Ultrafast Coherent Exciton Couplings and Many-Body Interactions in Monolayer WS2.

Transition metal dichalcogenides (TMDs) are quantum confined systems with interesting optoelectronic properties, governed by Coulomb interactions in the monolayer (1L) limit, where strongly bound excitons provide a sensitive probe for many-body interactions. Here, we use two-dimensional electronic spectroscopy (2DES) to investigate many-body interactions and their dynamics in 1L-WS2 at room temperature and with sub-10 fs time resolution. Our data reveal coherent interactions between the strongly detuned A and B exciton states in 1L-WS2. Pronounced ultrafast oscillations of the transient optical response of the B exciton are the signature of a coherent 50 meV coupling and coherent population oscillations between the two exciton states. Supported by microscopic semiconductor Bloch equation simulations, these coherent dynamics are rationalized in terms of Dexter-like interactions. Our work sheds light on the role of coherent exciton couplings and many-body interactions in the ultrafast temporal evolution of spin and valley states in TMDs.

Low-Loss Integrated Nanophotonic Circuits with Layered Semiconductor Materials.

Monolayer transition-metal dichalcogenides with direct bandgaps are emerging candidates for optoelectronic devices, such as photodetectors, light-emitting diodes, and electro-optic modulators. Here we report a low-loss integrated platform incorporating molybdenum ditelluride monolayers with silicon nitride photonic microresonators. We achieve microresonator quality factors >3 × 106 in the telecommunication O- to E-bands. This paves the way for low-loss, hybrid photonic integrated circuits with layered semiconductors, not requiring heterogeneous wafer bonding.

In Situ Observation of Low-Power Nano-Synaptic Response in Graphene Oxide Using Conductive Atomic Force Microscopy.

Multiple studies have reported the observation of electro-synaptic response in different metal/insulator/metal devices. However, most of them analyzed large (>1 µm2 ) devices that do not meet the integration density required by industry (1010  devices/mm2 ). Some studies emploied a scanning tunneling microscope (STM) to explore nano-synaptic response in different materials, but in this setup there is a nanogap between the insulator and one of the metallic electrodes (i.e., the STM tip), not present in real devices. Here, it is demonstrated how to use conductive atomic force microscopy to explore the presence and quality of nano-synaptic response in confined areas <50 nm2 . Graphene oxide (GO) is selected due to its easy fabrication. Metal/GO/metal nano-synapses exhibit potentiation and paired pulse facilitation with low write current levels <1 µA (i.e., power consumption ≈3 µW), controllable excitatory post-synaptic currents, and long-term potentiation and depression. The results provide a new method to explore nano-synaptic plasticity at the nanoscale, and point to GO as an important candidate for the fabrication of ultrasmall (<50 nm2 ) electronic synapses fulfilling the integration density requirements of neuromorphic systems.

Raman spectroscopy of GaSe and InSe post-transition metal chalcogenides layers.

III-VI post-transition metal chalcogenides (InSe and GaSe) are a new class of layered semiconductors, which feature a strong variation of size and type of their band gaps as a function of number of layers (N). Here, we investigate exfoliated layers of InSe and GaSe ranging from bulk crystals down to monolayer, encapsulated in hexagonal boron nitride, using Raman spectroscopy. We present the N-dependence of both intralayer vibrations within each atomic layer, as well as of the interlayer shear and layer breathing modes. A linear chain model can be used to describe the evolution of the peak positions as a function of N, consistent with first principles calculations.

HBN-Encapsulated, Graphene-based, Room-temperature Terahertz Receivers, with High Speed and Low Noise.

Uncooled terahertz photodetectors (PDs) showing fast (ps) response and high sensitivity (noise equivalent power (NEP) < nW/Hz1/2) over a broad (0.5-10 THz) frequency range are needed for applications in high-resolution spectroscopy (relative accuracy ∼10-11), metrology, quantum information, security, imaging, optical communications. However, present terahertz receivers cannot provide the required balance between sensitivity, speed, operation temperature, and frequency range. Here, we demonstrate uncooled terahertz PDs combining the low (∼2000 kB µm-2) electronic specific heat of high mobility (>50 000 cm2 V-1 s-1) hexagonal boron nitride-encapsulated graphene, with asymmetric field enhancement produced by a bow-tie antenna, resonating at 3 THz. This produces a strong photo-thermoelectric conversion, which simultaneously leads to a combination of high sensitivity (NEP ≤ 160 pW Hz-1/2), fast response time (≤3.3 ns), and a 4 orders of magnitude dynamic range, making our devices the fastest, broad-band, low-noise, room-temperature terahertz PD, to date.

