Heterostructures via a Solution-Based Anion Exchange in Microcrystalline 2D Layered Metal-Halide Perovskites.

Layered perovskites consist of stacks of inorganic semiconducting metal halide octahedra lattices sandwiched between organic layers with typically dielectric behavior. The in-plane confinement of electrical carriers in such two-dimensional metal halide perovskites drives a large range of appealing electronic properties, such as strong exciton binding, anisotropic charge diffusion, and directionality in polarization. Heterostructures can provide additional control on charge carrier diffusion and localization, and in-plane heterojunctions are particularly attractive because of the high charge mobility in this direction. Here, we demonstrate a versatile solution-based approach to fabricate in-plane heterostructures with different halide composition in two-dimesional lead-halide perovskite microscrystals. The exchange reaction leads to spatially separated halide phases with different band gap and light emission. The exposure of microcrystals to different halide salts in solution leads to a core-shell heterostructure architecture. Interestingly, the composition of the exchanged phase and the morphology of the phase boundary depends on the exchange route. For Br to I we observe a rugged boundary and a relatively pure exchanged crystal phase, while I to Br leads to alloyed phases in the exchanged region and a smooth interface. The different reaction mechanisms can be related to the preferred localisation of the halides at the equatorial or axial octahedra positions that either leads to dissolution and recrystallization of the octahedra lattice, or allows for ion diffusion within the lattice. These detailed insights on the ion exchange processes in layered perovskites will stimulate the development of heterostructures that can be tailored for different applications such as photocatalysis, energy storage, and light emission. This article is protected by copyright. All rights reserved.

Mapping emission heterogeneity in layered halide perovskites using cathodoluminescence.

Recent advancements in the fabrication of layered halide perovskites and their subsequent modification for optoelectronic applications have ushered in a need for innovative characterisation techniques. In particular, heterostructures containing multiple phases and consequently featuring spatially defined optoelectronic properties are very challenging to study. Here, we adopt an approach centered on cathodoluminescence, complemented by scanning electron microscopy coupled with energy-dispersive x-ray spectroscopy analysis. Cathodoluminescence enables assessment of local emission variations by injecting charges with a nanometer-scale electron probe, which we use to investigate emission changes in three different systems: PEA2PbBr4, PEA2PbI4and lateral heterostructures of the two, fabricated via halide substitution. We identify and map different emission bands that can be correlated with local chemical composition and geometry. One emission band is characteristic of bromine-based halide perovskite, while the other originates from iodine-based perovskite. The coexistence of these emissions bands in the halide-substituted sample confirms the formation of lateral heterostructures. To improve the signal quality of the acquired data, we employed multivariate analysis, specifically the non-negative matrix factorization algorithm, on both cathodoluminescence and compositional datasets. The resulting understanding of the halide replacement process and identification of potential synergies in the optical properties will lead to optimised architectures for optoelectronic applications.

Impact of the organic cation on the band-edge emission of two-dimensional lead-bromide perovskites.

Organic-inorganic low-dimensional layered metal-halide perovskites are semiconductors in which the optoelectronic properties can be tuned by the material composition and the design of the layered architecture. While the electronic band structure is mainly determined by the inorganic octahedra lattice, the binding and conformation of the organic cations induces related lattice distortions that can break the symmetry and lead to the splitting of the exciton energy levels, and influence the dielectric confinement. Furthermore, organic-induced lattice deformations lead to offsets in k-space (where k is the wavevector) that go along with the exciton energy level splitting. Hence, the electronic transitions between these levels require the momentum contribution of phonons, and contributions of phonons in the exciton recombination dynamics result in thermal broadening of the emission linewidth. In this work, we investigate the band-edge emission of two-dimensional Ruddlesden-Popper lead-bromide perovskites synthesized with different organic cations that vary in their binding head group and their alkyl chain length. We find several peaks in the low-temperature photoluminescence spectra, and the number of peaks in the band-edge emission and their decay dynamics depend strongly on the type of organic cation in the material, which we relate to the difference in the inorganic lattice distortions that the cations induce. For two-dimensional layered perovskites with mainly in-plane distortions, induced by short primary ammonium molecules, we find a two-fold splitting of the band edge emission at low temperatures. If also out-of-plane distortions are present, as for the long-chain primary ammoniums, a three-fold splitting is observed. Interestingly, the low-energy peaks of the split series merge into the highest energy peak with increasing temperature. Thermal broadening analysis of the temperature-dependent photoluminescence linewidth in the structures with out-of-plane distortions yields energies that are larger than those reported for the inorganic lattice phonons. This indicates the involvement of either high-frequency oscillations involving the organic cations, or the broadening might be related to higher order phonon scattering processes in the excitonic recombination process. The strong directionality of the phonon modes in the octahedral lattice could promote the involvement of multiple electron-phonon scattering processes in the exciton relaxation dynamics, for example involving modes with orthogonal directionality.

