Polymer-Waveguide-Integrated 2D Semiconductor Heterostructures for Optical Communications.

The demand for high-speed and low-loss interconnects in modern computer architectures is difficult to satisfy by using traditional Si-based electronics. Although optical interconnects offer a promising solution owing to their high bandwidth, low energy dissipation, and high-speed processing, integrating elements such as a light source, detector, and modulator, comprising different materials with optical waveguides, presents many challenges in an integrated platform. Two-dimensional (2D) van der Waals (vdW) semiconductors have attracted considerable attention in vertically stackable optoelectronics and advanced flexible photonics. In this study, optoelectronic components for exciton-based photonic circuits are demonstrated by integrating lithographically patterned poly(methyl methacrylate) (PMMA) waveguides on 2D vdW devices. The excitonic signals generated from the 2D materials by using laser excitation were transmitted through patterned PMMA waveguides. By introducing an external electric field and combining vdW heterostructures, an excitonic switch, phototransistor, and guided-light photovoltaic device on SiO2/Si substrates were demonstrated.

GeAs as an emerging p-type van der Waals semiconductor and its application in p-n photodiodes.

van der Waals (vdW) layered materials have shown great potential for future optoelectronic applications owing to their unique and variable properties. In particular, two-dimensional layered materials enable the creation of various circuital building blocks via vertical stacking, e.g. the vertical p-n junction as a key one. While numerous stable n-type layered materials have been discovered, p-type materials remain relatively scarce. Here, we report on the study of multilayer germanium arsenide (GeAs), another emerging p-type vdW layered material. We first verify the efficient hole transport in a multilayer GeAs field-effect transistor with Pt electrodes, which establish low contact potential barriers. Subsequently, we demonstrate a p-n photodiode featuring a vertical heterojunction of a multilayer GeAs and n-type MoS2monolayer, exhibiting a photovoltaic response. This study promotes that 2D GeAs is a promising candidate for p-type material in vdW optoelectronic devices.

van der Waals Metallic Transition Metal Dichalcogenides.

Transition metal dichalcogenides are layered materials which are composed of transition metals and chalcogens of the group VIA in a 1:2 ratio. These layered materials have been extensively investigated over synthesis and optical and electrical properties for several decades. It can be insulators, semiconductors, or metals revealing all types of condensed matter properties from a magnetic lattice distorted to superconducting characteristics. Some of these also feature the topological manner. Instead of covering the semiconducting properties of transition metal dichalcogenides, which have been extensively revisited and reviewed elsewhere, here we present the structures of metallic transition metal dichalcogenides and their synthetic approaches for not only high-quality wafer-scale samples using conventional methods (e.g., chemical vapor transport, chemical vapor deposition) but also local small areas by a modification of the materials using Li intercalation, electron beam irradiation, light illumination, pressures, and strains. Some representative band structures of metallic transition metal dichalcogenides and their strong layer-dependence are reviewed and updated, both in theoretical calculations and experiments. In addition, we discuss the physical properties of metallic transition metal dichalcogenides such as periodic lattice distortion, magnetoresistance, superconductivity, topological insulator, and Weyl semimetal. Approaches to overcome current challenges related to these materials are also proposed.

Probing graphene grain boundaries with optical microscopy.

Grain boundaries in graphene are formed by the joining of islands during the initial growth stage, and these boundaries govern transport properties and related device performance. Although information on the atomic rearrangement at graphene grain boundaries can be obtained using transmission electron microscopy and scanning tunnelling microscopy, large-scale information regarding the distribution of graphene grain boundaries is not easily accessible. Here we use optical microscopy to observe the grain boundaries of large-area graphene (grown on copper foil) directly, without transfer of the graphene. This imaging technique was realized by selectively oxidizing the underlying copper foil through graphene grain boundaries functionalized with O and OH radicals generated by ultraviolet irradiation under moisture-rich ambient conditions: selective diffusion of oxygen radicals through OH-functionalized defect sites was demonstrated by density functional calculations. The sheet resistance of large-area graphene decreased as the graphene grain sizes increased, but no strong correlation with the grain size of the copper was revealed, in contrast to a previous report. Furthermore, the influence of graphene grain boundaries on crack propagation (initialized by bending) and termination was clearly visualized using our technique. Our approach can be used as a simple protocol for evaluating the grain boundaries of other two-dimensional layered structures, such as boron nitride and exfoliated clays.

