Chemically isolated graphene nanoribbons reversibly formed in fluorographene using polymer nanowire masks

We demonstrated the fabrication of graphene nanoribbons (GNRs) as narrow as 35 nm created using scanning probe lithography to deposit a polymer mask(1-3) and then fluorinating the sample to isolate the masked graphene from the surrounding wide band gap fluorographene. The polymer protected the GNR from atmospheric adsorbates while the adjacent fluorographene stably p-doped the GNRs which had electron mobilities of ～2700 cm2/(V·s). Chemical isolation of the GNR enabled resetting the device to nearly pristine graphene.     

Characteristics of CVD graphene nanoribbon formed by a ZnO nanowire hardmask

A graphene nanoribbon (GNR) is an important basic structure to open a bandgap in graphene. The GNR processes reported in the literature are complex, time-consuming, and expensive; moreover, the device yield is relatively low. In this paper, a simple new process to fabricate a long and straight graphene nanoribbon with a high yield has been proposed. This process utilizes CVD graphene substrate and a ZnO nanowire as the hardmask for patterning. 8 μm long and 50-100 nm wide GNRs were successfully demonstrated in high density without any trimming, and ～ 10% device yield was realized with a top-down patterning process. After passivating the surfaces of the GNRs using a low temperature atomic layer deposition (ALD) of Al(2)O(3), high performance GNR MOSFETs with symmetric drain-current-gate-voltage (I(d)-V(g)) curves were demonstrated and a field effect mobility up to ～ 1200 cm(2) V(-1) s(-1) was achieved at V(d) = 10 mV.     

Heat conduction across monolayer and few-layer graphenes

We report the thermal conductance G of Au/Ti/graphene/SiO(2) interfaces (graphene layers 1 ≤ n ≤ 10) typical of graphene transistor contacts. We find G ≈ 25 MW m(-2) K(-1) at room temperature, four times smaller than the thermal conductance of a Au/Ti/SiO(2) interface, even when n = 1. We attribute this reduction to the thermal resistance of Au/Ti/graphene and graphene/SiO(2) interfaces acting in series. The temperature dependence of G from 50 ≤ T ≤ 500 K also indicates that heat is predominantly carried by phonons through these interfaces. Our findings suggest that metal contacts can limit not only electrical transport but also thermal dissipation from submicrometer graphene devices.     

Effects of gold nanorod concentration on the depth-related temperature increase during hyperthermic ablation

The photothermal properties of gold nanorods (GNRs) provide an opportunity for the clinical application of highly efficient and tumor-specific photothermal therapy. For the effective hyperthermic ablation of tumor tissue using GNRs, it is essential to maintain a homogeneous therapeutic temperature in the target tissue during treatment. This study investigates whether the concentration of GNRs affects the distribution of the temperature increase during hyperthermal therapy. The investigation is conducted using polyacrylamide phantoms containing varying amounts of GNRs. In 0.1, 0.25, and 0.5 nM GNR-suspended phantoms, the change in temperature is relatively uniform along the depth of each phantom during laser irradiation at 2 W cm(-2) . In 1.0, 2.0, and 5.0 nM GNR-suspended phantoms, the rates of temperature increase in the deep regions of the phantoms decrease with increasing GNR concentration. At a laser irradiation of 5 W cm(-2) , the temperature of the GNR-suspended phantoms increases at a faster rate, whereas the range of GNR concentrations for maintaining the homogeneity of the temperature increase is not affected. This suggests that the concentration of GNRs is the major determinant of the depth-related temperature increase during hyperthermic ablation. Therefore, prior to the clinical application of hyperthermic ablation using GNRs, the concentration of GNRs has to be optimized to ensure a homogeneous distribution of therapeutic temperature in the targeted tissue.     