Covalent Functionalization of CdSe Quantum Dot Films with Molecular [FeFe] Hydrogenase Mimics for Light-Driven Hydrogen Evolution.

CdSe quantum dots (QDs) combined with [FeFe] hydrogenase mimics as molecular catalytic reaction centers based on earth-abundant elements have demonstrated promising activity for photocatalytic hydrogen generation. Direct linking of the [FeFe] hydrogenase mimics to the QD surface is expected to establish a close contact between the [FeFe] hydrogenase mimics and the light-harvesting QDs, supporting the transfer and accumulation of several electrons needed to drive hydrogen evolution. In this work, we report on the functionalization of QDs immobilized in a thin-film architecture on a substrate with [FeFe] hydrogenase mimics by covalent linking via carboxylate groups as the anchoring functionality. The functionalization was monitored via UV/vis, photoluminescence, IR, and X-ray photoelectron spectroscopy and quantified via micro-X-ray fluorescence spectrometry. The activity of the functionalized thin film was demonstrated, and turn-over numbers in the range of 360-580 (short linkers) and 130-160 (long linkers) were achieved. This work presents a proof-of-concept study, showing the potential of thin-film architectures of immobilized QDs as a platform for light-driven hydrogen evolution without the need for intricate surface modifications to ensure colloidal stability in aqueous environments.

Nanostructured Silicon Matrix for Materials Engineering.

Tin-containing layers with different degrees of oxidation are uniformly distributed along the length of silicon nanowires formed by a top-down method by applying metalorganic chemical vapor deposition. The electronic and atomic structure of the obtained layers is investigated by applying nondestructive surface-sensitive X-ray absorption near edge spectroscopy using synchrotron radiation. The results demonstrated, for the first time, a distribution effect of the tin-containing phases in the nanostructured silicon matrix compared to the results obtained for planar structures at the same deposition temperatures. The amount and distribution of tin-containing phases can be effectively varied and controlled by adjusting the geometric parameters (pore diameter and length) of the initial matrix of nanostructured silicon. Due to the occurrence of intense interactions between precursor molecules and decomposition by-products in the nanocapillary, as a consequence of random thermal motion of molecules in the nanocapillary, which leads to additional kinetic energy and formation of reducing agents, resulting in effective reduction of tin-based compounds to a metallic tin state for molecules with the highest penetration depth in the nanostructured silicon matrix. This effect will enable clear control of the phase distributions of functional materials in 3D matrices for a wide range of applications.

Spectromicroscopy Studies of Silicon Nanowires Array Covered by Tin Oxide Layers.

The composition and atomic and electronic structure of a silicon nanowire (SiNW) array coated with tin oxide are studied at the spectromicroscopic level. SiNWs are covered from top to down with a wide bandgap tin oxide layer using a metal-organic chemical vapor deposition technique. Results obtained via scanning electron microscopy and X-ray diffraction showed that tin-oxide nanocrystals, 20 nm in size, form a continuous and highly developed surface with a complex phase composition responsible for the observed electronic structure transformation. The "one spot" combination, containing a chemically sensitive morphology and spectroscopic data, is examined via photoemission electron microscopy in the X-ray absorption near-edge structure spectroscopy (XANES) mode. The observed spectromicroscopy results showed that the entire SiNW surface is covered with a tin(IV) oxide layer and traces of tin(II) oxide and metallic tin phases. The deviation from stoichiometric SnO2 leads to the formation of the density of states sub-band in the atop tin oxide layer bandgap close to the bottom of the SnO2 conduction band. These observations open up the possibility of the precise surface electronic structures estimation using photo-electron microscopy in XANES mode.

Molecular Metallocorrole-Nanorod Photocatalytic System for Sustainable Hydrogen Production.

Invited for this month's cover is the group of Lilac Amirav at Technion-Israel Institute of Technology. The image shows the sustainable solar-driven photocatalytic generation of hydrogen from water using a molecular metallocorrole-nanorod photocatalytic system. The Research Article itself is available at 10.1002/cssc.202200804.

Molecular Metallocorrole-Nanorod Photocatalytic System for Sustainable Hydrogen Production.

Solar-driven photocatalytic generation of hydrogen from water is a potential source of clean and renewable fuel. Yet systems that are sufficiently stable and efficient for practical use have not been realized. Here, nanorod photocatalysts that have proven record activity for the water reduction half reaction were successfully combined with molecular metallocorroles suitable for catalyzing the accompanying oxidation reactions. Utilization of OH- /⋅OH redox species as charge transfer shuttle between freely mixed metallocorroles and rods resulted in quantum efficiency that peaked as high as 17 % for hydrogen production from water in the absence of sacrificial hole scavengers. While typically each sacrificial scavenger is able to extract but a single hole, here the molecular metallocorrole catalysts were found to successfully handle nearly 300,000 holes during their lifespan. The implications of the new system on the prospects of realizing practical overall water splitting and direct solar-to-fuel energy conversion were discussed.

