Chemical Vapor Deposition Graphene Research Articles

High mobility graphene field effect transistors on flexible EVA/PET foils

Monolayer graphene is a promising material for a wide range of applications, including sensors, optoelectronics, antennas, EMR shielding, flexible electronics, and conducting electrodes. Chemical vapor deposition (CVD) of carbon atoms on a metal catalyst is the most scalable and cost-efficient method for synthesizing high-quality, large-area monolayer graphene. The usual method of transferring the CVD graphene from the catalyst to a target substrate involves a polymer carrier which is dissolved after the transfer process is completed. Due to often unavoidable damage to graphene, as well as contamination and residues, carrier mobilities are typically 1000–3000 cm2(Vs)−1 , unless complex and elaborate measures are taken. Here, we report on a simple scalable fabrication method for flexible graphene field-effect transistors that eliminates the polymer interim carrier, by laminating the graphene directly onto office lamination foils, removing the catalyst, and depositing Parylene N as a gate dielectric and encapsulation layer. The fabricated transistors show field- and Hall-effect mobilities of 7000–10 000 cm2(Vs)−1 with a residual charge-carrier density of 2×1011 1 cm−2 at room temperature. We further validate the material quality by terahertz time-domain spectroscopy and observation of the quantum Hall effect at low temperatures in a moderate magnetic field of ∼5 T. The Parylene encapsulation provides long-term stability and protection against additional lithography steps, enabling vertical device integration in multilayer electronics on a flexible platform.

CVD graphene contacts for lateral heterostructure MoS2 field effect transistors

Intensive research has been carried out on two-dimensional materials, in particular molybdenum disulfide, towards high-performance field effect transistors for integrated circuits1. Fabricating transistors with ohmic contacts is a challenging task due to the formation of a high Schottky barrier that severely limits the performance of the transistors for real-world applications. Graphene-based heterostructures can be used in addition to, or as a substitute for unsuitable metals. In this paper, we present lateral heterostructure transistors made of scalable chemical vapor-deposited molybdenum disulfide and chemical vapor-deposited graphene achieving a low contact resistances of about 9 kΩ·µm and high on/off current ratios of 108. Furthermore, we also present a theoretical model calibrated on our experiments showing further potential for scaling transistors and contact areas into the few nanometers range and the possibility of a substantial performance enhancement by means of layer optimizations that would make transistors promising for use in future logic integrated circuits.

CVD graphene-MoS2 Van der Waals heterostructures on the millimeter-scale

This study investigates the interactions between chemical vapor-deposited graphene and metal-organic chemical vapor-deposited molybdenum disulfide (MoS2) in heterostructures assembled via wet transfer. We use Raman spectroscopy to quantitatively determine close coupling between graphene and MoS2 based on the peak separations in graphene. Although annealing seems to be necessary after transfer to establish a close coupling, its parameters do not have a significant impact on the quality of coupling (for 100 °C < T < 400 °C and 5 min < t < 120 min). Furthermore, the method is robust against variations in graphene thickness because bilayers can be distinguished by comparing the full width at half maximum of the graphene 2D peak. We expand our study to mm2-scale areas of graphene-MoS2 heterostructures finding that films assembled via wet-transfer technique exhibit considerable variability in terms of coupling strength. Evaluating such interactions in heterostructures on large areas is important for future practical applications in heterostructure devices.

Comparative Study of Field-Effect Transistors Based on Graphene Oxide and CVD Graphene in Highly Sensitive NT-proBNP Aptasensors.

