Exciton self-trapping causes picoseconds recombination in metal-organic chalcogenides hybrid quantum wells

Metal-organic species can be designed to self-assemble in large-scale, atomically defined, supramolecular architectures. Hybrid quantum wells, where inorganic two-dimensional (2D) planes are separated by organic ligands, are a particular example. The ligands effectively provide an intralayer confinement for charge carriers resulting in a 2D electronic structure, even in multilayered assemblies. Air-stable metal organic chalcogenides hybrid quantum wells have recently been found to host tightly bound 2D excitons with strong optical anisotropy in a bulk matrix. Here, we investigate the excited carrier dynamics in the prototypical metal organic chalcogenide [AgSePh], disentangling three excitonic resonances by low temperature transient absorption spectroscopy. Our analysis suggests a complex relaxation cascade comprising ultrafast screening and renormalization, inter-exciton relaxation, and self-trapping of excitons within few picoseconds. The ps-decay provided by the self-trapping mechanism may be leveraged to unlock the material's potential for ultrafast optoelectronic applications

Giant defect emission enhancement from ZnO nanowires through desulfurization process.

Zinc oxide (ZnO) is a stable, direct bandgap semiconductor emitting in the UV with a multitude of technical applications. It is well known that ZnO emission can be shifted into the green for visible light applications through the introduction of defects. However, generating consistent and efficient green emission through this process is challenging, particularly given that the chemical or atomic origin of the green emission in ZnO is still under debate. In this work we present a new method, for which we coin term desulfurization, for creating green emitting ZnO with significantly enhanced quantum efficiency. Solution grown ZnO nanowires are partially converted to ZnS, then desulfurized back to ZnO, resulting in a highly controlled concentration of oxygen defects as determined by X-ray photoelectron spectroscopy and electron paramagnetic resonance. Using this controlled placement of oxygen vacancies we observe a greater than 40-fold enhancement of integrated emission intensity and explore the nature of this enhancement through low temperature photoluminescence experiments

Characterizing Transition-Metal Dichalcogenide Thin-Films using Hyperspectral Imaging and Machine Learning

Atomically thin polycrystalline transition-metal dichalcogenides (TMDs) are relevant to both fundamental science investigation and applications. TMD thin-films present uniquely difficult challenges to effective nanoscale crystalline characterization. Here we present a method to quickly characterize the nanocrystalline grain structure and texture of monolayer WS2 films using scanning nanobeam electron diffraction coupled with multivariate statistical analysis of the resulting data. Our analysis pipeline is highly generalizable and is a useful alternative to the time consuming, complex, and system-dependent methodology traditionally used to analyze spatially resolved electron diffraction measurements

Experimental and Ab Initio Ultrafast Carrier Dynamics in Plasmonic Nanoparticles

Ultrafast pump-probe measurements of plasmonic nanostructures probe the nonequilibrium behavior of excited carriers, which involves several competing effects obscured in typical empirical analyses. Here we present pump-probe measurements of plasmonic nanoparticles along with a complete theoretical description based on first-principles calculations of carrier dynamics and optical response, free of any fitting parameters. We account for detailed electronic-structure effects in the density of states, excited carrier distributions, electron-phonon coupling, and dielectric functions that allow us to avoid effective electron temperature approximations. Using this calculation method, we obtain excellent quantitative agreement with spectral and temporal features in transient-absorption measurements. In both our experiments and calculations, we identify the two major contributions of the initial response with distinct signatures: short-lived highly nonthermal excited carriers and longer-lived thermalizing carriers

Electrically driven photon emission from individual atomic defects in monolayer WS2.

