Hexagonal Boron Nitride Slab Waveguides for Enhanced Spectroscopy of Encapsulated 2D Materials.

The layered insulator hexagonal boron nitride (hBN) is a critical substrate that brings out the exceptional intrinsic properties of two-dimensional (2D) materials such as graphene and transition metal dichalcogenides (TMDs). In this work, the authors demonstrate how hBN slabs tuned to the correct thickness act as optical waveguides, enabling direct optical coupling of light emission from encapsulated layers into waveguide modes. Molybdenum selenide (MoSe2 ) and tungsten selenide (WSe2 ) are integrated within hBN-based waveguides and demonstrate direct coupling of photoluminescence emitted by in-plane and out-of-plane transition dipoles (bright and dark excitons) to slab waveguide modes. Fourier plane imaging of waveguided photoluminescence from MoSe2 demonstrates that dry etched hBN edges are an effective out-coupler of waveguided light without the need for oil-immersion optics. Gated photoluminescence of WSe2 demonstrates the ability of hBN waveguides to collect light emitted by out-of-plane dark excitons.Numerical simulations explore the parameters of dipole placement and slab thickness, elucidating the critical design parameters and serving as a guide for novel devices implementing hBN slab waveguides. The results provide a direct route for waveguide-based interrogation of layered materials, as well as a way to integrate layered materials into future photonic devices at arbitrary positions whilst maintaining their intrinsic properties.

Acoustic cavities in 2D heterostructures.

Two-dimensional (2D) materials offer unique opportunities in engineering the ultrafast spatiotemporal response of composite nanomechanical structures. In this work, we report on high frequency, high quality factor (Q) 2D acoustic cavities operating in the 50-600 GHz frequency (f) range with f × Q up to 1 × 1014. Monolayer steps and material interfaces expand cavity functionality, as demonstrated by building adjacent cavities that are isolated or strongly-coupled, as well as a frequency comb generator in MoS2/h-BN systems. Energy dissipation measurements in 2D cavities are compared with attenuation derived from phonon-phonon scattering rates calculated using a fully microscopic ab initio approach. Phonon lifetime calculations extended to low frequencies (<1 THz) and combined with sound propagation analysis in ultrathin plates provide a framework for designing acoustic cavities that approach their fundamental performance limit. These results provide a pathway for developing platforms employing phonon-based signal processing and for exploring the quantum nature of phonons.

Enabling remote quantum emission in 2D semiconductors via porous metallic networks.

Here we report how two-dimensional crystal (2DC) overlayers influence the recrystallization of relatively thick metal films and the subsequent synergetic benefits this provides for coupling surface plasmon-polaritons (SPPs) to photon emission in 2D semiconductors. We show that annealing 2DC/Au films on SiO2 results in a reverse epitaxial process where initially nanocrystalline Au films gain texture, crystallographically orient with the 2D crystal overlayer, and form an oriented porous metallic network (OPEN) structure in which the 2DC can suspend above or coat the inside of the metal pores. Both laser excitation and exciton recombination in the 2DC semiconductor launch propagating SPPs in the OPEN film. Energy in-/out- coupling occurs at metal pore sites, alleviating the need for dielectric spacers between the metal and 2DC layer. At low temperatures, single-photon emitters (SPEs) are present across an OPEN-WSe2 film, and we demonstrate remote SPP-mediated excitation of SPEs at a distance of 17 µm.

Strong confinement of optical fields using localized surface phonon polaritons in cubic boron nitride.

Phonon polaritons (PhPs) are long-lived electromagnetic modes that originate from the coupling of infrared (IR) photons with the bound ionic lattice of a polar crystal. Cubic-boron nitride (cBN) is such a polar, semiconductor material which, due to the light atomic masses, can support high-frequency optical phonons. Here we report on random arrays of cBN nanostructures fabricated via an unpatterned reactive ion etching process. Fourier-transform infrared reflection spectra suggest the presence of localized surface PhPs within the reststrahlen band, with quality factors in excess of 38 observed. These can provide the basis of next-generation IR optical components such as antennas for communication, improved chemical spectroscopies, and enhanced emitters, sources, and detectors.

Work Function Variations in Twisted Graphene Layers.

