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Many applications of ultrafast and nonlinear optical microscopy require the measurement of small differential signals over large fields-of-view. Widefield configurations drastically reduce the acquisition time; however, they suffer from the low frame rates of two-dimensional detectors, which limit the modulation frequency, making the measurement sensitive to excess laser noise. Here we introduce a self-referenced detection configuration for widefield differential imaging. Employing regions of the field of view with no differential signal as references, we cancel probe fluctuations and increase the signal-to-noise ratio by an order of magnitude reaching noise levels only a few percent above the shot noise limit. We anticipate broad applicability of our method to transient absorption, stimulated Raman scattering and photothermal-infrared microscopies.

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The demands of modern electronic components require advanced computing platforms for efficient information processing to realize in-memory operations with a high density of data storage capabilities toward developing alternatives to von Neumann architectures. Herein, we demonstrate the multifunctionality of monolayer MoS2 memtransistors, which can be used as a high-geared intrinsic transistor at room temperature; however, at a high temperature (>350 K), they exhibit synaptic multilevel memory operations. The temperature-dependent memory mechanism is governed by interfacial physics, which solely depends on the gate field modulated ion dynamics and charge transfer at the MoS2/dielectric interface. We have proposed a non-volatile memory application using a single Field Effect Transistor (FET) device where thermal energy can be ventured to aid the memory functions with multilevel (3-bit) storage capabilities. Furthermore, our devices exhibit linear and symmetry in conductance weight updates when subjected to electrical potentiation and depression. This feature has enabled us to attain a high classification accuracy while training and testing the Modified National Institute of Standards and Technology datasets through artificial neural network simulation. This work paves the way toward reliable data processing and storage using 2D semiconductors with high-packing density arrays for brain-inspired artificial learning.

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Two-dimensional heterostructures have recently gained broad interest due to potential applications in optoelectronic devices. Their reduced dimensionality leads to novel physical effects beyond conventional bulk electronics. However, the optical properties of the 2D lateral heterojunctions have not been completely characterized due to the limited spatial resolution, requiring nano-optical techniques beyond the diffraction limit. Here, we investigate lateral monolayer WS2-MoS2 heterostructures in a plasmonic Au-Au tip-substrate picocavity using subdiffraction limited tip-enhanced photoluminescence (TEPL) spectroscopy with sub-nanometer tip-sample distance control. We observed more than 3 orders of magnitude PL enhancement by placing a plasmonic Au-coated tip at the resonantly excited heterojunction. We developed a theoretical model of the quantum plasmonic 2D heterojunction, where tunneling of hot electrons between the Au tip and MoS2 leads to the quenching of the MoS2 PL, while simultaneously increasing the WS2 PL, in contrast to the non-resonant reverse transfer. Our simulations show good agreement with the experiments, revealing a range of parameters and enhancement factors corresponding to the switching between the classical and quantum regimes. The controllable photoresponse of the 2D heterojunction can be used in novel nanodevices.

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Hybrid organometallic halide perovskite-based semitransparent solar cell research has garnered significant attention recently due to their promising applications for smart windows, tandem devices, wearable electronics, displays, and sustainable internet-of-things. Though considerable progress has been made, stability, controlling the crystalline qualities, and growth orientation in perovskite thin films play crucial roles in improving the photovoltaic (PV) performance. Recently, strain modulation within the perovskite gathers an immense interest that is achieved by the ex situ process. However, little work is reported on in situ strain modulation, which is presented here. Apart from the challenges in the fabrication of high-efficiency perovskite solar cell (PSC) devices under ambient conditions, the stability of organic hole-transporting materials needs urgent attention. Herein, a single-step deposition of formamidiniumchloride (FACl)-mediated CH3NH3PbI3 (MAPbI3) thin films without an inert atmosphere and CuI as the inorganic hole-transporting material is demonstrated for their potential application toward semitransparent PSCs. The FACl amount in MAPbI3 (mg/mL) plays a critical role in controlling the crystallinity, growth orientations, and in situ strains, which modulate the charge carrier transport dynamics, thereby improving the efficiency of the PSC device. A photoconversion efficiency of 16.01% has been achieved from MAPbI3 with 20 mg/mL of FACl additive incorporation. The modification of the structural, electronic, and optical properties and the origin of strain in the as-synthesized MAPbI3 domains due to the addition of FACl are further validated with experimental findings in detail using density functional theory simulations.

