Core/Shell-Like Localized Emission at Atomically Thin Semiconductor-Au Interface.

Localized emission in atomically thin semiconductors has sparked significant interest as single-photon sources. Despite comprehensive studies into the correlation between localized strain and exciton emission, the impacts of charge transfer on nanobubble emission remains elusive. Here, we report the observation of core/shell-like localized emission from monolayer WSe2 nanobubbles at room temperature through near-field studies. By altering the electronic junction between monolayer WSe2 and the Au substrate, one can effectively adjust the semiconductor to metal junction from a Schottky to an Ohmic junction. Through concurrent analysis of topography, potential, tip-enhanced photoluminescence, and a piezo response force microscope, we attribute the core/shell-like emissions to strong piezoelectric potential aided by induced polarity at the WSe2-Au Schottky interface which results in spatial confinement of the excitons. Our findings present a new approach for manipulating charge confinement and engineering localized emission within atomically thin semiconductor nanobubbles. These insights hold implications for advancing the nano and quantum photonics with low-dimensional semiconductors.

Interfacial Reaction and Diffusion at the One-Dimensional Interface of Two-Dimensional PtSe2.

Two-dimensional (2D) PtSe2 has potential applications in near-infrared optoelectronics because its band gap can be tuned by varying the layer thickness. There are several different platinum-selenide phases with different stoichiometries that result from high-temperature processing. In this report, we use in situ scanning/transmission electron microscopy (STEM) to investigate high-temperature phase transitions in 2D PtSe2 and observe interfacial reactions as well as the Kirkendall effect. The 2D nature of PtSe2 plays a key role in the unique one-dimensional interfaces that result during the formation of Se-poor phases (PtSe and PtSe1-x) at the edges of the PtSe2 crystals. The activation energy extracted for this formation suggests that the process is mediated by Se vacancies, as evidenced by the large strain variations in the material made via 4D STEM measurements. The observation of the Kirkendall effect in a 2D material suggests routes to engineer 1D edge chemistry for contact engineering in device applications.

Spatiotemporal Imaging of Thickness-Induced Band-Bending Junctions.

van der Waals materials exhibit naturally passivated surfaces and an ability to form versatile heterostructures to enable an examination of carrier transport mechanisms not seen in traditional materials. Here, we report a new type of homojunction termed a "band-bending junction" whose potential landscape depends solely on the difference in thickness between the two sides of the junction. Using MoS2 on Au as a prototypical example, we find that surface potential differences can arise from the degree of vertical band bending in thin and thick regions. Furthermore, by using scanning ultrafast electron microscopy, we examine the spatiotemporal dynamics of charge carriers generated at this junction and find that lateral carrier separation is enabled by differences in the band bending in the vertical direction, which we verify with simulations. Band-bending junctions may therefore enable new optoelectronic devices that rely solely on band bending arising from thickness variations to separate charge carriers.

Self-Hybridized Polaritonic Emission from Layered Perovskites.

Light-matter coupling in excitonic materials has been the subject of intense recent investigations due to emergence of new materials. Two-dimensional layered hybrid organic/inorganic perovskites (2D HOIPs) support strongly bound excitons at room temperature with some of the highest oscillator strengths and electric loss tangents among the known excitonic materials. Here, we report strong light-matter coupling in Ruddlesden-Popper phase 2D HOIP crystals without the necessity of an external cavity. We report the concurrent occurrence of multiple orders of hybrid light-matter states via both reflectance and luminescence spectroscopy in thick (>100 nm) crystals and near-unity absorption in thin (<20 nm) crystals. We observe resonances with quality factors of >250 in hybridized exciton-polaritons and identify a linear correlation between exciton-polariton mode splitting and extinction coefficient of the various 2D HOIPs. Our work opens the door to studying polariton dynamics in self-hybridized and open cavity systems with broad applications in optoelectronics and photochemistry.