Graphene-based materials are actively being investigated as sensing elements for the detection of different analytes. Both graphene grown by chemical vapor deposition (CVD) and graphene oxide (GO) produced by the modified Hummers' method are actively used in the development of biosensors. The production costs of CVD graphene- and GO-based sensors are similar; however, the question remains regarding the most efficient graphene-based material for the construction of point-of-care diagnostic devices. To this end, in this work, we compare CVD graphene aptasensors with the aptasensors based on reduced GO (rGO) for their capabilities in the detection of NT-proBNP, which serves as the gold standard biomarker for heart failure. Both types of aptasensors were developed using commercial gold interdigitated electrodes (IDEs) with either CVD graphene or GO formed on top as a channel of liquid-gated field-effect transistor (FET), yielding GFET and rGO-FET sensors, respectively. The functional properties of the two types of aptasensors were compared. Both demonstrate good dynamic range from 10 fg/mL to 100 pg/mL. The limit of detection for NT-proBNP in artificial saliva was 100 fg/mL and 1 pg/mL for rGO-FET- and GFET-based aptasensors, respectively. While CVD GFET demonstrates less variations in parameters, higher sensitivity was demonstrated by the rGO-FET due to its higher roughness and larger bandgap. The demonstrated low cost and scalability of technology for both types of graphene-based aptasensors may be applicable for the development of different graphene-based biosensors for rapid, stable, on-site, and highly sensitive detection of diverse biochemical markers.

Building a cm2 scale CVD graphene-based gas sensor: modelling the kinetic with a three-site adsorption/desorption Langmuir model

In this article, we aim to develop and study a highly sensitive and selective cm2 scale graphene-based gas sensor. We present the technology used to fabricate sensors which integrate monolayer chemical vapour deposition graphene: photolithography and transfer of layers. Characterization techniques (optical microscopy, AFM, micro-Raman spectroscopy, transport electrical measurements) ensure a diagnosis of graphene ribbons and allow good reproducibility of technological processes. We present the results of gas characterizations after a 200 ppm NO2 exposure. We propose a novel approach for the modelling of the sensor response with a three-site adsorption/desorption Langmuir model. This innovative way of modelling the sensor response should provide a better understanding of the sensor’s kinetic and help to overcome the long response time observed with graphene gas sensors.

Silicon oxide particles size evolution during CVD graphene growth on Cu substrates

Chemical vapor deposition (CVD) on metal substrates is presently the remarkably route for the synthesis of high-quality continuous graphene films at a large scale. Whereas, during the thermal processing procedure in the quartz tube, the formation of silicon oxide particles would degrade the performance of graphene. To better understand the origin of these particles , a series of CVD graphene growth experiments with were conducted on the Cu substrates. In this paper, we investigated the main component and morphology of the particles by X-Ray photoelectron spectroscopy (XPS), energy dispersive spectrometry (EDS) measurement in scanning electron microscopy (SEM) and revealed that the silicon oxide particles gradually increased in diameter across the graphene films on the Cu surface, which was found to be correlated with the working time of the quartz products. Raman spectroscopy was also applied to prove the drawback consequence of the contamination on the quality of the CVD graphene film. To mitigate this issue, we further propose a modification of the CVD system that a coaxial alumina or BN tube inside the quartz tube to screen the contaminants bringing about improved graphene growth.

Lightweight graphene foam composites with enhanced electrical conductivity and microwave absorption for electromagnetic interference shielding

Next-generation flexible electronics call for high-performance electromagnetic interference (EMI) shielding materials with lightweight and multifunctionality. Here, the chemical vapor deposition (CVD) graphene foam (GF) composites, containing flexible polymer matrix and magnetic Fe3O4 nanoparticles, are reported. The systematic manipulation of GF growth condition and the content of Fe3O4 reveals the effect of graphene thickness and integration of Fe3O4 on improving the electromagnetic shielding performance of composites. Owing to abundant internal interfaces, high conductivity from the three-dimensional interconnected graphene, and magnetic loss from Fe3O4, the ternary composites exhibit substantial improvement in microwave absorption, resulting in a superior EMI shielding effectiveness (SE) and absolute EMI SE up to 71 dB and 3641 dB·cm2/g, respectively, at a low density of 0.65 g/cm3 and minimal thickness of 0.3 mm. Moreover, the flexible composites display great EMI shielding stability after repeatedly bending, validating the composites as promising materials for practical applications in aerospace and flexible electronics.

