Nanoscale Manipulation of Exciton-Trion Interconversion in a MoSe2 Monolayer via Tip-Enhanced Cavity-Spectroscopy.

Emerging light-matter interactions in metal-semiconductor hybrid platforms have attracted considerable attention due to their potential applications in optoelectronic devices. Here, we demonstrate plasmon-induced near-field manipulation of trionic responses in a MoSe2 monolayer using tip-enhanced cavity-spectroscopy (TECS). The surface plasmon-polariton mode on the Au nanowire can locally manipulate the exciton (X0) and trion (X-) populations of MoSe2. Furthermore, we reveal that surface charges significantly influence the emission and interconversion processes of X0 and X-. In the TECS configuration, the localized plasmon significantly affects the distributions of X0 and X- due to the modified radiative decay rate. Additionally, within the TECS cavity, the electric doping effect and hot electron generation enable dynamic interconversion between X0 and X- at the nanoscale. This work advances our understanding of plasmon-exciton-hot electron interactions in metal-semiconductor-metal hybrid structures, providing a foundation for an optimal trion-based nano-optoelectronic platform.

Adaptive Gap-Tunable Surface-Enhanced Raman Spectroscopy.

Gap plasmon (GP) resonance in static surface-enhanced Raman spectroscopy (SERS) structures is generally too narrow and not tunable. Here, we present an adaptive gap-tunable SERS device to selectively enhance and modulate different vibrational modes via active flexible Au nanogaps, with adaptive optical control. The tunability of GP resonance is up to ∼1200 cm-1 by engineering gap width, facilitated by mechanical bending of a polyethylene terephthalate substrate. We confirm that the tuned GP resonance selectively enhances different Raman spectral regions of the molecules. Additionally, we dynamically control the SERS intensity through the wavefront shaping of excitation beams. Furthermore, we demonstrate simulation results, exhibiting the mechanical and optical properties of a one-dimensional flexible nanogap and their advantage in high-speed biomedical sensing. Our work provides a unique approach for observing and controlling the enhanced chemical responses with dynamic tunability.

Electrically Tunable Single Polaritonic Quantum Dot at Room Temperature.

Exciton-polaritons confined in plasmonic cavities are hybridized light-matter quasiparticles, with distinct optical characteristics compared to plasmons and excitons alone. Here, we demonstrate the electric tunability of a single polaritonic quantum dot operating at room temperature in electric-field tip-enhanced strong coupling spectroscopy. For a single quantum dot in the nanoplasmonic tip cavity with variable dc local electric field, we dynamically control the Rabi frequency with the corresponding polariton emission, crossing weak to strong coupling. We model the observed behaviors based on the quantum confined Stark effect in the strong coupling regime.

Tip-Enhanced Dark Exciton Nanoimaging and Local Strain Control in Monolayer WSe2.

Dark excitons in transition-metal dichalcogenides, with their long lifetimes and strong binding energies, provide potential platforms from photonic and optoelectronic applications to quantum information science even at room temperature. However, their spatial heterogeneity and sensitivity to strain is not yet understood. Here, we combine tip-enhanced photoluminescence spectroscopy with atomic force induced strain control to nanoimage dark excitons in WSe2 and their response to local strain. Dark exciton emission is facilitated by out-of-plane picocavity Purcell enhancement giving rise to spatially highly localized emission, providing for higher spatial resolution compared to bright exciton nanoimaging. Further, tip-antenna-induced dark exciton emission is enhanced in areas of higher strain associated with bubbles. In addition, active force control shows dark exciton emission to be more sensitive to strain with both compressive and tensile lattice deformation facilitating emission. This interplay between localized strain and Purcell effects provides novel pathways for nanomechanical exciton emission control.

Nanocavity Clock Spectroscopy: Resolving Competing Exciton Dynamics in WSe2/MoSe2 Heterobilayers.

