Layered Heterostructure of Graphene and TiO2 as a Highly Sensitive and Stable Photoassisted NO2 Sensor.

As an atomically thin electric conductor with a low density of highly mobile charge carriers, graphene is a suitable transducer for molecular adsorption. In this study, we demonstrate that the adsorption properties can be significantly enhanced with a laser-deposited TiO2 nanolayer on top of single-layer CVD graphene, whereas the effective charge transfer between the TiO2-adsorbed gas molecules and graphene is retained through the interface. The formation of such a heterostructure with optimally a monolayer thick oxide combined with ultraviolet irradiation (wavelength 365 nm, intensity <1 mW/mm2) dramatically enhances the gas-sensing properties. It provides an outstanding sensitivity for detecting NO2 in the range of a few ppb to a few hundred ppb-s in air, with response times below 30 s at room temperature. The effect of visible light (436 and 546 nm) was much weaker, indicating that the excitations due to light absorption in TiO2 play an essential role, while the characteristics of gas responses imply the involvement of both photoinduced adsorption and desorption. The sensing mechanism was confirmed by theoretical simulations on a NO2@Ti8O16C50 complex under periodic boundary conditions. The proposed sensor structure has significant additional merits, such as relative insensitivity to other polluting gases (CO, SO2, NH3) and air humidity, as well as long-term stability (>2 years) in ambient air. The results pave the way for an emerging class of gas sensor structures based on stacked 2D materials incorporating highly charge-sensitive transducer and selective receptor layers.

Tunable Adhesion for All-Dry Transfer of 2D Materials Enabled by the Freezing of Transfer Medium.

The real applications of chemical vapor deposition (CVD)-grown graphene films require the reliable techniques for transferring graphene from growth substrates onto application-specific substrates. The transfer approaches that avoid the use of organic solvents, etchants, and strong bases are compatible with industrial batch processing, in which graphene transfer should be conducted by dry exfoliation and lamination. However, all-dry transfer of graphene remains unachievable owing to the difficulty in precisely controlling interfacial adhesion to enable the crack- and contamination-free transfer. Herein, through controllable crosslinking of transfer medium polymer, the adhesion is successfully tuned between the polymer and graphene for all-dry transfer of graphene wafers. Stronger adhesion enables crack-free peeling of the graphene from growth substrates, while reduced adhesion facilitates the exfoliation of polymer from graphene surface leaving an ultraclean surface. This work provides an industrially compatible approach for transferring 2D materials, key for their future applications, and offers a route for tuning the interfacial adhesion that would allow for the transfer-enabled fabrication of van der Waals heterostructures.

The structure of chemical vapor deposited graphene substrates for graphene-enhanced Raman spectroscopy.

Defects and nanocrystalline grain structures play a critical role in graphene-enhanced Raman spectroscopy (GERS). In this study, we selected three types of few-layer, polycrystalline graphene films produced by chemical vapor deposition (CVD), and we tested them as GERS substrates. The graphene structure was controlled by decreasing the CVD temperature, thus obtaining (i) polycrystalline with negligible defect density, (ii) polycrystalline with high defect density, (iii) nanocrystalline. We applied rhodamine 6G as a probe molecule to investigate the Raman enhancement. Our results show that nanocrystalline graphene is the most sensitive GERS substrate, indicating that the GERS effect is primarily connected to the nanocrystalline structure, rather than to the presence of defects.

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.

Label-Free Direct Detection of Cylindrospermopsin via Graphene-Enhanced Surface Plasmon Resonance Aptasensor.

In this work, we report a novel method for the label-free detection of cyanotoxin molecules based on a direct assay utilizing a graphene-modified surface plasmon resonance (SPR) aptasensor. Molecular dynamic simulation of the aptamer's interaction with cylindrospermopsin (CYN) reveals the strongest binding sites between C18-C26 pairs. To modify the SPR sensor, the wet transfer method of CVD monolayer graphene was used. For the first time, we report the use of graphene functionalized by an aptamer as a bioreceptor in conjunction with SPR for the detection of CYN. In a direct assay with an anti-CYN aptamer, we demonstrated a noticeable change in the optical signal in response to the concentrations far below the maximum tolerable level of 1 µg/L and high specificity.