Electrical and thermal conductivity of low temperature CVD graphene: the effect of disorder

In this paper we present a study of graphene produced by chemical vapor deposition (CVD) under different conditions with the main emphasis on correlating the thermal and electrical properties with the degree of disorder. Graphene grown by CVD on Cu and Ni catalysts demonstrates the increasing extent of disorder at low deposition temperatures as revealed by the Raman peak ratio, IG/ID. We relate this ratio to the characteristic domain size, La, and investigate the electrical and thermal conductivity of graphene as a function of La. The electrical resistivity, ρ, measured on graphene samples transferred onto SiO2/Si substrates shows linear correlation with La(-1). The thermal conductivity, K, measured on the same graphene samples suspended on silicon pillars, on the other hand, appears to have a much weaker dependence on La, close to K～La1/3. It results in an apparent ρ～K3 correlation between them. Despite the progressively increasing structural disorder in graphene grown at lower temperatures, it shows remarkably high thermal conductivity (10(2)-10(3) W K(-1) m(-1)) and low electrical (10(3)-3×10(5) Ω) resistivities suitable for various applications.     

Low temperature raman study of the electron coherence length near graphene edges

We developed a novel optical defocusing method for studying spatial coherence of photoexcited electrons and holes near edges of graphene. Our method is applied to measure the localization l(D) of the disorder-induced Raman D band (～1350 cm(-1)) with a resolution of a few nanometers. Raman scattering experiments performed in a helium bath cryostat reveal that as temperature is decreased from 300 to 1.55 K, the length l(D) increases. We found that the localization of the D band varies as 1/T(1/2), giving strong evidence that l(D) scales with the coherence length of photoexcited electrons near graphene edges.     

Graphene bimetallic-like cantilevers: probing graphene/substrate interactions

The remarkable mechanical properties of graphene, the thinnest, lightest, and strongest material in existence, are desirable in applications ranging from composite materials to sensors and actuators. Here, we demonstrate that these mechanical properties are strongly affected by the interaction with the substrate onto which graphene is deposited. By measuring the temperature-dependent deflection of graphene/substrate "bimetallic" cantilevers we determine strain, thermal expansion coefficient, and the adhesion force acting on graphene films attached to a substrate. Graphene deposited on silicon nitride (SiN(x)) is under much larger strain, ε(g) ～ 1.5 × 10(-2), compared to graphene on gold (Au), ε(g) < 10(-3). The thermal expansion coefficient α(g) of graphene attached to SiN(x) is found to be negative, in the range from (- 5... - 1) × 10(-6)K(-1) and smaller in magnitude than α(g) of suspended graphene. We also estimate the interfacial shear strength of the graphene/SiN(x) interface to be ～1 GPa at room temperature.     

Observation of Raman g-peak split for graphene nanoribbons with hydrogen-terminated zigzag edges

Raman scattering of individual hydrogen-terminated zigzag-edged graphene nanoribbons (Z-GNRs) was studied with focus on the G-peak. In addition to the bulk graphene G-peak appearing at ～1594 cm(-1) (G(+)), an edge-related G-peak at ～1583 cm(-1) (G(-)) was observed for Z-GNRs. This additional Raman vibrational mode originates from the zigzag edges where localized metallic edge states are present. The relative intensity ratio G(-)/G(+) displays a strong dependence on the ribbon width (W). It increases gradually with decreasing W, and the G(+) finally vanishes at W = 5(±3) nm. Polarized Raman scattering was also employed to confirm the four-fold symmetry of the split TO modes, and the results are in good agreement with previous theoretical predictions. Our work offers the first direct experimental evidence to confirm the validity of predicted Raman scattering of GNRs.     

Graphene epitaxy by chemical vapor deposition on SiC

We demonstrate the growth of high quality graphene layers by chemical vapor deposition (CVD) on insulating and conductive SiC substrates. This method provides key advantages over the well-developed epitaxial graphene growth by Si sublimation that has been known for decades. (1) CVD growth is much less sensitive to SiC surface defects resulting in high electron mobilities of ～1800 cm(2)/(V s) and enables the controlled synthesis of a determined number of graphene layers with a defined doping level. The high quality of graphene is evidenced by a unique combination of angle-resolved photoemission spectroscopy, Raman spectroscopy, transport measurements, scanning tunneling microscopy and ellipsometry. Our measurements indicate that CVD grown graphene is under less compressive strain than its epitaxial counterpart and confirms the existence of an electronic energy band gap. These features are essential for future applications of graphene electronics based on wafer scale graphene growth.     

