Compact terahertz harmonic generation in the Reststrahlenband using a graphene-embedded metallic split ring resonator array.

Harmonic generation is a result of a strong non-linear interaction between light and matter. It is a key technology for optics, as it allows the conversion of optical signals to higher frequencies. Owing to its intrinsically large and electrically tunable non-linear optical response, graphene has been used for high harmonic generation but, until now, only at frequencies < 2 THz, and with high-power ultrafast table-top lasers or accelerator-based structures. Here, we demonstrate third harmonic generation at 9.63 THz by optically pumping single-layer graphene, coupled to a circular split ring resonator (CSRR) array, with a 3.21 THz frequency quantum cascade laser (QCL). Combined with the high graphene nonlinearity, the mode confinement provided by the optically-pumped CSRR enhances the pump power density as well as that at the third harmonic, permitting harmonic generation. This approach enables potential access to a frequency range (6-12 THz) where compact sources remain difficult to obtain, owing to the Reststrahlenband of typical III-V semiconductors.

Mapping nanoscale carrier confinement in polycrystalline graphene by terahertz spectroscopy.

Terahertz time-domain spectroscopy (THz-TDS) can be used to map spatial variations in electrical properties such as sheet conductivity, carrier density, and carrier mobility in graphene. Here, we consider wafer-scale graphene grown on germanium by chemical vapor deposition with non-uniformities and small domains due to reconstructions of the substrate during growth. The THz conductivity spectrum matches the predictions of the phenomenological Drude-Smith model for conductors with non-isotropic scattering caused by backscattering from boundaries and line defects. We compare the charge carrier mean free path determined by THz-TDS with the average defect distance assessed by Raman spectroscopy, and the grain boundary dimensions as determined by transmission electron microscopy. The results indicate that even small angle orientation variations below 5° within graphene grains influence the scattering behavior, consistent with significant backscattering contributions from grain boundaries.

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.

Controlled Growth of Single-Crystal Graphene Wafers on Twin-Boundary-Free Cu(111) Substrates.

Single-crystal graphene (SCG) wafers are needed to enable mass-electronics and optoelectronics owing to their excellent properties and compatibility with silicon-based technology. Controlled synthesis of high-quality SCG wafers can be done exploiting single-crystal Cu(111) substrates as epitaxial growth substrates recently. However, current Cu(111) films prepared by magnetron sputtering on single-crystal sapphire wafers still suffer from in-plane twin boundaries, which degrade the SCG chemical vapor deposition. Here, it is shown how to eliminate twin boundaries on Cu and achieve 4 in. Cu(111) wafers with ≈95% crystallinity. The introduction of a temperature gradient on Cu films with designed texture during annealing drives abnormal grain growth across the whole Cu wafer. In-plane twin boundaries are eliminated via migration of out-of-plane grain boundaries. SCG wafers grown on the resulting single-crystal Cu(111) substrates exhibit improved crystallinity with >97% aligned graphene domains. As-synthesized SCG wafers exhibit an average carrier mobility up to 7284 cm2 V-1 s-1 at room temperature from 103 devices and a uniform sheet resistance with only 5% deviation in 4 in. region.

Electrically Tunable Nonlinearity at 3.2 Terahertz in Single-Layer Graphene.

Graphene is a nonlinear material in the terahertz (THz) frequency range, with χ(3) ∼ 10-9 m2/V2 ∼ 15 orders of magnitude higher than that of other materials used in the THz range, such as GaAs or lithium niobate. This nonlinear behavior, combined with ultrafast dynamic for excited carriers, proved to be essential for third harmonic generation in the sub-THz and low (<2.5 THz) THz range, using moderate (60 kV/cm) fields and at room temperature. Here, we show that, for monochromatic high peak power (1.8 W) input THz signals, emitted by a quantum cascade laser, the nonlinearity can be controlled using an ionic liquid gate that tunes the graphene Fermi energy up to >1.2 eV. Pump and probe experiments reveal an intense absorption nonlinearity at 3.2 THz, with a dominant 3rd-order contribution at EF > 0.7 eV, hence opening intriguing perspectives per engineering novel architectures for light generation at frequencies > 9 THz.

Ultrafast Electronic Relaxation Dynamics of Atomically Thin MoS2 Is Accelerated by Wrinkling.