Transition-metal dichalcogenide heterostructures are an emergent platform for novel many-body states from exciton condensates to nanolasers. However, their exciton dynamics are difficult to disentangle due to multiple competing processes with time scales varying over many orders of magnitude. Using a configurable nano-optical cavity based on a plasmonic scanning probe tip, the radiative (rad) and nonradiative (nrad) relaxation of intra- and interlayer excitons is controlled. Tuning their relative rates in a WSe2/MoSe2 heterobilayer over 6 orders of magnitude in tip-enhanced photoluminescence spectroscopy reveals a cavity-induced crossover from nonradiative quenching to Purcell-enhanced radiation. Rate equation modeling with the interlayer charge transfer time as a reference clock allows for a comprehensive determination from the long interlayer exciton (IX) radiative lifetime τIXrad = (94 ± 27) ns to the 5 orders of magnitude faster competing nonradiative lifetime τIXnrad = (0.6 ± 0.2) ps. This approach of nanocavity clock spectroscopy is generally applicable to a wide range of excitonic systems with competing decay pathways.

In Liquid Infrared Scattering Scanning Near-Field Optical Microscopy for Chemical and Biological Nanoimaging.

Imaging biological systems with simultaneous intrinsic chemical specificity and nanometer spatial resolution in their typical native liquid environment has remained a long-standing challenge. Here, we demonstrate a general approach of chemical nanoimaging in liquid based on infrared scattering scanning near-field optical microscopy (IR s-SNOM). It is enabled by combining AFM operation in a fluid cell with evanescent IR illumination via total internal reflection, which provides spatially confined excitation for minimized IR water absorption, reduced far-field background, and enhanced directional signal emission and sensitivity. We demonstrate in-liquid IR s-SNOM vibrational nanoimaging and conformational identification of catalase nanocrystals and spatio-spectral analysis of biomimetic peptoid sheets with monolayer sensitivity and chemical specificity at the few zeptomole level. This work establishes the principles of in-liquid and in situ IR s-SNOM spectroscopic chemical nanoimaging and its general applicability to biomolecular, cellular, catalytic, electrochemical, or other interfaces and nanosystems in liquids or solutions.

Polarization Control with Plasmonic Antenna Tips: A Universal Approach to Optical Nanocrystallography and Vector-Field Imaging.

Controlling the propagation and polarization vectors in linear and nonlinear optical spectroscopy enables us to probe the anisotropy of optical responses providing structural symmetry selective contrast in optical imaging. Here, we present a novel tilted antenna-tip approach to control the optical vector-field by breaking the axial symmetry of the nanoprobe in tip-enhanced near-field microscopy. This gives rise to a localized plasmonic antenna effect with significantly enhanced optical field vectors with control of both in-plane and out-of-plane components. We use the resulting vector-field specificity in the symmetry selective nonlinear optical response of second-harmonic generation (SHG) for a generalized approach to optical nanocrystallography and imaging. In tip-enhanced SHG imaging of monolayer MoS2 films and single-crystalline ferroelectric YMnO3, we reveal nanocrystallographic details of domain boundaries and domain topology with enhanced sensitivity and nanoscale spatial resolution. The approach is applicable to any anisotropic linear and nonlinear optical response and enables the optical nanocrystallographic imaging of molecular or quantum materials.

Hybrid Tip-Enhanced Nanospectroscopy and Nanoimaging of Monolayer WSe2 with Local Strain Control.

Many classes of two-dimensional (2D) materials have emerged as potential platforms for novel electronic and optical devices. However, their physical properties are strongly influenced by nanoscale heterogeneities in the form of edges, twin boundaries, and nucleation sites. Using combined tip-enhanced Raman scattering and photoluminescence (PL) nanospectroscopy and nanoimaging, we study the associated effects on the excitonic properties in monolayer WSe2 grown by physical vapor deposition. With ∼15 nm spatial resolution, we resolve nanoscale correlations of PL spectral intensity and shifts with crystal edges and internal twin boundaries associated with the expected exciton diffusion length. Through an active atomic force tip interaction we can control the crystal strain on the nanoscale and tune the local bandgap in reversible (up to 24 meV shift) and irreversible (up to 48 meV shift) fashion. This allows us to distinguish the effect of strain from the dominant influence of defects on the PL modification at the different structural heterogeneities. Hybrid nano-optical spectroscopy and imaging with nanomechanical strain control thus enables the systematic study of the coupling of structural and mechanical degrees of freedom to the nanoscale electronic and optical properties in layered 2D materials.