By combining optical imaging, Raman spectroscopy, kelvin probe force microscopy (KFPM), and photoemission electron microscopy (PEEM), we show that graphene's layer orientation, as well as layer thickness, measurably changes the surface potential (Φ). Detailed mapping of variable-thickness, rotationally-faulted graphene films allows us to correlate Φ with specific morphological features. Using KPFM and PEEM we measure ΔΦ up to 39 mV for layers with different twist angles, while ΔΦ ranges from 36-129 mV for different layer thicknesses. The surface potential between different twist angles or layer thicknesses is measured at the KPFM instrument resolution of ≤ 200 nm. The PEEM measured work function of 4.4 eV for graphene is consistent with doping levels on the order of 1012cm-2. We find that Φ scales linearly with Raman G-peak wavenumber shift (slope = 22.2 mV/cm-1) for all layers and twist angles, which is consistent with doping-dependent changes to graphene's Fermi energy in the 'high' doping limit. Our results here emphasize that layer orientation is equally important as layer thickness when designing multilayer two-dimensional systems where surface potential is considered.

Evidence for Chemical Vapor Induced 2H to 1T Phase Transition in MoX2 (X = Se, S) Transition Metal Dichalcogenide Films.

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 MoS2 and MoSe2 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 MoS2 and MoSe2 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 MoS2 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.

Graphene Strained by Defects.

Using graphene nanomechanical resonators we demonstrate the extent to which the mechanical properties of multilayer graphene films are controllable, in real time, through introduction and rearrangement of defects. We show both static and re-entrant (cyclical) changes in the tensile stress using a combination of ion implantation, chemical functionalization, and thermal treatment. While the dramatic increase in static tensile stress achievable through laser annealing can be of importance for various MEMS applications, we view the direct observation of a time-variable stress as even more significant. We find that defect-rich films exhibit a slow relaxation component of the tensile stress that remains in the resonator long after the laser exposure is finished (trelax ≈ 100 s ≫ tcooling), analogous to a wind-up toy. We attribute this persistent component of the time-variable stress to a set of metastable, multivacancy structures formed during the laser anneal. Our results indicate that significant stress fields generated by multivacancies, in combination with their finite lifetime, could make them a powerful and flexible tool in nanomechanics.

Tunable Electrical Properties of Vanadium Oxide by Hydrogen-Plasma-Treated Atomic Layer Deposition.

In this study, a plasma-modified process was developed to control the electrical properties of atomic layer deposition (ALD)-grown vanadium dioxide (VO2), which is potentially useful for applications such as resistive switching devices, bolometers, and plasmonic metamaterials. By inserting a plasma pulse with varying H2 gas flow into each ALD cycle, the insulator-to-metal transition (IMT) temperature of postdeposition-annealed crystalline VO2 films was adjusted from 63 to 78 °C. Film analyses indicate that the tunability may arise from changes in grain boundaries, morphology, and compositional variation despite hydrogen not remaining in the annealed VO2 films. This growth method, which enables a systematic variation of the electronic behavior of VO2, provides capabilities beyond those of the conventional thermal ALD and plasma-enhanced ALD.

Room-Temperature Spin Filtering in Metallic Ferromagnet-Multilayer Graphene-Ferromagnet Junctions.

We report room-temperature negative magnetoresistance in ferromagnet-graphene-ferromagnet (FM|Gr|FM) junctions with minority spin polarization exceeding 80%, consistent with predictions of strong minority spin filtering. We fabricated arrays of such junctions via chemical vapor deposition of multilayer graphene on lattice-matched single-crystal NiFe(111) films and standard photolithographic patterning and etching techniques. The junctions exhibit metallic transport behavior, low resistance, and the negative magnetoresistance characteristic of a minority spin filter interface throughout the temperature range 10 to 300 K. We develop a device model to incorporate the predicted spin filtering by explicitly treating a metallic minority spin channel with spin current conversion and a tunnel barrier majority spin channel and extract spin polarization of at least 80% in the graphene layer in our structures. The junctions also show antiferromagnetic coupling, consistent with several recent predictions. The methods and findings are relevant to fast-readout low-power magnetic random access memory technology, spin logic devices, and low-power magnetic field sensors.

