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

Femtosecond X-ray emission study of the spin cross-over dynamics in haem proteins

In haemoglobin (consisting of four globular myoglobin-like subunits), the change from the low-spin (LS) hexacoordinated haem to the high spin (HS) pentacoordinated domed form upon ligand detachment and the reverse process upon ligand binding, represent the transition states that ultimately drive the respiratory function. Visible-ultraviolet light has long been used to mimic the ligand release from the haem by photodissociation, while its recombination was monitored using time-resolved infrared to ultraviolet spectroscopic tools. However, these are neither element- nor spin-sensitive. Here we investigate the transition state in the case of Myoglobin-NO (MbNO) using femtosecond Fe Kalpha and Kbeta non-resonant X-ray emission spectroscopy (XES) at an X-ray free-electron laser upon photolysis of the Fe-NO bond. We find that the photoinduced change from the LS (S = 1/2) MbNO to the HS (S = 2) deoxy-myoglobin (deoxyMb) haem occurs in ca. 800 fs, and that it proceeds via an intermediate (S = 1) spin state. The XES observables also show that upon NO recombination to deoxyMb, the return to the planar MbNO ground state is an electronic relaxation from HS to LS taking place in ca. 30 ps. Thus, the entire ligand dissociation-recombination cycle in MbNO is a spin cross-over followed by a reverse spin cross-over process

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

Ultrafast X-ray Spectroscopy of Heme Proteins

With the advent of X-ray free-electron lasers (XFELs) time-resolved X-ray spectroscopic techniques have advanced to the femtosecond regime. These are element selective techniques which offer unique insight into the electronic and chemical environment and dynamics of a sample. Specifically, X-ray emission spectroscopy probes the occupied density of states and is sensitive to the spin and local structure of the element of interest, whereas X-ray absorption spectroscopy is a tool for probing the unoccupied density of electronic states which makes it sensitive to the oxidation state, ligation and local structure around a specific atom. The tunable photon energy of the X-ray from XFELs allows to selectively probe the element of interest in the sample and additionally, the high intensity (1011 to 1012 photons per pulse) makes it possible to study dilute biological samples in physiological conditions. The sample studied in this work is myoglobin with nitric oxide as ligand, which has long been used as a model system to gain deeper understanding of the class of heme proteins. These proteins all have an iron porphyrine (heme) as an active center and play a crucial role in oxygen storage and transport in all mammals for example, amongst many other functions. In heme proteins, the change of the low-spin (LS) hexacoordinated heme (ground state) to the high spin (HS) pentacoordinated domed form (excited state) is promoted by a reversible light induced ligand detachment, representing the âtransition stateâ that ultimately drives the respiratory function. Here we investigate Myoglobin-NO (MbNO) by employing femtosecond Fe Kα and Kβ non-resonant X-ray emission spectroscopy (XES) at an XFEL upon photolysis of the Fe-NO bond. We find that the photoinduced change from the LS (S = 1/2) MbNO to the HS (S = 2) deoxy-myoglobin (deoxyMb) heme occurs in ~800 fs, and it proceeds via an intermediate (S = 1) spin state. The XES results also show that upon NO recombination to deoxyMb, the return to the planar MbNO ground state is an electronic relaxation from HS to LS taking place in ~30 ps. Thus, the en-tire ligand dissociation-recombination cycle in MbNO is a spin cross-over followed by a reverse spin cross-over process. Femtosecond X-ray absorption near edge spectroscopy (XANES) experiments also performed at an XFEL show that NO dissociates in <75 fs and the intermediate (S = 1) spin state which has antibonding character is populated in ~110 fs. The XANES spectrum at short time delays (t=1 ps) shows a similarity to the steady state difference spectrum (deoxyMb minus MbNO) suggesting that at 1 ps the present species is very similar to deoxyMb in terms of electronic and local geometric structure. XAS time-traces at the pre- and rising-edge (7112, 7122.5 and 7127 eV) reveal the shortest pathway of geminate recombination which takes ~30 ps

A von Hamos spectrometer for in situ sulfur speciation by non-resonant sulfur K alpha emission spectroscopy

A von Hamos geometry based wavelength dispersive spectrometer combined with an in situ reactor cell has been developed to measure non-resonant sulfur K alpha emission for the in situ speciation of low concentrations of sulfur. The spectrometer operates at 15 cm focusing radius, is equipped with a curved Si(111) crystal and a position sensitive detector, and is capable of achieving an energy resolution of 0.56 eV at 2.3 keV. We present the details of the spectrometer and dedicated sample-cell design to study chemical reactions in situ. The spectrometer capabilities are exemplified by an in situ study of sulfur speciation during H2S poisoning of SiO2 supported Ru nanoparticles performing CO methanation

Time-resolved Element-selective Probing of Charge Carriers in Solar Materials

We review our recent results on the implementation of picosecond (ps) X-ray absorption spectroscopy to probe the electronic and geometric structure of centres formed by photoexcitation of solar materials such as TiO2 polymorphs and inorganic Cs-based perovskites. The results show electron localization at Ti defects in TiO2 anatase and rutile and small hole polaron formation in the valence band of CsPbBr3, all within 80 ps. This method is promising for the study of the ultrafast time scales of such processes, especially with the advent of the Swiss X-ray Free Electron Laser (SwissFEL)

Time-resolved Element-selective Probing of Charge Carriers in Solar Materials

We review our recent results on the implementation of picosecond (ps) X-ray absorption spectroscopy to probe the electronic and geometric structure of centres formed by photoexcitation of solar materials such as TiO2 polymorphs and inorganic Cs-based perovskites. The results show electron localization at Ti defects in TiO2 anatase and rutile and small hole polaron formation in the valence band of CsPbBr3, all within 80 ps. This method is promising for the study of the ultrafast time scales of such processes, especially with the advent of the Swiss X-ray Free Electron Laser (SwissFEL)

Hard X-ray helical dichroism of disordered molecular media

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Hard X-ray helical dichroism of disordered molecular media

Chirality is a structural property of molecules lacking mirror symmetry that has strong implications in diverse fields, ranging from life sciences to materials science. Chirality-sensitive spectroscopic methods, such as circular dichroism, exhibit weak signal contributions on an achiral background. Helical dichroism, which is based on the orbital angular momentum (OAM) of light, offers a new approach to probe molecular chirality, but it has never been demonstrated on disordered samples. Furthermore, in the optical domain the challenge lies in the need to transfer the OAM of the photon to an electron that is localized on an ångström-size orbital. Here we overcome this challenge using hard X-rays with spiral Fresnel zone plates, which can induce an OAM. We present the helical dichroism spectra of a disordered powder sample of enantiopure salts of the molecular complex of [Fe(4,4′-diMebpy)3]2+ at the iron K edge (7.1 keV) with OAM-carrying beams. The asymmetry ratios for the helical dichroism spectra are within one to five percent for OAM beams with topological charges of one and three. These results open a new window into the studies of molecular chirality and its interaction with the OAM of light.</p