Topographic and spectroscopic characterization of electronic edge states in CVD grown graphene nanoribbons

We used scanning tunneling microscopy and spectroscopy (STM/S) techniques to analyze the relationships between the edge shapes and the electronic structures in as-grown chemical vapor deposition (CVD) graphene nanoribbons (GNRs). A rich variety of single-layered graphene nanoribbons exhibiting a width of several to 100 nm and up to 1 μm long were studied. High-resolution STM images highlight highly crystalline nanoribbon structures with well-defined and clean edges. Theoretical calculations indicate clear spin-split edge states induced by electron-electron Coulomb repulsion. The edge defects can significantly modify these edge states, and different edge structures for both sides of a single ribbon produce asymmetric electronic edge states, which reflect the more realistic features of CVD grown GNRs. Three structural models are proposed and analyzed to explain the observations. By comparing the models with an atomic resolution image at the edge, a pristine (2,1) structure was ruled out in favor of a reconstructed edge structure composed of 5-7 member rings, showing a better match with experimental results, and thereby suggesting the possibility of a defective morphology at the edge of CVD grown nanoribbons.     

Graphene films with large domain size by a two-step chemical vapor deposition process

The fundamental properties of graphene are making it an attractive material for a wide variety of applications. Various techniques have been developed to produce graphene and recently we discovered the synthesis of large area graphene by chemical vapor deposition (CVD) of methane on Cu foils. We also showed that graphene growth on Cu is a surface-mediated process and the films were polycrystalline with domains having an area of tens of square micrometers. In this paper, we report on the effect of growth parameters such as temperature, and methane flow rate and partial pressure on the growth rate, domain size, and surface coverage of graphene as determined by Raman spectroscopy, and transmission and scanning electron microscopy. On the basis of the results, we developed a two-step CVD process to synthesize graphene films with domains having an area of hundreds of square micrometers. Scanning electron microscopy and Raman spectroscopy clearly show an increase in domain size by changing the growth parameters. Transmission electron microscopy further shows that the domains are crystallographically rotated with respect to each other with a range of angles from about 13 to nearly 30°. Electrical transport measurements performed on back-gated FETs show that overall films with larger domains tend to have higher carrier mobility up to about 16,000 cm(2) V(-1) s(-1) at room temperature.     

Cascading Wafer-Scale Integrated Graphene Complementary Inverters under Ambient Conditions

The fundamental building blocks of digital electronics are logic gates which must be capable of cascading such that more complex logic functions can be realized. Here we demonstrate integrated graphene complementary inverters which operate with the same input and output voltage logic levels, thus allowing cascading. We obtain signal matching under ambient conditions with inverters fabricated from wafer-scale graphene grown by chemical vapor deposition (CVD). Monolayer graphene was incorporated in self-aligned field-effect transistors in which the top gate overlaps with the source and drain contacts. This results in full-channel gating and leads to the highest low-frequency voltage gain reported so far in top-gated CVD graphene devices operating in air ambient, A(v) ～ -5. Such gain enabled logic inverters with the same voltage swing of 0.56 V at their input and output. Graphene inverters could find their way in realistic applications where high-speed operation is desired but power dissipation is not a concern, similar to emitter-coupled logic.     