Rapid and Scalable Transfer of Large-Area Graphene Wafers.

Recently, scalable production of large-area graphene films on metal foils with promising qualities is successfully achieved by eliminating grain boundaries, wrinkles, and adlayers. The transfer of graphene from growth metal substrates onto functional substrates remains one inescapable obstacle on the road to the real commercial applications of chemical vaport deposition (CVD) graphene films. Current transfer methods still require time-consuming chemical reactions, which hinders its mass production, and produces cracks and contamination that strongly impede performance reproducibility. Therefore, graphene transfer techniques with fine intactness and cleanness of transferred graphene, and improved production efficiency would be ideal for the mass production of graphene films on destination substrates. Herein, through the engineering of interfacial forces enabled by sophisticated design of transfer medium, the crack-free and clean transfer of 4-inch-sized graphene wafers onto silicon wafers within only 15 min is realized. The reported transfer method is an important leap over the long-lasting obstacle of the batch-scale graphene transfer without degrading the quality of graphene, bringing the graphene products close to the real applications.

Impact of Physical and Chemical Modification of the Surface of Porous Al2O3 Ceramic Membranes on the Quality of Transferred HSMG® and CVD Graphene.

Graphene transfer onto ceramics, like Si/SiO2, is well-developed and described in the literature. However, it is problematic for other ceramic materials (e.g., Al2O3 and ZrO2), especially porous ones. In this case, it is mainly due to poor adhesion to the substrate, resulting in strong degradation of the graphene. For these reasons, the research topic of this study was undertaken. This article presents research on the development of the methodology of graphene transfer onto ceramic Al2O3 surfaces. Polycrystalline graphene chemical vapour deposition (CVD) monolayer and quasimonocrystalline high-strength metallurgical graphene (HSMG®) synthesised on liquid copper were used. When developing the transfer methodology, the focus was on solving the problem of graphene adhesion to the surface of this type of ceramic, and thus reducing the degree of graphene deterioration at the stage of producing a ceramic-graphene composite, which stands in the way of its practical use. Plasma and chemical ceramic surface modification were applied to change its hydrophobicity, and thus to improve the adhesion between the graphene and ceramic. The modification included the use of dielectric barrier discharge (DBD) plasma, oxygen plasma (RF PACVD method - Radio Frequency Plasma Assisted Chemical Vapour Deposition), and hydrofluoric acid treatment. Changes in surface properties caused by the modifications were determined by measuring the contact angle and (in the case of chemical modification) measuring the degree of surface development. The effectiveness of the applied surface preparation methodology was evaluated based on the damage degree of CVD and HSMG® graphene layer transferred onto modified Al2O3 using optical microscopy and Raman spectroscopy. The best average ID/IG ratio for the transferred HSMG® graphene was obtained after oxygen plasma modification (0.63 ± 0.18) and for CVD, graphene DBD plasma was the most appropriate method (0.17 ± 0.09). The total area of graphene defects after transfer to Al2O3 was the smallest for HSMG® graphene after modification with O2 plasma (0.251 mm2/cm2), and for CVD graphene after surface modification with DBD plasma (0.083 mm2/cm2).

A novel CVD graphene-based synaptic transistors with ionic liquid gate.

The synaptic devices based on various electronic materials have been widely investigated to realize functions of artificial information processing with low power consumption. In this work, a novel CVD graphene field-effect transistor is fabricated with ionic liquid gate to study the synaptic behaviors based on the electrical-double-layer mechanism. It is found that the excitative current is enhanced with the pulse width, voltage amplitude and frequency. With different situations of the applied pulse voltage, the inhibitory and excitatory behaviors are successfully simulated, at the same time the short-term memory is also realized. The corresponding ions migration and charge density variation are analyzed in the different time segments. This work provides the guidance for the design of artificial synaptic electronics with ionic liquid gate for low-power computing application.

Structural identification of graphene films and nanoislands on 6H-SiC(0001) by direct height measurement.