Strain engineering is an attractive approach for tuning the local optoelectronic properties of transition metal dichalcogenides (TMDs). While strain has been shown to affect the nanosecond carrier recombination dynamics of TMDs, its influence on the sub-picosecond electronic relaxation dynamics is still unexplored. Here, we employ a combination of time-resolved photoemission electron microscopy (TR-PEEM) and nonadiabatic ab initio molecular dynamics (NAMD) to investigate the ultrafast dynamics of wrinkled multilayer (ML) MoS2 comprising 17 layers. Following 2.41 eV photoexcitation, electronic relaxation at the Γ valley occurs with a time constant of 97 ± 2 fs for wrinkled ML-MoS2 and 120 ± 2 fs for flat ML-MoS2. NAMD shows that wrinkling permits larger amplitude motions of MoS2 layers, relaxes electron-phonon coupling selection rules, perturbs chemical bonding, and increases the electronic density of states. As a result, the nonadiabatic coupling grows and electronic relaxation becomes faster compared to flat ML-MoS2. Our study suggests that the sub-picosecond electronic relaxation dynamics of TMDs is amenable to strain engineering and that applications which require long-lived hot carriers, such as hot-electron-driven light harvesting and photocatalysis, should employ wrinkle-free TMDs.

Near- and Far-Field Observation of Phonon Polaritons in Wafer-Scale Multilayer Hexagonal Boron Nitride Prepared by Chemical Vapor Deposition.

Polaritons in layered materials (LMs) are a promising platform to manipulate and control light at the nanometer scale. Thus, the observation of polaritons in wafer-scale LMs is critically important for the development of industrially relevant nanophotonics and optoelectronics applications. In this work, phonon polaritons (PhPs) in wafer-scale multilayer hexagonal boron nitride (hBN) grown by chemical vapor deposition are reported. By infrared nanoimaging, the PhPs are visualized, and PhP lifetimes of ≈0.6 ps are measured, comparable to that of micromechanically exfoliated multilayer hBN. Further, PhP nanoresonators are demonstrated. Their quality factors of ≈50 are about 0.7 times that of state-of-the-art devices based on exfoliated hBN. These results can enable PhP-based surface-enhanced infrared spectroscopy (e.g., for gas sensing) and infrared photodetector applications.

Nanoscale Cathodoluminescence and Conductive Mode Scanning Electron Microscopy of van der Waals Heterostructures.

van der Waals heterostructures (vdW-HSs) integrate dissimilar materials to form complex devices. These rely on the manipulation of charges at multiple interfaces. However, at present, submicrometer variations in strain, doping, or electrical breakages may exist undetected within a device, adversely affecting macroscale performance. Here, we use conductive mode and cathodoluminescence scanning electron microscopy (CM-SEM and SEM-CL) to investigate these phenomena. As a model system, we use a monolayer WSe2 (1L-WSe2) encapsulated in hexagonal boron nitride (hBN). CM-SEM allows for quantification of the flow of electrons during the SEM measurements. During electron irradiation at 5 keV, up to 70% of beam electrons are deposited into the vdW-HS and can subsequently migrate to the 1L-WSe2. This accumulation of charge leads to dynamic doping of 1L-WSe2, reducing its CL efficiency by up to 30% over 30 s. By providing a path for excess electrons to leave the sample, near full restoration of the initial CL signal can be achieved. These results indicate that the trapping of charges in vdW-HSs during electron irradiation must be considered, in order to obtain and maintain optimal performance of vdW-HS devices during processes such as e-beam lithography or SEM. Thus, CM-SEM and SEM-CL form a toolkit through which nanoscale characterization of vdW-HS devices can be performed, allowing electrical and optical properties to be correlated.

Layered materials as a platform for quantum technologies.

Layered materials are taking centre stage in the ever-increasing research effort to develop material platforms for quantum technologies. We are at the dawn of the era of layered quantum materials. Their optical, electronic, magnetic, thermal and mechanical properties make them attractive for most aspects of this global pursuit. Layered materials have already shown potential as scalable components, including quantum light sources, photon detectors and nanoscale sensors, and have enabled research of new phases of matter within the broader field of quantum simulations. In this Review we discuss opportunities and challenges faced by layered materials within the landscape of material platforms for quantum technologies. In particular, we focus on applications that rely on light-matter interfaces.

Identification of Exciton Complexes in Charge-Tunable Janus WSeS Monolayers.

