Optical spectroscopic detection of Schottky barrier height at a two-dimensional transition-metal dichalcogenide/metal interface.

Atomically thin two-dimensional transition-metal dichalcogenides (2D-TMDs) have emerged as semiconductors for next-generation nanoelectronics. As 2D-TMD-based devices typically utilize metals as the contacts, it is crucial to understand the properties of the 2D-TMD/metal interface, including the characteristics of the Schottky barriers formed at the semiconductor-metal junction. Conventional methods for investigating the Schottky barrier height (SBH) at these interfaces predominantly rely on contact-based electrical measurements with complex gating structures. In this study, we introduce an all-optical approach for non-contact measurement of the SBH, utilizing high-quality WS2/Au heterostructures as a model system. Our approach employs a below-bandgap pump to excite hot carriers from the gold into WS2 with varying thicknesses. By monitoring the resultant carrier density changes within the WS2 layers with a broadband probe, we traced the dynamics and magnitude of charge transfer across the interface. A systematic sweep of the pump wavelength enables us to determine the SBH values and unveil an inverse relationship between the SBH and the thickness of the WS2 layers. First-principles calculations reveal the correlation between the probability of injection and the density of states near the conduction band minimum of WS2. The versatile optical methodology for probing TMD/metal interfaces can shed light on the intricate charge transfer characteristics within various 2D heterostructures, facilitating the development of more efficient and scalable nano-electronic and optoelectronic technologies.

Dynamics of self-hybridized exciton-polaritons in 2D halide perovskites.

Excitons, bound electron-hole pairs, in two-dimensional hybrid organic inorganic perovskites (2D HOIPs) are capable of forming hybrid light-matter states known as exciton-polaritons (E-Ps) when the excitonic medium is confined in an optical cavity. In the case of 2D HOIPs, they can self-hybridize into E-Ps at specific thicknesses of the HOIP crystals that form a resonant optical cavity with the excitons. However, the fundamental properties of these self-hybridized E-Ps in 2D HOIPs, including their role in ultrafast energy and/or charge transfer at interfaces, remain unclear. Here, we demonstrate that >0.5 µm thick 2D HOIP crystals on Au substrates are capable of supporting multiple-orders of self-hybridized E-P modes. These E-Ps have high Q factors (>100) and modulate the optical dispersion for the crystal to enhance sub-gap absorption and emission. Through varying excitation energy and ultrafast measurements, we also confirm energy transfer from higher energy E-Ps to lower energy E-Ps. Finally, we also demonstrate that E-Ps are capable of charge transport and transfer at interfaces. Our findings provide new insights into charge and energy transfer in E-Ps opening new opportunities towards their manipulation for polaritonic devices.

Observation of Sub-10 nm Transition Metal Dichalcogenide Nanocrystals in Rapidly Heated van der Waals Heterostructures.

Two-dimensional materials, such as transition metal dichalcogenides (TMDCs), have the potential to revolutionize the field of electronics and photonics due to their unique physical and structural properties. This research presents a novel method for synthesizing crystalline TMDCs crystals with <10 nm size using ultrafast migration of vacancies at elevated temperatures. Through in situ and ex situ processing and using atomic-level characterization techniques, we analyzed the shape, size, crystallinity, composition, and strain distribution of these nanocrystals. These nanocrystals exhibit electronic structure signatures that differ from the 2D bulk: i.e., uniform mono- and multilayers. Further, our in situ, vacuum-based synthesis technique allows observation and comparison of defect and phase evolution in these crystals formed under van der Waals heterostructure confinement versus unconfined conditions. Overall, this research demonstrates a solid-state route to synthesizing uniform nanocrystals of TMDCs and lays the foundation for materials science in confined 2D spaces under extreme conditions.

Valley-Polarized Interlayer Excitons in 2D Chalcogenide-Halide Perovskite-van der Waals Heterostructures.