Visible-frequency plasmonic enhancement at the edge of graphene/h-BN heterostructures on silicon substrate

Heterostructures of graphene and hexagonal boron nitride (G/h-BN) have been widely studied for controlling and utilizing graphene electronic properties. Here we characterize specific optical and electronic properties of G/h-BN heterostructures made of a high-quality single layer chemical vapor deposition (CVD) graphene laid over h-BN flakes, with focus on plasmonic effects. We compare the G/h-BN properties on Si and SiO2 substrates by micro-Raman spectroscopy mapping, Kelvin probe force microscopy, optical and atomic force microscopy. We observe highly enhanced Raman intensity (up to 280 %) from Si as well as graphene along the G/h-BN edge. It is attributed to localized concentration of electrons in graphene and suitable perpendicular orientation of plasmonic vibrations at the edge. The plasmonic Raman enhancement occurs under a visible light excitation (532 nm) and the effect can be tuned by the h-BN flake thickness (10–150 nm). The enhancement is specific to G/h-BN/Si structures, on G/h-BN/SiO2 structures the Raman signal is suppressed while I2D/IG ratio is increased. Vice versa, change of surface potential under visible light illumination (photovoltage) is on G/h-BN/Si negligible (within 10 mV) compared to the G/h-BN/SiO2 structures. These results open new prospects for broad utilization of localized visible plasmonic effects in graphene.

High current treated-passivated graphene (CTPG) towards stable nanoelectronic and spintronic circuits.

Achieving enhanced and stable electrical quality of scalable graphene is crucial for practical graphene device applications. Accordingly, encapsulation has emerged as an approach for improving electrical transport in graphene. In this study, we demonstrate high-current treatment of graphene passivated by AlOx nanofilms as a new means to enhance the electrical quality of graphene for its scalable utilization. Our experiments and electrical measurements on large-scale chemical vapor-deposited (CVD) graphene devices reveal that high-current treatment causes persistent and irreversible de-trapping density in both bare graphene and graphene covered by AlOx. Strikingly, despite possible interfacial defects in graphene covered with AlOx, the high-current treatment enhances its carrier mobility by up to 200% in contrast to bare graphene samples, where mobility decreases. Spatially resolved Raman spectroscopy mapping confirms that surface passivation by AlOx, followed by the current treatment, reduces the number of sp3 defects in graphene. These results suggest that for current treated-passivated graphene (CTPG), the high-current treatment considerably reduces charged impurity and trapped charge densities, thereby reducing Coulomb scattering while mitigating any electromigration of carbon atoms. Our study unveils CTPG as an innovative system for practical utilization in graphene nanoelectronic and spintronic integrated circuits.

Ultra-thin proton conducting carrier layers for scalable integration of atomically thin 2D materials with proton exchange polymers for next-generation PEMs.

Scalable approaches for synthesis and integration of proton selective atomically thin 2D materials with proton conducting polymers can enable next-generation proton exchange membranes (PEMs) with minimal crossover of reactants or undesired species while maintaining adequately high proton conductance for practical applications. Here, we systematically investigate facile and scalable approaches to interface monolayer graphene synthesized via scalable chemical vapor deposition (CVD) on Cu foil with the most widely used proton exchange polymer Nafion 211 (N211, ∼25 μm thick film) via (i) spin-coating a ∼700 nm thin Nafion carrier layer to transfer graphene (spin + scoop), (ii) casting a Nafion film and cold pressing (cold press), and (iii) hot pressing (hot press) while minimizing micron-scale defects to <0.3% area. Interfacing CVD graphene on Cu with N211 via cold press or hot press and subsequent removal of Cu via etching results in ∼50% lower areal proton conductance compared to membranes fabricated via the spin + scoop method. Notably, the areal proton conductance can be recovered by soaking the hot and cold press membranes in 0.1 M HCl, without significant damage to graphene. We rationalize our finding by the significantly smaller reservoir for cation uptake from Cu etching for the ∼700 nm thin carrier Nafion layer used for spin + scoop transfer compared to the ∼25 μm thick N211 film for hot and cold pressing. Finally, we demonstrate performance in H2 fuel cells with power densities of ∼0.23 W cm-2 and up to ∼41-54% reduction in H2 crossover for the N211|G|N211 sandwich membranes compared to the control N211|N211 indicating potential for our approach in enabling advanced PEMs for fuel cells, redox-flow batteries, isotope separations and beyond.