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Two-dimensional transition metal dichalcogenides provide flexible platforms for nanophotonic engineering due to their exceptional mechanical and optoelectronic properties. For example, continuous band gap tunability has been achieved in 2D TMDs by elastic strain engineering. Localized elastic deformations in nanobubbles behave as "artificial atoms" with a spatially varying band gap resulting in funnelling of excitons and photocarriers. Here we present a new method of nanobubble fabrication in monolayer 2D lateral heterostructures using high temperature superacid treatment. We fabricated MoS2 and WS2 nanobubbles and performed near-field imaging with nanoscale resolution using tip-enhanced photoluminescence (TEPL) spectroscopy. TEPL nanoimaging revealed the coupling between MoS2 and WS2 nanobubbles with a large synergistic PL enhancement due to the plasmonic tip, hot electrons, and exciton funnelling. We investigated the contributions of different enhancement mechanisms, and developed a quantum plasmonic model, in good agreement with the experiments. Our work opens new avenues in exploration of novel nanophotonic coupling schemes.

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Two-dimensional (2D) materials such as graphene, transition metal dichalcogenides (TMDs), and their heterojunctions are prospective materials for future electronics, optoelectronics, and quantum technologies. Assembling different 2D layers offers unique ways to control optical, electrical, thermal, magnetic, and topological phenomena. Controlled fabrications of electronic grade 2D heterojunctions are of paramount importance. Here, we enlist novel and scalable strategies to fabricate 2D vertical and lateral heterojunctions, consisting of semiconductors, metals, and/or semimetals. Critical issues that need to be addressed are the device-to-device variations, reliability, stability, and performances of 2D heterostructures in electronic and optoelectronic applications. Also, stacking order-dependent formation of moiré excitons in 2D heterostructures are emerging with exotic physics and new opportunities. Furthermore, the realization of 2D heterojunction-based novel devices, including excitonic and valleytronic transistors, demands more extensive research efforts for real-world applications. We also outline emergent phenomena in 2D heterojunctions central to nanoelectronics, optoelectronics, spintronics, and energy applications.

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Two-dimensional (2D) semiconducting materials have promising applications in flexible optoelectronics, nanophotonics, and sensing based on the broad tunability of their optical and electronic properties. 2D nanobubbles form exciton funnels due to localized strain that can be used as local emitters for information processing. Their nanoscale optical characterization requires the use of near-field scanning probe microscopy (SPM). However, previous near-field studies of 2D materials were performed on SiO2/Si and metallic substrates using the plasmonic gap mode to increase the signal-to-noise ratio. Another challenge is the deterministic control of bubble size and location. We addressed these challenges by investigating the photoluminescence (PL) signals of freestanding monolayer lateral WSe2-MoSe2 heterostructures under the influence of strain exerted by a plasmonic SPM tip. For first time, we performed tip-enhanced PL imaging of freestanding 2D materials and studied the competition between the PL enhancement mechanisms by nanoindentation as a function of the tip-sample distance. We observed the tunability of PL as a function of bubble size, which opens new possibilities to design optoelectronic nanodevices.

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Due to their uniqueness in tunable photophysics, transition metal dichalcogenide (TMD) based quantum dots (QDs) have emerged as the next-generation quantum materials for technology-based semiconductor applications. This demands frontline research on the rational synthesis of the TMD QDs with controlled shape, size, nature of charge migration at the interface, and their easy integration in optoelectronic devices. In this article, with a controlled solution-processed synthesis of MoS2 and WS2 QDs, we demonstrate the disparity in their structural, optical, and electrical characteristics in bulk and confinement. With a series of steady-state and time-resolved spectroscopic measurements in different media, we explore the uncommon photophysics of MoS2 and WS2 QDs such as excitation-dependent photoluminescence and assess their excited state charge transfer kinetics with a redox-active biomolecule, menadione (MQ). In comparison to the homogeneous aqueous medium, photoinduced charge transfer between the QDs and MQ becomes more plausible in encapsulated cetyltrimethylammonium bromide (CTAB) micelles. Current sensing atomic force microscopy (CS-AFM) measurements at a single molecular level reveal that the facilitated charge transfer of QDs with MQ strongly correlates with an enhancement in their charge transport behavior. An increase in charge transport further depends on the density of states of the QDs directing a change in Schottky emission to Fowler-Nordheim (FN) type of tunneling across the metal-QD-metal junction. The selective response of the TMD QDs while in proximity to external molecules can be used to design advanced optoelectronic devices and applications involving rectifiers and tunnel diodes for future quantum technology.

