Strong coupling of mid-infrared (mid-IR) vibrational transitions to optical cavities provides a means to modify and control a material’s chemical reactivity and offers a foundation for novel chemical detection technology.Currently, the relatively large volumes of the mid-IR photonic cavities and weak oscillator strengths of vibrational transitions restrict vibrational strong coupling (VSC) studies and devices to large ensembles of molecules, thus representing a potential limitation of this nascent field. Here, we experimentally and theoretically investigate the mid-IR optical properties of 3D-printed multimode metal–insulator–metal (MIM) plasmonic nanoscale cavities for enabling strong light–matter interactions at a deep subwavelength regime. We observe strong vibration-plasmon coupling between the two dipolar modes of the L-shaped cavity and the carbonyl stretch vibrational transition of the polymer dielectric. The cavity mode volume is half the size of a typical square-shaped MIM geometry,thus enabling a reduction in the number of vibrational oscillators to achieve strong coupling. The resulting three polariton modes are well described by a fully coupled multimode oscillator model where all coupling potentials are non-zero. The 3D printing technique of the cavities is a highly accessible and versatile means of printing arbitrarily shaped submicron-sized mid-IR plasmonic cavities capable of producing strong light–matter interactions for a variety of photonic or photochemical applications. Specifically, similar MIM structures fabricated with nanoscopic voids within the insulator region could constitute a promising microfluidic plasmonic cavity device platform for applications in chemical sensing or photochemistry.

Chemiresistive graphene sensors are promising for chemical sensing applications due to their simple device structure, high sensitivity, potential for miniaturization, low-cost, and fast response. In this work, we investigate the effect of (1) ZnO nanoparticle functionalization and (2) engineered defects onto graphene sensing channel on device resistance and low frequency electrical noise. The engineered defects of interest include 2D patterns of squares, stars, and circles and 1D patterns of slots parallel and transverse to the applied electric potential. The goal of this work is to determine which devices are best suited for chemical sensing applications. We find that, relative to pristine graphene devices, nanoparticle functionalization leads to reduced contact resistance but increased sheet resistance. In addition, functionalization lowers 1/f current noise on all but the uniform mesa device and the two devices with graphene strips parallel to carrier transport. The strongest correlations between noise and engineering defects, where normalized noise amplitude as a function of frequency f is described by a model of AN/fγ, are that γ increases with graphene area and contact area but decreases with device total perimeter, including internal features. We did not find evidence of a correlation between the scalar amplitude, AN, and the device channel geometries. In general, for a given device area, the least noise was observed on the least-etched device. These results will lead to an understanding of what features are needed to obtain the optimal device resistance and how to reduce the 1/f noise which will lead to improved sensor performance.

The demand for high-power electrical transmission continues to increase with technical advances in electric vehicles, unmanned drones, portable devices, and deployable military applications. In this study, significantly enhanced electrical properties (i.e., a 450% increase in the current density breakdown limit) are demonstrated by synthesizing axially continuous graphene layers on microscale-diameter wires. To elucidate the underlying mechanisms of the observed enhancements, the electrical properties of pure copper wires and axially continuous graphene-copper (ACGC) wires with three different diameters are characterized while controlling the experimental conditions, including ambient temperature, gases, and pressure. The study reveals that the main mechanism that allows the application of extremely large current densities (>400 000 A cm-2 ) through the ACGC wires is threefold: the continuous graphene layers considerably improve: 1) surface heat dissipation (224% higher), 2) electrical conductivity (41% higher), and 3) thermal stability (41.2% lower resistivity after thermal cycles up to 450 °C), compared with pure copper wires. In addition, it is observed, through the use of high-speed camera images, that the ACGC wires exhibit very different failure behavior near the current density limit, compared with the pure copper wires.

