Dynamic Photochemical and Optoelectronic Control of Photonic Fano Resonances via Monolayer MoS2 Trions.

Active tunability of photonic resonances is of great interest for various applications such as optical switching and modulation based on optoelectronic materials. Manipulation of charged excitons in atomically thin transition metal dichalcogenides (TMDCs) like monolayer MoS2 offers an unexplored route for diverse functionalities in optoelectronic nanodevices. Here, we experimentally demonstrate the dynamic photochemical and optoelectronic control of the photonic crystal Fano resonances by optical and electrical tuning of monolayer MoS2 refractive index via trions without any chemical treatment. The strong spatial and spectral overlap between the photonic Fano mode and the active MoS2 monolayer enables efficient modulation of the Fano resonance. Our approach offers new directions for potential applications in the development of optical modulators based on emerging 2D direct band gap semiconductors.

Unidirectional Doubly Enhanced MoS2 Emission via Photonic Fano Resonances.

Atomically thin transition metal dichalcogenides like MoS2 monolayers exhibit unique luminescent properties. However, weak quantum yield and low light absorption hinder their practical applications in two-dimensional light emitting devices. Here, we report 1300 times enhancement in photoluminescence emission from a MoS2 monolayer via simultaneous Fano resonances in a dielectric photonic crystal. The spatially extended double Fano resonance scheme allows resonant enhancement of both the MoS2 absorption and emission. We also achieve unidirectional emission within a narrow divergence angle of 5° by engineering the Fano resonance angular dispersion. Our approach provides a new platform for efficient light sources with high directionality based on emerging two-dimensional materials.

Electrical Tuning of Exciton-Plasmon Polariton Coupling in Monolayer MoS2 Integrated with Plasmonic Nanoantenna Lattice.

Active control of light-matter interactions in semiconductors is critical for realizing next generation optoelectronic devices with real-time control of the system's optical properties and hence functionalities via external fields. The ability to dynamically manipulate optical interactions by applied fields in active materials coupled to cavities with fixed geometrical parameters opens up possibilities of controlling the lifetimes, oscillator strengths, effective mass, and relaxation properties of a coupled exciton-photon (or plasmon) system. Here, we demonstrate electrical control of exciton-plasmon coupling strengths between strong and weak coupling limits in a two-dimensional semiconductor integrated with plasmonic nanoresonators assembled in a field-effect transistor device by electrostatic doping. As a result, the energy-momentum dispersions of such an exciton-plasmon coupled system can be altered dynamically with applied electric field by modulating the excitonic properties of monolayer MoS2 arising from many-body effects. In addition, evidence of enhanced coupling between charged excitons (trions) and plasmons was also observed upon increased carrier injection, which can be utilized for fabricating Fermionic polaritonic and magnetoplasmonic devices. The ability to dynamically control the optical properties of a coupled exciton-plasmonic system with electric fields demonstrates the versatility of the coupled system and offers a new platform for the design of optoelectronic devices with precisely tailored responses.

pH Sensing Properties of Flexible, Bias-Free Graphene Microelectrodes in Complex Fluids: From Phosphate Buffer Solution to Human Serum.

Advances in techniques for monitoring pH in complex fluids can have a significant impact on analytical and biomedical applications. This study develops flexible graphene microelectrodes (GEs) for rapid (<5 s), very-low-power (femtowatt) detection of the pH of complex biofluids by measuring real-time Faradaic charge transfer between the GE and a solution at zero electrical bias. For an idealized sample of phosphate buffer solution (PBS), the Faradaic current is varied monotonically and systematically with the pH, with a resolution of ≈0.2 pH unit. The current-pH dependence is well described by a hybrid analytical-computational model, where the electric double layer derives from an intrinsic, pH-independent (positive) charge associated with the graphene-water interface and ionizable (negative) charged groups. For ferritin solution, the relative Faradaic current, defined as the difference between the measured current response and a baseline response due to PBS, shows a strong signal associated with ferritin disassembly and the release of ferric ions at pH ≈2.0. For samples of human serum, the Faradaic current shows a reproducible rapid (<20 s) response to pH. By combining the Faradaic current and real-time current variation, the methodology is potentially suitable for use to detect tumor-induced changes in extracellular pH.