Gate-Tunable Semiconductor Heterojunctions from 2D/3D van der Waals Interfaces.

van der Waals (vdW) semiconductors are attractive for highly scaled devices and heterogeneous integration as they can be isolated into self-passivated, two-dimensional (2D) layers that enable superior electrostatic control. These attributes have led to numerous demonstrations of field-effect devices ranging from transistors to triodes. By exploiting the controlled, substitutional doping schemes in covalently bonded, three-dimensional (3D) semiconductors and the passivated surfaces of 2D semiconductors, one can construct devices that can exceed performance metrics of "all-2D" vdW heterojunctions. Here, we demonstrate 2D/3D semiconductor heterojunctions using MoS2 as the prototypical 2D semiconductor laid upon Si and GaN as the 3D semiconductor layers. By tuning the Fermi levels in MoS2, we demonstrate devices that concurrently exhibit over 7 orders of magnitude modulation in rectification ratios and conductance. Our results further suggest that the interface quality does not necessarily affect Fermi level tuning at the junction, opening up possibilities for novel 2D/3D heterojunction device architectures.

Functional polyelectrolyte nanospaced MoS2 multilayers for enhanced photoluminescence.

Molybdenum disulfide (MoS2) multilayers with functional polyelectrolyte nanospacing layers are presented. Taking advantage of the facile method of layer-by-layer (LbL) assembly, individual chemically exfoliated MoS2 layers are not only effectively isolated from interlayer coupling but also doped by functional polymeric layers. It is clearly demonstrated that MoS2 nanosheets separated by polymeric trilayers exhibit a much larger increase in photoluminescence (PL) as the number of layers is increased. The enhanced PL has been correlated to the ratio of excitons to trions with the type of polymeric spacers. Because uniform heterogeneous interfaces can be formed between various transition metal dichalcogenides and other soft materials, LbL assembly offers possibilities for further development in the solution-processable assemblies of two-dimensional materials.

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 gives rise to not only asymmetrical light propagation but also attenuation along two distinct polarizations, a phenomenon called linear dichroism (LD). Two-dimensional (2D) layered materials with high in-plane 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 multiquantum 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 the tunable in-plane anisotropic response of mithrene, which stem from its low symmetry crystal structure and strong 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 a polaritonic birefringent material for polarization-sensitive nanophotonic applications in the short wavelength regime.

Nonvolatile 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 the integration of 2D materials with ferroelectrics is a promising strategy; however, an experimental demonstration has remained elusive. Here, we fabricate ferroelectric field-effect transistors using a ML-WSe2 channel and an Al0.68Sc0.32N (AlScN) ferroelectric dielectric and experimentally demonstrate efficient tuning as well as non-volatile control of valley polarization. We measure a large array of transistors and obtain a maximum valley polarization of ∼27% at 80 K with stable retention up to 5400 s. The enhancement in the valley polarization is 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 for practical valleytronic device applications.

Tunable Localized Charge Transfer Excitons in Nanoplatelet-2D Chalcogenide van der Waals Heterostructures.

Observation of interlayer, charge transfer (CT) excitons in van der Waals heterostructures (vdWHs) based on 2D-2D systems has been well investigated. While conceptually interesting, these charge transfer excitons are highly delocalized and spatially localizing them requires twisting layers at very specific angles. This issue of localizing the CT excitons can be overcome via making nanoplate-2D material heterostructures (N2DHs) where one of the components is a spatially quantum confined medium. Here, we demonstrate the formation of CT excitons in a mixed dimensional system comprising MoSe2 and WSe2 monolayers and CdSe/CdS-based core/shell nanoplates (NPLs). Spectral signatures of CT excitons in our N2DHs were resolved locally at the 2D/single-NPL heterointerface using tip-enhanced photoluminescence (TEPL) at room temperature. By varying both the 2D material and the shell thickness of the NPLs and applying an out-of-plane electric field, the exciton resonance energy was tuned by up to 100 meV. Our finding is a significant step toward the realization of highly tunable N2DH-based next-generation photonic devices.

Confinement of excited states in two-dimensional, in-plane, quantum heterostructures.