The potential of graphene coatings as neural interfaces.

Recent advances in nanotechnology design and fabrication have shaped the landscape for the development of ideal cell interfaces based on biomaterials. A holistic evaluation of the requirements for a cell interface is a highly complex task. Biocompatibility is a crucial requirement which is affected by the interface's properties, including elemental composition, morphology, and surface chemistry. This review explores the current state-of-the-art on graphene coatings produced by chemical vapor deposition (CVD) and applied as neural interfaces, detailing the key properties required to design an interface capable of physiologically interacting with neural cells. The interfaces are classified into substrates and scaffolds to differentiate the planar and three-dimensional environments where the cells can adhere and proliferate. The role of specific features such as mechanical properties, porosity and wettability are investigated. We further report on the specific brain-interface applications where CVD graphene paved the way to revolutionary advances in biomedicine. Future studies on the long-term effects of graphene-based materials in vivo will unlock even more potentially disruptive neuro-applications.

Preparation of Electrodes with β-Nickel Hydroxide/CVD-Graphene/3D-Nickel Foam Composite Structures to Enhance the Capacitance Characteristics of Supercapacitors.

Supercapacitors have the characteristics of high power density, long cycle life, and fast charge and discharge rates, making them promising alternatives to traditional capacitors and batteries. The use of transition-metal compounds as electrode materials for supercapacitors has been a compelling research topic in recent years because their use can effectively enhance the electrical performance of supercapacitors. The current research on capacitor electrode materials can mainly be divided into the following three categories: carbon-based materials, metal oxides, and conductive polymers. Nickel hydroxide (Ni(OH)2) is a potential electrode material for use in supercapacitors. Depending on the preparation conditions, two crystal phases of nickel hydroxide, α and β, can be produced. When compared to α-NiOH, the structure of β-Ni(OH)2 does not experience ion intercalation. As a result, the carrier transmission rate of α-Ni(OH)2 is slower, and its specific capacitance value is smaller. Its carrier transport rate can be improved by adding conductive materials, such as graphene. β-Ni(OH)2 was chosen as an electrode material for a supercapacitor in this study. Homemade low-pressure chemical vapor deposition graphene (LPCVD-Graphene) conductive material was introduced to modify β-Ni(OH)2 in order to increase its carrier transport rate. The LPCVD method was used to grow high-quality graphene films on three-dimensional (3D) nickel foam substrates. Then, a hydrothermal synthesis method was used to grow β-Ni(OH)2 nanostructures on the 3D graphene/nickel foam substrate. In order to improve the electrical properties of the composite structure, a high-quality graphene layer was incorporated between the nickel hydroxide and the 3D nickel foam substrate. The effect of the conductive graphene layer on the growth of β-Ni(OH)2, as well as its electrical properties and electrochemical performance, was studied. When this β-Ni(OH)2/CVD-Graphene/3D-NF (nickel foam) material was used as the working electrodes of the supercapacitor under a current density of 1 A/g and 3 A/g, they exhibited a specific capacitance of 2015 F/g and 1218.9 F/g, respectively. This capacitance value is 2.62 times higher than that of the structure without modification with a graphene layer. The capacitance value remains at 99.2% even after 1000 consecutive charge and discharge cycles at a current density of 20 A/g. This value also improved compared to the structure without graphene layer modification (94.7%).

Probing the Intrinsic Strain in Suspended Graphene Films Using Electron and Optical Microscopy.

Quantifying the intrinsic properties of 2D materials is of paramount importance for advancing their applications. Large-scale production of 2D materials merits the need for approaches that provide direct information about the role of growth substrate on 2D material properties. Transferring the 2D material from its growth substrates can modify the intrinsic properties of the asgrown 2D material. In this study, suspended chemical vapor deposition (CVD) graphene films are prepared directly on their growth substrates in a high-density grid array. The approach facilitates the quantification of intrinsic strain and doping in suspended CVD graphene films. To achieve this, transmission electron microscopy and large-area Raman mapping are employed. Remarkably, the analysis reveals consistent patterns of compressive strain (≈-0.2%) both in the diffraction patterns and Raman maps obtained from these suspended graphene films. By conducting investigations directly on the growth substrates, the potential influences introduced during the transfer process are circumvented effectively. Consequently, the methodology offers a robust and reliable means of studying the intrinsic properties of 2D materials in their authentic form, uninfluenced by the transfer-induced alterations that may skew the interpretation of their properties.

