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Lead halide perovskites (LHPs) exhibit large spin-orbit coupling (SOC), leading to only twofold-degenerate valence and conduction bands and therefore allowing for efficient optical orientation. This makes them ideal materials to study charge carrier spins. With this study we elucidate the spin dynamics of photoexcited charge carriers and the underlying spin relaxation mechanisms in CsPbI3 nanocrystals by employing time-resolved differential transmission spectroscopy (DTS). We find that the photoinduced spin polarization significantly diminishes during thermalization and cooling toward the energetically favorable band edge. Temperature-dependent DTS reveals a decay in spin polarization that is more than 1 order of magnitude faster at room temperature (3 ps) than at cryogenic temperatures (32 ps). We propose that spin relaxation of free charge carriers in large-SOC materials like LHPs occurs as a result of carrier-phonon scattering, as described by the Elliott-Yafet mechanism.

Two-dimensional triphenylene-based metal-organic frameworks (TP-MOFs) attract significant scientific interest due to their long-range order combined with significant electrical conductivity. The deposition of these structures as oriented films is expected to promote their incorporation into diverse optoelectronic devices. However, to date, a controlled deposition strategy applicable for the different members of this MOF family has not been reported yet. Herein, we present the synthesis of highly oriented thin films of TP-MOFs by vapor-assisted conversion (VAC). We targeted the M-CAT-1 series comprising hexahydroxytriphenylene organic ligands and metal-ions such as Ni

The easily tunable emission of halide perovskite nanocrystals throughout the visible spectrum makes them an extremely promising material for light-emitting applications. Whereas high quantum yields and long-term colloidal stability have already been achieved for nanocrystals emitting in the red and green spectral range, the blue region currently lags behind with low quantum yields, broad emission profiles, and insufficient colloidal stability. In this work, we present a facile synthetic approach for obtaining two-dimensional CsPbBr3 nanoplatelets with monolayer-precise control over their thickness, resulting in sharp photoluminescence and electroluminescence peaks with a tunable emission wavelength between 432 and 497 nm due to quantum confinement. Subsequent addition of a PbBr2-ligand solution repairs surface defects likely stemming from bromide and lead vacancies in a subensemble of weakly emissive nanoplatelets. The overall photoluminescence quantum yield of the blue-emissive colloidal dispersions is consequently enhanced up to a value of 73 ± 2%. Transient optical spectroscopy measurements focusing on the excitonic resonances further confirm the proposed repair process. Additionally, the high stability of these nanoplatelets in films and to prolonged ultraviolet light exposure is shown., Magdalene College, Cambridge

Exciton-exciton annihilation (EEA) and Auger recombination are detrimental processes occurring in semiconductor optoelectronic devices at high carrier densities. Despite constituting one of the main obstacles for realizing lasing in semiconductor nanocrystals (NCs), the dependencies on NC size are not fully understood, especially for those with both weakly and strongly confined dimensions. Here, we use differential transmission spectroscopy to investigate the dependence of EEA on the physical dimensions of thickness-controlled 2D halide perovskite nanoplatelets (NPls). We find the EEA lifetimes to be extremely short on the order of 7-60 ps. Moreover, they are strongly determined by the NPl thickness with a power-law dependence according to {\tau}_2~d^5.3. Additional measurements show that the EEA lifetimes also increase for NPls with larger lateral dimensions. These results show that a precise control of the physical dimensions is critical for deciphering the fundamental laws governing the process especially in 1D and 2D NCs.

Colloidal InP-based quantum dots are a promising material for light-emitting applications as an environment friendly alternative to their Cd-containing counterparts. Especially for their use in optoelectronic devices, it is essential to understand how charge carriers relax to the emitting state after injection with excess energy and if all of them arrive at this desired state. Herein, we report time-resolved differential transmission measurements on colloidal InP/ZnS and InP/ZnSe core/shell quantum dots. By optically exciting and probing individual transitions, we are able to distinguish between electron and hole relaxation. This, in turn, allows us to determine how the initial excess energy of the charge carriers affects the relaxation processes. According to the electronic level scheme, one expects a strong phonon bottleneck for electrons, whereas holes should relax easier as their energy levels are more closely spaced. On the contrary, we find that electrons relax faster than holes. The fast electron relaxation occurs

