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When plasmonic excitations of metallic interfaces and nanostructures interact with electronic excitations in semiconductors, new states emerge that hybridize the characteristics of the uncoupled states. The engendered properties make these hybrid states appealing for a broad range of applications, ranging from photovoltaic devices to integrated circuitry for quantum devices. Here, through quantum modeling, the coupling of surface plasmon polaritons and mobile two-dimensional excitons such as those in atomically thin semiconductors is examined with emphasis on the case of strong coupling. Our model shows that at around the energy crossing of the dispersion relationships of the uncoupled species, they strongly interact and polariton states—propagating plexcitons—emerge. The temporal evolution of the system where surface plasmon polaritons are continuously injected into the system is simulated to gain initial insight on potential experimental realizations of these states. The results show a steady state that is dominated by the lower-energy polariton. The study theoretically further establishes the possible existence of propagating plexcitons in atomically thin semiconductors and provides important guidance for the experimental detection and characterization of such states for a wide range of optoelectronic technologies.

Light matter interactions are greatly enhanced in two-dimensional (2D) semiconductors because of strong excitonic effects. Many optoelectronic applications would benefit from creating stacks of atomically thin 2D semiconductors separated by insulating barrier layers, forming multiquantum-well structures. However, most 2D transition metal chalcogenide systems require serial stacking to create van der Waals multilayers. Hybrid metal organic chalcogenolates (MOChas) are self-assembling hybrid materials that combine multiquantum-well properties with scalable chemical synthesis and air stability. In this work, we use spatially resolved linear and nonlinear optical spectroscopies over a range of temperatures to study the strongly excitonic optical properties of mithrene, that is, silver benzeneselenolate, and its synthetic isostructures. We experimentally probe s-type bright excitons and p-type excitonic dark states formed in the quantum confined 2D inorganic monolayers of silver selenide with exciton binding energy up to ∼0.4 eV, matching recent theoretical predictions of the material class. We further show that mithrene's highly efficient blue photoluminescence, ultrafast exciton radiative dynamics, as well as flexible tunability of molecular structure and optical properties demonstrate great potential of MOChas for constructing optoelectronic and quantum excitonic devices.

The equilibrium and non-equilibrium optical properties of single-layer transition metal dichalcogenides (TMDs) are determined by strongly bound excitons. Exciton relaxation dynamics in TMDs have been extensively studied by time-domain optical spectroscopies. However, the formation dynamics of excitons following non-resonant photoexcitation of free electron-hole pairs have been challenging to directly probe because of their inherently fast timescales. Here, we use extremely short optical pulses to non-resonantly excite an electron-hole plasma and show the formation of two-dimensional excitons in single-layer MoS2 on the timescale of 30 fs via the induced changes to photo-absorption. These formation dynamics are significantly faster than in conventional 2D quantum wells and are attributed to the intense Coulombic interactions present in 2D TMDs. A theoretical model of a coherent polarization that dephases and relaxes to an incoherent exciton population reproduces the experimental dynamics on the sub-100-fs timescale and sheds light into the underlying mechanism of how the lowest-energy excitons, which are the most important for optoelectronic applications, form from higher-energy excitations. Importantly, a phonon-mediated exciton cascade from higher energy states to the ground excitonic state is found to be the rate-limiting process. These results set an ultimate timescale of the exciton formation in TMDs and elucidate the exceptionally fast physical mechanism behind this process., The formation dynamics of excitons in 2D transition metal dichalcogenides are challenging to probe directly because of their inherently fast timescales. Here, the authors use extremely short optical pulses to excite an electron-hole plasma, and show the formation of 2D excitons in MoS2 on the timescale of 30 fs.

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.

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 information

A contactless charge-injection scheme that allows the local and quasi-permanent manipulation of atomically thin 2D materials, such as monolayer (1L-)MoS2, over spatial extents of several tens of micrometers, is reported. The possibility to precisely position and localize the charge-injection source to the micrometer scale post-fabrication allows the investigation of local unperturbed electronic structure of the 2D material. Thanks to this novel approach, the important impact of sample inhomogeneity on the charge-carrier percolation that occurs over the entire extent of the 2D flake and proliferates up to 40 μm away from the localized charge injection is elucidated. The apparent driving force for carrier relocation is the initial inhomogeneous electronic landscape of the 2D material. These studies demonstrate that local and contactless charge injection with submicrometer precision delivers an alternative route for charge injection and indicates that local 2D material electronic structure can serve as a key element for novel nanoscale device design.

