CVD-grown Graphene Research Articles

Oxygen intercalation at the graphene/Ni(111) interface: Evidences of non-metal islands underneath graphene layer

This paper reports on a comparative study of the electronic properties of ultra-thin film of NiO(100)/Ni(111) and graphene/Ni(111) intercalated with oxygen atoms. A way to combine a high quality CVD-grown graphene and a reduced interaction with the supporting substrate is to insert atomic species underneath carbon layer. Moreover, the intercalation of oxygen atoms allows, in some condition, to obtain graphene-insulating system, essential for a new generation of electronic devices. As a result of intercalation process, Electron Energy Loss Spectra reveal the presence of NiO islands underneath epitaxial graphitic layer and a dramatic change in the character of the energy dispersion curve of the graphene π plasmon.

Measuring the size dependence of thermal conductivity of suspended graphene disks using null-point scanning thermal microscopy.

Using null-point scanning thermal microscopy (NP SThM), we have measured and analyzed the size dependence of the thermal conductivity of graphene. To do so, we rigorously re-derived the principal equation of NP SThM in terms of thermal property measurements so as to explain how this technique can be effectively used to quantitatively measure the local thermal resistance with nanoscale spatial resolution. This technique has already been proven to resolve the major problems of conventional SThM, and to quantitatively measure the temperature profile. Using NP SThM, we measured the variation in the thermal resistance of suspended chemical vapor deposition (CVD)-grown graphene disks with radii of 50-3680 nm from the center to the edge with respect to the size. By thoroughly analyzing the size dependence of the thermal resistance, we show that, with increasing graphene size, the ballistic resistance becomes more dominant in the thermal resistance experienced by a heat source of finite size and that the thermal conductivity experienced by such a heat source can even decrease. The results of this study reveal that the thermal conductivity of graphene detected by a heat source depends on the size of the heat source relative to that of the suspended graphene and on how the heat source and graphene are connected. As demonstrated in this study, NP SThM will be very useful for quantitative thermal characterization of not only CVD-grown graphene but also various other nanomaterials and nanodevices.

Controlling the ripple density and heights: a new way to improve the electrical performance of CVD-grown graphene.

We report a new way to enhance the electrical performances of large area CVD-grown graphene through controlling the ripple density and heights after transfer onto SiO2/Si substrates by employing different cooling rates during fabrication. We find that graphene films prepared with a high cooling rate have reduced ripple density and heights and improved electrical characteristics such as higher electron/hole mobilities as well as reduced sheet resistance. The corresponding Raman analysis also shows a significant decrease of the defects when a higher cooling rate is employed. We suggest a model that explains the improved morphology of the graphene film obtained with higher cooling rates. From these points of view, we can suggest a new pathway toward a relatively lower density and heights of ripples in order to reduce the flexural phonon-electron scattering effect, leading to higher lateral carrier mobilities.

Heavily N-doped monolayer graphene electrodes used for high-performance N-channel polymeric thin film transistors

Recently graphene attracted much attention as a promising electrode material for organic field effect transistors (OFETs). However the electrodes used in most of the graphene-based OFETs were prepared from pristine graphene which suffers from relatively low conductivity and poor controlling of work function. In this work, we report the N-doping by Cs2CO3 of the CVD-grown single-layer graphene (SLG) via a facial spin-coating process. The Cs2CO3-engineered SLGs exhibit a heavy and stable N-doping, as well as significantly decreased work function (3.9 eV) compared to pristine graphene. The doped graphene was used as the source/drain electrodes in the bottom-contact top-gated OFETs based on a good electron transporter poly{[N,N′-bis(2-octyldodecyl)-1,4,5,8-naphthalenedicarboximide-2,6-diyl]-alt-5,5′-(2,2′-bithiophene)} (P(NDI2OD-T2)). The polymeric FETs show an enhancement of electron mobility by a factor of 10, as well as a reduction of contact resistance compared to the devices using pristine graphene. It is attributed to a remarkable lowering of electron injection barrier at the polymer/graphene electrode due to the decreased work function of graphene. In addition, the microstructural observations reveal that the face-on molecular packing and morphological feature do not change for the P(NDI2OD-T2) films coated on the doped graphene electrodes compared to those on the SiO2 dielectric, in spite of a highly hydrophobic surface of the graphene.

High Current-Induced Electron Redistribution in a CVD-Grown Graphene Wide Constriction

Investigating the charge transport behavior in one-dimensional quantum confined system such as the localized states and interference effects due to the nanoscale grain boundaries and merged domains in wide chemical vapor deposition graphene constriction is highly desirable since it would help to realize industrial graphene-based electronic device applications. Our data suggests a crossover from interference coherent transport to carriers flushing into grain boundaries and merged domains when increasing the current. Moreover, many-body fermionic carriers with disordered system in our case can be statistically described by mean-field Gross-Pitaevskii equation via a single wave function by means of the quantum hydrodynamic approximation. The novel numerical simulation method supports the experimental results and suggests that the extreme high barrier potential regions on graphene from the grain boundaries and merged domains can be strongly affected by additional hot charges. Such interesting results could pave the way for quantum transport device by supplying additional hot current to flood into the grain boundaries and merged domains in one-dimensional quantum confined CVD graphene, a great advantage for developing graphene-based coherent electronic devices.

