Polychromatic femtosecond fluorescence studies of metal–polypyridine complexes in solution

Femtosecond-resolved broadband fluorescence studies are reported for[M(bpy)3]2+ (M = Fe, Ru), RuN3 and RuN719 complexes in solution. We investigated the pump wavelength dependence of the fluorescence of aqueous [Fe(bpy)3]2+ and the solvent and ligand dependence of the fluorescence of Ru-complexes excited at 400 nm. For all complexes, the 1MLCT fluorescence appears at zero time delay with a mirror-like image with respect to the absorption. It decays in 630–45 fs due to intersystem crossing to the 3MLCT states, but a longer lived component of 190 fs additionally shows up in RuN719 and RuN3. No solvent effects are detected. The very early dynamics are characterized by internal conversion (IC) and intramolecular vibrational redistribution (IVR) processes on a time scale which we estimate to 610 fs using the 1MLCT lifetime as an internal clock

Time-Resolved IR Spectroscopy Reveals a Mechanism with TiO2 as a Reversible Electron Acceptor in a TiO2 - Re Catalyst CO2 Photoreduction System

Attaching the phosphonated molecular catalyst [Re$^{I}$Br(bpy)(CO)₃]⁰ to the wide-band gap semiconductor TiO₂ strongly enhances the rate of visible-light driven reduction of CO₂ to CO in dimethyl formamide (DMF) with triethanolamine (TEOA) as sacrificial electron donor. Herein, we show by transient mid-IR spectroscopy that the mechanism of catalyst photoreduction is initiated by ultrafast electron injection into TiO₂, followed by rapid (ps-ns) and sequential two-electron oxidation of TEOA that is coordinated to the Re center. The injected electrons can be stored in the conduction band (CB) of TiO₂ on a ms-s time scale, and we propose they lead to further reduction of the Re-catalyst and completion of the catalytic cycle. Thus, the excited Re catalyst gives away one electron and would eventually get three electrons back. The function of an electron reservoir would represent a role for TiO₂ in photo-catalytic CO₂ reduction that has previously not been considered. We propose that the increase in photocatalytic activity upon heterogenisation of the catalyst to TiO₂ is due to the slow charge recombination and the high oxidative power of the ReII species after electron injection, as compared to the excited MLCT state of the unbound Re catalyst or when immobilized on ZrO₂, which results in a more efficient reaction with TEOA.Knut and Alice Wallenberg Foundation, Swedish Energy Agency, Swedish Research Council, Austrian Christian Doppler Research Association, OMV Grou

The Role of Site-Specific Hydrogen Bonding Interactions in the Solvation Dynamics of N‑Acetyltryptophanamide

Measurements of the ultrafast broadband UV fluorescence of N-acetyltryptophanamide (NATA) provide detailed information on its relaxation patterns in three different solvents: methanol (MeOH), water and acetonitrile (ACN). Several processes leading to excited state solvation and cooling are found to occur on different characteristic time scales and are thoroughly analyzed. Comparison between protic MeOH and aprotic ACN allows one to single out a 12 ps component in the former, which is attributed to the rearrangement of H-bonds existing between the protic solvent and excited NATA. This significantly stabilizes the excited state and provides the molecule with an efficient cooling mechanism. The corresponding dynamics in water are much faster (<1.5 ps). Comparison with static spectroscopic properties stresses the role of site-specific Hbonding in controlling the fluorescence quantum yield of NATA in protic solvents. These findings are consistent with existing models that describe tryptophan quenching as a result of charge transfer from the indole to the amide assisted by H-bonding at the carbonyl site

Metal Halide Perovskite and Phosphorus Doped g-C<inf>3</inf>N<inf>4</inf> Bulk Heterojunctions for Air-Stable Photodetectors

In this work, we fabricate photodetectors made of methylammonium lead trihalide perovskite (MLHP) and phosphorus-doped graphitic carbon nitride nanosheets (PCN-S). Using thermal polymerization, PCN-S with a reduced band gap, are synthesized from low-cost precursors, making it feasible to form type-II bulk heterojunctions with perovskites. Owing to the bulk heterojunctions between PCN-S and MLHP, the dark current of the photodetectors significantly decreases from ∼10-9 A for perovskite-only devices to ∼10-11 A for heterojunction devices. As a result, not only does the on/off ratio of the hybrid devices increase from 103 to 105 but also the photodetectivity is enhanced by more than 1 order of magnitude (up to 1013 Jones) and the responsivity reaches a value of 14 A W-1. Moreover, the hybridization of MLHP with PCN-S significantly modifies the hydrophilicity and morphology of the perovskite films, which dramatically increases their stability under ambient conditions. The hybrid photodetectors, described here, present a promising new direction toward stable and efficient optoelectronic applications

