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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 (2D) protein sheets using orthogonal bioconjugation reactions, organizing quantum dots (QDs), gold nanoparticles (AuNPs), and upconverting nanoparticles 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 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 short 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.

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.

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.

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.

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.

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.

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.

Multiphoton imaging techniques that convert low-energy excitation to higher energy emission are widely used to improve signal over background, reduce scatter, and limit photodamage. Lanthanide-doped upconverting nanoparticles (UCNPs) are among the most efficient multiphoton probes, but even UCNPs with optimized lanthanide dopant levels require laser intensities that may be problematic. Here, we develop protein-sized, alloyed UCNPs (aUCNPs) that can be imaged individually at laser intensities >300-fold lower than needed for comparably sized doped UCNPs. Using single UCNP characterization and kinetic modeling, we find that addition of inert shells changes optimal lanthanide content from Yb3+, Er3+-doped NaYF4 nanocrystals to fully alloyed compositions. At high levels, emitter Er3+ ions can adopt a second role to enhance aUCNP absorption cross-section by desaturating sensitizer Yb3+ or by absorbing photons directly. Core/shell aUCNPs 12 nm in total diameter can be imaged through deep tissue in live mice using a laser intensity of 0.1 W cm-2.

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.

One of the major challenges to the widespread adoption of plasmonic and nano-optical devices in real-life applications is the difficulty to mass-fabricate nano-optical antennas in parallel and reproducible fashion, and the capability to precisely place nanoantennas into devices with nanometer-scale precision. In this study, we present a solution to this challenge using the state-of-the-art ultraviolet nanoimprint lithography (UV-NIL) to fabricate functional optical transformers onto the core of an optical fiber in a single step, mimicking the 'campanile' near-field probes. Imprinted probes were fabricated using a custom-built imprinter tool with co-axial alignment capability with sub

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.

Using two-photon tomography, carrier lifetimes are mapped in polycrystalline CdTe photovoltaic devices. These 3D maps probe subsurface carrier dynamics that are inaccessible with traditional optical techniques. They reveal that CdCl2 treatment of CdTe solar cells suppresses nonradiative recombination and enhances carrier lifetimes throughout the film with substantial improvements particularly near subsurface grain boundaries and the critical buried p-n junction.

2D transition metal dichalcogenides (TMDs) are commonly grown by chemical vapor deposition using transition metal oxides as solid precursors. Despite the widespread use of this technique, challenges in reproducibility, coverage, and material quality are pervasive, suggestive of unknown and uncontrolled process parameters. In this communication, we demonstrate the impact of water vapor on this growth process. Our results show a direct correlation between gas phase water content and the morphology of TMD films. In particular, we show that the presence of water enhances volatilization, and therefore the vapor transport of tungsten and molybdenum oxide. Surprisingly, we find that water not only plays an important role in volatilization but is also compatible with TMD growth. In fact, carefully controlled humidity can consistently produce high quality, luminescent materials.

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.

The rise of two-dimensional (2D) materials research took place following the isolation of graphene in 2004. These new 2D materials include transition metal dichalcogenides, mono-elemental 2D sheets, and several carbide- and nitride-based materials. The number of publications related to these emerging materials has been drastically increasing over the last five years. Thus, through this comprehensive review, we aim to discuss the most recent groundbreaking discoveries as well as emerging opportunities and remaining challenges. This review starts out by delving into the improved methods of producing these new 2D materials via controlled exfoliation, metal organic chemical vapor deposition, and wet chemical means. We look into recent studies of doping as well as the optical properties of 2D materials and their heterostructures. Recent advances towards applications of these materials in 2D electronics are also reviewed, and include the tunnel MOSFET and ways to reduce the contact resistance for fabricating high-quality devices. Finally, several unique and innovative applications recently explored are discussed as well as perspectives of this exciting and fast moving field.

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.

Localized states in two-dimensional (2D) transition metal dichalcogenides (TMDCs) have been the subject of intense study, driven by potential applications in quantum information science. Despite the rapidly growing knowledge surrounding these emitters, their microscopic nature is still not fully understood, limiting their production and application. Motivated by this challenge, and by recent theoretical and experimental evidence showing that nanowrinkles generate strain-localized room-temperature emitters, we demonstrate a method to intentionally induce wrinkles with collections of stressors, showing that long-range wrinkle direction and position are controllable with patterned array design. Nano-photoluminescence (nano-PL) imaging combined with detailed strain modeling based on measured wrinkle topography establishes a correlation between wrinkle properties, particularly shear strain, and localized exciton emission. Beyond the array-induced wrinkles, nano-PL spatial maps further reveal that the strain environment around individual stressors is heterogeneous due to the presence of fine wrinkles that are less deterministic. At cryogenic temperatures, antibunched emission is observed, confirming that the nanocone-induced strain is sufficiently large for the formation of quantum emitters. At 300 K, detailed nanoscale hyperspectral images uncover a wide range of low-energy emission peaks originating from the fine wrinkles, and show that the states can be tightly confined to regions <10 nm, even in ambient conditions. These results establish a promising potential route towards realizing room temperature quantum emission in 2D TMDC systems. Here, the authors report on the fabrication of strained wrinkles in monolayer WSe2 by placing the material on Au nanoconical substrates. They investigate the correlation between topographical stress factors and localised, quantum-dot-like photoluminescence emission. [ABSTRACT FROM AUTHOR]

The article focuses on a quantum dot–like single-photon sources in transition metal dichalcogenides (TMDs) exhibit appealing quantum optical properties but lack a well-defined atomic structure. It mentions that electrically stimulated photon emission from individual atomic defects in monolayer WS2 and correlate the emission with the local atomic and electronic structure. It also mentions the applied tip-sample voltage determines the transition energy.

The interactions between two π-conjugated oligomers templated in molecular scaffolds are revealed as a function of separation and orientation, providing models of intermolecular interactions in bulk organic semiconductor materials. For a variety of dimer geometries (acyclic and macrocyclic) of the same model oligomer, no change in fluorescence spectra, fluorescence dynamics, or low-temperature single-molecule emission characteristics is observed. A small red-shift and slowing of fluorescence in the most closely spaced macrocyclic dimer structure is thought to arise both due to an intramolecular solvatochromic shift as well as from weak intramolecular aggregate formation. No corresponding effect is observed in bulk films of the acyclic model oligomer, implying the absence of intermolecular aggregate or excimer formation due to random relative dipole orientations. The largest effect of intramolecular geometry of the model dimer structures is seen in transient fluorescence depolarization, where an open ring geometry leads to rapid depolarization, compared to the corresponding macrocycle, due to the presence of a range of molecular transition dipole moment orientations. Self-assembled monolayers of the molecules on HOPG investigated by scanning-tunneling microscopy further illustrate the conformational variability of the open dimers in contrast to the fixed conformation of the closed dimers.