By combining non-contact atomic force microscopy (nc-AFM) and Kelvin probe microscopy (KPFM) in ultra high vacuum environment (UHV), we directly measure the height and work function of graphene monolayer on the Si-face of 6H-SiC(0001) with a precision that allows us to differentiate three different types of graphene structures : zero layer graphene (ZLG), Quasi free-standing monolayer graphene (QFMLG) and bilayer graphene (BLG). The height and work function of ZLG are 2.62 ± 0.22 Å and 4.42 ± 0.05 eV respectively, when they are 4.09 ± 0.11 Å and 4.63 ± 0.05 eV for QFMLG. The work function is 4.83 ± 0.05 eV for the BLG. Unlike any other available technique, the local nc-AFM/KPFM dual probe makes it possible to directly identify the nature of nanometer-sized graphene islands that constitute the early nuclei of graphene monolayer grown on 6H-SiC(0001) by chemical vapor deposition.

Passivating Graphene and Suppressing Interfacial Phonon Scattering with Mechanically Transferred Large-Area Ga2O3.

We demonstrate a large-area passivation layer for graphene by mechanical transfer of ultrathin amorphous Ga2O3 synthesized on liquid Ga metal. A comparison of temperature-dependent electrical measurements of millimeter-scale passivated and bare graphene on SiO2/Si indicates that the passivated graphene maintains its high field effect mobility desirable for applications. Surprisingly, the temperature-dependent resistivity is reduced in passivated graphene over a range of temperatures below 220 K, due to the interplay of screening of the surface optical phonon modes of the SiO2 by high-dielectric-constant Ga2O3 and the relatively high characteristic phonon frequencies of Ga2O3. Raman spectroscopy and electrical measurements indicate that Ga2O3 passivation also protects graphene from further processing such as plasma-enhanced atomic layer deposition of Al2O3.

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.

Electrochemical Deposition of ZnO Nanowires on CVD-Graphene/Copper Substrates.

ZnO nanostructures were electrochemically synthesized on Cu and on chemical vapor deposited (CVD)-graphene/Cu electrodes. The deposition was performed at different electrode potentials ranging from -0.8 to -1.2 V, employing a zinc nitrate bath, and using voltametric and chronoamperometric techniques. The effects of the electrode nature and of the working electrode potential on the structural, morphological, and optical properties of the ZnO structures were investigated. It was found that all the samples crystallize in hexagonal wurtzite structure with a preferential orientation along the c-axis. Scanning electron microscopy (SEM) images confirm that the presence of a graphene covered electrode led to the formation of ZnO nanowires with a smaller diameter compared with the deposition directly on copper surface. The photoluminescence (PL) measurements revealed that the ZnO nanowires grown on graphene/Cu exhibit stronger emission compared to the nanowires grown on Cu. The obtained results add another possibility of tailoring the properties of such nanostructured films according to the specific functionality required.

Defect seeded remote epitaxy of GaAs films on graphene.

Remote epitaxy is an emerging materials synthesis technique which employs a 2D interface layer, often graphene, to enable the epitaxial deposition of low defect single crystal films while restricting bonding between the growth layer and the underlying substrate. This allows for the subsequent release of the epitaxial film for integration with other systems and reuse of growth substrates. This approach is applicable to material systems with an ionic component to their bonding, making it notably appealing for III-V alloys, which are a technologically important family of materials. Chemical vapour deposition growth of graphene and wet transfer to a III-V substrate with a polymer handle is a potentially scalable and low cost approach to producing the required growth surface for remote epitaxy of these materials, however, the presence of water promotes the formation of a III-V oxide layer, which degrades the quality of subsequently grown epitaxial films. This work demonstrates the use of an argon ion beam for the controlled introduction of defects in a monolayer graphene interface layer to enable the growth of a single crystal GaAs film by molecular beam epitaxy, despite the presence of a native oxide at the substrate/graphene interface. A hybrid mechanism of defect seeded lateral overgrowth with remote epitaxy contributing the coalescence of the film is indicated. The exfoliation of the GaAs films reveals the presence of defect seeded nucleation sites, highlighting the need to balance the benefits of defect seeding on crystal quality against the requirement for subsequent exfoliation of the film, for future large area development of this approach.

High Hydrogen Isotope Separation Efficiency: Graphene or Catalyst?