Effects of light on the resistivity of chemical vapor deposited graphene films

We report that the resistance of a chemical vapor deposition (CVD) grown graphene film transferred onto an SiO 2 substrate increases to higher saturation values upon exposure to light of decreasing wavelength from the visible to ultraviolet. Light in the visible range causes a slight increase of up to 10% in saturation resistance. A significant increase in resistance is found starting at about 400 nm. The saturation resistance approaches up to 3 times the original resistance at 254 nm after 5 min. When the light is removed, the resistance falls to its original value with a time constant of several days. The effect is not observed for samples of CVD-grown graphene films on SiO 2 that have been heated in vacuum at 600 ℃, nor single-crystal graphene mechanically exfoliated onto SiO 2 . We attribute the effect to photo dissociation of interfacial molecules such as H 2 O adsorbed between the CVD-grown film and SiO 2 substrate at grain boundaries in the film.

Effects of thermally-induced changes of Cu grains on domain structure and electrical performance of CVD-grown graphene.

During the chemical vapor deposition (CVD) growth of graphene on Cu foils, evaporation of Cu and changes in the dimensions of Cu grains in directions both parallel and perpendicular to the foils are induced by thermal effects. Such changes in the Cu foil could subsequently change the shape and distribution of individual graphene domains grown on the foil surface, and thus influence the domain structure and electrical properties of the resulting graphene films. Here, a slower cooling rate is used after the CVD process, and the graphene films are found to have an improved electrical performance, which is considered to be associated with the Cu surface evaporation and grain structure changes in the Cu substrate.

Probing electronic lifetimes and phonon anharmonicities in high-quality chemical vapor deposited graphene by magneto-Raman spectroscopy

We present a magneto-Raman study on high-quality single-layer graphene grown by chemical vapor deposition (CVD) that is fully encapsulated in hexagonal boron nitride by a dry transfer technique. By analyzing the Raman D, G, and 2D peaks, we find that the structural quality of the samples is comparable with state-of-the-art exfoliated graphene flakes. From B-field dependent Raman measurements, we extract the broadening and associated lifetime of the G peak due to anharmonic effects. Furthermore, we determine the decay width and lifetime of Landau level (LL) transitions from magneto-phonon resonances as a function of laser power. At low laser power, we find a minimal decay width of 140 cm−1 highlighting the high electronic quality of the CVD-grown graphene. At higher laser power, we observe an increase of the LL decay width leading to a saturation, with the corresponding lifetime saturating at a minimal value of 18 fs.

Enhancement of the Electrical Properties of CVD-Grown Graphene with Ascorbic Acid Treatment

Ascorbic acid was used to modify to chemical vapor deposition (CVD)-grown graphene films transferred onto SiO2 substrate. Residual polymer (polymethyl methacrylate), Fe3+, Cl−, H2O, and O2 affected the electrical and thermal properties on graphene during the transfer or device fabrication processes. Exposure of transferred graphene to ascorbic acid resulted in significantly enhanced electrical properties with increased charge carrier mobility. All devices exhibited more than 30% improvement in room temperature carrier mobility in air. The carrier mobility of the treated graphene did not significantly decrease in 21 days. This result can be attributed to electron donation to graphene through the −OH functional group in ascorbic acid that is absorbed in graphene. This work provides a method to enhance the electrical properties of CVD-grown graphene.

Ultrafast Electron Transfer Kinetics of Graphene Grown by Chemical Vapor Deposition

High electrochemical reactivity is required for various energy and sensing applications of graphene grown by chemical vapor deposition (CVD). Herein, we report that heterogeneous electron transfer can be remarkably fast at CVD-grown graphene electrodes that are fabricated without using the conventional poly(methyl methacrylate) (PMMA) for graphene transfer from a growth substrate. We use nanogap voltammetry based on scanning electrochemical microscopy to obtain very high standard rate constants k(0) ≥25 cm s(-1) for ferrocenemethanol oxidation at polystyrene-supported graphene. The rate constants are at least 2-3 orders of magnitude higher than those at PMMA-transferred graphene, which demonstrates an anomalously weak dependence of electron-transfer rates on the potential. Slow kinetics at PMMA-transferred graphene is attributed to the presence of residual PMMA. This unprecedentedly high reactivity of PMMA-free CVD-grown graphene electrodes is fundamentally and practically important.