Janus transition-metal dichalcogenide monolayers are artificial materials, where one plane of chalcogen atoms is replaced by chalcogen atoms of a different type. Theory predicts an in-built out-of-plane electric field, giving rise to long-lived, dipolar excitons, while preserving direct-bandgap optical transitions in a uniform potential landscape. Previous Janus studies had broad photoluminescence (>18 meV) spectra obfuscating their specific excitonic origin. Here, we identify the neutral and the negatively charged inter- and intravalley exciton transitions in Janus WSeS monolayers with ∼6 meV optical line widths. We integrate Janus monolayers into vertical heterostructures, allowing doping control. Magneto-optic measurements indicate that monolayer WSeS has a direct bandgap at the K points. Our results pave the way for applications such as nanoscale sensing, which relies on resolving excitonic energy shifts, and the development of Janus-based optoelectronic devices, which requires charge-state control and integration into vertical heterostructures.

Control of Raman Scattering Quantum Interference Pathways in Graphene.

Graphene is an ideal platform to study the coherence of quantum interference pathways by tuning doping or laser excitation energy. The latter produces a Raman excitation profile that provides direct insight into the lifetimes of intermediate electronic excitations and, therefore, on quantum interference, which has so far remained elusive. Here, we control the Raman scattering pathways by tuning the laser excitation energy in graphene doped up to 1.05 eV. The Raman excitation profile of the G mode indicates its position and full width at half-maximum are linearly dependent on doping. Doping-enhanced electron-electron interactions dominate the lifetimes of Raman scattering pathways and reduce Raman interference. This will provide guidance for engineering quantum pathways for doped graphene, nanotubes, and topological insulators.

Self-Induced Mode-Locking in Electrically Pumped Far-Infrared Random Lasers.

Mode locking, the self-starting synchronous oscillation of electromagnetic modes in a laser cavity, is the primary way to generate ultrashort light pulses. In random lasers, without a cavity, mode-locking, the nonlinear coupling amongst low spatially coherent random modes, can be activated via optical pumping, even without the emission of short pulses. Here, by exploiting the combination of the inherently giant third-order χ(3) nonlinearity of semiconductor heterostructure lasers and the nonlinear properties of graphene, the authors demonstrate mode-locking in surface-emitting electrically pumped random quantum cascade lasers at terahertz frequencies. This is achieved by either lithographically patterning a multilayer graphene film to define a surface random pattern of light scatterers, or by coupling on chip a saturable absorber graphene reflector. Intermode beatnote mapping unveils self-induced phase-coherence between naturally incoherent random modes. Self-mixing intermode spectroscopy reveals phase-locked random modes. This is an important milestone in the physics of disordered systems. It paves the way to the development of a new generation of miniaturized, electrically pumped mode-locked light sources, ideal for broadband spectroscopy, multicolor speckle-free imaging applications, and reservoir quantum computing.

Resistive Switching Crossbar Arrays Based on Layered Materials.

Resistive switching (RS) devices are metal/insulator/metal cells that can change their electrical resistance when electrical stimuli are applied between the electrodes, and they can be used to store and compute data. Planar crossbar arrays of RS devices can offer a high integration density (>108  devices mm- 2 ) and this can be further enhanced by stacking them three-dimensionally. The advantage of using layered materials (LMs) in RS devices compared to traditional phase-change materials and metal oxides is that their electrical properties can be adjusted with a higher precision. Here, the key figures-of-merit and procedures to implement LM-based RS devices are defined. LM-based RS devices fabricated using methods compatible with industry are identified and discussed. The focus is on small devices (size < 9 µm2 ) arranged in crossbar structures, since larger devices may be affected by artifacts, such as grain boundaries and flake junctions. How to enhance device performance, so to accelerate the development of this technology, is also discussed.

Unbiased Plasmonic-Assisted Integrated Graphene Photodetectors.

Photonic integrated circuits (PICs) for next-generation optical communication interconnects and all-optical signal processing require efficient (∼A/W) and fast (≥25 Gbs-1) light detection at low (

Moiré Modulation of Van Der Waals Potential in Twisted Hexagonal Boron Nitride.

When a twist angle is applied between two layered materials (LMs), the registry of the layers and the associated change in their functional properties are spatially modulated, and a moiré superlattice arises. Several works explored the optical, electric, and electromechanical moiré-dependent properties of such twisted LMs but, to the best of our knowledge, no direct visualization and quantification of van der Waals (vdW) interlayer interactions has been presented, so far. Here, we use tapping mode atomic force microscopy phase-imaging to probe the spatial modulation of the vdW potential in twisted hexagonal boron nitride. We find a moiré superlattice in the phase channel only when noncontact (long-range) forces are probed, revealing the modulation of the vdW potential at the sample surface, following AB and BA stacking domains. The creation of scalable electrostatic domains, modulating the vdW potential at the interface with the environment by means of layer twisting, could be used for local adhesion engineering and surface functionalization by affecting the deposition of molecules or nanoparticles.