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2D heterostructures made of transition metal dichalcogenides (TMD) have emerged as potential building blocks for new-generation 2D electronics due to their interesting physical properties at the interfaces. The bandgap, work function, and optical constants are composition dependent, and the spectrum of applications can be expanded by producing alloy-based heterostructures. Herein, the successful synthesis of monolayer and bilayer lateral heterostructures, based on ternary alloys of MoS2(1- x ) Se2 x -WS2(1- x ) Se2 x , is reported by modifying the ratio of the source precursors; the bandgaps of both materials in the heterostructure are continuously tuned in the entire range of chalcogen compositions. Raman and photoluminescence (PL) spatial maps show good intradomain composition homogeneity. Kelvin probe measurements in different heterostructures reveal composition-dependent band alignments, which can further be affected by unintentional electronic doping during the growth. The fabrication of sequential multijunction lateral heterostructures with three layers of thickness, composed of quaternary and ternary alloys, is also reported. These results greatly expand the available tools kit for optoelectronic applications in the 2D realm.

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Microchannels can be used to simulate xylem vessels and investigate phytopathogen colonization under controlled conditions. In this work, we explore surface functionalization strategies for polydimethylsiloxane and glass microchannels to study microenvironment colonization by Xylella fastidiosa subsp. pauca cells. We closely monitored cell initial adhesion, growth, and motility inside microfluidic channels as a function of chemical environments that mimic those found in xylem vessels. Carboxymethylcellulose (CMC), a synthetic cellulose, and an adhesin that is overexpressed during early stages of X. fastidiosa biofilm formation, XadA1 protein, were immobilized on the device's internal surfaces. This latter protocol increased bacterial density as compared with CMC. We quantitatively evaluated the different X. fastidiosa attachment affinities to each type of microchannel surface using a mathematical model and experimental observations acquired under constant flow of culture medium. We thus estimate that bacterial cells present ∼4 and 82% better adhesion rates in CMC- and XadA1-functionalized channels, respectively. Furthermore, variable flow experiments show that bacterial adhesion forces against shear stresses approximately doubled in value for the XadA1-functionalized microchannel as compared with the polydimethylsiloxane and glass pristine channels. These results show the viability of functionalized microchannels to mimic xylem vessels and corroborate the important role of chemical environments, and particularly XadA1 adhesin, for early stages of X. fastidiosa biofilm formation, as well as adhesivity modulation along the pathogen life cycle.

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The optical and electronic properties of 2D semiconductors are intrinsically linked via the strong interactions between optically excited bound species and free carriers. Here we use near-field scanning microwave microscopy (SMM) to image spatial variations in photoconductivity in MoS2-WS2 lateral multijunction heterostructures using photon energy-resolved narrowband illumination. We find that the onset of photoconductivity in individual domains corresponds to the optical absorption onset, confirming that the tightly bound excitons in transition metal dichalcogenides can nonetheless dissociate into free carriers. These photogenerated carriers are most likely n-type and are seen to persist for up to days. Informed by finite element modeling we reveal that they can increase the carrier density by up to 200 times. This persistent photoconductivity appears to be dominated by contributions from the multilayer MoS2 domains, and we attribute the flake-wide response in part to charge transfer across the heterointerface. Spatial correlation of our SMM imaging with photoluminescence (PL) mapping confirms the strong link between PL peak emission photon energy, PL intensity, and the local accumulated charge. This work reveals the spatially and temporally complex optoelectronic response of these systems and cautions that properties measured during or after illumination may not reflect the true dark state of these materials but rather a metastable charged state.

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Electrons commonly couple through Fröhlich interactions with longitudinal optical phonons to form polarons. However, trions possess a finite angular momentum and should therefore couple instead to rotational optical phonons. This creates a polaronic trion whose binding energy is determined by the crystallographic orientation of the lattice. Here, we demonstrate theoretically within the Fröhlich approach and experimentally by photoluminescence emission that the bare trion binding energy (20 meV) is significantly enhanced by the phonons at the interface between the two-dimensional semiconductor MoS_{2} and the bulk transition metal oxide SrTiO_{3}. The low-temperature binding energy changes from 60 meV in [001]-oriented substrates to 90 meV for [111] orientation, as a result of the counterintuitive interplay between the rotational axis of the MoS_{2} trion and that of the SrTiO_{3} phonon mode.