Controlled patterning of nanoparticles on bioassemblies enables synthesis of complex materials for applications in optics, nanoelectronics, and sensing. Biomolecular self-assembly offers molecular control for engineering patterned nanomaterials, but current approaches have been limited in their ability to combine high nanoparticle coverage with generality that enables incorporation of multiple nanoparticle types. Here, we synthesize photonic materials on crystalline two-dimensional protein sheets using orthogonal bioconjugation reactions, organizing quantum dots (QDs), gold nanoparticles (AuNPs), and upconverting nanoparticles (UCNPs) along the surface-layer (S-layer) protein SbsB from the extremophile Geobacillus stearothermophilus. We use electron and optical microscopy to show that isopeptide bond-forming SpyCatcher and SnoopCatcher systems enable the simultaneous and controlled conjugation of multiple types of nanoparticles (NPs) at high densities along the SbsB sheets. These NP conjugation reactions are orthogonal to each other and to Au-thiol bond formation, allowing tailorable nanoparticle combinations at sufficient labeling efficiencies (up to 30%) to permit optical interactions between nanoparticles. Fluorescence lifetime imaging of SbsB sheets conjugated to QDs and AuNPs at distinct attachment sites shows spatially heterogeneous QD emission, with shorter radiative decays and brighter fluorescence arising from plasmonic enhancement at close interparticle distances. This specific, stable, and efficient conjugation of NPs to 2D protein sheets enables the exploration of interactions between pairs of nanoparticles at defined distances for the engineering of protein-based photonic nanomaterials.

Transition metal dichalcogenide semiconductors are ultrathin thin semiconductors that host a rich suite of photophysical phenomena. Excitons govern light-matter interactions in these 2D semiconductors and are fundamental packets of energy that can be manipulated with external stimuli and nanofabricated environments for next-generation technologies. Using nano-optical spectroscopy techniques to access excitonic physics at extreme length scales, a striking diversity of excitonic phenomena has been identified in these 2D materials, including heterogeneity due to edge states and charge puddles. Our latest findings highlight how strain localizes excitons on length scales that are commensurate with their size due to wrinkling phenomena that are unique to 2D materials. These results demonstrate the potential of monolayer semiconductors to be utilized for nanoscale optoelectronic devices with unique functionalities derived from excitonic physics.

The nature of the interface in lateral heterostructures of 2D monolayer semiconductors including its composition, size, and heterogeneity critically impacts the functionalities it engenders on the 2D system for next-generation optoelectronics. Here, we use tip-enhanced Raman scattering (TERS) to characterize the interface in a single-layer MoS2/WS2 lateral heterostructure with a spatial resolution of 50 nm. Resonant and non-resonant TERS spectroscopies reveal that the interface is alloyed with a size that varies over an order of magnitude-from 50-600 nm-within a single crystallite. Nanoscale imaging of the continuous interfacial evolution of the resonant and non-resonant Raman spectra enables the deconvolution of defect-activation, resonant enhancement, and material composition for several vibrational modes in single-layer MoS2, MoxW1-xS2, and WS2. The results demonstrate the capabilities of nanoscale TERS spectroscopy to elucidate macroscopic structure-property relationships in 2D materials and to characterize lateral interfaces of 2D systems on length scales that are imperative for devices., Comment: 47 pages, 7 main figures, 7 SI Figures, submitted

Two-dimensional (2D) excitons arise from electron–hole confinement along one spatial dimension. Such excitations are often described in terms of Frenkel or Wannier limits according to the degree of exciton spatial localization and the surrounding dielectric environment. In hybrid material systems, such as the 2D perovskites, the complex underlying interactions lead to excitons of an intermediate nature, whose description lies somewhere between the two limits, and a better physical description is needed. Here, we explore the photophysics of a tuneable materials platform where covalently bonded metal-chalcogenide layers are spaced by organic ligands that provide confinement barriers for charge carriers in the inorganic layer. We consider self-assembled, layered bulk silver benzeneselenolate, [AgSePh]∞, and use a combination of transient absorption spectroscopy and ab initio GW plus Bethe–Salpeter equation calculations. We demonstrate that in this non-polar dielectric environment, strongly anisotropic excitons dominate the optical transitions of [AgSePh]∞. We find that the transient absorption measurements at room temperature can be understood in terms of low-lying excitons confined to the AgSe planes with in-plane anisotropy, featuring anisotropic absorption and emission. Finally, we present a pathway to control the exciton behaviour by changing the chalcogen in the material lattice. Our studies unveil unexpected excitonic anisotropies in an unexplored class of tuneable, yet air-stable, hybrid quantum wells, offering design principles for the engineering of an ordered, yet complex dielectric environment and its effect on the excitonic phenomena in such emerging materials.