Single-layer graphene has been demonstrated to be a high-efficiency hydrogen isotope sieving membrane in the electrochemical hydrogen pumping system. In this work, we transferred this membrane to proton exchange membrane water electrolysis (PEMWE), which has wide industrial applications. Two membrane electrode assemblies with decorated Pt and ink-coated Pt were investigated. The graphene with the decorated Pt scheme acquired the reported highest proton-to-tritium separation factor of 19.50 in PEMWE. However, rather than graphene, the decorated catalyst was demonstrated to be responsible for this remarkable separation efficiency. Previous studies from Geim's group underestimated the enhanced separation efficiency of decorated Pt over ink-coated Pt, resulting in an exaggerated separation efficiency for graphene. The behavior of proton transfer with hydrogen isotope separation through graphene was interpreted by a serial-parallel circuit model, which suggested that hydrogen isotope separation occurs at defect sites. The limited separation efficiency for graphene was also well understood by a density functional theory (DFT) calculation using an SW 55-77 model and the transition state theory for the kinetic isotope effect. This research provides a thorough understanding of proton transfer with hydrogen isotope separation through graphene.

Field Electron Emission from Crumpled CVD Graphene Patterns Printed via Laser-Induced Forward Transfer.

A new approach to the fabrication of graphene field emitters on a variety of substrates at room temperature and in an ambient environment is demonstrated. The required shape and orientation of the graphene flakes along the field are created by the blister-based laser-induced forward transfer of CVD high-quality single-layer graphene. The proposed technique allows the formation of emitting crumpled graphene patterns without losing the quality of the initially synthesized graphene, as shown by Raman spectroscopy. The electron field emission properties of crumpled graphene imprints 1 × 1 mm2 in size were studied. The transferred graphene flakes demonstrated good adhesion and emission characteristics.

Enhanced Electromagnetic Shielding and Thermal Conductive Properties of Polyolefin Composites with a Ti3C2Tx MXene/Graphene Framework Connected by a Hydrogen-Bonded Interface.

The rapid increase of operation speed, transmission efficiency, and power density of miniaturized devices leads to a rising demand for electromagnetic interference (EMI) shielding and thermal management materials in the semiconductor industry. Therefore, it is essential to improve both the EMI shielding and thermal conductive properties of commonly used polyolefin components (such as polyethylene (PE)) in electronic systems. Currently, melt compounding is the most common method to fabricate polyolefin composites, but the difficulty of filler dispersion and high resistance at the filler/filler or filler/matrix interface limits their properties. Here, a fold fabrication strategy was proposed to prepare PE composites by incorporation of a well-aligned, seamless graphene framework premodified with MXene nanosheets into the matrix. We demonstrate that the physical properties of the composites can be further improved at the same filler loading by nanoscale interface engineering: the formation of hydrogen bonds at the graphene/MXene interface and the development of a seamlessly interconnected graphene framework. The obtained PE composites exhibit an EMI shielding property of ∼61.0 dB and a thermal conductivity of 9.26 W m-1 K-1 at a low filler content (∼3 wt %, including ∼0.4 wt % MXene). Moreover, other thermoplastic composites with the same results can also be produced based on our method. Our study provides an idea toward rational design of the filler interface to prepare high-performance polymer composites for use in microelectronics and microsystems.

Quantum transport in CVD graphene synthesized with liquid carbon precursor.

Large-area high-quality graphene enabled by chemical vapor deposition (CVD) can possibly pave the path for advanced flexible electronics and spintronics. CVD-grown method utilizing liquid carbon precursor has recently been demonstrated as an appealing choice for mass graphene production, thanks to its low cost and safe operation. However, the quality of the graphene film has been the major obstacle for the implementation of the liquid-precursor-based CVD method. Here we report the growth of centimeter-scale easily-transferable single-layer graphene (SLG) using acetone as a liquid carbon precursor. The dry-transfer technique was used to prepare the graphene device. The typical mobility of the dry-transferred SLG device is as high as 12 500 cm2V-1s-1at room temperature. Thanks to the high quality of the device, the robust quantum Hall effect can survive up to room temperature. The excellent device quality also enables us to observe the Shubnikov-de Haas oscillation in the low magnetic field regime and systemically study the leading scattering mechanism. We extracted both the transport scattering timeτtand the quantum scattering timeτqover a wide range of carrier density. The ratio of the scattering times suggests that the charged-impurity resided near the surface of the graphene restricted the device performance.

