Photoluminescence in MoS2 Multilayers with Functional Polyelectrolyte Nanospacing

Department of PhysicsPhotoluminescence phenomenon in multilayers of molybdenum disulfide (MoS2) spaced by nano-thick polyelectrolyte layers are demonstrated on behalf of various transition metal dichalcogenides. Using facile method of layer-by-layer (LbL) assembly, negative charged MoS2 sheet and positive charged polymeric layers are sequentially stacked on various substrates. In this structure, individual MoS2 monolayers are not only effectively screened from interlayer coupling but also p-doped by functional polymeric layers. The Raman analysis demonstrates that MoS2 nanosheets separated by polymeric trilayers display much larger increase in photoluminescence (PL) as the number of layers is increased. Furthermore, it was also found that the enhanced PL has been correlated to the ratio of excitons to trions with type of polymeric spacers. Because uniform heterogeneous interfaces can be formed between various transition metal dichalcogenides and other soft materials, we expect that the result will be a trigger to fabricate hetero vertical architecture with other 2D analogues and will offer potential electronic and optoelectronic applications.ope

Giant Optical Anisotropy in 2D Metal-Organic Chalcogenates

Optical anisotropy is a fundamental attribute of some crystalline materials and is quantified via birefringence. A birefringent crystal not only gives rise to asymmetrical light propagation but also attenuation along two distinct polarizations, a phenomenon called linear dichroism (LD). Two-dimensional (2D) layered materials with high in- and out-of-plane anisotropy have garnered interest in this regard. Mithrene, a 2D metal-organic chalcogenate (MOCHA) compound, exhibits strong excitonic resonances due to its naturally occurring multi-quantum well (MQW) structure and in-plane anisotropic response in the blue wavelength (~400-500 nm) regime. The MQW structure and the large refractive indices of mithrene allow the hybridization of the excitons with photons to form self-hybridized exciton-polaritons in mithrene crystals with appropriate thicknesses. Here, we report the giant birefringence (~1.01) and tunable in-plane anisotropic response of mithrene, which stem from its low symmetry crystal structure and unique excitonic properties. We show that the LD in mithrene can be tuned by leveraging the anisotropic exciton-polariton formation via the cavity coupling effect exhibiting giant in-plane LD (~77.1%) at room temperature. Our results indicate that mithrene is an ideal polaritonic birefringent material for polarization-sensitive nanophotonic applications in the short wavelength regime

Facile synthesis of hybrid graphene and carbon nanotubes as a metal-free electrocatalyst with active dual interfaces for efficient oxygen reduction reaction

We report metal-free electrocatalysts to enhance utilization of dissolved and gaseous oxygen during oxygen reduction reaction (ORR). Proper balance between hydrophobicity and hydrophilicity is achieved using reduced graphene oxide (rGO) and polyelectrolyte functionalized multiwalled carbon nanotubes (pMWNTs). In this unique architecture, both two- and three-phase reactions in ORR can be maximized with a quasi-four-electron pathway.close6

Spatiotemporal Imaging of Thickness-Induced Band Bending Junctions

Van der Waals materials exhibit naturally passivated surfaces and can form versatile heterostructures, enabling observation of carrier transport mechanisms not seen in three-dimensional materials. Here we report observation of a "band bending junction", a new type of semiconductor homojunction whose surface potential landscape depends solely on a difference in thickness between the two semiconductor regions atop a buried heterojunction interface. Using MoS2 on Au to form a buried heterojunction interface, we find that lateral surface potential differences can arise in MoS2 from the local extent of vertical band bending in thin and thick MoS2 regions. Using scanning ultrafast electron microscopy, we examine the spatiotemporal dynamics of photogenerated charge carriers and find that lateral carrier separation is enabled by a band bending junction, which is confirmed with semiconductor transport simulations. Band bending junctions may therefore enable new electronic and optoelectronic devices in Van der Waals materials that rely on thickness variations rather than doping to separate charge carriers.Comment: 16 pages, 4 figure

Direct Nano-Imaging of Light-Matter Interactions in Nanoscale Excitonic Emitters

Strong light-matter interactions in localized nano-emitters when placed near metallic mirrors have been widely reported via spectroscopic studies in the optical far-field. Here, we report a near-field nano-spectroscopic study of the localized nanoscale emitters on a flat Au substrate. We observe strong-coupling of the excitonic dipoles in quasi 2-dimensional CdSe/CdxZnS1-xS nanoplatelets with gap mode plasmons formed between the Au tip and substrate. We also observe directional propagation on the Au substrate of surface plasmon polaritons launched from the excitons of the nanoplatelets as wave-like fringe patterns in the near-field photoluminescence maps. These fringe patterns were confirmed via extensive electromagnetic wave simulations to be standing-waves formed between the tip and the emitter on the substrate plane. We further report that both light confinement and the in-plane emission can be engineered by tuning the surrounding dielectric environment of the nanoplatelets. Our results lead to renewed understanding of in-plane, near-field electromagnetic signal transduction from the localized nano-emitters with profound implications in nano and quantum photonics as well as resonant optoelectronics.Comment: manuscript + supporting informatio

Non-Volatile Control of Valley Polarized Emission in 2D WSe2-AlScN Heterostructures

Achieving robust and electrically controlled valley polarization in monolayer transition metal dichalcogenides (ML-TMDs) is a frontier challenge for realistic valleytronic applications. Theoretical investigations show that integration of 2D materials with ferroelectrics is a promising strategy; however, its experimental demonstration has remained elusive. Here, we fabricate ferroelectric field-effect transistors using a ML-WSe2 channel and a AlScN ferroelectric dielectric, and experimentally demonstrate efficient tuning as well as non-volatile control of valley polarization. We measured a large array of transistors and obtained a maximum valley polarization of ~27% at 80 K with stable retention up to 5400 secs. The enhancement in the valley polarization was ascribed to the efficient exciton-to-trion (X-T) conversion and its coupling with an out-of-plane electric field, viz. the quantum-confined Stark effect. This changes the valley depolarization pathway from strong exchange interactions to slow spin-flip intervalley scattering. Our research demonstrates a promising approach for achieving non-volatile control over valley polarization and suggests new design principles for practical valleytronic devices.Comment: Manuscript (22 pages and 5 figures), supporting informatio