Dynamics of chemical vapor sensing with MoS2 using 1T/2H phase contacts/channel.

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.

Nitrogen-Doped Graphene and Twisted Bilayer Graphene via Hyperthermal Ion Implantation with Depth Control.

We investigate hyperthermal ion implantation (HyTII) as a means for substitutionally doping layered materials such as graphene. In particular, this systematic study characterizes the efficacy of substitutional N-doping of graphene using HyTII over an N(+) energy range of 25-100 eV. Scanning tunneling microscopy results establish the incorporation of N substituents into the graphene lattice during HyTII processing. We illustrate the differences in evolution of the characteristic Raman peaks following incremental doses of N(+). We use the ratios of the integrated D and D' peaks, I(D)/I(D') to assess the N(+) energy-dependent doping efficacy, which shows a strong correlation with previously reported molecular dynamics (MD) simulation results and a peak doping efficiency regime ranging between approximately 30 and 50 eV. We also demonstrate the inherent monolayer depth control of the HyTII process, thereby establishing a unique advantage over other less-specific methods for doping. We achieve this by implementing twisted bilayer graphene (TBG), with one layer of isotopically enriched (13)C and one layer of natural (12)C graphene, and modify only the top layer of the TBG sample. By assessing the effects of N-HyTII processing, we uncover dose-dependent shifts in the transfer characteristics consistent with electron doping and we find dose-dependent electronic localization that manifests in low-temperature magnetotransport measurements.

Synthesis of Large-Area WS2 monolayers with Exceptional Photoluminescence.

Monolayer WS2 offers great promise for use in optical devices due to its direct bandgap and high photoluminescence intensity. While fundamental investigations can be performed on exfoliated material, large-area and high quality materials are essential for implementation of technological applications. In this work, we synthesize monolayer WS2 under various controlled conditions and characterize the films using photoluminescence, Raman and x-ray photoelectron spectroscopies. We demonstrate that the introduction of hydrogen to the argon carrier gas dramatically improves the optical quality and increases the growth area of WS2, resulting in films exhibiting mm(2) coverage. The addition of hydrogen more effectively reduces the WO3 precursor and protects against oxidative etching of the synthesized monolayers. The stoichiometric WS2 monolayers synthesized using Ar + H2 carrier gas exhibit superior optical characteristics, with photoluminescence emission full width half maximum (FWHM) values below 40 meV and emission intensities nearly an order of magnitude higher than films synthesized in a pure Ar environment.

Electronic hybridization of large-area stacked graphene films.

Direct, tunable coupling between individually assembled graphene layers is a next step toward designer two-dimensional (2D) crystal systems, with relevance for fundamental studies and technological applications. Here we describe the fabrication and characterization of large-area (>cm(2)), coupled bilayer graphene on SiO(2)/Si substrates. Stacking two graphene films leads to direct electronic interactions between layers, where the resulting film properties are determined by the local twist angle. Polycrystalline bilayer films have a "stained-glass window" appearance explained by the emergence of a narrow absorption band in the visible spectrum that depends on twist angle. Direct measurement of layer orientation via electron diffraction, together with Raman and optical spectroscopy, confirms the persistence of clean interfaces over large areas. Finally, we demonstrate that interlayer coupling can be reversibly turned off through chemical modification, enabling optical-based chemical detection schemes. Together, these results suggest that 2D crystals can be individually assembled to form electronically coupled systems suitable for large-scale applications.

Engineering graphene mechanical systems.

We report a method to introduce direct bonding between graphene platelets that enables the transformation of a multilayer chemically modified graphene (CMG) film from a "paper mache-like" structure into a stiff, high strength material. On the basis of chemical/defect manipulation and recrystallization, this technique allows wide-range engineering of mechanical properties (stiffness, strength, density, and built-in stress) in ultrathin CMG films. A dramatic increase in the Young's modulus (up to 800 GPa) and enhanced strength (sustainable stress ≥1 GPa) due to cross-linking, in combination with high tensile stress, produced high-performance (quality factor of 31,000 at room temperature) radio frequency nanomechanical resonators. The ability to fine-tune intraplatelet mechanical properties through chemical modification and to locally activate direct carbon-carbon bonding within carbon-based nanomaterials will transform these systems into true "materials-by-design" for nanomechanics.