Transform-Limited Photons From a Coherent Tin-Vacancy Spin in Diamond.

Solid-state quantum emitters that couple coherent optical transitions to long-lived spin qubits are essential for quantum networks. Here we report on the spin and optical properties of individual tin-vacancy (SnV) centers in diamond nanostructures. Through cryogenic magneto-optical and spin spectroscopy, we verify the inversion-symmetric electronic structure of the SnV, identify spin-conserving and spin-flipping transitions, characterize transition linewidths, measure electron spin lifetimes, and evaluate the spin dephasing time. We find that the optical transitions are consistent with the radiative lifetime limit even in nanofabricated structures. The spin lifetime is phonon limited with an exponential temperature scaling leading to T_{1}>10 ms, and the coherence time, T_{2}^{*} reaches the nuclear spin-bath limit upon cooling to 2.9 K. These spin properties exceed those of other inversion-symmetric color centers for which similar values require millikelvin temperatures. With a combination of coherent optical transitions and long spin coherence without dilution refrigeration, the SnV is a promising candidate for feasable and scalable quantum networking applications.

Waveguide-Integrated, Plasmonic Enhanced Graphene Photodetectors.

We present a micrometer-scale, on-chip integrated, plasmonic enhanced graphene photodetector (GPD) for telecom wavelengths operating at zero dark current. The GPD is designed to directly generate a photovoltage by the photothermoelectric effect. It is made of chemical vapor deposited single layer graphene, and has an external responsivity ∼12.2 V/W with a 3 dB bandwidth ∼42 GHz. We utilize Au split-gates to electrostatically create a p-n-junction and simultaneously guide a surface plasmon polariton gap-mode. This increases the light-graphene interaction and optical absorption and results in an increased electronic temperature and steeper temperature gradient across the GPD channel. This paves the way to compact, on-chip integrated, power-efficient graphene based photodetectors for receivers in tele- and datacom modules.

Multi-Valley Superconductivity in Ion-Gated MoS2 Layers.

Layers of transition metal dichalcogenides (TMDs) combine the enhanced effects of correlations associated with the two-dimensional limit with electrostatic control over their phase transitions by means of an electric field. Several semiconducting TMDs, such as MoS2, develop superconductivity (SC) at their surface when doped with an electrostatic field, but the mechanism is still debated. It is often assumed that Cooper pairs reside only in the two electron pockets at the K/K' points of the Brillouin Zone. However, experimental and theoretical results suggest that a multivalley Fermi surface (FS) is associated with the SC state, involving six electron pockets at Q/Q'. Here, we perform low-temperature transport measurements in ion-gated MoS2 flakes. We show that a fully multivalley FS is associated with the SC onset. The Q/Q' valleys fill for doping ≳ 2 × 1013 cm-2, and the SC transition does not appear until the Fermi level crosses both spin-orbit split sub-bands Q 1 and Q 2. The SC state is associated with the FS connectivity and promoted by a Lifshitz transition due to the simultaneous population of multiple electron pockets. This FS topology will serve as a guideline in the quest for new superconductors.

Excitonic Emission of Monolayer Semiconductors Near-Field Coupled to High-Q Microresonators.

We present quantum yield measurements of single layer WSe2 (1L-WSe2) integrated with high-Q ( Q > 106) optical microdisk cavities, using an efficient (η > 90%) near-field coupling scheme based on a tapered optical fiber. Coupling of the excitonic emission is achieved by placing 1L-WSe2 in the evanescent cavity field. This preserves the microresonator high intrinsic quality factor ( Q > 106) below the bandgap of 1L-WSe2. The cavity quantum yield is QYc ≈ 10-3, consistent with operation in the broad emitter regime (i.e., the emission lifetime of 1L-WSe2 is significantly shorter than the bare cavity decay time). This scheme can serve as a precise measurement tool for the excitonic emission of layered materials into cavity modes, for both in plane and out of plane excitation.

