Interaction of graphene and WS2 with neutrophils and mesenchymal stem cells: implications for peripheral nerve regeneration.

Graphene and bidimensional (2D) materials have been widely used in nerve conduits to boost peripheral nerve regeneration. Nevertheless, the experimental and commercial variability in graphene-based materials generates graphene forms with different structures and properties that can trigger entirely diverse biological responses from all the players involved in nerve repair. Herein, we focus on the graphene and tungsten disulfide (WS2) interaction with non-neuronal cell types involved in nerve tissue regeneration. We synthesize highly crystalline graphene and WS2 with scalable techniques such as thermal decomposition and chemical vapor deposition. The materials were able to trigger the activation of a neutrophil human model promoting Neutrophil Extracellular Traps (NETs) production, particularly under basal conditions, although neutrophils were not able to degrade graphene. Of note is that pristine graphene acts as a repellent for the NET adhesion, a beneficial property for nerve conduit long-term applications. Mesenchymal stem cells (MSCs) have been proposed as a promising strategy for nerve regeneration in combination with a conduit. Thus, the interaction of graphene with MSCs was also investigated, and reduced viability was observed only on specific graphene substrates. Overall, the results confirm the possibility of regulating the cell response by varying graphene properties and selecting the most suitable graphene forms.

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.

Sub-THz wireless transmission based on graphene-integrated optoelectronic mixer.

Optoelectronics is a valuable solution to scale up wireless links frequency to sub-THz in the next generation antenna systems and networks. Here, we propose a low-power consumption, small footprint building block for 6 G and 5 G new radio wireless transmission allowing broadband capacity (e.g., 10-100 Gb/s per link and beyond). We demonstrate a wireless datalink based on graphene, reaching setup limited sub-THz carrier frequency and multi-Gbit/s data rate. Our device consists of a graphene-based integrated optoelectronic mixer capable of mixing an optically generated reference oscillator approaching 100 GHz, with a baseband electrical signal. We report >96 GHz optoelectronic bandwidth and -44 dB upconversion efficiency with a footprint significantly smaller than those of state-of-the-art photonic transmitters (i.e., <0.1 mm2). These results are enabled by an integrated-photonic technology based on wafer-scale high-mobility graphene and pave the way towards the development of optoelectronics-based arrayed-antennas for millimeter-wave technology.

Strong Coupling of Coherent Phonons to Excitons in Semiconducting Monolayer MoTe2.

The coupling of the electron system to lattice vibrations and their time-dependent control and detection provide unique insight into the nonequilibrium physics of semiconductors. Here, we investigate the ultrafast transient response of semiconducting monolayer 2H-MoTe2 encapsulated with hBN using broadband optical pump-probe microscopy. The sub-40 fs pump pulse triggers extremely intense and long-lived coherent oscillations in the spectral region of the A' and B' exciton resonances, up to ∼20% of the maximum transient signal, due to the displacive excitation of the out-of-plane A1g phonon. Ab initio calculations reveal a dramatic rearrangement of the optical absorption of monolayer MoTe2 induced by an out-of-plane stretching and compression of the crystal lattice, consistent with an A1g -type oscillation. Our results highlight the extreme sensitivity of the optical properties of monolayer TMDs to small structural modifications and their manipulation with light.

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.

Scalable High-Mobility Graphene/hBN Heterostructures.

Graphene-hexagonal boron nitride (hBN) scalable heterostructures are pivotal for the development of graphene-based high-tech applications. In this work, we demonstrate the realization of high-quality graphene-hBN heterostructures entirely obtained with scalable approaches. hBN continuous films were grown via ion beam-assisted physical vapor deposition directly on commercially available SiO2/Si and used as receiving substrates for graphene single-crystal matrixes grown by chemical vapor deposition on copper. The structural, chemical, and electronic properties of the heterostructure were investigated by atomic force microscopy, Raman spectroscopy, and electrical transport measurements. We demonstrate graphene carrier mobilities exceeding 10,000 cm2/Vs in ambient conditions, 30% higher than those directly measured on SiO2/Si. We prove the scalability of our approach by measuring more than 100 transfer length method devices over a centimeter scale, which present an average carrier mobility of 7500 ± 850 cm2/Vs. The reported high-quality all-scalable heterostructures are of relevance for the development of graphene-based high-performing electronic and optoelectronic applications.