Role of alkali metal promoter in enhancing lateral growth of monolayer transition metal dichalcogenides.

Synthesis of monolayer transition metal dichalcogenides (TMDs) via chemical vapor deposition relies on several factors such as precursor, promoter, substrate, and surface treatment of substrate. Among them, the use of promoter is crucial for obtaining uniform and large-area monolayer TMDs. Although promoters have been speculated to enhance adhesion of precursors to the substrate, their precise role in the growth mechanism has rarely been discussed. Here, we report the role of alkali metal promoter in growing monolayer TMDs. The growth occurred via the formation of sodium metal oxides which prevent the evaporation of metal precursor. Furthermore, the silicon oxide substrate helped to decrease the Gibbs free energy by forming sodium silicon oxide compounds. The resulting sodium metal oxide was anchored within such concavities created by corrosion of silicon oxide. Consequently, the wettability of the precursors to silicon oxide was improved, leading to enhance lateral growth of monolayer TMDs.

Stranski-Krastanov and Volmer-Weber CVD Growth Regimes To Control the Stacking Order in Bilayer Graphene.

Aside from unusual properties of monolayer graphene, bilayer has been shown to have even more interesting physics, in particular allowing bandgap opening with dual gating for proper interlayer symmetry. Such properties, promising for device applications, ignited significant interest in understanding and controlling the growth of bilayer graphene. Here we systematically investigate a broad set of flow rates and relative gas ratio of CH4 to H2 in atmospheric pressure chemical vapor deposition of multilayered graphene. Two very different growth windows are identified. For relatively high CH4 to H2 ratios, graphene growth is relatively rapid with an initial first full layer forming in seconds upon which new graphene flakes nucleate then grow on top of the first layer. The stacking of these flakes versus the initial graphene layer is mostly turbostratic. This growth mode can be likened to Stranski-Krastanov growth. With relatively low CH4 to H2 ratios, growth rates are reduced due to a lower carbon supply rate. In addition bi-, tri-, and few-layer flakes form directly over the Cu substrate as individual islands. Etching studies show that in this growth mode subsequent layers form beneath the first layer presumably through carbon radical intercalation. This growth mode is similar to that found with Volmer-Weber growth and was shown to produce highly oriented AB-stacked materials. These systematic studies provide new insight into bilayer graphene formation and define the synthetic range where gapped bilayer graphene can be reliably produced.

Electron Excess Doping and Effective Schottky Barrier Reduction on the MoS2/h-BN Heterostructure.

Layered hexagonal boron nitride (h-BN) thin film is a dielectric that surpasses carrier mobility by reducing charge scattering with silicon oxide in diverse electronics formed with graphene and transition metal dichalcogenides. However, the h-BN effect on electron doping concentration and Schottky barrier is little known. Here, we report that use of h-BN thin film as a substrate for monolayer MoS2 can induce ∼6.5 × 1011 cm-2 electron doping at room temperature which was determined using theoretical flat band model and interface trap density. The saturated excess electron concentration of MoS2 on h-BN was found to be ∼5 × 1013 cm-2 at high temperature and was significantly reduced at low temperature. Further, the inserted h-BN enables us to reduce the Coulombic charge scattering in MoS2/h-BN and lower the effective Schottky barrier height by a factor of 3, which gives rise to four times enhanced the field-effect carrier mobility and an emergence of metal-insulator transition at a much lower charge density of ∼1.0 × 1012 cm-2 (T = 25 K). The reduced effective Schottky barrier height in MoS2/h-BN is attributed to the decreased effective work function of MoS2 arisen from h-BN induced n-doping and the reduced effective metal work function due to dipole moments originated from fixed charges in SiO2.