Electron-stimulated photon emission from individual point defects in monolayer WS2 could be visualized with atomic resolution., 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.

We report a new localized and electrodeless charge injection scheme that quasi-permanently modifies monolayer (1L-)MoS2 doping levels to extents competing with electrostatic gating. The key innovation is to use Sn-doped In2O3 (ITO) nanocrystals (NCs) as contactless light-driven charge injection sources triggered solely by light. Each nanocrystal can store and transfer multiple charges after ultraviolet illumination within the diffraction limited laser spot. This results in reductions in carrier density in the underlying 1L-MoS2 up to 1×1013 cm-2 and is observed throughout the extent of the 2D material flake. The long-distance charge separation proliferates up to 40 µm away from the localized charge injection and persists over months. The apparent driving force for carrier relocation is the initial inhomogeneous electronic landscape of the 2D material. These studies demonstrate a novel all-optically controlled tool to locally inject carriers with sub-micrometer precision. This new ability allows us to extract important aspects of inhomogeneity in 2D materials undisturbed by bulky electronic contacts and indicates that local 2D material manipulation can serve as a key element for novel nanoscale device design.

When layers of van der Waals materials are deposited via exfoliation or viscoelastic stamping, nanobubbles are sometimes created from aggregated trapped fluids. Though they can be considered a nuisance, nanobubbles have attracted scientific interest in their own right owing to their ability to generate large in-plane strain gradients that lead to rich optoelectronic phenomena, especially in the semiconducting transition metal dichalcogenides. Determination of the strain within the nanobubbles, which is crucial to understanding these effects, can be approximated using elasticity theory. However, the Foppl–von Karman equations that describe strain in a distorted thin plate are highly nonlinear and often necessitate assuming circular symmetry to achieve an analytical solution. Here, we present an easily implemented numerical method to solve for strain tensors of nanobubbles with arbitrary symmetry in 2D crystals. The method only requires topographic information from atomic force microscopy and the Poisson ratio of the 2D material. We verify that this method reproduces the strain for circularly symmetric nanobubbles that have known analytical solutions. Finally, we use the method to reproduce the Gruneisen parameter of the E′ mode for 1L-WS2 nanobubbles on template-stripped Au by comparing the derived strain with measured Raman shifts from tip-enhanced Raman spectroscopy, demonstrating the utility of our method for estimating localized strain in 2D crystals.

In monolayer transition metal dichalcogenides, quantum emitters are associated with localized strain that can be deterministically applied to create designer nano-arrays of single photon sources. Despite an overwhelming empirical correlation with local strain, the nanoscale interplay between strain, excitons, defects and local crystalline structure that gives rise to these quantum emitters is poorly understood. Here, we combine room-temperature nano-optical imaging and spectroscopy of excitons in nanobubbles of localized strain in monolayer WSe2 with atomistic structural models to elucidate how strain induces nanoscale confinement potentials that give rise to highly localized exciton states in 2D semiconductors. Nano-optical imaging of nanobubbles in low-defect monolayers reveal localized excitons on length scales of approximately 10 nm at multiple sites along the periphery of individual nanobubbles, which is in stark contrast to predictions of continuum models of strain. These results agree with theoretical confinement potentials that are atomistically derived from measured topographies of existing nanobubbles. Our results provide one-of-a-kind experimental and theoretical insight of how strain-induced confinement - without crystalline defects - can efficiently localize excitons on length scales commensurate with exciton size, providing key nanoscale structure-property information for quantum emitter phenomena in monolayer WSe2., 18 pages, 4 figures