Strong Exciton-Plasmon Coupling in MoS2 Coupled with Plasmonic Lattice.

We demonstrate strong exciton-plasmon coupling in silver nanodisk arrays integrated with monolayer MoS2 via angle-resolved reflectance microscopy spectra of the coupled system. Strong exciton-plasmon coupling is observed with the exciton-plasmon coupling strength up to 58 meV at 77 K, which also survives at room temperature. The strong coupling involves three types of resonances: MoS2 excitons, localized surface plasmon resonances (LSPRs) of individual silver nanodisks and plasmonic lattice resonances of the nanodisk array. We show that the exciton-plasmon coupling strength, polariton composition, and dispersion can be effectively engineered by tuning the geometry of the plasmonic lattice, which makes the system promising for realizing novel two-dimensional plasmonic polaritonic devices.

Optomechanical Enhancement of Doubly Resonant 2D Optical Nonlinearity.

Emerging two-dimensional semiconductor materials possess a giant second order nonlinear response due to excitonic effects while the monolayer thickness of such active materials limits their use in practical nonlinear devices. Here, we report 3300 times optomechanical enhancement of second harmonic generation from a MoS2 monolayer in a doubly resonant on-chip optical cavity. We achieve this by engineering the nonlinear light-matter interaction in a microelectro-mechanical system enabled optical frequency doubling device based on an electrostatically tunable Fabry-Perot microresonator. Our versatile optomechanical approach will pave the way for next generation efficient on-chip tunable light sources, sensors, and systems based on molecularly thin materials.

Band Alignment and Minigaps in Monolayer MoS2-Graphene van der Waals Heterostructures.

Two-dimensional layered MoS2 shows great potential for nanoelectronic and optoelectronic devices due to its high photosensitivity, which is the result of its indirect to direct band gap transition when the bulk dimension is reduced to a single monolayer. Here, we present an exhaustive study of the band alignment and relativistic properties of a van der Waals heterostructure formed between single layers of MoS2 and graphene. A sharp, high-quality MoS2-graphene interface was obtained and characterized by micro-Raman spectroscopy, high-resolution X-ray photoemission spectroscopy (HRXPS), and scanning high-resolution transmission electron microscopy (STEM/HRTEM). Moreover, direct band structure determination of the MoS2/graphene van der Waals heterostructure monolayer was carried out using angle-resolved photoemission spectroscopy (ARPES), shedding light on essential features such as doping, Fermi velocity, hybridization, and band-offset of the low energy electronic dynamics found at the interface. We show that, close to the Fermi level, graphene exhibits a robust, almost perfect, gapless, and n-doped Dirac cone and no significant charge transfer doping is detected from MoS2 to graphene. However, modification of the graphene band structure occurs at rather larger binding energies, as the opening of several miniband-gaps is observed. These miniband-gaps resulting from the overlay of MoS2 and the graphene layer lattice impose a superperiodic potential.

Monolayer Single-Crystal 1T'-MoTe2 Grown by Chemical Vapor Deposition Exhibits Weak Antilocalization Effect.

Growth of transition metal dichalcogenide (TMD) monolayers is of interest due to their unique electrical and optical properties. Films in the 2H and 1T phases have been widely studied but monolayers of some 1T'-TMDs are predicted to be large-gap quantum spin Hall insulators, suitable for innovative transistor structures that can be switched via a topological phase transition rather than conventional carrier depletion [ Qian et al. Science 2014 , 346 , 1344 - 1347 ]. Here we detail a reproducible method for chemical vapor deposition of monolayer, single-crystal flakes of 1T'-MoTe2. Atomic force microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy confirm the composition and structure of MoTe2 flakes. Variable temperature magnetotransport shows weak antilocalization at low temperatures, an effect seen in topological insulators and evidence of strong spin-orbit coupling. Our approach provides a pathway to systematic investigation of monolayer, single-crystal 1T'-MoTe2 and implementation in next-generation nanoelectronic devices.