Metal-Insulator-Semiconductor Diode Consisting of Two-Dimensional Nanomaterials.

We present a novel metal-insulator-semiconductor (MIS) diode consisting of graphene, hexagonal BN, and monolayer MoS2 for application in ultrathin nanoelectronics. The MIS heterojunction structure was fabricated by vertically stacking layered materials using a simple wet chemical transfer method. The stacking of each layer was confirmed by confocal scanning Raman spectroscopy and device performance was evaluated using current versus voltage (I-V) and photocurrent measurements. We clearly observed better current rectification and much higher current flow in the MIS diode than in the p-n junction and the metal-semiconductor diodes made of layered materials. The I-V characteristic curve of the MIS diode indicates that current flows mainly across interfaces as a result of carrier tunneling. Moreover, we observed considerably high photocurrent from the MIS diode under visible light illumination.

Dependence of Raman and absorption spectra of stacked bilayer MoS2 on the stacking orientation.

Stacked bilayer molybdenum disulfide (MoS2) exhibits interesting physical properties depending on the stacking orientation and interlayer coupling strength. Although optical properties, such as photoluminescence, Raman, and absorption properties, are largely dependent on the interlayer coupling of stacked bilayer MoS2, the origin of variations in these properties is not clearly understood. We performed comprehensive confocal Raman and absorption mapping measurements to determine the dependence of these spectra on the stacking orientation of bilayer MoS2. The results indicated that with 532-nm laser excitation, the Raman scattering intensity gradually increased upon increasing the stacking angle from 0° to 60°, whereas 458-nm laser excitation resulted in the opposite trend of decreasing Raman intensity with increasing stacking angle. This opposite behavior of the Raman intensity dependence was explained by the varying resonance condition between the Raman excitation wavelength and C exciton absorption energy of bilayer MoS2. Our work sheds light on the intriguing effect of the subtle interlayer interaction in stacked MoS2 bilayers on the resulting optical properties.

Fano Resonance and Spectrally Modified Photoluminescence Enhancement in Monolayer MoS2 Integrated with Plasmonic Nanoantenna Array.

The manipulation of light-matter interactions in two-dimensional atomically thin crystals is critical for obtaining new optoelectronic functionalities in these strongly confined materials. Here, by integrating chemically grown monolayers of MoS2 with a silver-bowtie nanoantenna array supporting narrow surface-lattice plasmonic resonances, a unique two-dimensional optical system has been achieved. The enhanced exciton-plasmon coupling enables profound changes in the emission and excitation processes leading to spectrally tunable, large photoluminescence enhancement as well as surface-enhanced Raman scattering at room temperature. Furthermore, due to the decreased damping of MoS2 excitons interacting with the plasmonic resonances of the bowtie array at low temperatures stronger exciton-plasmon coupling is achieved resulting in a Fano line shape in the reflection spectrum. The Fano line shape, which is due to the interference between the pathways involving the excitation of the exciton and plasmon, can be tuned by altering the coupling strengths between the two systems via changing the design of the bowties lattice. The ability to manipulate the optical properties of two-dimensional systems with tunable plasmonic resonators offers a new platform for the design of novel optical devices with precisely tailored responses.

Selective Amplification of the Primary Exciton in a MoS_{2} Monolayer.

Optoelectronics applications for transition-metal dichalcogenides are still limited by weak light absorption and their complex exciton modes are easily perturbed by varying excitation conditions because they are inherent in atomically thin layers. Here, we propose a method of selectively amplifying the primary exciton (A^{0}) among the exciton complexes in monolayer MoS_{2} via cyclic reexcitation of cavity-free exciton-coupled plasmon propagation. This was implemented by partially overlapping a Ag nanowire on a MoS_{2} monolayer separated by a thin SiO_{2} spacer. Exciton-coupled plasmons in the nanowire enhance the A^{0} radiation in MoS_{2}. The cumulative amplification of emission enhancement by cyclic plasmon traveling reaches approximately twentyfold selectively for the A^{0}, while excluding other B exciton and multiexciton by significantly reduced band filling, without oscillatory spectra implying plasmonic cavity effects.