Interlayer excitons (IXs) in two-dimensional (2D) heterostructures provide an exciting avenue for exploring optoelectronic and valleytronic phenomena. Presently, valleytronic research is limited to transition metal dichalcogenide (TMD) based 2D heterostructure samples, which require strict lattice (mis) match and interlayer twist angle requirements. Here, we explore a 2D heterostructure system with experimental observation of spin-valley layer coupling to realize helicity-resolved IXs, without the requirement of a specific geometric arrangement, i.e., twist angle or specific thermal annealing treatment of the samples in 2D Ruddlesden-Popper (2DRP) halide perovskite/2D TMD heterostructures. Using first-principle calculations, time-resolved and circularly polarized luminescence measurements, we demonstrate that Rashba spin-splitting in 2D perovskites and strongly coupled spin-valley physics in monolayer TMDs render spin-valley-dependent optical selection rules to the IXs. Consequently, a robust valley polarization of ∼14% with a long exciton lifetime of ∼22 ns is obtained in type-II band aligned 2DRP/TMD heterostructure at ∼1.54 eV measured at 80 K. Our work expands the scope for studying spin-valley physics in heterostructures of disparate classes of 2D semiconductors.

Nanomaterials for Quantum Information Science and Engineering.

Quantum information science and engineering (QISE)-which entails the use of quantum mechanical states for information processing, communications, and sensing-and the area of nanoscience and nanotechnology have dominated condensed matter physics and materials science research in the 21st century. Solid-state devices for QISE have, to this point, predominantly been designed with bulk materials as their constituents. This review considers how nanomaterials (i.e., materials with intrinsic quantum confinement) may offer inherent advantages over conventional materials for QISE. The materials challenges for specific types of qubits, along with how emerging nanomaterials may overcome these challenges, are identified. Challenges for and progress toward nanomaterials-based quantum devices are condidered. The overall aim of the review is to help close the gap between the nanotechnology and quantum information communities and inspire research that will lead to next-generation quantum devices for scalable and practical quantum applications.

Reconfigurable Compute-In-Memory on Field-Programmable Ferroelectric Diodes.

The deluge of sensors and data generating devices has driven a paradigm shift in modern computing from arithmetic-logic centric to data-centric processing. Data-centric processing require innovations at the device level to enable novel compute-in-memory (CIM) operations. A key challenge in the construction of CIM architectures is the conflicting trade-off between the performance and their flexibility for various essential data operations. Here, we present a transistor-free CIM architecture that permits storage, search, and neural network operations on sub-50 nm thick Aluminum Scandium Nitride ferroelectric diodes (FeDs). Our circuit designs and devices can be directly integrated on top of Silicon microprocessors in a scalable process. By leveraging the field-programmability, nonvolatility, and nonlinearity of FeDs, search operations are demonstrated with a cell footprint <0.12 µm2 when projected onto 45 nm node technology. We further demonstrate neural network operations with 4-bit operation using FeDs. Our results highlight FeDs as candidates for efficient and multifunctional CIM platforms.

Light-matter coupling in large-area van der Waals superlattices.

Two-dimensional (2D) crystals have renewed opportunities in design and assembly of artificial lattices without the constraints of epitaxy. However, the lack of thickness control in exfoliated van der Waals (vdW) layers prevents realization of repeat units with high fidelity. Recent availability of uniform, wafer-scale samples permits engineering of both electronic and optical dispersions in stacks of disparate 2D layers with multiple repeating units. Here we present optical dispersion engineering in a superlattice structure comprising alternating layers of 2D excitonic chalcogenides and dielectric insulators. By carefully designing the unit cell parameters, we demonstrate greater than 90% narrow band absorption in less than 4 nm of active layer excitonic absorber medium at room temperature, concurrently with enhanced photoluminescence in square-centimetre samples. These superlattices show evidence of strong light-matter coupling and exciton-polariton formation with geometry-tuneable coupling constants. Our results demonstrate proof of concept structures with engineered optical properties and pave the way for a broad class of scalable, designer optical metamaterials from atomically thin layers.

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.

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.

Enhanced Room-Temperature Photoluminescence Quantum Yield in Morphology Controlled J-Aggregates.