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.

Intrinsic Properties of Suspended MoS2 on SiO2/Si Pillar Arrays for Nanomechanics and Optics.

Semiconducting two-dimensional (2D) materials, such as transition-metal dichalcogenides (TMDs), are emerging in nanomechanics, optoelectronics, and thermal transport. In each of these fields, perfect control over 2D material properties including strain, doping, and heating is necessary, especially on the nanoscale. Here, we study clean devices consisting of membranes of single-layer MoS2 suspended on pillar arrays. Using Raman and photoluminescence spectroscopy, we have been able to extract, separate, and simulate the different contributions on the nanoscale and to correlate these to the pillar array design. This control has been used to design a periodic MoS2 mechanical membrane with a high reproducibility and to perform optomechanical measurements on arrays of similar resonators with a high-quality factor of 600 at ambient temperature, hence opening the way to multiresonator applications with 2D materials. At the same time, this study constitutes a reference for the future development of well-controlled optical emissions within 2D materials on periodic arrays with reproducible behavior. We measured a strong reduction of the MoS2 band gap induced by the strain generated from the pillars. A transition from direct to indirect band gap was observed in isolated tent structures made of MoS2 and pinched by a pillar. In fully suspended devices, simulations were performed allowing both the extraction of the thermal conductance and doping of the layer. Using the correlation between the influences of strain and doping on the MoS2 Raman spectrum, we have developed a simple, elegant method to extract the local strain in suspended and nonsuspended parts of a membrane. This opens the way to experimenting with tunable coupling between light emission and vibration.

Crystalline Bilayer Graphene with Preferential Stacking from Ni-Cu Gradient Alloy.

We developed a high-yield synthesis of highly crystalline bilayer graphene (BLG) with two preferential stacking modes using a Ni-Cu gradient alloy growth substrate. Previously reported approaches for BLG growth include flat growth substrates of Cu or Ni-Cu uniform alloys and "copper pocket" structures. Use of flat substrates has the advantage of being scalable, but the growth mechanism is either "surface limited" (for Cu) or carbon precipitation (for uniform Ni-Cu), which results in multicrystalline BLG grains. For copper pockets, growth proceeds through a carbon back-diffusion mechanism, which leads to the formation of highly crystalline BLG, but scaling of the copper pocket structure is expected to be difficult. Here we demonstrate a Ni-Cu gradient alloy that combines the advantages of these earlier methods: the substrate is flat, so easy to scale, while growth proceeds by a carbon back-diffusion mechanism leading to high-yield growth of BLG with high crystallinity. The BLG layer stacking was almost exclusively Bernal or twisted with an angle of 30°, consistent with first-principles calculations we conducted. Furthermore, we demonstrated scalable production of transistor arrays based crystalline Bernal-stacked BLG with a band gap that was tunable at room temperature.

Highly active single-layer MoS2 catalysts synthesized by swift heavy ion irradiation.

Two-dimensional molybdenum-disulfide (MoS2) catalysts can achieve high catalytic activity for the hydrogen evolution reaction upon appropriate modification of their surface. The intrinsic inertness of the compound's basal planes can be overcome by either increasing the number of catalytically active edge sites or by enhancing the activity of the basal planes via a controlled creation of sulfur vacancies. Here, we report a novel method of activating the MoS2 surface using swift heavy ion irradiation. The creation of nanometer-scale structures by an ion beam, in combination with the partial sulfur depletion of the basal planes, leads to a large increase of the number of low-coordinated Mo atoms, which can form bonds with adsorbing species. This results in a decreased onset potential for hydrogen evolution, as well as in a significant enhancement of the electrochemical current density by over 160% as compared to an identical but non-irradiated MoS2 surface.