Scalable production of highly sensitive nanosensors based on graphene functionalized with a designed G protein-coupled receptor.

We have developed a novel, all-electronic biosensor for opioids that consists of an engineered µ-opioid receptor protein, with high binding affinity for opioids, chemically bonded to a graphene field-effect transistor to read out ligand binding. A variant of the receptor protein that provided chemical recognition was computationally redesigned to enhance its solubility and stability in an aqueous environment. A shadow mask process was developed to fabricate arrays of hundreds of graphene transistors with average mobility of ∼1500 cm(2) V(-1) s(-1) and yield exceeding 98%. The biosensor exhibits high sensitivity and selectivity for the target naltrexone, an opioid receptor antagonist, with a detection limit of 10 pg/mL.

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

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

Continuous Template Growth of Large-Scale Tellurene Films on 1T'-MoTe2.

Use of a template triggers an epitaxial interaction with the depositing material during synthesis. Recent studies have demonstrated that two-dimensional tellurium (tellurene) can be directionally oriented when grown on transition metal dichalcogenide (TMD) templates. Specifically, employing a T-phase TMD, such as WTe2, restricts the growth direction even further due to its anisotropic nature, which allows for the synthesis of well-oriented tellurene films. Despite this, producing large-area epitaxial films still remains a significant challenge. Here, we report the continuous synthesis of a 1T'-MoTe2 template via chemical vapor deposition and tellurene via vapor transport. The interaction between helical Te and the 1T'-MoTe2 template facilitates the Te chains to collapse into ribbon shapes, enhancing lateral growth at a rate approximately 6 times higher than in the vertical direction, as confirmed by scanning electron microscopy and atomic force microscopy. Interestingly, despite the predominance of the lateral growth, cross-sectional transmission electron microscopy analysis of the tellurene ribbons revealed a consistent 60-degree incline at the edges. This suggests that the edges of the tellurene ribbons, where they contact the template surface, are favorable sites for additional Te absorption, which then stacks along the incline angle to expand. Furthermore, controlling the synthesis temperature, duration, and preheating time has facilitated the successful synthesis of tellurene films. The resultant tellurene exhibited hole mobility as high as ∼400 cm2/V s. After removing the underlying metallic template with plasma treatment, the film showed a current on/off ratio of ∼103. This ratio was confirmed by two-terminal field-effect transistor measurements and supported by near-field terahertz (THz) spectroscopy mapping.

Small hysteresis nanocarbon-based integrated circuits on flexible and transparent plastic substrate.

We report small hysteresis integrated circuits by introducing monolayer graphene for the electrodes and a single-walled carbon nanotube network for the channel. Small hysteresis of the device originates from a defect-free graphene surface, where hysteresis was modulated by oxidation. This uniquely combined nanocarbon material device with transparent and flexible properties shows remarkable device performance; subthreshold voltage of 220 mV decade(-1), operation voltage of less than 5 V, on/off ratio of approximately 10(4), mobility of 81 cm(2) V(-1) s(-1), transparency of 83.8% including substrate, no significant transconductance changes in 1000 times of bending test, and only 36% resistance decrease at a tensile strain of 50%. Furthermore, because of the nearly Ohmic contact nature between the graphene and carbon nanotubes, this device demonstrated a contact resistance 100 times lower and a mobility 20 times higher, when compared to an Au electrode.

Influence of copper morphology in forming nucleation seeds for graphene growth.