Highly Sensitive Hall Sensors Based on Chemical Vapor Deposition Graphene

Highly Sensitive Hall Sensors Based on Chemical Vapor Deposition Graphene

Surface enhancement Raman spectroscopy of CVD graphene and graphene oxide

SERS has been of interest as an influential analytical characterization method for scientific studies to detect chemical and biological molecules. The selection of suitable SERS substrates is a major challenge for specific detection of molecules. Here, two different types of graphene-based SERS substrates were prepared and their SERS activities were compared. Our chemical vapor-deposited graphene (CVDG) SERS substrates showed an excellent limit of detection of 10−13 M. 10−13 M is the lowest concentration achieved so far in the as grown graphene-based SERS substrates without the use of noble metal or other materials for R6G molecules. When a flexible and transparent SERS substrate with a large surface area is desired, substrates made of CVDG SERS substrates are more suitable, while modified graphene oxide (MGO) may be preferred in powder, colloid and thin film SERS applications. MGO showed better signal enhancement compared to CVDG and SiO2 reference substrates in high concentration R6G solution. The differences between the SERS activities of the substrates were discussed in detail in terms of the differences in the chemical, electrical, optical, and surface properties of CVDG and MGO. Understanding the enhancement activities of non-resonant graphene-based SERS materials is critical for the next generation of Raman spectrometer instruments.

Defect-engineered graphene-on-silicon-carbide platform for magnetic field sensing at greatly elevated temperatures

High-temperature electrical properties of p-type hydrogen-intercalated quasi-free-standing epitaxial Chemical Vapor Deposition graphene on semi-insulating vanadium-compensated on-axis 6H-SiC(0001) and high-purity on-axis 4H-SiC(0001) originate from the double-carrier system of spontaneous-polarization-induced holes in graphene and thermally-activated electrons in the substrate. In this study, we pre-epitaxially modify SiC by implanting hydrogen (H+) and helium (He+) ions with energies ranging from 20 keV to 50 keV to reconstruct its post-epitaxial defect structure and suppress the thermally-developed electron channel. Through a combination of dark current measurements and High-Resolution Photo-Induced Transient Spectroscopy between 300 K and 700 K, we monitor the impact of ion bombardment on the transport properties of SiC and reveal activation energies of the individual deep-level defects. We find that the ion implantation has a negligible effect on 6H-SiC. Yet in 4H-SiC, it shifts the Fermi level from ∼600 meV to ∼800 meV below the minimum of the conduction band and reduces the electron concentration by two orders of magnitude. Specifically, it eliminates deep electron traps related to silicon vacancies in the charge state (2-/-) occupying the h and k sites of the 4H-SiC lattice. Finally, we directly implement the protocol of deep-level defect engineering in the technology of amorphous-aluminum-oxide-passivated Hall effect sensors and introduce a mature sensory platform with record-linear current-mode sensitivity of approximately 80 V/AT with -0.03-%/K stability in a broad temperature range between 300 K and 770 K, and likely far beyond 770 K.

Spectroscopic properties of close-to-perfect-monolayer quasi-free-standing epitaxial graphene on 6H[sbnd]SiC(0001)

In this report, we present transfer-free p-type hydrogen-intercalated quasi-free-standing epitaxial Chemical Vapor Deposition graphene on 15-mm × 15-mm semi-insulating vanadium-compensated on-axis 6HSiC(0001), characterized in that its room-temperature direct-current Hall-effect-derived hole mobility μp= 5019 cm2/Vs, and its statistical number of layers (N), as indicated by the relative intensity of the SiC-related Raman-active longitudinal optical A1 mode at 964 cm−1, equals N= 1.05. The distribution of the ellipsometric angle Ψ measured at an angle of incidence of 50° and λ= 490 nm points out to N= 0.97. The close-to-unity value of N implies that the material under study is a close-to-perfect quasi-free-standing monolayer, which is further confirmed by High-Resolution Transmission Electron Microscopy. Therefore, its spectroscopic properties, which include the SiH peak at 2131 cm−1, the histograms of Ψ and Δ, and the Raman G and 2D band positions, widths, and the 2D-to-G band intensity ratios, constitute a valuable reference for this class of materials.