Non-lithographic SERS substrates: tailoring surface chemistry for Au nanoparticle cluster assembly.

Near-field plasmonic coupling and local field enhancement in metal nanoarchitectures, such as arrangements of nanoparticle clusters, have application in many technologies from medical diagnostics, solar cells, to sensors. Although nanoparticle-based cluster assemblies have exhibited signal enhancements in surface-enhanced Raman scattering (SERS) sensors, it is challenging to achieve high reproducibility in SERS response using low-cost fabrication methods. Here an innovative method is developed for fabricating self-organized clusters of metal nanoparticles on diblock copolymer thin films as SERS-active structures. Monodisperse, colloidal gold nanoparticles are attached via a crosslinking reaction on self-organized chemically functionalized poly(methyl methacrylate) domains on polystyrene-block-poly(methyl methacrylate) templates. Thereby nanoparticle clusters with sub-10-nanometer interparticle spacing are achieved. Varying the molar concentration of functional chemical groups and crosslinking agent during the assembly process is found to affect the agglomeration of Au nanoparticles into clusters. Samples with a high surface coverage of nanoparticle cluster assemblies yield relative enhancement factors on the order of 109 while simultaneously producing uniform signal enhancements in point-to-point measurements across each sample. High enhancement factors are associated with the narrow gap between nanoparticles assembled in clusters in full-wave electromagnetic simulations. Reusability for small-molecule detection is also demonstrated. Thus it is shown that the combination of high signal enhancement and reproducibility is achievable using a completely non-lithographic fabrication process, thereby producing SERS substrates having high performance at low cost.

Quantum linear magnetoresistance in multilayer epitaxial graphene.

We report the first observation of linear magnetoresistance (LMR) in multilayer epitaxial graphene grown on SiC. We show that multilayer epitaxial graphene exhibits large LMR from 2.2 K up to room temperature and that it can be best explained by a purely quantum mechanical model. We attribute the observation of LMR to inhomogeneities in the epitaxially grown graphene film. The large magnitude of the LMR suggests potential for novel applications in areas such as high-density data storage and magnetic sensors and actuators.

Properties of fluorinated graphene films.

Graphene films grown on Cu foils have been fluorinated with xenon difluoride (XeF(2)) gas on one or both sides. When exposed on one side the F coverage saturates at 25% (C(4)F), which is optically transparent, over 6 orders of magnitude more resistive than graphene, and readily patterned. Density functional calculations for varying coverages indicate that a C(4)F configuration is lowest in energy and that the calculated band gap increases with increasing coverage, becoming 2.93 eV for one C(4)F configuration. During defluorination, we find hydrazine treatment effectively removes fluorine while retaining graphene's carbon skeleton. The same films may be fluorinated on both sides by transferring graphene to a silicon-on-insulator substrate enabling XeF(2) gas to etch the Si underlayer and fluorinate the backside of the graphene film to form perfluorographane (CF) for which calculated the band gap is 3.07 eV. Our results indicate single-side fluorination provides the necessary electronic and optical changes to be practical for graphene device applications.

Technique for the dry transfer of epitaxial graphene onto arbitrary substrates.

To make graphene technologically viable, the transfer of graphene films to substrates appropriate for specific applications is required. We demonstrate the dry transfer of epitaxial graphene (EG) from the C-face of 4H-SiC onto SiO(2), GaN and Al(2)O(3) substrates using a thermal release tape. Subsequent Hall effect measurements illustrated that minimal degradation in the carrier mobility was induced following the transfer process in lithographically patterned devices. Correspondingly, a large drop in the carrier concentration was observed following the transfer process, supporting the notion that a gradient in the carrier density is present in C-face EG, with lower values being observed in layers further removed from the SiC interface. X-ray photoemission spectra collected from EG films attached to the transfer tape revealed the presence of atomic Si within the EG layers, which may indicate the identity of the unknown intrinsic dopant in EG. Finally, this transfer process is shown to enable EG films amenable for use in device fabrication on arbitrary substrates and films that are deemed most beneficial to carrier transport, as flexible electronic devices or optically transparent contacts.