Intravalley Spin-Flip Relaxation Dynamics in Single-Layer WS2.

In monolayer (1L) transition metal dichalcogenides (TMDs) the valence and conduction bands are spin-split because of the strong spin-orbit interaction. In tungsten-based TMDs the spin-ordering of the conduction band is such that the so-called dark excitons, consisting of electrons and holes with opposite spin orientation, have lower energy than A excitons. The transition from bright to dark excitons involves the scattering of electrons from the upper to the lower conduction band at the K point of the Brillouin zone, with detrimental effects for the optoelectronic response of 1L-TMDs, since this reduces their light emission efficiency. Here, we exploit the valley selective optical selection rules and use two-color helicity-resolved pump-probe spectroscopy to directly measure the intravalley spin-flip relaxation dynamics in 1L-WS2. This occurs on a sub-ps time scale, and it is significantly dependent on temperature, indicative of phonon-assisted relaxation. Time-dependent ab initio calculations show that intravalley spin-flip scattering occurs on significantly longer time scales only at the K point, while the occupation of states away from the minimum of the conduction band significantly reduces the scattering time. Our results shed light on the scattering processes determining the light emission efficiency in optoelectronic and photonic devices based on 1L-TMDs.

Electrically Controlled Nano and Micro Actuation in Memristive Switching Devices with On-Chip Gas Encapsulation.

Nanoactuators are a key component for developing nanomachinery. Here, an electrically driven device yielding actuation stresses exceeding 1 MPa withintegrated optical readout is demonstrated. 10 nm thick Al2 O3 electrolyte films are sandwiched between graphene and Au electrodes. These allow reversible room-temperature solid-state redox reactions, producing Al metal and O2 gas in a memristive-type switching device. The resulting high-pressure oxygen micro-fuel reservoirs are encapsulated under the graphene, swelling to heights of up to 1 µm, which can be dynamically tracked by plasmonic rulers. Unlike standard memristors where the memristive redox reaction occurs in single or few conductive filaments, the mechanical deformation forces the creation of new filaments over the whole area of the inflated film. The resulting on-off resistance ratios reach 108 in some cycles. The synchronization of nanoactuation and memristive switching in these devices is compatible with large-scale fabrication and has potential for precise and electrically monitored actuation technology.

On-Chip Integrated, Silicon-Graphene Plasmonic Schottky Photodetector with High Responsivity and Avalanche Photogain.

We report an on-chip integrated metal graphene-silicon plasmonic Schottky photodetector with 85 mA/W responsivity at 1.55 µm and 7% internal quantum efficiency. This is one order of magnitude higher than metal-silicon Schottky photodetectors operated in the same conditions. At a reverse bias of 3 V, we achieve avalanche multiplication, with 0.37A/W responsivity and avalanche photogain ∼2. This paves the way to graphene integrated silicon photonics.

Raman Fingerprints of Atomically Precise Graphene Nanoribbons.

Bottom-up approaches allow the production of ultranarrow and atomically precise graphene nanoribbons (GNRs) with electronic and optical properties controlled by the specific atomic structure. Combining Raman spectroscopy and ab initio simulations, we show that GNR width, edge geometry, and functional groups all influence their Raman spectra. The low-energy spectral region below 1000 cm(-1) is particularly sensitive to edge morphology and functionalization, while the D peak dispersion can be used to uniquely fingerprint the presence of GNRs and differentiates them from other sp(2) carbon nanostructures.

Graphene Near-Degenerate Four-Wave Mixing for Phase Characterization of Broadband Pulses in Ultrafast Microscopy.

We investigate near-degenerate four-wave mixing in graphene using femtosecond laser pulse shaping microscopy. Intense near-degenerate four-wave mixing signals on either side of the exciting laser spectrum are controlled by amplitude and phase shaping. Quantitative signal modeling for the input pulse parameters shows a spectrally flat phase response of the near-degenerate four-wave mixing due to the linear dispersion of the massless Dirac Fermions in graphene. Exploiting these properties we demonstrate that graphene is uniquely suited for the intrafocus phase characterization and compression of broadband laser pulses, circumventing disadvantages of common methods utilizing second or third harmonic light.