Quantum dot-like single-photon sources in transition metal dichalcogenides (TMDs) exhibit appealing quantum optical properties but lack a well-defined atomic structure and are subject to large spectral variability. Here, we demonstrate electrically stimulated photon emission from individual atomic defects in monolayer WS2 and directly correlate the emission with the local atomic and electronic structure. Radiative transitions are locally excited by sequential inelastic electron tunneling from a metallic tip into selected discrete defect states in the WS2 bandgap. Coupling to the optical far field is mediated by tip plasmons, which transduce the excess energy into a single photon. The applied tip-sample voltage determines the transition energy. Atomically resolved emission maps of individual point defects closely resemble electronic defect orbitals, the final states of the optical transitions. Inelastic charge carrier injection into localized defect states of two-dimensional materials provides a powerful platform for electrically driven, broadly tunable, atomic-scale single-photon sources

Long-Range Exciton Diffusion in Two-Dimensional Assemblies of Cesium Lead Bromide Perovskite Nanocrystals

F\"orster Resonant Energy Transfer (FRET)-mediated exciton diffusion through artificial nanoscale building block assemblies could be used as a new optoelectronic design element to transport energy. However, so far nanocrystal (NC) systems supported only diffusion length of 30 nm, which are too small to be useful in devices. Here, we demonstrate a FRET-mediated exciton diffusion length of 200 nm with 0.5 cm2/s diffusivity through an ordered, two-dimensional assembly of cesium lead bromide perovskite nanocrystals (PNC). Exciton diffusion was directly measured via steady-state and time-resolved photoluminescence (PL) microscopy, with physical modeling providing deeper insight into the transport process. This exceptionally efficient exciton transport is facilitated by PNCs high PL quantum yield, large absorption cross-section, and high polarizability, together with minimal energetic and geometric disorder of the assembly. This FRET-mediated exciton diffusion length matches perovskites optical absorption depth, opening the possibility to design new optoelectronic device architectures with improved performances, and providing insight into the high conversion efficiencies of PNC-based optoelectronic devices

A nanochannel through a plasmonic antenna gap: an integrated device for single particle counting

Plasmonic nanoantennas are ideal for single molecule detection since they nano-focus the light beyond diffraction and enhance the optical fields by several orders of magnitude. But delivering the molecules into these nanometric hot-spots is a real challenge. Here, we present a dynamic sensor, with label-free real-time detection capabilities, which can detect and count molecules and particles one by one in their native environment independently of their concentration. To this end, we have integrated a 35 nm gap plasmonic bowtie antenna with a 30 nm × 30 nm nanochannel. The channel runs through the antenna gap, and delivers the analyte directly into the hot spot. We show how the antenna probes into zeptoliter volumes inside the nanochannel by observing the dark field resonance shift during the filling process of a non-fluorescent liquid. Moreover, we detect and count single quantum dots, one by one, at ultra-high concentrations of up to 25 mg mL-1. The nano-focusing of light, reduces the observation volume in five orders of magnitude compared to the diffraction limited spot, beating the diffraction limit. These results prove the unique sensitivity of the device and in the future can be extended to detection of a variety of molecules for biomedical applications

Lithographically defined synthesis of transition metal dichalcogenides

Transition metal dichalcogenides (TMDs) promise to revolutionize optoelectronic applications. While monolayer exfoliation and vapor phase growth produce extremely high quality 2D materials, direct fabrication at wafer scale remains a significant challenge. Here, we present a method that we call ‘lateral conversion’, which enables the synthesis of patterned TMD structures, with control over the thickness down to a few layers, at lithographically predefined locations. In this method, chemical conversion of a metal-oxide film to TMD layers proceeds by diffusion of precursor propagating laterally between silica layers, resulting in structures where delicate chalcogenide films are protected from contamination or oxidation. Lithographically patterned WS2 structures were synthesized by lateral conversion and analyzed in detail by hyperspectral Raman imaging, scanning electron microscopy and transmission electron microscopy. The rate of conversion was investigated as a function of time, temperature, and thickness of the converted film. In addition, the process was extended to grow patterned MoS2, WSe2, MoSe2 structures, and to demonstrate unique WS2/SiO2 multilayer structures. We believe this method will be applicable to a variety of additional chalcogenide materials, and enable their incorporation into novel architectures and devices