Two-dimensional (2D) semiconductors are promising candidates for optoelectronic application and quantum information processes due to their inherent out-of-plane 2D confinement. In addition, they offer the possibility of achieving low-dimensional in-plane exciton confinement, similar to zero-dimensional quantum dots, with intriguing optical and electronic properties via strain or composition engineering. However, realizing such laterally confined 2D monolayers and systematically controlling size-dependent optical properties remain significant challenges. Here, we report the observation of lateral confinement of excitons in epitaxially grown in-plane MoSe2 quantum dots (~15-60 nm wide) inside a continuous matrix of WSe2 monolayer film via a sequential epitaxial growth process. Various optical spectroscopy techniques reveal the size-dependent exciton confinement in the MoSe2 monolayer quantum dots with exciton blue shift (12-40 meV) at a low temperature as compared to continuous monolayer MoSe2. Finally, single-photon emission (g2(0) ~ 0.4) was also observed from the smallest dots at 1.6 K. Our study opens the door to compositionally engineered, tunable, in-plane quantum light sources in 2D semiconductors.

Direct nano-imaging of light-matter interactions in nanoscale excitonic emitters.

Strong light-matter interactions in localized nano-emitters 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 localized nanoscale emitters on a flat Au substrate. Using quasi 2-dimensional CdSe/CdxZn1-xS nanoplatelets, we 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 edge-up assembled nano-emitters on the substrate plane. We further report that both light confinement and 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.

High-Density, Localized Quantum Emitters in Strained 2D Semiconductors.

Two-dimensional chalcogenide semiconductors have recently emerged as a host material for quantum emitters of single photons. While several reports on defect- and strain-induced single-photon emission from 2D chalcogenides exist, a bottom-up, lithography-free approach to producing a high density of emitters remains elusive. Further, the physical properties of quantum emission in the case of strained 2D semiconductors are far from being understood. Here, we demonstrate a bottom-up, scalable, and lithography-free approach for creating large areas of localized emitters with high density (∼150 emitters/um2) in a WSe2 monolayer. We induce strain inside the WSe2 monolayer with high spatial density by conformally placing the WSe2 monolayer over a uniform array of Pt nanoparticles with a size of 10 nm. Cryogenic, time-resolved, and gate-tunable luminescence measurements combined with near-field luminescence spectroscopy suggest the formation of localized states in strained regions that emit single photons with a high spatial density. Our approach of using a metal nanoparticle array to generate a high density of strained quantum emitters will be applied to scalable, tunable, and versatile quantum light sources.

Stable aqueous dispersion of reduced graphene nanosheets via non-covalent functionalization with conducting polymers and application in transparent electrodes.

We developed a simple and facile method of producing a stable aqueous suspension of reduced graphene oxide (RGO) nanosheets through the chemical reduction of graphene oxide in the presence of a conducting polymer dispersant, poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS). This approach involves the cooperative interactions of strong π- π interactions between a two-dimensional graphene sheet and a rigid backbone of PEDOT and the intermolecular electrostatic repulsions between negatively charged PSS bound on the RGO sheets, which impart the colloidal stability of the resulting hybrid nanocomposite of RGO/PEDOT. Moreover, our one-step solution-based method allows preserving the intrinsic chemical and electronic properties of both components, yielding a hybrid film of RGO nanosheets of high conductivity of 2.3 kΩ/sq with a transmittance of 80%. By taking advantage of conducting network structure of conducting polymers which provides an additional flexibility and mechanical stability of RGO nanosheets, we demonstrate the potential application of hybrid RGO/PEDOT as highly flexible and transparent electrodes.

Exciton-Photonics: From Fundamental Science to Applications.

