Azobenzene-based optoelectronic transistors for neurohybrid building blocks.

Exploiting the light-matter interplay to realize advanced light responsive multimodal platforms is an emerging strategy to engineer bioinspired systems such as optoelectronic synaptic devices. However, existing neuroinspired optoelectronic devices rely on complex processing of hybrid materials which often do not exhibit the required features for biological interfacing such as biocompatibility and low Young's modulus. Recently, organic photoelectrochemical transistors (OPECTs) have paved the way towards multimodal devices that can better couple to biological systems benefiting from the characteristics of conjugated polymers. Neurohybrid OPECTs can be designed to optimally interface neuronal systems while resembling typical plasticity-driven processes to create more sophisticated integrated architectures between neuron and neuromorphic ends. Here, an innovative photo-switchable PEDOT:PSS was synthesized and successfully integrated into an OPECT. The OPECT device uses an azobenzene-based organic neuro-hybrid building block to mimic the retina's structure exhibiting the capability to emulate visual pathways. Moreover, dually operating the device with opto- and electrical functions, a light-dependent conditioning and extinction processes were achieved faithful mimicking synaptic neural functions such as short- and long-term plasticity.

Industrial Graphene Coating of Low-Voltage Copper Wires for Power Distribution.

Copper (Cu) is the electrical conductor of choice in many categories of electrical wiring, with household and building installation being the major market of this metal. This work demonstrates the coating of Cu wires-with diameters relevant for low-voltage (LV) applications-with graphene. The chemical vapor deposition (CVD) coating process is rapid, safe, scalable, and industrially compatible. Graphene-coated Cu wires display good oxidation resistance and increased electrical conductivity (up to 1% immediately after coating and up to 3% after 24 months), allowing for wire diameter reduction and thus significant savings in wire production costs. Combined spectroscopic and diffraction analysis indicates that the conductivity increase is due to a change in Cu crystallinity induced by the coating process conditions, while electrical testing of aged wires shows that graphene plays a major role in maintaining improved electrical performances over long periods of time. Finally, graphene coating of Cu wires using an ambient-pressure roll-to-roll (R2R) CVD reactor is demonstrated. This enables the in-line production of graphene-coated metallic wires as required for industrial scale-up.

Ultra-clean high-mobility graphene on technologically relevant substrates.

Graphene grown via chemical vapour deposition (CVD) on copper foil has emerged as a high-quality, scalable material, that can be easily integrated on technologically relevant platforms to develop promising applications in the fields of optoelectronics and photonics. Most of these applications require low-contaminated high-mobility graphene (i.e., approaching 10 000 cm2 V-1 s-1 at room temperature) to reduce device losses and implement compact device design. To date, these mobility values are only obtained when suspending or encapsulating graphene. Here, we demonstrate a rapid, facile, and scalable cleaning process, that yields high-mobility graphene directly on the most common technologically relevant substrate: silicon dioxide on silicon (SiO2/Si). Atomic force microscopy (AFM) and spatially-resolved X-ray photoelectron spectroscopy (XPS) demonstrate that this approach is instrumental to rapidly eliminate most of the polymeric residues which remain on graphene after transfer and fabrication and that have adverse effects on its electrical properties. Raman measurements show a significant reduction of graphene doping and strain. Transport measurements of 50 Hall bars (HBs) yield hole mobility µh up to ∼9000 cm2 V-1 s-1 and electron mobility µe up to ∼8000 cm2 V-1 s-1, with average values µh ∼ 7500 cm2 V-1 s-1 and µe ∼ 6300 cm2 V-1 s-1. The carrier mobility of ultraclean graphene reaches values nearly double than those measured in graphene processed with acetone cleaning, which is the method widely adopted in the field. Notably, these mobility values are obtained over large-scale and without encapsulation, thus paving the way to the adoption of graphene in optoelectronics and photonics.

Local Optical Properties in CVD-Grown Monolayer WS2 Flakes.

Excitons dominate the light absorption and re-emission spectra of monolayer transition-metal dichalcogenides (TMD). Microscopic investigations of the excitonic response in TMD almost invariably extract information from the radiative recombination step, which only constitutes one part of the picture. Here, by exploiting imaging spectroscopic ellipsometry (ISE), we investigate the spatial dependence of the dielectric function of chemical vapor deposition (CVD)-grown WS2 flakes with a microscopic lateral resolution, thus providing information about the spatially varying, exciton-induced light absorption in the monolayer WS2. Comparing the ISE results with imaging photoluminescence spectroscopy data, the presence of several correlated features was observed, along with the unexpected existence of a few uncorrelated characteristics. The latter demonstrates that the exciton-induced absorption and emission features are not always proportional at the microscopic scale. Microstructural modulations across the flakes, having a different influence on the absorption and re-emission of light, are deemed responsible for the effect.