MXenes for Plasmonic Photodetection

MXenes have recently shown impressive optical and plasmonic properties associated with their ultrathin-atomic-layer structure. However, their potential use in photonic and plasmonic devices has been only marginally explored. Photodetectors made of five different MXenes are fabricated, among which molybdenum carbide MXene (Mo2CTx) exhibits the best performance. Mo2CTx MXene thin films deposited on paper substrates exhibit broad photoresponse in the range of 400–800 nm with high responsivity (up to 9 A W−1), detectivity (≈5 × 1011 Jones), and reliable photoswitching characteristics at a wavelength of 660 nm. Spatially resolved electron energy-loss spectroscopy and ultrafast femtosecond transient absorption spectroscopy of the MXene nanosheets reveal that the photoresponse of Mo2CTx is strongly dependent on its surface plasmon-assisted hot carriers. Additionally, Mo2CTx thin-film devices are shown to be relatively stable under ambient conditions, continuous illumination and mechanical stresses, illustrating their durable photodetection operation in the visible spectral range. Micro-Raman spectroscopy conducted on bare Mo2CTx film and on gold electrodes allowing for surface-enhanced Raman scattering demonstrates surface chemistry and a specific low-frequency band that is related to the vibrational modes of the single nanosheets. The specific ability to detect and excite individual surface plasmon modes provides a viable platform for various MXene-based optoelectronic applications

MAPbI<inf>3</inf> Single Crystals Free from Hole-Trapping Centers for Enhanced Photodetectivity

Perovskite single crystals (PSCs) are considered the next breakthrough in optoelectronics research due to their free-grain boundary and much lower density of trap states compared to those of their polycrystalline counterparts. However, the inevitable formation of triiodide-based intrinsic defects during high-temperature crystal growth is one of the major challenges impeding the further development of optoelectronic devices based on PSCs. Here, we not only identified the existence of these triiodide ions as hole-trapping centers and their tremendous negative impact on the performance of PSCs, but more importantly, we used a reduction treatment to prevent their formation during crystal growth. The removal of such defect centers resulted in much higher charge carrier mobility and longer carrier lifetime than the untreated counterparts, leading to enhanced photodetection properties. The I3-free MAPbI3 single crystal (MSC) devices consistently generated a more than 100 times higher photocurrent than that generated by I3-rich devices under the same light intensity

Double charged surface layers in lead halide perovskite crystals

Understanding defect chemistry, particularly ion migration, and its significant effect on the surface’s optical and electronic properties is one of the major challenges impeding the development of hybrid perovskite-based devices. Here, using both experimental and theoretical approaches, we demonstrate that the surface layers of the perovskite crystals may acquire a high concentration of positively charged halide vacancies with the complementary negatively charged halide ions pushed to the surface. This charge separation near to the surface generate an electric field that can induce a shift in the optical band gap of the surface layers to higher energy compared to the bulk counterpart. We found that the charge separation, electric field and the amplitude of shift in the bandgap strongly depend on the halides and organic moieties of perovskites crystals. Our findings reveal the peculiarity of surface effects that is currently limiting the application of perovskite crystals and more importantly explain their origins, thus enabling viable surface passivation strategies to remediate them

Double charged surface layers in lead halide perovskite crystals

Understanding defect chemistry, particularly ion migration, and its significant effect on the surface’s optical and electronic properties is one of the major challenges impeding the development of hybrid perovskite-based devices. Here, using both experimental and theoretical approaches, we demonstrate that the surface layers of the perovskite crystals may acquire a high concentration of positively charged halide vacancies with the complementary negatively charged halide ions pushed to the surface. This charge separation near to the surface generate an electric field that can induce a shift in the optical band gap of the surface layers to higher energy compared to the bulk counterpart. We found that the charge separation, electric field and the amplitude of shift in the bandgap strongly depend on the halides and organic moieties of perovskites crystals. Our findings reveal the peculiarity of surface effects that is currently limiting the application of perovskite crystals and more importantly explain their origins, thus enabling viable surface passivation strategies to remediate them