Ambient effects on electrical characteristics of CVD-grown monolayer MoS2 field-effect transistors.

Monolayer materials are sensitive to their environment because all of the atoms are at their surface. We investigate how exposure to the environment affects the electrical properties of CVD-grown monolayer MoS2 by monitoring electrical parameters of MoS2 field-effect transistors as their environment is changed from atmosphere to high vacuum. The mobility increases and contact resistance decreases simultaneously as either the pressure is reduced or the sample is annealed in vacuum. We see a previously unobserved, non-monotonic change in threshold voltage with decreasing pressure. This result could be explained by charge transfer on the MoS2 channel and Schottky contact formation due to adsorbates at the interface between the gold contacts and MoS2. Additionally, from our electrical measurements it is plausible to infer that at room temperature and pressure water and oxygen molecules adsorbed on the surface act as interface traps and scattering centers with a density of several 1012 cm-2 eV-1, degrading the electrical properties of monolayer MoS2.

Intrinsic Phonon Bands in High-Quality Monolayer T' Molybdenum Ditelluride.

The topologically nontrivial and chemically functional distorted octahedral (T') transition-metal dichalcogenides (TMDCs) are a type of layered semimetal that has attracted significant recent attention. However, the properties of monolayer (1L) T'-TMDC, a fundamental unit of the system, are still largely unknown due to rapid sample degradation in air. Here we report that well-protected 1L CVD T'-MoTe2 exhibits sharp and robust intrinsic Raman bands, with intensities about 1 order of magnitude stronger than those from bulk T'-MoTe2. The high-quality samples enabled us to reveal the set of all nine even-parity zone-center optical phonons, providing reliable fingerprints for the previously elusive crystal. By performing light polarization and crystal orientation resolved scattering analysis, we can effectively distinguish the intrinsic modes from Te-metalloid-like modes A (∼122 cm-1) and B (∼141 cm-1), which are related to the sample degradation. Our studies offer a powerful nondestructive method for assessing sample quality and for monitoring sample degradation in situ, representing a solid advance in understanding the fundamental properties of 1L-T'-TMDCs.

Recoil Effect and Photoemission Splitting of Trions in Monolayer MoS2.

The 2D geometry nature and low dielectric constant in transition-metal dichalcogenides lead to easily formed strongly bound excitons and trions. Here, we studied the photoluminescence of van der Waals heterostructures of monolayer MoS2 and graphene at room temperature and observed two photoluminescence peaks that are associated with trion emission. Further study of different heterostructure configurations confirms that these two peaks are intrinsic to MoS2 and originate from a bound state and Fermi level, respectively, of which both accept recoiled electrons from trion recombination. We demonstrate that the recoil effect allows us to electrically control the photon energy of trion emission by adjusting the gate voltage. In addition, significant thermal smearing at room temperature results in capture of recoil electrons by bound states, creating photoemission peak at low doping level whose photon energy is less sensitive to gate voltage tuning. This discovery reveals an unexpected role of bound states for photoemission, where binding of recoil electrons becomes important.

Tunable Doping in Hydrogenated Single Layered Molybdenum Disulfide.

Structural defects in the molybdenum disulfide (MoS2) monolayer are widely known for strongly altering its properties. Therefore, a deep understanding of these structural defects and how they affect MoS2 electronic properties is of fundamental importance. Here, we report on the incorporation of atomic hydrogen in monolayered MoS2 to tune its structural defects. We demonstrate that the electronic properties of single layer MoS2 can be tuned from the intrinsic electron (n) to hole (p) doping via controlled exposure to atomic hydrogen at room temperature. Moreover, this hydrogenation process represents a viable technique to completely saturate the sulfur vacancies present in the MoS2 flakes. The successful incorporation of hydrogen in MoS2 leads to the modification of the electronic properties as evidenced by high resolution X-ray photoemission spectroscopy and density functional theory calculations. Micro-Raman spectroscopy and angle resolved photoemission spectroscopy measurements show the high quality of the hydrogenated MoS2 confirming the efficiency of our hydrogenation process. These results demonstrate that the MoS2 hydrogenation could be a significant and efficient way to achieve tunable doping of transition metal dichalcogenides (TMD) materials with non-TMD elements.