Ultrafast Electron Transfer from CdSe Quantum Dots to an [FeFe]-Hydrogenase Mimic.

The combination of CdSe nanoparticles as photosensitizers with [FeFe]-hydrogenase mimics is known to result in efficient systems for light-driven hydrogen generation with reported turnover numbers in the order of 104-106. Nevertheless, little is known about the details of the light-induced charge-transfer processes. Here, we investigate the time scale of light-induced electron transfer kinetics for a simple model system consisting of CdSe quantum dots (QDs) of 2.0 nm diameter and a simple [FeFe]-hydrogenase mimic adsorbed to the QD surface under noncatalytic conditions. Our (time-resolved) spectroscopic investigation shows that both hot electron transfer on a sub-ps time scale and band-edge electron transfer on a sub-10 ps time scale from photoexcited QDs to adsorbed [FeFe]-hydrogenase mimics occur. Fast recombination via back electron transfer is observed in the absence of a sacrificial agent or protons which, under real catalytic conditions, would quench remaining holes or could stabilize the charge separation, respectively.

Silicon Suboxides as Driving Force for Efficient Light-Enhanced Hydrogen Generation on Silicon Nanowires.

Efficient light-stimulated hydrogen generation from top-down produced highly doped n-type silicon nanowires (SiNWs) with silver nanoparticles (AgNPs) in water-containing medium under white light irradiation is reported. It is observed that SiNWs with AgNPs generate at least 2.5 times more hydrogen than SiNWs without AgNPs. The authors' results, based on vibrational, UV-vis, and X-ray spectroscopy studies, strongly suggest that the sidewalls of the SiNWs are covered by silicon suboxides, by up to a thickness of 120 nm, with wide bandgap semiconductor properties that are similar to those of titanium dioxide and remain stable during hydrogen evolution in a water-containing medium for at least 3 h of irradiation. Based on synchrotron studies, it is found that the increase in the silicon bandgap is related to the energetically beneficial position of the valence band in nanostructured silicon, which renders these promising structures for efficient hydrogen generation.

Optical Properties of Silicon Nanowires Fabricated by Environment-Friendly Chemistry.

Silicon nanowires (SiNWs) were fabricated by metal-assisted chemical etching (MACE) where hydrofluoric acid (HF), which is typically used in this method, was changed into ammonium fluoride (NH4F). The structure and optical properties of the obtained SiNWs were investigated in details. The length of the SiNW arrays is about 2 µm for 5 min of etching, and the mean diameter of the SiNWs is between 50 and 200 nm. The formed SiNWs demonstrate a strong decrease of the total reflectance near 5-15 % in the spectral region λ < 1 µm in comparison to crystalline silicon (c-Si) substrate. The interband photoluminescence (PL) and Raman scattering intensities increase strongly for SiNWs in comparison with the corresponding values of the c-Si substrate. These effects can be interpreted as an increase of the excitation intensity of SiNWs due to the strong light scattering and the partial light localization in an inhomogeneous optical medium. Along with the interband PL was also detected the PL of SiNWs in the spectral region of 500-1100 nm with a maximum at 750 nm, which can be explained by the radiative recombination of excitons in small Si nanocrystals at nanowire sidewalls in terms of a quantum confinement model. So SiNWs, which are fabricated by environment-friendly chemistry, have a great potential for use in photovoltaic and photonics applications.

Electronic levels in silicon MaWCE nanowires: evidence of a limited diffusion of Ag.

Deep level transient spectroscopy (DLTS) was performed on lowly n-doped silicon nanowires grown by metal-assisted wet chemical etching (MaWCE) with silver as the catalyst in order to investigate the energetic scheme inside the bandgap. To observe the possible diffusion of atoms into the bulk, DLTS investigation was also performed on the samples after removing the nanowires. Two of the four energy levels observed in the nanowires were also detected inside the substrate. Based on these results and on literature data about deep levels in bulk silicon, some hypotheses are advanced regarding the identification of the defects responsible for the energy levels revealed.

Influence of surface pre-treatment on the electronic levels in silicon MaWCE nanowires.

Deep level transient spectroscopy (DLTS) was performed on n-doped silicon nanowires grown by metal-assisted wet chemical etching (MaWCE) with gold as the catalyst in order to investigate the energetic scheme inside the bandgap. To observe the possible dependence of the level scheme on the processing temperature, DLTS measurements were performed on the nanowires grown on a non-treated Au/Si surface and on a thermally pre-treated Au/Si surface. A noticeable modification of the configuration of the energy levels was observed, induced by the annealing process. Based on our results on these MaWCE nanowires and on literature data about deep levels in bulk silicon, some hypotheses were advanced regarding the identification of the defects responsible of the energy levels revealed.