Beyond the intrinsic properties of 2D materials, another advantage is the tunability that follows from their low dimensionality. Here, large‐area Nb‐doped MoS 2 monolayer films deposited by metal organic chemical vapor deposition that can function as electrical contacts or chemical sensors are demonstrated. Compared to pristine MoS 2 , Nb‐doped MoS 2 exhibits a relatively faster growth rate and quenched PL due to formation of mid‐gap energy bands. When the Nb concentration reaches 5 at%, doped MoS 2 shows clear p‐type characteristics, evident by a 1.7 eV shift of the Fermi level toward the valence band maximum. Doping also impacts transport at the metal/MoS 2 interface, demonstrated by Pt–Ir metallization that is Schottky‐limited when in contact with undoped MoS 2 but Ohmic on Nb‐MoS 2 . Moreover, a 50 × improved signal‐to‐noise ratio is demonstrated in sensing triethylamine compared to undoped MoS 2 , with < 15 parts‐per‐billion detection limit.

Two-photon lithography allows writing of arbitrary nanoarchitectures in photopolymers. This design flexibility opens almost limitless possibilities for biological studies, but the acrylate-based polymers frequently used do not allow for adhesion and growth of some types of cells. Indeed, we found that lithographically defined structures made from OrmoComp do not support E18 murine cortical neurons. We reacted OrmoComp structures with several diamines, thereby rendering the surfaces directly permissive for neuron attachment and growth by presenting a surface coating similar to the traditional cell biology coating achieved with poly-d-lysine (PDL) and laminin. However, in contrast to PDL-laminin coatings that cover the entire surface, the amine-terminated OrmoComp structures are orthogonally modified in deference to the surrounding glass or plastic substrate, adding yet another design element for advanced biological studies.

The integration of graphene and 2D materials into device technologies requires a detailed understanding of how intrinsic and extrinsic forces impact their properties, as well as the development of engineering strategies to vary their properties for a specific response. In this paper we describe and review our efforts for hybridizing graphene in different ways so as to modify or enhance a range of properties. This hybridization comes in the form of chemical or electronic modification for use in applications ranging from chem/bio sensors to nanoelectronics. We discuss results on exploiting chemistry and defects in graphene for chemical vapor sensing, on hybridizing graphene with fluorine atoms for potential use in nanoelectronics, and on electronically hybridizing graphene in multilayer stacks that give rise to new optical and surface properties.

Gap surface plasmons (GSPs) serve a diverse range of plasmonic applications, including energy harvesting, communications, molecular sensing, and optical detection. GSPs may be realized where tightly spaced plasmonic structures exhibit strong spatial overlap between the evanescent fields. We demonstrate that within similar, nested geometries that the near-fields of the GSPs within the individual nanostructures are hybridized. This creates two or more distinct resonances exhibiting near-field distributions extended over adjacent spatial regions. In contrast, dissimilar, nested structures exhibit two distinct resonances with nominally uncoupled near-fields, resulting in two or more individual antenna resonance modes. We deploy plasmonic band structure calculations to provide insight into the type and degree of hybridization within these systems, comparing the individual components. This understanding can be used in the optimized design of polaritonic metamaterial structures for desired applications.

Advancing electronic devices that interface with biology will require a thorough understanding of the electrochemical pathways that transduce electronic currents into the ionic currents.

Electron-donors can impart charge to the surface of transition metal dichalcogenide (TMD) films while interacting with the film via a weak physisorption bond, making them ideal for vapor and gas sensors. We expose monolayer MoS 2 and MoSe 2 films to strong electron-donor chemical vapor analytes. After analyzing the resultant behavior and taking into consideration doping effects, we conclude that exposure to strong electron-donors could be a method of inducing the semiconductor-metal 2H-1T TMD phase transition. We find that the conductance response to strong electron donors in both monolayer MoS 2 and MoSe 2 FET devices ceases after moderate exposure, with final value of the conductance being on order of that expected for the 1T phase. Full device relaxation back to a semiconducting state is accomplished by annealing in vacuum at 400 °C. We also examine chemically exposed TMD films intermittently interrogated with Raman and photoluminescence spectroscopy. We observe the appearance of weak characteristic 1T phase Raman features for MoS 2 and we observed a quenching of the photoluminescence of both TMD films that is recoverable with annealing. Considering all of our data together, the effects cannot be described by doping alone. Additionally, our results suggest a mechanism for a new type of passive chemical vapor sensor.

