysts prepared with and without chelating additives were determined with in situ 1s2p Resonant Inelastic X-ray Scattering (RIXS) and X-ray Absorption Spectroscopy (XAS). Based on evaluation of thiophene HDS activity as function of the Co/Mo ratio, it was determined that only for Co/Mo < 0.1 cobalt is exclusively in interaction with the MoS2 phase, making these compositions ideal for identifying the nature of the active cobalt sites for hydrogenolysis. These cobalt promoter atoms were in centrosymmetric coordination to the MoS2 phase with six sulfur ligands coordinated to each cobalt center. The octahedral coordination of cobalt in Co-Mo-S in alumina-supported HDS catalysts contrasts the tetrahedral cobalt coordination found in Co-promoted MoS2 model systems supported on gold or carbon. We attribute the difference to more disordered MoS2 structures in technical alumina-supported HDS catalysts. The number of Co-Mo-S sites depended strongly on the catalyst preparation method. Chelating additives, such as citric acid and nitrilotriacetic acid, increased the number of Co-Mo-S sites without significantly altering their intrinsic activity. These results demonstrate that state-of-the-art structural characterization tools, such as RIXS, identify the structure of active sites in actual catalysts and that these structures may be different from model systems. Combining such characterization tools with guided catalyst design can provide insight into the structure of amorphous, nanostructured materials aiding the development of improved heterogeneous catalysts.ISSN:2155-543