Ternary structure is an important design strategy to obtain high-efficiency non-fullerene organic photovoltaics (OPVs). However, the role of the third component to the standard binary system is still unclear. Here, a wide-bandgap small-molecule acceptor, denoted IDT-T, is synthesized and used together with a wide-bandgap donor polymer, PBDB-T, and a low-bandgap acceptor, ITIC, for fullerene-free ternary solar cells. The ternary cell features an enhanced power conversion efficiency (PCE) up to 12.2%, together with improved photocurrent density, open-circuit voltage (VOC), and fill factor. Studies of the thin films indicate that IDT-T functions as an energy-level mediator, a fluorescence resonance energy-transfer donor, an electron acceptor, and a crystallization modulator in the blend, which contribute synergistically in the ternary blend to deliver a higher VOC, more efficient exciton generation, suppressed bimolecular charge recombination and enhanced charge transport, and an overall high photovoltaic performance. Very recently, non-fullerene acceptors (NFAs) based on low-bandgap small molecules have emerged as a new class of acceptors that rival the dominance of fullerene-based acceptors. Such discovery also stimulates promising device architectures such as ternary solar cells, with a handful that have achieved high power conversion efficiencies above 12%. The primary effort, however, has been focusing on low-bandgap NFAs that exploit complementary absorption and energy-level cascade. Herein we report a rare example of a wide-bandgap NFA that leads to high-performance ternary solar cells without relying on full absorption complementarity of all three components. Detailed studies revealed the multiple roles of this acceptor in blend films, which contribute synergistically to improved device characteristics. This work may inspire new design principles of potent wide-bandgap NFAs, which will open the door to high-efficiency organic photovoltaic devices through new opportunities such as multi-component solar cells. The marriage of non-fullerene acceptors (NFAs) and ternary solar cell architecture has brought about great advances in organic photovoltaics. The primary effort, however, has been focusing on low-bandgap NFAs that exploit complementary absorption and energy-level cascade. Here we report a wide-bandgap NFA IDT-T that functions as an energy-level mediator, a fluorescence resonance energy-transfer donor, an electron acceptor, and a crystallization modulator, which contribute synergistically in a ternary blend to yield high organic photovoltaic device performance.

Evaluating and tuning the properties of two-dimensional (2D) materials is a major focus of advancing 2D science and technology. While many claim that the photonic properties of a 2D layer provide evidence that the material is “high quality”, this may not be true for electronic performance. In this work, we deconvolute the photonic and electronic response of synthetic monolayer molybdenum disulfide. We demonstrate that enhanced photoluminescence can be robustly engineered via the proper choice of substrate, where growth of MoS2 on r-plane sapphire can yield >100x enhancement in PL and carrier lifetime due to increased molybdenum-oxygen bonding compared to that of traditionally grown MoS2 on c-plane sapphire. These dramatic enhancements in optical properties are similar to those of super-acid treated MoS2, and suggest that the electronic properties of the MoS2 are also superior. However, a direct comparison of the charge transport properties indicates that the enhanced PL due to increased Mo-O bonding leads to p-type compensation doping, and is accompanied by a 2x degradation in transport properties compared to MoS2 grown on c-plane sapphire. This work provides a foundation for understanding the link between photonic and electronic performance of 2D semiconducting layers, and demonstrates that they are not always correlated.

Broadband optoelectronics such as artificial light harvesting technologies necessitate efficient and, ideally, tunable coupling of excited states over a wide range of energies. In monolayer MoS2, a prototypical two-dimensional layered semiconductor, the excited state manifold spans the visible electromagnetic spectrum and is comprised of an interconnected network of excitonic and free-carrier excitations. Here, photoluminescence excitation spectroscopy is used to reveal the energetic and spatial dependence of broadband excited state coupling to the ground-state luminescent excitons of monolayer MoS2. Photoexcitation of the direct band gap excitons is found to strengthen with increasing energy, demonstrating that interexcitonic coupling across the Brillouin zone is more efficient than previously reported, and thus bolstering the import and appeal of these materials for broadband optoelectronic applications. Narrow excitation resonances that are superimposed on the broadband photoexcitation spectrum are ide...

In monolayer transition-metal dichalcogenides, localized strain can be used to design nanoarrays of single photon sources. Despite strong empirical correlation, the nanoscale interplay between excitons and local crystalline structure that gives rise to these quantum emitters is poorly understood. Here, we combine room-temperature nano-optical imaging and spectroscopic analysis of excitons in nanobubbles of monolayer WSe

Here we exploit transient reflectivity with sub-20fs temporal resolution to extract the exciton formation timescale from the build up of A/B exciton dynamics of 1L-MoS2. The timescale for this process ranges from ~15fs to ~35fs. © 2020 The Author(s)

We report the first demonstration of light-driven permanent charge separation across an ultrathin solid-state zero-dimensional (0D)/2D hybrid interface by coupling photoactive Sn-doped In2O3 nanocr...