Variable-Temperature Tip-Enhanced Raman Spectroscopy of Single-Molecule Fluctuations and Dynamics.

Structure, dynamics, and coupling involving single-molecules determine function in catalytic, electronic or biological systems. While vibrational spectroscopy provides insight into molecular structure, rapid fluctuations blur the molecular trajectory even in single-molecule spectroscopy, analogous to spatial averaging in measuring large ensembles. To gain insight into intramolecular coupling, substrate coupling, and dynamic processes, we use tip-enhanced Raman spectroscopy (TERS) at variable and cryogenic temperatures, to slow and control the motion of a single molecule. We resolve intrinsic line widths of individual normal modes, allowing detailed and quantitative investigation of the vibrational modes. From temperature dependent line narrowing and splitting, we quantify ultrafast vibrational dephasing, intramolecular coupling, and conformational heterogeneity. Through statistical correlation analysis of fluctuations of individual modes, we observe rotational motion and spectral fluctuations of the molecule. This work demonstrates single-molecule vibrational spectroscopy beyond chemical identification, opening the possibility for a complete picture of molecular motion ranging from femtoseconds to minutes.

Operation of a wet near-field scanning optical microscope in stable zones by minimizing the resonance change of tuning forks.

A resonant shift and a decrease of resonance quality of a tuning fork attached to a conventional fiber optic probe in the vicinity of liquid is monitored systematically while varying the protrusion length and immersion depth of the probe. Stable zones where the resonance modification as a function of immersion depth is minimized are observed. A wet near-field scanning optical microscope (wet-NSOM) is operated for a sample within water by using such a stable zone.

Laser fabrication of gold nanoparticle clustered tips for use in apertureless near-field scanning optical microscopy.

A laser fabrication method was developed to make gold nanoparticle clustered (GNC) tips for apertureless near-field scanning optical microscopes (ANSOMs) and tip-enhanced Raman spectroscopy (TERS). The near-field Rayleigh and Raman scattering of samples are highly enhanced when a gold nanoparticle cluster is synthesized on the end of the tip. This is due to the lightning rod effect in the sharp tips. The localized electromagnetic field enhancement and the spatial resolution (~30 nm) of the fabricated GNC tip were verified by TERS and ANSOM measurements of carbon nanotubes.

Dynamical control of nanoscale light-matter interactions in low-dimensional quantum materials.

Tip-enhanced nano-spectroscopy and -imaging have significantly advanced our understanding of low-dimensional quantum materials and their interactions with light, providing a rich insight into the underlying physics at their natural length scale. Recently, various functionalities of the plasmonic tip expand the capabilities of the nanoscopy, enabling dynamic manipulation of light-matter interactions at the nanoscale. In this review, we focus on a new paradigm of the nanoscopy, shifting from the conventional role of imaging and spectroscopy to the dynamical control approach of the tip-induced light-matter interactions. We present three different approaches of tip-induced control of light-matter interactions, such as cavity-gap control, pressure control, and near-field polarization control. Specifically, we discuss the nanoscale modifications of radiative emissions for various emitters from weak to strong coupling regime, achieved by the precise engineering of the cavity-gap. Furthermore, we introduce recent works on light-matter interactions controlled by tip-pressure and near-field polarization, especially tunability of the bandgap, crystal structure, photoluminescence quantum yield, exciton density, and energy transfer in a wide range of quantum materials. We envision that this comprehensive review not only contributes to a deeper understanding of the physics of nanoscale light-matter interactions but also offers a valuable resource to nanophotonics, plasmonics, and materials science for future technological advancements.

Quantum tunneling high-speed nano-excitonic modulator.