Impact of material and tunnel barrier quality on spin transport in a CVD graphene non-local spin valve device array

Wafer-scale graphene films produced via chemical vapor deposition (CVD) are now commercially available, however these films inherently contain randomly distributed defects such as adlayers and grain boundaries. This report discusses the impact of these defects on the signal integrity of an array of graphene-based non-local spin valves (NLSVs). It was found that critical spin parameters fluctuate drastically between adjacent identical devices. Investigation of the channel quality indicated that adlayers do not affect spin signal significantly even when located directly in the spin transport region of the device. In contrast, grain boundary defects within the spin transport region have significant impact on spin signal. Poor tunnel barrier integrity due to residue from the fabrication process also remains a dominant factor driving device variability.

G phonon linewidth and phonon-phonon interaction in p-type doped CVD graphene crystals

We employed conventional and time-resolved Raman spectroscopy to study the effects of electron-phonon and phonon-phonon interactions on the linewidth of the G phonon in both unintentionally and intentionally doped polycrystalline chemical vapor deposited (CVD) graphene samples. We directly measured the G phonon lifetime, observing a ≈14% decrease with doping up to EF = 270 meV. The anticipated reduction of G phonon linewidth due to a decrement in electron-phonon contribution deviates from first principles calculations. CVD samples exhibit a ≈30% decrease in the electron-phonon coupling constant, λΓ(EF = 0), compared to exfoliated graphene samples. Additionally, phonon-defect scattering makes a significant contribution to the G band linewidth in CVD graphene samples, owing to their lower crystal quality compared to exfoliated graphene.

(Digital Presentation) Deconstructing Proton Transport through Atomically Thin Monolayer CVD Graphene Membranes

Selective proton (H+) permeation through the atomically thin lattice of graphene and other 2D materials offers new opportunities for energy conversion/storage and novel separations. Practical applications necessitate scalable synthesis via approaches such as chemical vapor deposition (CVD) that inevitably introduce sub-nanometer defects, grain boundaries and wrinkles, and understanding their influence on H+ transport and selectivity for large-area membranes is imperative but remains elusive. Using electrically driven transport of H+ and potassium ions (K+) we probe the influence of intrinsic sub-nanometer defects in monolayer CVD graphene across length-scales for the first time. At the micron scale, the areal H+ conductance of CVD graphene (∼4.5–6 mS cm−2) is comparable to that of mechanically exfoliated graphene indicating similarly high crystalline quality within a domain, albeit with K+ transport (∼1.7 mS cm−2). However, centimeter-scale Nafion|graphene|Nafion devices with several graphene domains show areal H+ conductance of ∼339 mS cm−2 and K+ conductance of ∼23.8 mS cm−2 (graphene conductance for H+ is ∼1735 mS cm−2 and for K+ it is ∼47.6 mS cm−2). Using a mathematical-transport-model and Nafion filled polycarbonate track etched supports, we systematically deconstruct the observed orders of magnitude increase in H+ conductance for centimeter-scale CVD graphene. The mitigation of defects (>1.6 nm), wrinkles and tears via interfacial polymerization results in a conductance of ∼1848 mS cm−2 for H+ and ∼75.3 mS cm−2 for K+ (H+/K+ selectivity of ∼24.5) via intrinsic sub-nanometer proton selective defects in CVD graphene. We demonstrate atomically thin membranes with significantly higher ionic selectivity than state-of-the-art proton exchange membranes while maintaining comparable H+ conductance. Our work provides a new framework to assess H+ conductance and selectivity of large-area 2D membranes and highlights the role of intrinsic sub-nanometer proton selective defects for practical applications.