Control of impurity concentrations in semiconducting materials is essential to device technology. Because of their intrinsic confinement, the properties of two-dimensional semiconductors such as transition metal dichalcogenides (TMDs) are more sensitive to defects than traditional bulk materials. The technological adoption of TMDs is dependent on the mitigation of deleterious defects and guided incorporation of functional foreign atoms. The first step toward impurity control is the identification of defects and assessment of their electronic properties. Here, we present a comprehensive study of point defects in monolayer tungsten disulfide (WS

Two-dimensional materials with engineered composition and structure will provide designer materials beyond conventional semiconductors. However, the potentials of defect engineering remain largely untapped, because it hinges on a precise understanding of electronic structure and excitonic properties, which are not yet predictable by theory alone. Here, we utilize correlative, nanoscale photoemission spectroscopy to visualize how local introduction of defects modifies electronic and excitonic properties of two-dimensional materials at the nanoscale. As a model system, we study chemical vapor deposition grown monolayer WS2, a prototypical, direct gap, two-dimensional semiconductor. By cross-correlating nanoscale angle-resolved photoemission spectroscopy, core level spectroscopy, and photoluminescence, we unravel how local variations in defect density influence electronic structure, lateral band alignment, and excitonic phenomena in synthetic WS2 monolayers.

Two-dimensional materials with engineered composition and structure will provide designer materials beyond conventional semiconductors. However, the potentials of defect engineering remain largely untapped, because it hinges on a precise understanding of electronic structure and excitonic properties, which are not yet predictable by theory alone. Here, we utilize correlative, nanoscale photoemission spectroscopy to visualize how local introduction of defects modifies electronic and excitonic properties of two-dimensional materials at the nanoscale. As a model system, we study chemical vapor deposition grown monolayer WS

Plasmonic metasurfaces have spawned the field of flat optics using nanostructured planar metallic or dielectric surfaces that can replace bulky optical elements and enhance the capabilities of traditional far-field optics. Furthermore, the potential of flat optics can go far beyond far-field modulation, and can be exploited for functionality in the near-field itself. Here, we design metasurfaces based on aperiodic arrays of plasmonic Au nanostructures for tailoring the optical near-field in the visible and near-infrared spectral range. The basic element of the arrays is a rhomboid that is modulated in size, orientation and position to achieve the desired functionality of the micron-size metasurface structure. Using two-photon-photoluminescence as a tool to probethe near-field profiles in the plane of the metasurfaces, we demonstrate the molding of light into different near-field intensity patterns and active pattern control via the far-field illumination. Finite element method simulations reveal that the near-field modulation occurs via a combination of the plasmonic resonances of the rhomboids and field enhancement in the nanoscale gaps in between the elements. This approach enables optical elements that can switch the near-field distribution across the metasurface via wavelength and polarization of the incident far-field light, and provides pathways for light matter interaction in integrated devices., Comment: 26 pages, 7 figures

Control of impurity concentrations in semiconducting materials is essential to device technology. Because of their intrinsic confinement, the properties of two-dimensional semiconductors such as transition metal dichalcogenides (TMDs) are more sensitive to defects than traditional bulk materials. The technological adoption of TMDs is dependent on the mitigation of deleterious defects and guided incorporation of functional foreign atoms. The first step toward impurity control is the identification of defects and assessment of their electronic properties. Here, we present a comprehensive study of point defects in monolayer tungsten disulfide (WS2) grown by chemical vapor deposition using scanning tunneling microscopy/spectroscopy, CO-tip noncontact atomic force microscopy, Kelvin probe force spectroscopy, density functional theory, and tight-binding calculations. We observe four different substitutional defects: chromium (CrW) and molybdenum (MoW) at a tungsten site, oxygen at sulfur sites in both top and bottom layers (OS top/bottom), and two negatively charged defects (CD type I and CD type II). Their electronic fingerprints unambiguously corroborate the defect assignment and reveal the presence or absence of in-gap defect states. CrW forms three deep unoccupied defect states, two of which arise from spin-orbit splitting. The formation of such localized trap states for CrW differs from the MoW case and can be explained by their different d shell energetics and local strain, which we directly measured. Utilizing a tight-binding model the electronic spectra of the isolectronic substitutions OS and CrW are mimicked in the limit of a zero hopping term and infinite on-site energy at a S and W site, respectively. The abundant CDs are negatively charged, which leads to a significant band bending around the defect and a local increase of the contact potential difference. In addition, CD-rich domains larger than 100 nm are observed, causing a work function increase of 1.1 V. While most defects are electronically isolated, we also observed hybrid states formed between CrW dimers. The important role of charge localization, spin-orbit coupling, and strain for the formation of deep defect states observed at substitutional defects in WS2 as reported here will guide future efforts of targeted defect engineering and doping of TMDs.