Probing Enhanced Electron-Phonon Coupling in Graphene by Infrared Resonance Raman Spectroscopy.

We report on resonance Raman spectroscopy measurements with excitation photon energy down to 1.16 eV on graphene, to study how low-energy carriers interact with lattice vibrations. Thanks to the excitation energy close to the Dirac point at K, we unveil a giant increase of the intensity ratio between the double-resonant 2D and 2D^{'} peaks with respect to that measured in graphite. Comparing with fully ab initio theoretical calculations, we conclude that the observation is explained by an enhanced, momentum-dependent coupling between electrons and Brillouin zone-boundary optical phonons. This finding applies to two-dimensional Dirac systems and has important consequences for the modeling of transport in graphene devices operating at room temperature.

Local dielectric function of hBN-encapsulated WS2flakes grown by chemical vapor deposition.

Hexagonal boron nitride (hBN), sometimes referred to as white graphene, receives growing interest in the scientific community, especially when combined into van der Waals (vdW) homo- and heterostacks, in which novel and interesting phenomena may arise. hBN is also commonly used in combination with two-dimensional (2D) semiconducting transition metal dichalcogenides (TMDCs). The realization of hBN-encapsulated TMDC homo- and heterostacks can indeed offer opportunities to investigate and compare TMDC excitonic properties in various stacking configurations. In this work, we investigate the optical response at the micrometric scale of mono- and homo-bilayer WS2grown by chemical vapor deposition and encapsulated between two single layers of hBN. Imaging spectroscopic ellipsometry is exploited to extract the local dielectric functions across one single WS2flake and detect the evolution of excitonic spectral features from monolayer to bilayer regions. Exciton energies undergo a redshift by passing from hBN-encapsulated single layer to homo-bilayer WS2, as also confirmed by photoluminescence spectra. Our results can provide a reference for the study of the dielectric properties of more complex systems where hBN is combined with other 2D vdW materials into heterostructures and are stimulating towards the investigation of the optical response of other technologically-relevant heterostacks.

Strain-Induced Plasmon Confinement in Polycrystalline Graphene.

Terahertz spectroscopy is a perfect tool to investigate the electronic intraband conductivity of graphene, but a phenomenological model (Drude-Smith) is often needed to describe disorder. By studying the THz response of isotropically strained polycrystalline graphene and using a fully atomistic computational approach to fit the results, we demonstrate here the connection between the Drude-Smith parameters and the microscopic behavior. Importantly, we clearly show that the strain-induced changes in the conductivity originate mainly from the increased separation between the single-crystal grains, leading to enchanced localization of the plasmon excitations. Only at the lowest strain values explored, a behavior consistent with the deformation of the individual grains can instead be observed.

Graphene-based nanomaterials for peripheral nerve regeneration.

Emerging nanotechnologies offer numerous opportunities in the field of regenerative medicine and have been widely explored to design novel scaffolds for the regeneration and stimulation of nerve tissue. In this review, we focus on peripheral nerve regeneration. First, we introduce the biomedical problem and the present status of nerve conduits that can be used to guide, fasten and enhance regeneration. Then, we thoroughly discuss graphene as an emerging candidate in nerve tissue engineering, in light of its chemical, tribological and electrical properties. We introduce the graphene forms commonly used as neural interfaces, briefly review their applications, and discuss their potential toxicity. We then focus on the adoption of graphene in peripheral nervous system applications, a research field that has gained in the last years ever-increasing attention. We discuss the potential integration of graphene in guidance conduits, and critically review graphene interaction not only with peripheral neurons, but also with non-neural cells involved in nerve regeneration; indeed, the latter have recently emerged as central players in modulating the immune and inflammatory response and accelerating the growth of new tissue.