Supramolecular assemblies from organic dyes forming J-aggregates are known to exhibit narrowband photoluminescence with full-width at half maximum of ≈9 nm (260 cm-1). Applications of these high color purity emitters, however, are hampered by the rather low photoluminescence quantum yields reported for cyanine J-aggregates, even when formed in solution. Here, it is demonstrated that cyanine J-aggregates can reach an order of magnitude higher photoluminescence quantum yield (increase from 5% to 60%) in blend solutions of water and alkylamines at room temperature. By means of time-resolved photoluminescence studies, an increase in the exciton lifetime as a result of the suppression of non-radiative processes is shown. Small-angle neutron scattering studies suggest a necessary condition for the formation of such highly emissive J-aggregates: the presence of a sharp water/amine interface for J-aggregate assembly and the coexistence of nanoscale-sized water and amine domains to restrict the J-aggregate size and solubilize monomers, respectively.

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.

Excitonic channels from bio-inspired templated supramolecular assembly of J-aggregate nanowires.

Supramolecular assemblies with controlled morphology are of paramount importance for energy transport in organic semiconductors. Despite considerable freedom in molecular design, the preparation of dyes that form one dimensional J-aggregates is challenging. Here, we demonstrate a simple and effective route to functionalize dendronized polymers (DPs) with J-aggregates to construct tubular DP/J-aggregate nanowires. When J-aggregates are adsorbed onto DPs anchored to glass substrates, they assemble into microcrystalline domains typical for J-aggregates adsorbed on functionalized surfaces. Differently, the complexation between the dendronized polymer and J-aggregates in solution leads to dense packing of J-aggregate strands on the periphery of the DPs. Using a layer-by-layer (LBL) technique, DPs loaded with J-aggregates can also be adsorbed onto a DP monolayer. In this case, the thin film absorption spectra are narrower and indicate higher ratios of J-aggregate to monomer and dimer absorption than bare J-aggregates deposited similarly. The demonstration of J-aggregate adsorption on filamentous polymeric templates is a promising step toward artificial 1D light harvesting antennas, with potential applications in opto-electronic devices.

Insights into photovoltaic properties of ternary organic solar cells from phase diagrams.

The efficiency of ternary organic solar cells relies on the spontaneous establishment of a nanostructured network of donor and acceptor phases during film formation. A fundamental understanding of phase composition and arrangement and correlations to photovoltaic device parameters is of utmost relevance for both science and technology. We demonstrate a general approach to understanding solar cell behavior from simple thermodynamic principles. For two ternary blend systems we construct and model phase diagrams. Details of EQE and solar cell parameters can be understood from the phase behavior. Our blend system is composed of PC70BM, PBDTTT-C and a near-infrared absorbing cyanine dye. Cyanine dyes are accompanied by counterions, which, in a first approximation, do not change the photophysical properties of the dye, but strongly influence the morphology of the ternary blend. We argue that counterion dissociation is responsible for different mixing behavior. For the dye with a hexafluorophosphate counterion a hierarchical morphology develops, the dye phase separates on a large scale from PC70BM and cannot contribute to photocurrent. Differently, a cyanine dye with a TRISPHAT counterion shows partial miscibility with PC70BM. A large two-phase region dictated by the PC70BM: PBDTTT-C mixture is present and the dye greatly contributes to the short-circuit current.

Squaraine Dye for a Visibly Transparent All-Organic Optical Upconversion Device with Sensitivity at 1000 nm.

Efficient light detection in the near-infrared (NIR) wavelength region is central to emerging applications such as medical imaging and machine vision. An organic upconverter (OUC) consists of a NIR-sensitive organic photodetector (OPD) and an visible organic light-emitting diode (OLED), connected in series. The device converts NIR light directly to visible light, allowing imaging of a NIR scene in the visible. Here, we present an OUC composed of a NIR-selective squaraine dye-based OPD and a fluorescent OLED. The OPD has a peak sensitivity at 980 nm and an internal photon-to-current conversion efficiency of ∼100%. The OUC conversion efficiency (0.27%) of NIR to visible light is close to the expected maximum. The materials of the OUC multilayer stack absorb very little light in the visible wavelength range. In combination with an optimized semitransparent metal top electrode, this enabled the fabrication of transparent OUCs with an average visible transmittance of 65% and a peak transmittance of 80% at 620 nm. Visibly transparent OUCs are interesting for window-integrated electronic circuits or imaging systems that allow for the simultaneous detection of directly transmitted visible and NIR upconverted light.