Individual luminescent nanoparticles enable thermometry with sub-diffraction limited spatial resolution, but potential self-heating effects from high single-particle excitation intensities remain largely uninvestigated because thermal models predict negligible self-heating. Here, we report that the common “ratiometric” thermometry signal of individual NaYF4:Yb3+,Er3+ nanoparticles unexpectedly increases with excitation intensity, implying a temperature rise over 50 K if interpreted as thermal. Luminescence lifetime thermometry, which we demonstrate for the first time using individual NaYF4:Yb3+,Er3+ nanoparticles, indicates a similar temperature rise. To resolve this apparent contradiction between model and experiment, we systematically vary the nanoparticle’s thermal environment: the substrate thermal conductivity, nanoparticle-substrate contact resistance, and nanoparticle size. The apparent self-heating remains unchanged, demonstrating that this effect is an artifact, not a real temperature rise. Using rate equation modeling, we show that this artifact results from increased radiative and non-radiative relaxation from higher-lying Er3+ energy levels. This study has important implications for single-particle thermometry., Nanoparticles are often used as nanothermometers by measuring their luminescence from upconverted energy under illumination. The authors uncover the artificial appearance of a temperature rise at high excitation intensities due to effects involving higher energy states.

We demonstrate far-field optical thermometry using individual NaYF4 nanoparticles doped with 2% Er(3+) and 20% Yb(3+). Isolated 20 × 20 × 40 nm(3) particles were identified using only far-field optical imaging, confirmed by subsequent scanning electron microscopy. The luminescence thermometry response for five such single particles was characterized for temperatures from 300 K to 400 K. A standard Arrhenius model widely used for larger particles can still be accurately applied to these sub-50 nm particles, with good particle-to-particle uniformity (response coefficients exhibited standard deviations below 5%). With its spatial resolution on the order of 50 nm when imaging a single particle, far below the diffraction limit, this technique has potential applications for both fundamental thermal measurements and nanoscale metrology in industrial applications.

Reduced-dimensionality materials for photonic and optoelectronic applications including energy conversion, solid-state lighting, sensing, and information technology are undergoing rapid development. The search for novel materials based on reduced-dimensionality is driven by new physics. Understanding and optimizing material properties requires characterization at the relevant length scale, which is often below the diffraction limit. Three important material systems are chosen for review here, all of which are under investigation at the Molecular Foundry, to illustrate the current state of the art in nanoscale optical characterization: 2D semiconducting transition metal dichalcogenides; 1D semiconducting nanowires; and energy-transfer in assemblies of 0D semiconducting nanocrystals. For each system, the key optical properties, the principal experimental techniques, and important recent results are discussed. Applications and new developments in near-field optical microscopy and spectroscopy, scanning probe microscopy, and cathodoluminescence in the electron microscope are given detailed attention. Work done at the Molecular Foundry is placed in context within the fields under review. A discussion of emerging opportunities and directions for the future closes the review.

Reducing the size of lasers to microscale dimensions enables new technologies1 that are specifically tailored for operation in confined spaces ranging from ultra-high-speed microprocessors2 to live brain tissue3. However, reduced cavity sizes increase optical losses and require greater input powers to reach lasing thresholds. Multiphoton-pumped lasers4-7 that have been miniaturized using nanomaterials such as lanthanide-doped upconverting nanoparticles (UCNPs)8 as lasing media require high pump intensities to achieve ultraviolet and visible emission and therefore operate under pulsed excitation schemes. Here, we make use of the recently described energy-looping excitation mechanism in Tm3+-doped UCNPs9 to achieve continuous-wave upconverted lasing action in stand-alone microcavities at excitation fluences as low as 14 kW cm-2. Continuous-wave lasing is uninterrupted, maximizing signal and enabling modulation of optical interactions10. By coupling energy-looping nanoparticles to whispering-gallery modes of polystyrene microspheres, we induce stable lasing for more than 5 h at blue and near-infrared wavelengths simultaneously. These microcavities are excited in the biologically transmissive second near-infrared (NIR-II) window and are small enough to be embedded in organisms, tissues or devices. The ability to produce continuous-wave lasing in microcavities immersed in blood serum highlights practical applications of these microscale lasers for sensing and illumination in complex biological environments.