We report that highly crystalline graphene can be obtained from well-controlled surface morphology of the copper substrate. Flat copper surface was prepared by using a chemical mechanical polishing method. At early growth stage, the density of graphene nucleation seeds from polished Cu film was much lower and the domain sizes of graphene flakes were larger than those from unpolished Cu film. At later growth stage, these domains were stitched together to form monolayer graphene, where the orientation of each domain crystal was unexpectedly not much different from each other. We also found that grain boundaries and intentionally formed scratched area play an important role for nucleation seeds. Although the best monolayer graphene was grown from polished Cu with a low sheet resistance of 260 Ω/sq, a small portion of multilayers were also formed near the impurity particles or locally protruded parts.

Plasmon-exciton couplings in the MoS2/AuNP plasmonic hybrid structure.

The understanding and engineering of the plasmon-exciton coupling are necessary to control the innovative optoelectronic device platform. In this study, we investigated the intertwined mechanism of each plasmon-exciton couplings in monolayer molybdenum disulfide (MoS2) and plasmonic hybrid structure. The results of absorption, simulation, electrostatics, and emission spectra show that interaction between photoexcited carrier and exciton modes are successfully coupled by energy transfer and exciton recombination processes. Especially, neutral exciton, trion, and biexciton can be selectively enhanced by designing the plasmonic hybrid platform. All of these results imply that there is another degree of freedom to control the individual enhancement of each exciton mode in the development of nano optoelectronic devices.

Control of electronic structure of graphene by various dopants and their effects on a nanogenerator.

It is essential to control the electronic structure of graphene in order to apply graphene films for use in electrodes. We have introduced chemical dopants that modulate the electronic properties of few-layer graphene films synthesized by chemical vapor deposition. The work function, sheet carrier density, mobility, and sheet resistance of these films were systematically modulated by the reduction potential values of dopants. We further demonstrated that the power generation of a nanogenerator was strongly influenced by the choice of a graphene electrode with a modified work function. The off-current was well quenched in graphene films with high work functions (Au-doped) due to the formation of high Schottky barrier heights, whereas leakage current was observed in graphene films with low work functions (viologen-doped), due to nearly ohmic contact.

Anomalous Conductance near Percolative Metal-Insulator Transition in Monolayer MoS2 at Low Voltage Regime.

Conductivity of the insulating phase increases generally at an elevated drain-source voltage due to the field-enhanced hopping or heating effect. Meanwhile, a transport mechanism governed by percolation in a low compensated semiconductor gives rise to the reduced conductivity at a low-field regime. Here, in addition to this behavior, we report the anomalous conductivity behavior to transform from a percolative metallic to an insulating phase at the low voltage regime in monolayer molybdenum disulfide (MoS2). Percolation transport at low source-drain voltage is governed by inhomogeneously distributed potential in strongly interacting monolayer MoS2 with a substrate, distinct from the quantum phase transition in multilayer MoS2. At a high source-drain voltage regime, the insulating phase is transformed further to a metallic phase, exhibiting multiphases of metallic-insulating-metallic transitions in monolayer MoS2. These behaviors highlight MoS2 as a model system to study various classical and quantum transports as well as metal-insulator transition in two-dimensional systems.

Edge Contact for Carrier Injection and Transport in MoS2 Field-Effect Transistors.

The contact properties of van der Waals layered semiconducting materials are not adequately understood, particularly for edge contact. Edge contact is extremely helpful in the case of graphene, for producing efficient contacts to vertical heterostructures, and for improving the contact resistance through strong covalent bonding. Herein, we report on edge contacts to MoS2 of various thicknesses. The carrier-type conversion is robustly controlled by changing the flake thickness and metal work functions. Regarding the ambipolar behavior, we suggest that the carrier injection is segregated in a relatively thick MoS2 channel; that is, electrons are in the uppermost layers, and holes are in the inner layers. Calculations reveal that the strength of the Fermi-level pinning (FLP) varies layer-by-layer, owing to the inhomogeneous carrier concentration, and particularly, there is negligible FLP in the inner layer, supporting the hole injection. The contact resistance is large despite the significantly reduced contact resistivity normalized by the contact area, which is attributed to the current-crowding effect arising from the narrow contact area.