Semiconductors in all dimensionalities ranging from 0D quantum dots and molecules to 3D bulk crystals support bound electron-hole pair quasiparticles termed excitons. Over the past two decades, the emergence of a variety of low-dimensional semiconductors that support excitons combined with advances in nano-optics and photonics has burgeoned an advanced area of research that focuses on engineering, imaging, and modulating the coupling between excitons and photons, resulting in the formation of hybrid quasiparticles termed exciton-polaritons. This advanced area has the potential to bring about a paradigm shift in quantum optics, as well as classical optoelectronic devices. Here, we present a review on the coupling of light in excitonic semiconductors and previous investigations of the optical properties of these hybrid quasiparticles via both far-field and near-field imaging and spectroscopy techniques. Special emphasis is given to recent advances with critical evaluation of the bottlenecks that plague various materials toward practical device implementations including quantum light sources. Our review highlights a growing need for excitonic material development together with optical engineering and imaging techniques to harness the utility of excitons and their host materials for a variety of applications.

Direct Optoelectronic Imaging of 2D Semiconductor-3D Metal Buried Interfaces.

The semiconductor-metal junction is one of the most critical factors for high-performance electronic devices. In two-dimensional (2D) semiconductor devices, minimizing the voltage drop at this junction is particularly challenging and important. Despite numerous studies concerning contact resistance in 2D semiconductors, the exact nature of the buried interface under a three-dimensional (3D) metal remains unclear. Herein, we report the direct measurement of electrical and optical responses of 2D semiconductor-metal buried interfaces using a recently developed metal-assisted transfer technique to expose the buried interface, which is then directly investigated using scanning probe techniques. We characterize the spatially varying electronic and optical properties of this buried interface with <20 nm resolution. To be specific, potential, conductance, and photoluminescence at the buried metal/MoS2 interface are correlated as a function of a variety of metal deposition conditions as well as the type of metal contacts. We observe that direct evaporation of Au on MoS2 induces a large strain of ∼5% in the MoS2 which, coupled with charge transfer, leads to degenerate doping of the MoS2 underneath the contact. These factors lead to improvement of contact resistance to record values of 138 kΩ µm, as measured using local conductance probes. This approach was adopted to characterize MoS2-In/Au alloy interfaces, demonstrating contact resistance as low as 63 kΩ µm. Our results highlight that the MoS2/metal interface is sensitive to device fabrication methods and provide a universal strategy to characterize buried contact interfaces involving 2D semiconductors.

Hybrid exciton-plasmon-polaritons in van der Waals semiconductor gratings.

Van der Waals materials and heterostructures that manifest strongly bound exciton states at room temperature also exhibit emergent physical phenomena and are of great promise for optoelectronic applications. Here, we demonstrate that nanostructured, multilayer transition metal dichalcogenides (TMDCs) by themselves provide an ideal platform for excitation and control of excitonic modes, paving the way to exciton-photonics. Hence, we show that by patterning the TMDCs into nanoresonators, strong dispersion and avoided crossing of exciton, cavity photons and plasmon polaritons with effective separation energy exceeding 410 meV can be controlled with great precision. We further observe that inherently strong TMDC exciton absorption resonances may be completely suppressed due to excitation of hybrid light-matter states and their interference. Our work paves the way to the next generation of integrated exciton optoelectronic nano-devices and applications in light generation, computing, and sensing.

Substrate-directed synthesis of MoS2 nanocrystals with tunable dimensionality and optical properties.

Two-dimensional transition-metal dichalcogenide (TMD) crystals are a versatile platform for optoelectronic, catalytic and quantum device studies. However, the ability to tailor their physical properties through explicit synthetic control of their morphology and dimensionality is a major challenge. Here we demonstrate a gas-phase synthesis method that substantially transforms the structure and dimensionality of TMD crystals without lithography. Synthesis of MoS2 on Si(001) surfaces pre-treated with phosphine yields high-aspect-ratio nanoribbons of uniform width. We systematically control the width of these nanoribbons between 50 and 430 nm by varying the total phosphine dosage during the surface treatment step. Aberration-corrected electron microscopy reveals that the nanoribbons are predominantly 2H phase with zig-zag edges and an edge quality that is comparable to, or better than, that of graphene and TMD nanoribbons prepared through conventional top-down processing. Owing to their restricted dimensionality, the nominally one-dimensional MoS2 nanocrystals exhibit photoluminescence 50 meV higher in energy than that from two-dimensional MoS2 crystals. Moreover, this emission is precisely tunable through synthetic control of crystal width. Directed crystal growth on designer substrates has the potential to enable the preparation of low-dimensional materials with prescribed morphologies and tunable or emergent optoelectronic properties.