The colloidal synthesis and assembly of semiconductor nanowires continues to attract a great deal of interest. Herein, we describe the single-step ligand-mediated synthesis of single-crystalline CsPbBr3 perovskite nanowires (NWs) directly from the precursor powders. Studies of the reaction process and the morphological evolution revealed that the initially formed CsPbBr3 nanocubes are transformed into NWs through an oriented-attachment mechanism. The optical properties of the NWs can be tuned across the entire visible range by varying the halide (Cl, Br, and I) composition through subsequent halide ion exchange. Single-particle studies showed that these NWs exhibit strongly polarized emission with a polarization anisotropy of 0.36. More importantly, the NWs can self-assemble in a quasi-oriented fashion at an air/liquid interface. This process should also be easily applicable to perovskite nanocrystals of different morphologies for their integration into nanoscale optoelectronic devices.

We study the optical properties of ${\mathrm{Cs}}_{3}{\mathrm{Bi}}_{2}{\mathrm{I}}_{9}$ nanoplatelets using a combination of first-principles density functional theory, $\mathit{GW}$ plus Bethe-Salpeter equation calculations, and spectroscopic experiments. We show that the material exhibits flat bands and hence high effective masses. This manifests itself in the lowest-energy transition in the absorption spectrum arising from excitons with a high binding energy of 300 meV and a Bohr radius smaller than 6 nm. Due to the indirect band gap, electrons and holes are efficiently separated in reciprocal space and recombine slowly across the band gap, leading to very weak photoluminescence. Our results resolve inconsistencies in previous studies on ${\mathrm{Cs}}_{3}{\mathrm{Bi}}_{2}{\mathrm{I}}_{9}$ and lay the groundwork for further applications of this material, reliant on charge separation.

Full water splitting into hydrogen and oxygen on semiconductor nanocrystals is a challenging task; overpotentials must be overcome for both half-reactions and different catalytic sites are needed to facilitate them. Additionally, efficient charge separation and prevention of back reactions are necessary. Here, we report simultaneous H-2 and O-2 evolution by CdS nanorods decorated with nanoparticulate reduction and molecular oxidation co-catalysts. The process proceeds entirely without sacrificial agents and relies on the nanorod morphology of CdS to spatially separate the reduction and oxidation sites. Hydrogen is generated on Pt nanoparticles grown at the nanorod tips, while Ru(tpy)(bpy)Cl-2-based oxidation catalysts are anchored through dithiocarbamate bonds onto the sides of the nanorod. O-2 generation from water was verified by O-18 isotope labelling experiments, and time-resolved spectroscopic results confirmed efficient charge separation and ultrafast electron and hole transfer to the reaction sites. The system demonstrates that combining nanoparticulate and molecular catalysts on anisotropic nanocrystals provides an effective pathway for visible-light-driven photocatalytic water splitting.

Phased-antenna metasurfaces can impart abrupt, spatially dependent changes to the amplitude, phase, and polarization of light and thus mold wavefronts in a desired fashion. Here we present an experimental and computational near-field study of metasurfaces based on near-resonant V-shaped antennas and connect their near- and far-field optical responses. We show that far fields can be obtained from limited, experimentally obtained knowledge of the near fields, paving the way for experimental near-field characterization of metasurfaces and other optical nanostructures and prediction of their far fields from the near-field measurements.

Perovskite nanocrystals have emerged as an interesting material for light-emitting and other optoelectronic applications. Excitons are known to play an important role in determining the optical properties of these nanocrystals and their energetic levels as well as quantization properties have been extensively explored. Despite this, there are still many aspects of perovskites that are still not well-known, for example, the homogeneous and inhomogeneous line widths of the energetic transitions, quantities that cannot be directly extracted by linear absorption optical spectroscopy on nanocrystal ensembles. Here, we present temperature-dependent absorption and four-wave mixing (FWM) experiments on thick methylammonium lead iodide (MAPI) perovskite nanoplatelets exhibiting bulk-like absorption and emission spectra. Dephasing times T2 of excitons are determined to lie in the range of several hundreds of femtoseconds at low temperatures. This value enables us to distinguish between the homogeneous and inhomogen...