Survival of Floquet-Bloch States in the Presence of Scattering.

Floquet theory has spawned many exciting possibilities for electronic structure control with light, with enormous potential for future applications. The experimental demonstration in solids, however, remains largely unrealized. In particular, the influence of scattering on the formation of Floquet-Bloch states remains poorly understood. Here we combine time- and angle-resolved photoemission spectroscopy with time-dependent density functional theory and a two-level model with relaxation to investigate the survival of Floquet-Bloch states in the presence of scattering. We find that Floquet-Bloch states will be destroyed if scattering-activated by electronic excitations-prevents the Bloch electrons from following the driving field coherently. The two-level model also shows that Floquet-Bloch states reappear at high field intensities where energy exchange with the driving field dominates over energy dissipation to the bath. Our results clearly indicate the importance of long scattering times combined with strong driving fields for the successful realization of various Floquet phenomena.

Hot-Carrier Cooling in High-Quality Graphene Is Intrinsically Limited by Optical Phonons.

Many promising optoelectronic devices, such as broadband photodetectors, nonlinear frequency converters, and building blocks for data communication systems, exploit photoexcited charge carriers in graphene. For these systems, it is essential to understand the relaxation dynamics after photoexcitation. These dynamics contain a sub-100 fs thermalization phase, which occurs through carrier-carrier scattering and leads to a carrier distribution with an elevated temperature. This is followed by a picosecond cooling phase, where different phonon systems play a role: graphene acoustic and optical phonons, and substrate phonons. Here, we address the cooling pathway of two technologically relevant systems, both consisting of high-quality graphene with a mobility >10 000 cm2 V-1 s-1 and environments that do not efficiently take up electronic heat from graphene: WSe2-encapsulated graphene and suspended graphene. We study the cooling dynamics using ultrafast pump-probe spectroscopy at room temperature. Cooling via disorder-assisted acoustic phonon scattering and out-of-plane heat transfer to substrate phonons is relatively inefficient in these systems, suggesting a cooling time of tens of picoseconds. However, we observe much faster cooling, on a time scale of a few picoseconds. We attribute this to an intrinsic cooling mechanism, where carriers in the high-energy tail of the hot-carrier distribution emit optical phonons. This creates a permanent heat sink, as carriers efficiently rethermalize. We develop a macroscopic model that explains the observed dynamics, where cooling is eventually limited by optical-to-acoustic phonon coupling. These fundamental insights will guide the development of graphene-based optoelectronic devices.

Synthesis of Large-Scale Monolayer 1T'-MoTe2 and Its Stabilization via Scalable hBN Encapsulation.

Out of the different structural phases of molybdenum ditelluride (MoTe2), the distorted octahedral 1T' possesses great interest for fundamental physics and is a promising candidate for the implementation of innovative devices such as topological transistors. Indeed, 1T'-MoTe2 is a semimetal with superconductivity, which has been predicted to be a Weyl semimetal and a quantum spin Hall insulator in bulk and monolayer form, respectively. Large instability of monolayer 1T'-MoTe2 in environmental conditions, however, has made its investigation extremely challenging so far. In this work, we demonstrate homogeneous growth of large single-crystal (up to 500 µm) monolayer 1T'-MoTe2 via chemical vapor deposition (CVD) and its stabilization in air with a scalable encapsulation approach. The encapsulant is obtained by electrochemically delaminating CVD hexagonal boron nitride (hBN) from copper foil, and it is applied on the freshly grown 1T'-MoTe2 via a top-down dry lamination step. The structural and electrical properties of encapsulated 1T'-MoTe2 have been monitored over several months to assess the degree of degradation of the material. We find that when encapsulated with hBN, the lifetime of monolayer 1T'-MoTe2 successfully increases from a few minutes to more than a month. Furthermore, the encapsulated monolayer can be subjected to transfer, device processing, and heating and cooling cycles without degradation of its properties. The potential of this scalable heterostack is confirmed by the observation of signatures of low-temperature phase transition in monolayer 1T'-MoTe2 by both Raman spectroscopy and electrical measurements. The growth and encapsulation methods reported in this work can be employed for further fundamental studies of this enticing material as well as facilitate the technological development of monolayer 1T'-MoTe2.

Scanning Probe Spectroscopy of WS2/Graphene Van Der Waals Heterostructures.