Evaluating and tuning the properties of two-dimensional (2D) materials is a major focus of advancing 2D science and technology. While many claim that the photonic properties of a 2D layer provide evidence that the material is “high quality”, this may not be true for electronic performance. In this work, we deconvolute the photonic and electronic response of synthetic monolayer molybdenum disulfide. We demonstrate that enhanced photoluminescence can be robustly engineered via the proper choice of substrate, where growth of MoS2 on r-plane sapphire can yield >100x enhancement in PL and carrier lifetime due to increased molybdenum-oxygen bonding compared to that of traditionally grown MoS2 on c-plane sapphire. These dramatic enhancements in optical properties are similar to those of super-acid treated MoS2, and suggest that the electronic properties of the MoS2 are also superior. However, a direct comparison of the charge transport properties indicates that the enhanced PL due to increased Mo-O bonding leads to p-type compensation doping, and is accompanied by a 2x degradation in transport properties compared to MoS2 grown on c-plane sapphire. This work provides a foundation for understanding the link between photonic and electronic performance of 2D semiconducting layers, and demonstrates that they are not always correlated.

Optoelectronic excitations in monolayer ${\mathrm{MoS}}_{2}$ manifest from a hierarchy of electrically tunable, Coulombic free-carrier and excitonic many-body phenomena. Investigating the fundamental interactions underpinning these phenomena---critical to both many-body physics exploration and device applications---presents challenges, however, due to a complex balance of competing optoelectronic effects and interdependent properties. Here, optical detection of bound- and free-carrier photoexcitations is used to directly quantify carrier-induced changes of the quasiparticle band gap and exciton binding energies. The results explicitly disentangle the competing effects and highlight longstanding theoretical predictions of large carrier-induced band gap and exciton renormalization in two-dimensional semiconductors.

Optoelectronic excitations in monolayer MoS_{2} manifest from a hierarchy of electrically tunable, Coulombic free-carrier and excitonic many-body phenomena. Investigating the fundamental interactions underpinning these phenomena-critical to both many-body physics exploration and device applications-presents challenges, however, due to a complex balance of competing optoelectronic effects and interdependent properties. Here, optical detection of bound- and free-carrier photoexcitations is used to directly quantify carrier-induced changes of the quasiparticle band gap and exciton binding energies. The results explicitly disentangle the competing effects and highlight longstanding theoretical predictions of large carrier-induced band gap and exciton renormalization in two-dimensional semiconductors.

The reabsorption of photoluminescence within a medium, an effect known as the inner filter effect (IFE), has been well studied in solutions, but has garnered less attention in regards to solid-state nanocomposites. Photoluminescence from a quantum dot (QD) can selectively excite larger QDs around it resulting in a net red-shift in the reemitted photon. In CdSe/CdS core/shell QD-polymer nanocomposites, we observe a large spectral red-shift of over a third of the line width of the photoluminescence of the nanocomposites over a distance of 100 μm resulting from the IFE. Unlike fluorescent dyes, which do not show a large IFE red-shift, QDs have a component of inhomogeneous broadening that originates from their size distribution and quantum confinement. By controlling the photoluminescence broadening as well as the sample dispersion and concentration, we show that the magnitude of the IFE within the nanocomposite can be tuned. We further demonstrate that this shift can be exploited in order to spectroscopically monitor the vertical displacement of a nanocomposite in a fluorescence microscope. Large energetic shifts in the measured emission with displacement can be maximized, resulting in a displacement sensor with submicrometer resolution. We further show that the composite can be easily attached to biological samples and is able to measure deformations with high temporal and spatial precision.

Spatially resolved 3D carrier-lifetime maps were measured using 2P tomography to uncover carrier dynamics at buried structures in CdTe thin-films photovoltaics. When thin-film CdTe solar cells are initially deposited, we observe increased nonradiative carrier recombination at GBs throughout the 3D volume of the film, which is most pronounced in the critical junction region where small nucleation grains form at the buried CdTe/CdS interface. The data on CdTe films treated by exposure to CdCl2vapor reveal that a critical function of the treatment is to reduce surface, interface and GB recombination throughout the entirety of these polycrystalline films. The CdCl2treatment may also compensate CdTe films, making it difficult to exceed a hole density of 1015m-3and achieve higher current density and efficiency.