Towards Perfect Absorption of Single Layer CVD Graphene in an Optical Resonant Cavity: Challenges and Experimental Achievements.

Graphene is emerging as a promising material for the integration in the most common Si platform, capable to convey some of its unique properties to fabricate novel photonic and optoelectronic devices. For many real functions and devices however, graphene absorption is too low and must be enhanced. Among strategies, the use of an optical resonant cavity was recently proposed, and graphene absorption enhancement was demonstrated, both, by theoretical and experimental studies. This paper summarizes our recent progress in graphene absorption enhancement by means of Si/SiO2-based Fabry-Perot filters fabricated by radiofrequency sputtering. Simulations and experimental achievements carried out during more than two years of investigations are reported here, detailing the technical expedients that were necessary to increase the single layer CVD graphene absorption first to 39% and then up to 84%. Graphene absorption increased when an asymmetric Fabry-Perot filter was applied rather than a symmetric one, and a further absorption increase was obtained when graphene was embedded in a reflective rather than a transmissive Fabry-Perot filter. Moreover, the effect of the incident angle of the electromagnetic radiation and of the polarization of the light was investigated in the case of the optimized reflective Fabry-Perot filter. Experimental challenges and precautions to avoid evaporation or sputtering induced damage on the graphene layers are described as well, disclosing some experimental procedures that may help other researchers to embed graphene inside PVD grown materials with minimal alterations.

Simultaneous Extraction of the Grain Size, Single-Crystalline Grain Sheet Resistance, and Grain Boundary Resistivity of Polycrystalline Monolayer Graphene.

The electrical properties of polycrystalline graphene grown by chemical vapor deposition (CVD) are determined by grain-related parameters-average grain size, single-crystalline grain sheet resistance, and grain boundary (GB) resistivity. However, extracting these parameters still remains challenging because of the difficulty in observing graphene GBs and decoupling the grain sheet resistance and GB resistivity. In this work, we developed an electrical characterization method that can extract the average grain size, single-crystalline grain sheet resistance, and GB resistivity simultaneously. We observed that the material property, graphene sheet resistance, could depend on the device dimension and developed an analytical resistance model based on the cumulative distribution function of the gamma distribution, explaining the effect of the GB density and distribution in the graphene channel. We applied this model to CVD-grown monolayer graphene by characterizing transmission-line model patterns and simultaneously extracted the average grain size (~5.95 µm), single-crystalline grain sheet resistance (~321 Ω/sq), and GB resistivity (~18.16 kΩ-µm) of the CVD-graphene layer. The extracted values agreed well with those obtained from scanning electron microscopy images of ultraviolet/ozone-treated GBs and the electrical characterization of graphene devices with sub-micrometer channel lengths.

Roll-to-Roll Dry Transfer of Large-Scale Graphene.

A major challenge for graphene applications is the lack of mass production technology for large-scale and high-quality graphene growth and transfer. Here, a roll-to-roll (R2R) dry transfer process for large-scale graphene grown by chemical vapor deposition is reported. The process is fast, controllable, and environmentally benign. It avoids chemical contamination and allows the reuse of graphene growth substrates. By controlling tension and speed of the R2R dry transfer process, the electrical sheet resistance is achieved as 9.5 kΩ sq-1 , the lowest ever reported among R2R dry transferred graphene samples. The R2R dry transferred samples are used to fabricate graphene-based field-effect transistors (GFETs) on polymer. It is demonstrated that these flexible GFETs feature a near-zero doping level and a gate leakage current one to two orders of magnitude lower than those fabricated using wet-chemical etched graphene samples. The scalability and uniformity of the R2R dry transferred graphene is further demonstrated by successfully transferring a 3 × 3 in2 sample and measuring its field-effect mobility with 36 millimeter-scaled GFETs evenly spaced on the sample. The field-effect mobility of the R2R dry transferred graphene is determined to be 205 ± 36 cm2  V-1 .