Moiré-Induced Transport in CVD-Based Small-Angle Twisted Bilayer Graphene.

To realize the applicative potential of 2D twistronic devices, scalable synthesis and assembly techniques need to meet stringent requirements in terms of interface cleanness and twist-angle homogeneity. Here, we show that small-angle twisted bilayer graphene assembled from separated CVD-grown graphene single-crystals can ensure high-quality transport properties, determined by a device-scale-uniform moiré potential. Via low-temperature dual-gated magnetotransport, we demonstrate the hallmarks of a 2.4°-twisted superlattice, including tunable regimes of interlayer coupling, reduced Fermi velocity, large interlayer capacitance, and density-independent Brown-Zak oscillations. The observation of these moiré-induced electrical transport features establishes CVD-based twisted bilayer graphene as an alternative to "tear-and-stack" exfoliated flakes for fundamental studies, while serving as a proof-of-concept for future large-scale assembly.

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.

Unexpected Electron Transport Suppression in a Heterostructured Graphene-MoS2 Multiple Field-Effect Transistor Architecture.

We demonstrate a graphene-MoS2 architecture integrating multiple field-effect transistors (FETs), and we independently probe and correlate the conducting properties of van der Waals coupled graphene-MoS2 contacts with those of the MoS2 channels. Devices are fabricated starting from high-quality single-crystal monolayers grown by chemical vapor deposition. The heterojunction was investigated by scanning Raman and photoluminescence spectroscopies. Moreover, transconductance curves of MoS2 are compared with the current-voltage characteristics of graphene contact stripes, revealing a significant suppression of transport on the n-side of the transconductance curve. On the basis of ab initio modeling, the effect is understood in terms of trapping by sulfur vacancies, which counterintuitively depends on the field effect, even though the graphene contact layer is positioned between the backgate and the MoS2 channel.

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.

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.

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.

Acoustic streaming of microparticles using graphene-based interdigital transducers.

Surface acoustic wave (SAW) devices offer many benefits in chemistry and biomedicine, enabling precise manipulation of micro-droplets, mixing of liquids by acoustic streaming and pumping of liquids in enclosed channels, while presenting a cost-effective and easy fabrication and integration with electronic devices. In this work, we present microfluidic devices which use graphene-based interdigital transducers (IDTs) to generate SAWs with a frequency of 100 MHz and an amplitude of up to 200 pm, which allow us to manipulate microparticle solutions by acoustic streaming. Due to the negligible mass loading of the piezoelectric surface by graphene, the SAWs generated by these devices have no frequency shift, typically observed when metal IDTs are used.

Wafer-Scale Integration of Graphene-Based Photonic Devices.

Graphene and related materials can lead to disruptive advances in next-generation photonics and optoelectronics. The challenge is to devise growth, transfer and fabrication protocols providing high (≥5000 cm2 V-1 s-1) mobility devices with reliable performance at the wafer scale. Here, we present a flow for the integration of graphene in photonics circuits. This relies on chemical vapor deposition (CVD) of single layer graphene (SLG) matrices comprising up to ∼12000 individual single crystals, grown to match the geometrical configuration of the devices in the photonic circuit. This is followed by a transfer approach which guarantees coverage over ∼80% of the device area, and integrity for up to 150 mm wafers, with room temperature mobility ∼5000 cm2 V-1 s-1. We use this process flow to demonstrate double SLG electro-absorption modulators with modulation efficiency ∼0.25, 0.45, 0.75, 1 dB V-1 for device lengths ∼30, 60, 90, 120 µm. The data rate is up to 20 Gbps. Encapsulation with single-layer hexagonal boron nitride (hBN) is used to protect SLG during plasma-enhanced CVD of Si3N4, ensuring reproducible device performance. The processes are compatible with full automation. This paves the way for large scale production of graphene-based photonic 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.