High-speed electrical control of nano-optoelectronic properties in two-dimensional semiconductors is a building block for the development of excitonic devices, allowing the seamless integration of nano-electronics and -photonics. Here, we demonstrate a high-speed electrical modulation of nanoscale exciton behaviors in a MoS2 monolayer at room temperature through a quantum tunneling nanoplasmonic cavity. Electrical control of tunneling electrons between Au tip and MoS2 monolayer facilitates the dynamic switching of neutral exciton- and trion-dominant states at the nanoscale. Through tip-induced spectroscopic analysis, we locally characterize the modified recombination dynamics, resulting in a significant change in the photoluminescence quantum yield. Furthermore, by obtaining a time-resolved second-order correlation function, we demonstrate that this electrically-driven nanoscale exciton-trion interconversion achieves a modulation frequency of up to 8 MHz. Our approach provides a versatile platform for dynamically manipulating nano-optoelectronic properties in the form of transformable excitonic quasiparticles, including valley polarization, recombination, and transport dynamics.

Photoluminescence of MoS2 on Plasmonic Gold Nanoparticles Depending on the Aggregate Size.

Transition metal dichalcogenides (TMDs) are promising candidates for ultrathin functional semiconductor devices. In particular, incorporating plasmonic nanoparticles into TMD-based devices enhances the light-matter interaction for increased absorption efficiency and enables control of device performance such as electronic, electrical, and optical properties. In this heterohybrid structure, manipulating the number of TMD layers and the aggregate size of plasmonic nanoparticles is a straightforward approach to tailoring device performance. In this study, we use photoluminescence (PL) spectroscopy, which is a commonly employed technique for monitoring device performance, to analyze the changes in electronic and optical properties depending on the number of MoS2 layers and the size of the gold nanoparticle (AuNP) aggregate under nonresonant and resonant excitation conditions. The PL intensity in monolayer MoS2/AuNPs increases as the size of aggregates increases irrespective of the excitation conditions. The strain induced by AuNPs causes a red shift, but as the aggregates grow larger, the effect of p-doping increases and the blue shift becomes prominent. In multilayer MoS2/AuNPs, quenched PL intensity is observed under nonresonant excitation, while enhancement is noted under resonant excitation, which is mainly contributed by p-doping and LSPR, respectively. Remarkably, the alteration in the spectral shape due to resonant excitation is evident solely in small aggregates of AuNPs across all layers.

Time-resolved ultraviolet near-field scanning optical microscope for characterizing photoluminescence lifetime of light-emitting devices.

We developed a instrument consisting of an ultraviolet (UV) near-field scanning optical microscope (NSOM) combined with time-correlated single photon counting, which allows efficient observation of temporal dynamics of near-field photoluminescence (PL) down to the sub-wavelength scale. The developed time-resolved UV NSOM system showed a spatial resolution of 110 nm and a temporal resolution of 130 ps in the optical signal. The proposed microscope system was successfully demonstrated by characterizing the near-field PL lifetime of InGaN/GaN multiple quantum wells.

Direct 3D-printed CdSe quantum dots via scanning micropipette.

The micropipette, pencil-shaped with an aperture diameter of a few micrometers, is a potentially promising tool for the three-dimensional (3D) printing of individual microstructures based on its capability to deliver low volumes of nanomaterial solution on a desired spot resulting in micro/nanoscale patterning. Here, we demonstrate a direct 3D printing technique in which a micropipette with a cadmium selenide (CdSe) quantum dot (QD) solution is guided by an atomic force microscope with no electric field and no piezo-pumping schemes. We define the printed CdSe QD wires, which are a composite material with a QD-liquid coexistence phase, by using photoluminescence and Raman spectroscopy to analyze their intrinsic properties and additionally demonstrate a means of directional falling.

Tunable interlayer excitons and switchable interlayer trions via dynamic near-field cavity.