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Two-dimensional lateral heterojunctions based on monolayer transition-metal dichalcogenides (TMDs) have received increasing attention given that their direct band gap makes them very attractive for optoelectronic applications. Although bilayer TMDs present an indirect band gap, their electrical properties are expected to be less susceptible to ambient conditions, with higher mobilities and density of states when compared to monolayers. Bilayers and few-layers single domain devices have already demonstrated higher performance in radio frequency and photosensing applications. Despite these advantages, lateral heterostructures based on bilayer domains have been less explored. Here, we report the controlled synthesis of multi-junction bilayer lateral heterostructures based on MoS2-WS2 and MoSe2-WSe2 monodomains. The heterojunctions are created via sequential lateral edge-epitaxy that happens simultaneously in both the first and the second layers. A phenomenological mechanism is proposed to explain the growth mode with self-limited thickness that happens within a certain window of growth conditions. With respect to their as-grown monolayer counterparts, bilayer lateral heterostructures yield nearly 1 order of magnitude higher rectification currents. They also display a clear photovoltaic response, with short circuit currents ∼103 times larger than those extracted from the as-grown monolayers, in addition to room-temperature electroluminescence. The improved performance of bilayer heterostructures significantly expands the potential of two-dimensional materials for optoelectronics.

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We present time-integrated four-wave mixing measurements on monolayer MoSe2 in magnetic fields up to 25 T. The experimental data together with time-dependent density function theory calculations provide interesting insights into the biexciton formation and dynamics. In the presence of magnetic fields the coherence at negative and positive time delays is dominated by intervalley biexcitons. We demonstrate that magnetic fields can serve as a control to enhance the biexciton formation and help search for more exotic states of matter, including the creation of multiple exciton complexes and excitonic condensates.

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Two-dimensional heterojunctions of transition-metal dichalcogenides have great potential for application in low-power, high-performance and flexible electro-optical devices, such as tunnelling transistors, light-emitting diodes, photodetectors and photovoltaic cells. Although complex heterostructures have been fabricated via the van der Waals stacking of different two-dimensional materials, the in situ fabrication of high-quality lateral heterostructures with multiple junctions remains a challenge. Transition-metal-dichalcogenide lateral heterostructures have been synthesized via single-step, two-step or multi-step growth processes. However, these methods lack the flexibility to control, in situ, the growth of individual domains. In situ synthesis of multi-junction lateral heterostructures does not require multiple exchanges of sources or reactors, a limitation in previous approaches as it exposes the edges to ambient contamination, compromises the homogeneity of domain size in periodic structures, and results in long processing times. Here we report a one-pot synthetic approach, using a single heterogeneous solid source, for the continuous fabrication of lateral multi-junction heterostructures consisting of monolayers of transition-metal dichalcogenides. The sequential formation of heterojunctions is achieved solely by changing the composition of the reactive gas environment in the presence of water vapour. This enables selective control of the water-induced oxidation and volatilization of each transition-metal precursor, as well as its nucleation on the substrate, leading to sequential edge-epitaxy of distinct transition-metal dichalcogenides. Photoluminescence maps confirm the sequential spatial modulation of the bandgap, and atomic-resolution images reveal defect-free lateral connectivity between the different transition-metal-dichalcogenide domains within a single crystal structure. Electrical transport measurements revealed diode-like responses across the junctions. Our new approach offers greater flexibility and control than previous methods for continuous growth of transition-metal-dichalcogenide-based multi-junction lateral heterostructures. These findings could be extended to other families of two-dimensional materials, and establish a foundation for the development of complex and atomically thin in-plane superlattices, devices and integrated circuits.

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Electrically active field-effect transistors (FET) based biosensors are of paramount importance in life science applications, as they offer direct, fast, and highly sensitive label-free detection capabilities of several biomolecules of specific interest. In this work, we report a detailed investigation on surface functionalization and covalent immobilization of biomarkers using biocompatible ethanolamine and poly(ethylene glycol) derivate coatings, as compared to the conventional approaches using silica monoliths, in order to substantially increase both the sensitivity and molecular selectivity of nanowire-based FET biosensor platforms. Quantitative fluorescence, atomic and Kelvin probe force microscopy allowed detailed investigation of the homogeneity and density of immobilized biomarkers on different biofunctionalized surfaces. Significantly enhanced binding specificity, biomarker density, and target biomolecule capture efficiency were thus achieved for DNA as well as for proteins from pathogens. This optimized functionalization methodology was applied to InP nanowires that due to their low surface recombination rates were used as new active transducers for biosensors. The developed devices provide ultrahigh label-free detection sensitivities ∼1 fM for specific DNA sequences, measured via the net change in device electrical resistance. Similar levels of ultrasensitive detection of ∼6 fM were achieved for a Chagas Disease protein marker (IBMP8-1). The developed InP nanowire biosensor provides thus a qualified tool for detection of the chronic infection stage of this disease, leading to improved diagnosis and control of spread. These methodological developments are expected to substantially enhance the chemical robustness, diagnostic reliability, detection sensitivity, and biomarker selectivity for current and future biosensing devices.