Artificial photosynthesis relies on the availability of semiconductors that are chemically stable and can efficiently capture solar energy. Although metal oxide semiconductors have been investigated for their promise to resist oxidative attack, materials in this class can suffer from chemical and photochemical instability. Here we present a methodology for evaluating corrosion mechanisms and apply it to bismuth vanadate, a state-of-the-art photoanode. Analysis of changing morphology and composition under solar water splitting conditions reveals chemical instabilities that are not predicted from thermodynamic considerations of stable solid oxide phases, as represented by the Pourbaix diagram for the system. Computational modelling indicates that photoexcited charge carriers accumulated at the surface destabilize the lattice, and that self-passivation by formation of a chemically stable surface phase is kinetically hindered. Although chemical stability of metal oxides cannot be assumed, insight into corrosion mechanisms aids development of protection strategies and discovery of semiconductors with improved stability., Metal oxide semiconductors are promising materials for solar energy capture but can suffer from stability problems. Here, the authors present a methodology for evaluating corrosion mechanisms and apply it to BiVO4, revealing chemical instabilities that are not predicted from thermodynamic considerations alone.

The optical properties of fractal silver films grown using the Tollens silver mirror reaction enable highly reproducible single molecule surface-enhanced Raman scattering (SERS). These characteristics are a result of the nanostructure morphology which supports strongly localized surface plasmon polariton excitations that dramatically enhance the incident electromagnetic field in nanoscale regions called hot spots. Besides SERS, the local field amplification enhances an array of other linear and nonlinear optical effects such as silver luminescence and second-harmonic and continuum generation. By varying film growth conditions, we establish that the intrinsic linear and nonlinear responses qualitatively correlate with film morphology in the same manner as reported for SERS. We probe the polarization anisotropy, polarization memory, power dependence, emission spectra, excitation wavelength and temperature dependence, blinking, spectral diffusion, and emission decay dynamics of both hot spot species. Strikin...

By enabling the probing of light–matter interactions at the functionally relevant length scales of most materials, near-field optical imaging and spectroscopy accesses information that is unobtainable with other methods. The advent of apertureless techniques, which exploit the ultralocalized and enhanced near-fields created by sharp metallic tips or plasmonic nanoparticles, has resulted in rapid adoption of near-field approaches for studying novel materials and phenomena, with spatial resolution approaching sub-molecular levels. However, these approaches are generally limited by the dominant out-of-plane polarization response of apertureless tips, restricting the exploration and discovery of many material properties. This has led to recent design and fabrication breakthroughs in near-field tips engineered specifically for enhancing in-plane interactions with near-field light components. This mini-review provides a perspective on recent progress and emerging directions aimed at utilizing and controlling in-plane optical polarization, highlighting key application spaces where in-plane near-field tip responses have enabled recent advancements in the understanding and development of new nanostructured materials and devices.

Temperature-dependent single-particle spectroscopy is used to study interfacial energy transfer in model light-harvesting CdSe/CdS core–shell tetrapod nanocrystals. Using alternating excitation energies, we identify two thermalized exciton states in single nanoparticles that are attributed to a strain-induced interfacial barrier. At cryogenic temperatures, emission from both states exemplifies the effects of intraparticle disorder and enables their simultaneous characterization, revealing that the two states are distinct in regards to emission polarization, spectral diffusion, and blinking.

Two-dimensional monolayer transition metal dichalcogenide semiconductors are ideal building blocks for atomically thin, flexible optoelectronic and catalytic devices. Although challenging for two-dimensional systems, sub-diffraction optical microscopy provides a nanoscale material understanding that is vital for optimizing their optoelectronic properties. Here we use the ‘Campanile' nano-optical probe to spectroscopically image exciton recombination within monolayer MoS2 with sub-wavelength resolution (60 nm), at the length scale relevant to many critical optoelectronic processes. Synthetic monolayer MoS2 is found to be composed of two distinct optoelectronic regions: an interior, locally ordered but mesoscopically heterogeneous two-dimensional quantum well and an unexpected ∼300-nm wide, energetically disordered edge region. Further, grain boundaries are imaged with sufficient resolution to quantify local exciton-quenching phenomena, and complimentary nano-Auger microscopy reveals that the optically defective grain boundary and edge regions are sulfur deficient. The nanoscale structure–property relationships established here are critical for the interpretation of edge- and boundary-related phenomena and the development of next-generation two-dimensional optoelectronic devices., Understanding the dynamics of light-induced carriers is vital for employing two-dimensional materials in optoelectronic applications. Here, the authors use a sub diffraction-limit optical technique to reveal the excitonic properties of monolayer molybdenum disulfide at the nanoscale.