Electrically Tunable Nonequilibrium Optical Response of Graphene.

The ability to tune the optical response of a material via electrostatic gating is crucial for optoelectronic applications, such as electro-optic modulators, saturable absorbers, optical limiters, photodetectors, and transparent electrodes. The band structure of single layer graphene (SLG), with zero-gap, linearly dispersive conduction and valence bands, enables an easy control of the Fermi energy, EF, and of the threshold for interband optical absorption. Here, we report the tunability of the SLG nonequilibrium optical response in the near-infrared (1000-1700 nm/0.729-1.240 eV), exploring a range of EF from -650 to 250 meV by ionic liquid gating. As EF increases from the Dirac point to the threshold for Pauli blocking of interband absorption, we observe a slow-down of the photobleaching relaxation dynamics, which we attribute to the quenching of optical phonon emission from photoexcited charge carriers. For EF exceeding the Pauli blocking threshold, photobleaching eventually turns into photoinduced absorption, because the hot electrons' excitation increases the SLG absorption. The ability to control both recovery time and sign of the nonequilibrium optical response by electrostatic gating makes SLG ideal for tunable saturable absorbers with controlled dynamics.

Chip-Scalable, Room-Temperature, Zero-Bias, Graphene-Based Terahertz Detectors with Nanosecond Response Time.

The scalable synthesis and transfer of large-area graphene underpins the development of nanoscale photonic devices ideal for new applications in a variety of fields, ranging from biotechnology, to wearable sensors for healthcare and motion detection, to quantum transport, communications, and metrology. We report room-temperature zero-bias thermoelectric photodetectors, based on single- and polycrystal graphene grown by chemical vapor deposition (CVD), tunable over the whole terahertz range (0.1-10 THz) by selecting the resonance of an on-chip patterned nanoantenna. Efficient light detection with noise equivalent powers <1 nWHz-1/2 and response time ∼5 ns at room temperature are demonstrated. This combination of specifications is orders of magnitude better than any previous CVD graphene photoreceiver operating in the sub-THz and THz range. These state-of-the-art performances and the possibility of upscaling to multipixel architectures on complementary metal-oxide-semiconductor platforms are the starting points for the realization of cost-effective THz cameras in a frequency range still not covered by commercially available microbolometer arrays.

Shear and Breathing Modes of Layered Materials.

Layered materials (LMs), such as graphite, hexagonal boron nitride, and transition-metal dichalcogenides, are at the center of an ever-increasing research effort, due to their scientific and technological relevance. Raman and infrared spectroscopies are accurate, non-destructive approaches to determine a wide range of properties, including the number of layers, N, and the strength of the interlayer interactions. We present a general approach to predict the complete spectroscopic fan diagrams, i.e., the relations between frequencies and N for the optically active shear and layer-breathing modes of any multilayer comprising N ≥ 2 identical layers. In order to achieve this, we combine a description of the normal modes in terms of a one-dimensional mechanical model, with symmetry arguments that describe the evolution of the point group as a function of N. Group theory is then used to identify which modes are Raman- and/or infrared-active, and to provide diagrams of the optically active modes for any stack composed of identical layers. We implement the method and algorithms in an open-source tool to assist researchers in the prediction and interpretation of such diagrams. Our work will underpin future efforts on Raman and infrared characterization of known, and yet not investigated, LMs.

High-yield parallel fabrication of quantum-dot monolayer single-electron devices displaying Coulomb staircase, contacted by graphene.

It is challenging for conventional top-down lithography to fabricate reproducible devices very close to atomic dimensions, whereas identical molecules and very similar nanoparticles can be made bottom-up in large quantities, and can be self-assembled on surfaces. The challenge is to fabricate electrical contacts to many such small objects at the same time, so that nanocrystals and molecules can be incorporated into conventional integrated circuits. Here, we report a scalable method for contacting a self-assembled monolayer of nanoparticles with a single layer of graphene. This produces single-electron effects, in the form of a Coulomb staircase, with a yield of 87 ± 13% in device areas ranging from < 800 nm2 to 16 µm2, containing up to 650,000 nanoparticles. Our technique offers scalable assembly of ultra-high densities of functional particles or molecules that could be used in electronic integrated circuits, as memories, switches, sensors or thermoelectric generators.