In this paper, we present a study of tungsten disulfide (WS2) two-dimensional (2D) crystals, grown on epitaxial Graphene. In particular, we have employed scanning electron microscopy (SEM) and µRaman spectroscopy combined with multifunctional scanning probe microscopy (SPM), operating in peak force-quantitative nano mechanical (PF-QNM), ultrasonic force microscopy (UFM) and electrostatic force microscopy (EFM) modes. This comparative approach provides a wealth of useful complementary information and allows one to cross-analyze on the nanoscale the morphological, mechanical, and electrostatic properties of the 2D heterostructures analyzed. Herein, we show that PF-QNM can accurately map surface properties, such as morphology and adhesion, and that UFM is exceptionally sensitive to a broader range of elastic properties, helping to uncover subsurface features located at the buried interfaces. All these data can be correlated with the local electrostatic properties obtained via EFM mapping of the surface potential, through the cantilever response at the first harmonic, and the dielectric permittivity, through the cantilever response at the second harmonic. In conclusion, we show that combining multi-parametric SPM with SEM and µRaman spectroscopy helps to identify single features of the WS2/Graphene/SiC heterostructures analyzed, demonstrating that this is a powerful tool-set for the investigation of 2D materials stacks, a building block for new advanced nano-devices.

Epitaxial Growth of Wafer-Scale Molybdenum Disulfide/Graphene Heterostructures by Metal-Organic Vapor-Phase Epitaxy and Their Application in Photodetectors.

Van der Waals heterostructures have attracted increasing interest, owing to the combined benefits of their constituents. These hybrid nanostructures can be realized via epitaxial growth, which offers a promising approach for the controlled synthesis of the desired crystal phase and the interface between van der Waals layers. Here, the epitaxial growth of a continuous molybdenum disulfide (MoS2) film on large-area graphene, which was directly grown on a sapphire substrate, is reported. Interestingly, the grain size of MoS2 grown on graphene increases, whereas that of MoS2 grown on SiO2 decreases with an increasing amount of hydrogen in the chemical vapor deposition reactor. In addition, to achieve the same quality, MoS2 grown on graphene requires a much lower growth temperature (400 °C) than that grown on SiO2 (580 °C). The MoS2/graphene heterostructure that was epitaxially grown on a transparent platform was investigated to explore its photosensing properties and was found to exhibit inverse photoresponse with highly uniform photoresponsivity in the photodetector pixels fabricated across a full wafer. The MoS2/graphene heterostructure exhibited ultrahigh photoresponsivity (4.3 × 104 A W-1) upon exposure to visible light of a wide range of wavelengths, confirming the growth of a high-quality MoS2/graphene heterostructure with a clean interface.

Ultrafast, Zero-Bias, Graphene Photodetectors with Polymeric Gate Dielectric on Passive Photonic Waveguides.

We report compact, scalable, high-performance, waveguide integrated graphene-based photodetectors (GPDs) for telecom and datacom applications, not affected by dark current. To exploit the photothermoelectric (PTE) effect, our devices rely on a graphene/polymer/graphene stack with static top split gates. The polymeric dielectric, poly(vinyl alcohol) (PVA), allows us to preserve graphene quality and to generate a controllable p-n junction. Both graphene layers are fabricated using aligned single-crystal graphene arrays grown by chemical vapor deposition. The use of PVA yields a low charge inhomogeneity ∼8 × 1010 cm-2 at the charge neutrality point, and a large Seebeck coefficient ∼140 µV K-1, enhancing the PTE effect. Our devices are the fastest GPDs operating with zero dark current, showing a flat frequency response up to 67 GHz without roll-off. This performance is achieved on a passive, low-cost, photonic platform, and does not rely on nanoscale plasmonic structures. This, combined with scalability and ease of integration, makes our GPDs a promising building block for next-generation optical communication devices.

Direct evidence for efficient ultrafast charge separation in epitaxial WS2/graphene heterostructures.

We use time- and angle-resolved photoemission spectroscopy (tr-ARPES) to investigate ultrafast charge transfer in an epitaxial heterostructure made of monolayer WS2 and graphene. This heterostructure combines the benefits of a direct-gap semiconductor with strong spin-orbit coupling and strong light-matter interaction with those of a semimetal hosting massless carriers with extremely high mobility and long spin lifetimes. We find that, after photoexcitation at resonance to the A-exciton in WS2, the photoexcited holes rapidly transfer into the graphene layer while the photoexcited electrons remain in the WS2 layer. The resulting charge-separated transient state is found to have a lifetime of ∼1 ps. We attribute our findings to differences in scattering phase space caused by the relative alignment of WS2 and graphene bands as revealed by high-resolution ARPES. In combination with spin-selective optical excitation, the investigated WS2/graphene heterostructure might provide a platform for efficient optical spin injection into graphene.

Semiconductor to metal transition in two-dimensional gold and its van der Waals heterostack with graphene.