Dry Transfer of van der Waals Crystals to Noble Metal Surfaces To Enable Characterization of Buried Interfaces.

Two-dimensional (2D) transition-metal dichalcogenides (TMDCs) have been explored for many optoelectronic applications. Most of these applications require them to be on insulating substrates. However, for many fundamental property characterizations, such as mapping surface potential or conductance, insulating substrates are nonideal as they lead to charging and doping effects or impose the inhomogeneity of their charge environment on the atomically thin 2D layers. Here, we report a simple method of residue-free dry transfer of 2D TMDC crystal layers. This method is enabled via noble-metal (gold, silver) thin films and allows comprehensive nanoscale characterization of transferred TMDC crystals with multiple scanning probe microscopy techniques. In particular, intimate contact with underlying metal allows efficient tip-enhanced Raman scattering characterization, providing high spatial resolution (<20 nm) for Raman spectroscopy. Further, scanning Kelvin probe force microscopy allows high-resolution mapping of surface potential on transferred crystals, revealing their spatially varying structural and electronic properties. The layer-dependent contact potential difference is clearly observed and explained by charge transfer from contacts with Au and Ag. The demonstrated sample preparation technique can be generalized to probe many different 2D material surfaces and has broad implications in understanding of the metal contacts and buried interfaces in 2D material-based devices.

Coaxial struts and microfractured structures of compressible thermoelectric foams for self-powered pressure sensors.

Long-term operation of wearable pressure sensors to detect body movement requires self-powered human-based energy sources to minimize the need for recharging. Recently, pressure sensors with thermoelectric properties based on conducting polymers have been reported; however, these devices are limited in their ability to simultaneously achieve sufficient power generation and sensitivity of the sensor. In this article, we suggest a coaxial strut structure of poly(styrene-ethylene/butylene-styrene)(SEBS)-poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)(PEDOT:PSS)-melamine foam (MF) with a fractured microstructure for a highly sensitive, efficient self-powered pressure sensor. In the coaxial struts, the MF core provides a compressible and elastic framework; the intermediate PEDOT:PSS acts as a conductor and a thermoelectric material; and the SEBS shell ensures mechanical stability and resilience to stabilize the brittle PEDOT:PSS layer under high loading conditions. Additionally, by compressing the coaxial foam to 1/20, partial microfracture of PEDOT:PSS occurs only in the SEBS shell; thus, the pressure sensitivity increases significantly while maintaining high conductivity and thermoelectric performance. The coaxial foam was assembled into a wearable TEG to generate 338 nW from the forearms and demonstrate the high sensitivity of pressure sensors without an external power supply.

Flexible and Robust Thermoelectric Generators Based on All-Carbon Nanotube Yarn without Metal Electrodes.

As practical interest in flexible/or wearable power-conversion devices increases, the demand for high-performance alternatives to thermoelectric (TE) generators based on brittle inorganic materials is growing. Herein, we propose a flexible and ultralight TE generator (TEG) based on carbon nanotube yarn (CNTY) with excellent TE performance. The as-prepared CNTY shows a superior electrical conductivity of 3147 S/cm due to increased longitudinal carrier mobility derived from a highly aligned structure. Our TEG is innovative in that the CNTY acts as multifunctions in the same device. The CNTY is alternatively doped into n- and p-types using polyethylenimine and FeCl3, respectively. The highly conductive CNTY between the doped regions is used as electrodes to minimize the circuit resistance, thereby forming an all-carbon TEG without additional metal deposition. A flexible TEG based on 60 pairs of n- and p-doped CNTY shows the maximum power density of 10.85 and 697 µW/g at temperature differences of 5 and 40 K, respectively, which are the highest values among reported TEGs based on flexible materials. We believe that the strategy proposed here to improve the power density of flexible TEG by introducing highly aligned CNTY and designing a device without metal electrodes shows great potential for the flexible/or wearable power-conversion devices.