Towards an Accurate Measurement of Thermal Contact Resistance at Chemical Vapor Deposition-Grown Graphene/SiO<SUB>2</SUB> Interface Through Null Point Scanning Thermal Microscopy

In the development of graphene-based electronic devices, it is crucial to characterize the thermal contact resistance between the graphene and the substrate precisely. In this study, we demonstrate that the thermal contact resistance between CVD-grown graphene and SiO2 substrate can be obtained by measuring the temperature drop occurring at the graphene/SiO2 interface with null point scanning thermal microscopy (NP SThM), which profiles the temperature distribution quantitatively with nanoscale spatial resolution (-50 nm) without the shortcomings of the conventional SThM. The thermal contact resistance between the CVD-grown graphene and SiO2 substrate is measured as (1.7 ± 0.27) x 10(-6) M2K/W. This abnormally large thermal contact resistance seems to be caused by extrinsic factors such as ripples and metal-based contamination, which inevitably form in CVD-grown graphene during the production and transfer processes.

Synthesis of large-area multilayer hexagonal boron nitride for high material performance.

Although hexagonal boron nitride (h-BN) is a good candidate for gate-insulating materials by minimizing interaction from substrate, further applications to electronic devices with available two-dimensional semiconductors continue to be limited by flake size. While monolayer h-BN has been synthesized on Pt and Cu foil using chemical vapour deposition (CVD), multilayer h-BN is still absent. Here we use Fe foil and synthesize large-area multilayer h-BN film by CVD with a borazine precursor. These films reveal strong cathodoluminescence and high mechanical strength (Young's modulus: 1.16±0.1 TPa), reminiscent of formation of high-quality h-BN. The CVD-grown graphene on multilayer h-BN film yields a high carrier mobility of ∼24,000 cm2 V−1 s−1 at room temperature, higher than that (∼13,000 2 V−1 s−1) with exfoliated h-BN. By placing additional h-BN on a SiO2/Si substrate for a MoS2 (WSe2) field-effect transistor, the doping effect from gate oxide is minimized and furthermore the mobility is improved by four (150) times.

An Atomistic Tomographic Study of Oxygen and Hydrogen Atoms and their Molecules in CVD Grown Graphene.

The properties and growth processes of graphene are greatly influenced by the elemental distributions of impurity atoms and their functional groups within or on the hexagonal carbon lattice. Oxygen and hydrogen atoms and their functional molecules (OH, CO, and CO2 ) positions' and chemical identities are tomographically mapped in three dimensions in a graphene monolayer film grown on a copper substrate, at the atomic part-per-million (atomic ppm) detection level, employing laser assisted atom-probe tomography. The atomistic plan and cross-sectional views of graphene indicate that oxygen, hydrogen, and their co-functionalities, OH, CO, and CO2 , which are locally clustered under or within the graphene lattice. The experimental 3D atomistic portrait of the chemistry is combined with computational density-functional theory (DFT) calculations to enhance the understanding of the surface state of graphene, the positions of the chemical functional groups, their interactions with the underlying Cu substrate, and their influences on the growth of graphene.

A novel method for transferring graphene onto PDMS

Graphene has been attracting great attention from scientific community due to its astonishing mechanical, optical, and electrical properties, especially, graphene films synthesized by chemical vapor deposition (CVD) method are large, uniform and high-quality. CVD-grown graphene films have been successfully transferred onto various kinds of substrates such as SiO2/Si, quartz, PET, and plastics. However, graphene transfer onto polydimethylsiloxane (PDMS) substrates for device development has been limited due to the very low surface energy of PDMS. Here, we present a novel method to transfer graphene onto PDMS substrates by utilizing a thin layer of SU-8 as an adhesion layer. The SU-8 adhesion layer significantly improves the adhesion between the graphene layer and the PDMS substrate resulting in successful graphene transfer onto the PDMS substrate. This opens up a great potential of using graphene on PDMS substrates for the development of a wide range of graphene-based transparent and flexible devices.

Roll-to-Roll Green Transfer of CVD Graphene onto Plastic for a Transparent and Flexible Triboelectric Nanogenerator.

A novel roll-to-roll, etching-free, clean transfer of CVD-grown graphene from copper to plastic using surface-energy-assisted delamination in hot deionized water is reported. The delamination process is realized by water penetration between the hydrophobic graphene and a hydrophilic native oxide layer on a copper foil.The transferred graphene on plastic is used as a high-output flexible and transparent triboelectric nanogenerator.