Role of Cooperative Interactions in the Intercalation of Heteroatoms between Graphene and a Metal Substrate.

The intercalation of heteroatoms between graphene and a metal substrate has been studied intensively over the past few years, due to its effect on the graphene properties, and as a method to create vertical heterostructures. Various intercalation processes have been reported with different combinations of heteroatoms and substrates. Here we study Si intercalation between graphene and Ru(0001). We elucidate the role of cooperative interactions between hetero-atoms, graphene, and substrate. By combining scanning tunneling microscopy with density functional theory, the intercalation process is confirmed to consist of four key steps, involving creation of defects, migration of heteroatoms, self-repairing of graphene, and growth of an intercalated monolayer. Both theory and experiments indicate that this mechanism applies also to other combinations of hetero-atoms and substrates.

Controlling subnanometer gaps in plasmonic dimers using graphene.

Graphene is used as the thinnest possible spacer between gold nanoparticles and a gold substrate. This creates a robust, repeatable, and stable subnanometer gap for massive plasmonic field enhancements. White light spectroscopy of single 80 nm gold nanoparticles reveals plasmonic coupling between the particle and its image within the gold substrate. While for a single graphene layer, spectral doublets from coupled dimer modes are observed shifted into the near-infrared, these disappear for increasing numbers of layers. These doublets arise from charger-transfer-sensitive gap plasmons, allowing optical measurement to access out-of-plane conductivity in such layered systems. Gating the graphene can thus directly produce plasmon tuning.

Terahertz near-field microscopy of metallic circular split ring resonators with graphene in the gap.

Optical resonators are fundamental building blocks of photonic systems, enabling meta-surfaces, sensors, and transmission filters to be developed for a range of applications. Sub-wavelength size (< λ/10) resonators, including planar split-ring resonators, are at the forefront of research owing to their potential for light manipulation, sensing applications and for exploring fundamental light-matter coupling phenomena. Near-field microscopy has emerged as a valuable tool for mode imaging in sub-wavelength size terahertz (THz) frequency resonators, essential for emerging THz devices (e.g. negative index materials, magnetic mirrors, filters) and enhanced light-matter interaction phenomena. Here, we probe coherently the localized field supported by circular split ring resonators with single layer graphene (SLG) embedded in the resonator gap, by means of scattering-type scanning near-field optical microscopy (s-SNOM), using either a single-mode or a frequency comb THz quantum cascade laser (QCL), in a detectorless configuration, via self-mixing interferometry. We demonstrate deep sub-wavelength mapping of the field distribution associated with in-plane resonator modes resolving both amplitude and phase of the supported modes, and unveiling resonant electric field enhancement in SLG, key for high harmonic generation.

Ultrafast Charge Transfer and Recombination Dynamics in Monolayer-Multilayer WSe2 Junctions Revealed by Time-Resolved Photoemission Electron Microscopy.

The ultrafast carrier dynamics of junctions between two chemically identical, but electronically distinct, transition metal dichalcogenides (TMDs) remains largely unknown. Here, we employ time-resolved photoemission electron microscopy (TR-PEEM) to probe the ultrafast carrier dynamics of a monolayer-to-multilayer (1L-ML) WSe2 junction. The TR-PEEM signals recorded for the individual components of the junction reveal the sub-ps carrier cooling dynamics of 1L- and 7L-WSe2, as well as few-ps exciton-exciton annihilation occurring on 1L-WSe2. We observe ultrafast interfacial hole (h) transfer from 1L- to 7L-WSe2 on an ∼0.2 ps time scale. The resultant excess h density in 7L-WSe2 decays by carrier recombination across the junction interface on an ∼100 ps time scale. Reminiscent of the behavior at a depletion region, the TR-PEEM image reveals the h density accumulation on the 7L-WSe2 interface, with a decay length ∼0.60 ± 0.17 µm. These charge transfer and recombination dynamics are in agreement with ab initio quantum dynamics. The computed orbital densities reveal that charge transfer occurs from the basal plane, which extends over both 1L and ML regions, to the upper plane localized on the ML region. This mode of charge transfer is distinctive to chemically homogeneous junctions of layered materials and constitutes an additional carrier deactivation pathway that should be considered in studies of 1L-TMDs found alongside their ML, a common occurrence in exfoliated samples.