Emerging photo-induced excitonic processes in transition metal dichalcogenide (TMD) heterobilayers, e.g., interplay of intra- and inter-layer excitons and conversion of excitons to trions, allow new opportunities for ultrathin hybrid photonic devices. However, with the associated large degree of spatial heterogeneity, understanding and controlling their complex competing interactions in TMD heterobilayers at the nanoscale remains a challenge. Here, we present an all-round dynamic control of interlayer-excitons and -trions in a WSe2/Mo0.5 W0.5 Se2 heterobilayer using multifunctional tip-enhanced photoluminescence (TEPL) spectroscopy with <20 nm spatial resolution. Specifically, we demonstrate the bandgap tunable interlayer excitons and the dynamic interconversion between interlayer-trions and -excitons, through the combinational tip-induced engineering of GPa-scale pressure and plasmonic hot electron injection, with simultaneous spectroscopic TEPL measurements. This unique nano-opto-electro-mechanical control approach provides new strategies for developing versatile nano-excitonic/trionic devices using TMD heterobilayers.

Nanocavity-Integrated van der Waals Heterobilayers for Nano-excitonic Transistor.

Optical computing with optical transistors has emerged as a possible solution to the exponentially growing computational workloads, yet an on-chip nano-optical modulation remains a challenge due to the intrinsically noninteracting nature of photons in addition to the diffraction limit. Here, we present an all-optical approach toward nano-excitonic transistors using an atomically thin WSe2/Mo0.5W0.5Se2 heterobilayer inside a plasmonic tip-based nanocavity. Through optical wavefront shaping, we selectively modulate tip-enhanced photoluminescence (TEPL) responses of intra- and interlayer excitons in a ∼25 nm2 area, demonstrating the enabling concept of an ultrathin 2-bit nano-excitonic transistor. We suggest a simple theoretical model describing the underlying adaptive TEPL modulation mechanism, which relies on the additional spatial degree of freedom provided by the presence of the plasmonic tip. Furthermore, we experimentally demonstrate a concept of a 2-trit nano-excitonic transistor, which can provide a technical basis for processing the massive amounts of data generated by emerging artificial intelligence technologies.

Recent progress of exciton transport in two-dimensional semiconductors.

Spatial manipulation of excitonic quasiparticles, such as neutral excitons, charged excitons, and interlayer excitons, in two-dimensional semiconductors offers unique capabilities for a broad range of optoelectronic applications, encompassing photovoltaics, exciton-integrated circuits, and quantum light-emitting systems. Nonetheless, their practical implementation is significantly restricted by the absence of electrical controllability for neutral excitons, short lifetime of charged excitons, and low exciton funneling efficiency at room temperature, which remain a challenge in exciton transport. In this comprehensive review, we present the latest advancements in controlling exciton currents by harnessing the advanced techniques and the unique properties of various excitonic quasiparticles. We primarily focus on four distinct control parameters inducing the exciton current: electric fields, strain gradients, surface plasmon polaritons, and photonic cavities. For each approach, the underlying principles are introduced in conjunction with its progression through recent studies, gradually expanding their accessibility, efficiency, and functionality. Finally, we outline the prevailing challenges to fully harness the potential of excitonic quasiparticles and implement practical exciton-based optoelectronic devices.

All-optical control of high-purity trions in nanoscale waveguide.

The generation of high-purity localized trions, dynamic exciton-trion interconversion, and their spatial modulation in two-dimensional (2D) semiconductors are building blocks for the realization of trion-based optoelectronic devices. Here, we present a method for the all-optical control of the exciton-to-trion conversion process and its spatial distributions in a MoS2 monolayer. We induce a nanoscale strain gradient in a 2D crystal transferred on a lateral metal-insulator-metal (MIM) waveguide and exploit propagating surface plasmon polaritons (SPPs) to localize hot electrons. These significantly increase the electrons and efficiently funnel excitons in the lateral MIM waveguide, facilitating complete exciton-to-trion conversion even at ambient conditions. Additionally, we modulate the SPP mode using adaptive wavefront shaping, enabling all-optical control of the exciton-to-trion conversion rate and trion distribution in a reversible manner. Our work provides a platform for harnessing excitonic quasiparticles efficiently in the form of trions at ambient conditions, enabling high-efficiency photoconversion.