Monolayer WS2 Nanopores for DNA Translocation with Light-Adjustable Sizes.

Two-dimensional materials are promising for a range of applications, as well as testbeds for probing the physics of low-dimensional systems. Tungsten disulfide (WS2) monolayers exhibit a direct band gap and strong photoluminescence (PL) in the visible range, opening possibilities for advanced optoelectronic applications. Here, we report the realization of two-dimensional nanometer-size pores in suspended monolayer WS2 membranes, allowing for electrical and optical response in ionic current measurements. A focused electron beam was used to fabricate nanopores in WS2 membranes suspended on silicon-based chips and characterized using PL spectroscopy and aberration-corrected high-resolution scanning transmission electron microscopy. It was observed that the PL intensity of suspended WS2 monolayers is ∼10-15 times stronger when compared to that of substrate-supported monolayers, and low-dose scanning transmission electron microscope viewing and drilling preserves the PL signal of WS2 around the pore. We establish that such nanopores allow ionic conductance and DNA translocations. We also demonstrate that under low-power laser illumination in solution, WS2 nanopores grow slowly in size at an effective rate of ∼0.2-0.4 nm/s, thus allowing for atomically controlled nanopore size using short light pulses.

Transfer of monolayer TMD WS2 and Raman study of substrate effects.

A facile transfer process for transition metal dichalcogenide WS2 flakes is reported and the effect of the underlying substrate on the flake properties is investigated using Raman spectroscopy. The flakes are transferred from their growth substrate using polymethyl methacrylate (PMMA) and a wet etch to allow the user to transfer the flakes to a final substrate using a microscope and micromanipulator combined with semi-transparent Kapton tape. The substrates used range from insulators such as industry standard high-k dielectric HfO2 and "green polymer" parylene-C, to conducting chemical vapor deposition (CVD) grown graphene. Raman spectroscopy is used first to confirm the material quality of the transferred flakes to the substrates and subsequently to analyze and separate the effects arising from material transfer from those arising from interactions with the substrate. We observe changes in the Raman spectra associated with the interactions between the substrates in the flakes. These interactions affect both in-plane and out-of-plane modes in different ways depending on their sources, for example strain or surface charge. These changes vary with final substrate, with the strongest effects being observed for WS2 transferred onto graphene and HfO2, demonstrating the importance of understanding substrate interaction for fabrication of future devices.

Synthesis and Physical Properties of Phase-Engineered Transition Metal Dichalcogenide Monolayer Heterostructures.

Heterostructures of transition metal dichalcogenides (TMDs) offer the attractive prospect of combining distinct physical properties derived from different TMD structures. Here, we report direct chemical vapor deposition of in-plane monolayer heterostructures based on 1H-MoS2 and 1T'-MoTe2. The large lattice mismatch between these materials led to intriguing phenomena at their interface. Atomic force microscopy indicated buckling in the 1H region. Tip-enhanced Raman spectroscopy showed mode structure consistent with Te substitution in the 1H region during 1T'-MoTe2 growth. This was confirmed by atomic resolution transmission electron microscopy, which also revealed an atomically stitched, dislocation-free 1H/1T' interface. Theoretical modeling revealed that both the buckling and absence of interfacial misfit dislocations were explained by lateral gradients in Te substitution levels within the 1H region and elastic coupling between 1H and 1T' domains. Phase field simulations predicted 1T' morphologies with spike-shaped islands at specific orientations consistent with experiments. Electrical measurements across the heterostructure confirmed its electrical continuity. This work demonstrates the feasibility of dislocation-free stitching of two different atomic configurations and a pathway toward direct synthesis of monolayer TMD heterostructures of different phases.