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The pathogenicity of Xylella fastidiosa is associated with its systematic colonization of the plant xylem, forming bacterial biofilms. Mechanisms of bacterial transport among different xylem vessels, however, are not completely understood yet, but are strongly influenced by the presence of extracellular polymeric substances (EPS), which surrounds the assembly of cells forming the biofilm. In this work, we show quantitative measurements on the elastic properties of the system composed by EPS and bacterial cell. In order to investigate the mechanical properties of this system, force spectroscopy and confocal Raman measurements were carried out during Xylella fastidiosa subsp. pauca initial stages of adhesion and cluster formation. We show that stiffness progressively decreases with increasing culture growth time, from two to five days. For early adhesion samples, stiffness values are quite different at the bacterial polar and body regions. Lower stiffness values at the cell pole suggest a flexible mechanical response at this region, associated with first cell adhesion to a surface. These results correlate very well with our observations of cell motion within microchannels, under conditions simulating xylem flow. Both the oscillatory movement of vertically attached single cells, as well as the transport of cell clusters within the biofilm matrix can be explained by the presence of softer materials at the cell pole and EPS matrix. Our results may thus add to a more detailed understanding of mechanisms used by cells to migrate among vessels in plant xylem.

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A fragment of the human prion protein spanning residues 106-126 (PrP106-126) recapitulates many essential properties of the disease-causing protein such as amyloidogenicity and cytotoxicity. PrP106-126 has an amphipathic characteristic that resembles many antimicrobial peptides (AMPs). Therefore, the toxic effect of PrP106-126 could arise from a direct association of monomeric peptides with the membrane matrix. Several experimental approaches are employed to scrutinize the impacts of monomeric PrP106-126 on model lipid membranes. Porous defects in planar bilayers are observed by using solution atomic force microscopy. Adding cholesterol does not impede defect formation. A force spectroscopy experiment shows that PrP106-126 reduces Young's modulus of planar lipid bilayers. We use Raman microspectroscopy to study the effect of PrP106-126 on lipid atomic vibrational dynamics. For phosphatidylcholine lipids, PrP106-126 disorders the intrachain conformation, while the interchain interaction is not altered; for phosphatidylethanolamine lipids, PrP106-126 increases the interchain interaction, while the intrachain conformational order remains similar. We explain the observed differences by considering different modes of peptide insertion. Finally, electron paramagnetic resonance spectroscopy shows that PrP106-126 progressively decreases the orientational order of lipid acyl chains in magnetically aligned bicelles. Together, our experimental data support the proposition that monomeric PrP106-126 can disrupt lipid membranes by using similar mechanisms found in AMPs.

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Surface attachment of a planktonic bacteria, mediated by adhesins and extracellular polymeric substances (EPS), is a crucial step for biofilm formation. Some pathogens can modulate cell adhesiveness, impacting host colonization and virulence. A framework able to quantify cell-surface interaction forces and their dependence on chemical surface composition may unveil adhesiveness control mechanisms as new targets for intervention and disease control. Here we employed InP nanowire arrays to dissect factors involved in the early stage biofilm formation of the phytopathogen Xylella fastidiosa. Ex vivo experiments demonstrate single-cell adhesion forces up to 45 nN, depending on the cell orientation with respect to the surface. Larger adhesion forces occur at the cell poles; secreted EPS layers and filaments provide additional mechanical support. Significant adhesion force enhancements were observed for single cells anchoring a biofilm and particularly on XadA1 adhesin-coated surfaces, evidencing molecular mechanisms developed by bacterial pathogens to create a stronger holdfast to specific host tissues.

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In this work, nanofilms of hyaluronan/chitosan (HA/CHI) assembled layer by layer were synthesized; their application as a potential antimicrobial material was demonstrated for the phytopathogen Xylella fastidiosa, a gram-negative bacterium, here used as a model. For the synthesis, the influence of pH and ionic strength of these natural polymer stem-solutions on final characteristics of the HA/CHI nanofilms was studied in detail. The antibacterial effect was evaluated using widefield fluorescence microscopy. These results were correlated with the chemical properties of the nanofilms, studied by FTIR and Raman spectroscopy, as well as with their morphology and surface properties characterized using SEM and AFM. The present findings can be extended to design and optimize HA/CHI nanofilms with enhanced antimicrobial behavior for other type of phytopathogenic gram-negative bacteria species, such as Xanthomonas citri, Xanthomas campestri and Ralstonia solanacearum.

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