Graphene reduction dynamics unveiled

The reduction dynamics of micron-sized defects created on chemical vapor deposition- (CVD) grown graphene through scanning probe lithography (SPL) is reported here. CVD-grown graphene was locally oxidized using SPL and subsequently reduced, making use of a focused beam of soft x-rays. During this whole process, the reduction dynamics was monitored using a combination of micro-Raman spectroscopy (μ-RS) and micro-x-ray photoelectron spectroscopy (μ-XPS). After x-ray reduction, the graphene film was found to be chemically identical (μ-XPS) but structurally different (μ-RS) from the original graphene. During reduction the population of C–C bonds was found to first increase dramatically and then decrease exponentially. By modeling the dynamics of the C=O → C–O → C–C → C=C reduction process with four coupled-rate equations and three rate constants, the conversion from C–C to C=C bonds was found to be the limiting rate.

Large‐Scale Diffusion Barriers from CVD Grown Graphene

Graphene has been long thought of as a perfect barrier material due to its impermeability to all gases as well as mechanical and chemical durability. Moreover, graphene layers are transparent and conductive, significantly widening the field of potential applications beyond simple barrier coatings. However, it is very challenging to realize such barriers on a macro­scopic scale as immaculate large area films are not available. In this work, a highly effective oxygen gas barrier made from multiple layers of chemical vapor deposited graphene is presented. The individual graphene layers are stacked using a modified polymer‐assisted transfer method, avoiding polymer residue yielding an oxygen‐tight arrangement. A stack of three layers of graphene transmitted 6.9 cm3 m−2 d−1 of O2 which corresponds to 1.10 × 10−17 cm3 cm/cm2 s (cm Hg) when normalized to thickness and pressure. This is several orders of magnitude better than any macroscale graphene coating reported to date and performs on a level that can compete with most modern coatings while being much thinner and conductive.

Fabrication of Ultrasensitive Field-Effect Transistor DNA Biosensors by a Directional Transfer Technique Based on CVD-Grown Graphene

Most graphene field-effect transistor (G-FET) biosensors are fabricated through a routine process, in which graphene is transferred onto a Si/SiO2 substrate and then devices are subsequently produced by micromanufacture processes. However, such a fabrication approach can introduce contamination onto the graphene surface during the lithographic process, resulting in interference for the subsequent biosensing. In this work, we have developed a novel directional transfer technique to fabricate G-FET biosensors based on chemical-vapor-deposition- (CVD-) grown single-layer graphene (SLG) and applied this biosensor for the sensitive detection of DNA. A FET device with six individual array sensors was first fabricated, and SLG obtained by the CVD-growth method was transferred onto the sensor surface in a directional manner. Afterward, peptide nucleic acid (PNA) was covalently immobilized on the graphene surface, and DNA detection was realized by applying specific target DNA to the PNA-functionalized G-FET biosensor. The developed G-FET biosensor was able to detect target DNA at concentrations as low as 10 fM, which is 1 order of magnitude lower than those reported in a previous work. In addition, the biosensor was capable of distinguishing the complementary DNA from one-base-mismatched DNA and noncomplementary DNA. The directional transfer technique for the fabrication of G-FET biosensors is simple, and the as-constructed G-FET DNA biosensor shows ultrasensitivity and high specificity, indicating its potential application in disease diagnostics as a point-of-care tool.

High-performance ultraviolet photodetectors based on solution-grown ZnS nanobelts sandwiched between graphene layers.

Ultraviolet (UV) light photodetectors constructed from solely inorganic semiconductors still remain unsatisfactory because of their low electrical performances. To overcome this limitation, the hybridization is one of the key approaches that have been recently adopted to enhance the photocurrent. High-performance UV photodetectors showing stable on-off switching and excellent spectral selectivity have been fabricated based on the hybrid structure of solution-grown ZnS nanobelts and CVD-grown graphene. Sandwiched structures and multilayer stacking strategies have been applied to expand effective junction between graphene and photoactive ZnS nanobelts. A multiply sandwich-structured photodetector of graphene/ZnS has shown a photocurrent of 0.115 mA under illumination of 1.2 mWcm−2 in air at a bias of 1.0 V, which is higher 107 times than literature values. The multiple-sandwich structure of UV-light sensors with graphene having high conductivity, flexibility, and impermeability is suggested to be beneficial for the facile fabrication of UV photodetectors with extremely efficient performances.

Microengineered CH3NH3PbI3 Nanowire/Graphene Phototransistor for Low-Intensity Light Detection at Room Temperature.

Methylammonium lead iodide perovskite has revolutionized the field of third generation solid-state solar cells leading to simple solar cell structures1 and certified efficiencies up to 20.1%. Recently the peculiar light harvesting properties of organometal halide perovskites have been exploited in photodetectors where responsivities of ~3.5 A/W and 180 A/W have been respectively achieved for pure perovskite-based devices and hybrid nanostructures. Here, we report on the first hybrid phototransistors where the performance of a network of photoactive Methylammonium Lead Iodide nanowires (hereafter MAPbI$_3$NW) are enhanced by CVD-grown monolayer graphene. These devices show responsivities as high as ~2.6x10$^6$ A/W in the visible range showing potential as room-temperature single-electron detector.