The synthesis of two-dimensional (2D) transition metals has attracted growing attention for both fundamental and application-oriented investigations, such as 2D magnetism, nanoplasmonics and non-linear optics. However, the large-area synthesis of this class of materials in a single-layer form poses non-trivial difficulties. Here we present the synthesis of a large-area 2D gold layer, stabilized in between silicon carbide and monolayer graphene. We show that the 2D-Au ML is a semiconductor with the valence band maximum 50 meV below the Fermi level. The graphene and gold layers are largely non-interacting, thereby defining a class of van der Waals heterostructure. The 2D-Au bands, exhibit a 225 meV spin-orbit splitting along the [Formula: see text] direction, making it appealing for spin-related applications. By tuning the amount of gold at the SiC/graphene interface, we induce a semiconductor to metal transition in the 2D-Au, which has not yet been observed and hosts great interest for fundamental physics.

30°-Twisted Bilayer Graphene Quasicrystals from Chemical Vapor Deposition.

The artificial stacking of atomically thin crystals suffers from intrinsic limitations in terms of control and reproducibility of the relative orientation of exfoliated flakes. This drawback is particularly severe when the properties of the system critically depends on the twist angle, as in the case of the dodecagonal quasicrystal formed by two graphene layers rotated by 30°. Here we show that large-area 30°-rotated bilayer graphene can be grown deterministically by chemical vapor deposition on Cu, eliminating the need of artificial assembly. The quasicrystals are easily transferred to arbitrary substrates and integrated in high-quality hexagonal boron nitride-encapsulated heterostructures, which we process into dual-gated devices exhibiting carrier mobility up to 105 cm2/(V s). From low-temperature magnetotransport, we find that the graphene quasicrystals effectively behave as uncoupled graphene layers, showing 8-fold degenerate quantum Hall states. This result indicates that the Dirac cones replica detected by previous photoemission experiments do not contribute to the electrical transport.

Wafer-Scale Synthesis of Graphene on Sapphire: Toward Fab-Compatible Graphene.

The adoption of graphene in electronics, optoelectronics, and photonics is hindered by the difficulty in obtaining high-quality material on technologically relevant substrates, over wafer-scale sizes, and with metal contamination levels compatible with industrial requirements. To date, the direct growth of graphene on insulating substrates has proved to be challenging, usually requiring metal-catalysts or yielding defective graphene. In this work, a metal-free approach implemented in commercially available reactors to obtain high-quality monolayer graphene on c-plane sapphire substrates via chemical vapor deposition is demonstrated. Low energy electron diffraction, low energy electron microscopy, and scanning tunneling microscopy measurements identify the Al-rich reconstruction 31 × 31 R ± 9 ° of sapphire to be crucial for obtaining epitaxial graphene. Raman spectroscopy and electrical transport measurements reveal high-quality graphene with mobilities consistently above 2000 cm2 V-1 s-1 . The process is scaled up to 4 and 6 in. wafers sizes and metal contamination levels are retrieved to be within the limits for back-end-of-line integration. The growth process introduced here establishes a method for the synthesis of wafer-scale graphene films on a technologically viable basis.

Electronic properties of single-layer tungsten disulfide on epitaxial graphene on silicon carbide.

This work reports an electronic and micro-structural study of an appealing system for optoelectronics: tungsten disulfide (WS2) on epitaxial graphene (EG) on SiC(0001). The WS2 is grown via chemical vapor deposition (CVD) onto the EG. Low-energy electron diffraction (LEED) measurements assign the zero-degree orientation as the preferential azimuthal alignment for WS2/EG. The valence-band (VB) structure emerging from this alignment is investigated by means of photoelectron spectroscopy measurements, with both high space and energy resolution. We find that the spin-orbit splitting of monolayer WS2 on graphene is of 462 meV, larger than what is reported to date for other substrates. We determine the value of the work function for the WS2/EG to be 4.5 ± 0.1 eV. A large shift of the WS2 VB maximum is observed as well, due to the lowering of the WS2 work function caused by the donor-like interfacial states of EG. Density functional theory (DFT) calculations carried out on a coincidence supercell confirm the experimental band structure to an excellent degree. X-ray photoemission electron microscopy (XPEEM) measurements performed on single WS2 crystals confirm the van der Waals nature of the interface coupling between the two layers. In virtue of its band alignment and large spin-orbit splitting, this system gains strong appeal for optical spin-injection experiments and opto-spintronic applications in general.

Ballistic bipolar junctions in chemically gated graphene ribbons.

The realization of ballistic graphene pn-junctions is an essential task in order to study Klein tunneling phenomena. Here we show that intercalation of Ge under the buffer layer of pre-structured SiC-samples succeeds to make truly nano-scaled pn-junctions. By means of local tunneling spectroscopy the junction width is found to be as narrow as 5 nm which is a hundred times smaller compared to electrically gated structures. The ballistic transmission across the junction is directly proven by systematic transport measurements with a 4-tip STM. Various npn- and pnp-junctions are studied with respect to the barrier length. The pn-junctions are shown to act as polarizer and analyzer with the second junction becoming transparent in case of a fully ballistic barrier. This can be attributed to the almost full suppression of electron transmission through the junction away from normal incidence.