Ultra-thin transition metal dichalcogenides (TMDs) films show remarkable potential for use in chemical vapor sensing devices. Electronic devices fabricated from TMD films are inexpensive, inherently flexible, low-power, amenable to industrial-scale processing because of emergent growth techniques, and have shown high sensitivity and selectivity to electron donor analyte molecules important for explosives and nerve gas detection. However, for devices reported to date, the conductance response to chemical vapors is dominated by Schottky contacts, to the detriment of the sensitivity, selectivity, recovery, and obscuring their intrinsic behavior. Here, we use contact engineering to transition the contacts in a MoS2 FET-based chemical vapor sensor to the 1T conducting phase, while leaving the channel in the 2H semiconducting state, and thus providing Ohmic contacts to the film. We demonstrate that the resultant sensors have much improved electrical characteristics, are more selective, and recover fully after chemical vapor exposure-all major enhancements to previously MoS2 sensor devices. We identify labile nitrogen-containing electron donors as the primary species that generate a response in MoS2, and we study the dynamics of the sensing reactions, identifying two possible qualitative models for the chemical sensing reaction.

Although robust chemical vapor detection by chemielectric point sensors remains as a largely unmet challenge at present, the best performance to date and the most likely avenue for future progress is with sensor designs in which the transductive element is a disordered nanostructured material. We here review the evidence for this claim, with illustrations drawn from recent work on sensors made from gold nanoparticles, carbon nanotubes, and reduced graphene oxide nanoplatelets. These examples can be regarded as being prototypical of disordered nanostructured films formed of primitive objects that are nanoscopic in 3-D, 2-D, and 1-D, respectively.

Metamaterials designed for the visible or near IR wavelengths require patterning on the nanometer scale. To achieve this, e-beam lithography is used, but it is extremely difficult and can only produce 2D structures. A new alternative technique to produce 2D and 3D structures involves laser fabrication using the Nanoscribe 3D laser lithography system. This is a direct laser writing technique which can form arbitrary 3D nanostructures on the nanometer scale and is based on multi-photon polymerization. We are creating 2D and 3D metamaterials via this technique, and subsequently conformally coating them using Atomic Layer Deposition of oxides and Ag. We will discuss the optical properties of these novel composite structures and their potential for dual resonant metamaterials.

MoS2, in single to few-layer format, is of interest because of its potential for advanced transistor and sensor applications. Its sizable bandgap enables single layer transistors with large on/off current ratios, and the large surface-to-volume ratio provides sensitive transduction of surface physisorption to the channel conductivity. Here, we discuss aspects of transistor device fabrication and of chemical vapor sensing experiments. We expose MoS2 chemical sensors to a variety of analytes, find the largest response to triethylamine, a nerve gas by-product, and explain our results based on a donor-acceptor model. We show that our MoS2 sensors provide comparable sensitivity and much higher selectivity than other low-dimensional sensors such as carbon nanotube and graphene chemical sensors. We present results for back-gated sensing and light sensitivity for our monolayer MoS2 sensors, and compare the results with multilayer MoS2 sensors. Published by Elsevier Ltd.

Two-dimensional materials such as graphene show great potential for future nanoscale electronic devices. The high surface-to-volume ratio is a natural asset for applications such as chemical sensing, where perturbations to the surface resulting in charge redistribution are readily manifested in the transport characteristics. Here we show that single monolayer MoS(2) functions effectively as a chemical sensor, exhibiting highly selective reactivity to a range of analytes and providing sensitive transduction of transient surface physisorption events to the conductance of the monolayer channel. We find strong response upon exposure to triethylamine, a decomposition product of the V-series nerve gas agents. We discuss these results in the context of analyte/sensor interaction in which the analyte serves as either an electron donor or acceptor, producing a temporary charge perturbation of the sensor material. We find highly selective response to electron donors and little response to electron acceptors, consistent with the weak n-type character of our MoS(2). The MoS(2) sensor exhibits a much higher selectivity than carbon nanotube-based sensors.