Graphene Nanoribbons: On-Surface Synthesis and Integration into Electronic Devices

Graphene nanoribbons (GNRs) are quasi-1D graphene strips, which have attracted attention as a novel class of semiconducting materials for various applications in electronics and optoelectronics. GNRs exhibit unique electronic and optical properties, which sensitively depend on their chemical structures, especially the width and edge configuration. Therefore, precision synthesis of GNRs with chemically defined structures is crucial for their fundamental studies as well as device applications. In contrast to top-down methods, bottom-up chemical synthesis using tailor-made molecular precursors can achieve atomically precise GNRs. Here, the synthesis of GNRs on metal surfaces under ultrahigh vacuum (UHV) and chemical vapor deposition (CVD) conditions is the main focus, and the recent progress in the field is summarized. The UHV method leads to successful unambiguous visualization of atomically precise structures of various GNRs with different edge configurations. The CVD protocol, in contrast, achieves simpler and industry-viable fabrication of GNRs, allowing for the scale up and efficient integration of the as-grown GNRs into devices. The recent updates in device studies are also addressed using GNRs synthesized by both the UHV method and CVD, mainly for transistor applications. Furthermore, views on the next steps and challenges in the field of on-surface synthesized GNRs are provided.     

Densely aligned graphene nanoribbons at ∼35 nm pitch

We demonstrate the fabrication of high-density aligned graphene nanoribbon (GNR) arrays by plasma etching of graphene sheets through a nanomask derived from self-assembled poly (styrene-block-dimethylsiloxane) (PS-PDMS) diblock copolymer films. This approach produces parallel GNR (～12 nm wide) arrays at ～35 nm pitch. Microscopy and polarized Raman spectroscopy are used to reveal the high-degree of alignment of GNRs. Electrical measurements show that parallel GNRs in a 1 μm wide region can deliver ～0.38 mA current at a source-drain bias of 1 V. This novel patterning approach allows for the fabrication of densely aligned GNR arrays on various substrates and could provide a route to large scale integration of GNRs into nanoelectronics, optoelectronics and biosensors.

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All graphene-based thin film transistors on flexible plastic substrates

High-performance, flexible all graphene-based thin film transistor (TFT) was fabricated on plastic substrates using a graphene active layer, graphene oxide (GO) dielectrics, and graphene electrodes. The GO dielectrics exhibit a dielectric constant (3.1 at 77 K), low leakage current (17 mA/cm(2)), breakdown bias (1.5 × 10(6) V/cm), and good mechanical flexibility. Graphene-based TFTs showed a hole and electron mobility of 300 and 250 cm(2)/(V·s), respectively, at a drain bias of -0.1 V. Moreover, graphene TFTs on the plastic substrates exhibited remarkably good mechanical flexibility and optical transmittance. This method explores a significant step for the application of graphene toward flexible and stretchable electronics.     

Nano- and microstructuring of graphene using UV-NIL

In this work we demonstrate for the first time the micro-?and nanostructuring of graphene by means of UV-nanoimprint lithography. Exfoliated graphene on SiO(2) substrates, as well as graphene deposited by chemical vapor deposition (CVD) on polycrystalline nickel and copper, and transferred CVD graphene on dielectric substrates, were used to demonstrate that our technique is suitable for large-area patterning (2?×?2?cm(2)) of graphene on various types of substrates. The demonstrated fabrication procedure of micrometer as well as nanometer-sized graphene structures with feature sizes down to 20?nm by a wafer-scale process opens up an avenue for the low-cost and high-throughput manufacturing of graphene-based optical and electronic applications. The processed graphene films show electron mobilities of up to 4.6?×?10(3)?cm(2)?V (-1)?s(-1), which confirms them to exhibit state-of-the-art electronic quality with respect to the current literature.     

Correlating defect density with carrier mobility in large-scaled graphene films: Raman spectral signatures for the estimation of defect density

We report a correlation between carrier mobility and defect density in large-scaled graphene films prepared by chemical vapor deposition (CVD). Raman spectroscopy is used for investigating the layer number and the crystal quality of graphene films, and the defect density is estimated by the intensity ratios of the D and G peaks. By carefully controlling the growth parameters, especially the H(2)/CH(4) ratios during growth, and employing H(2) during cooling, monolayer-dominant graphene films can be obtained with different D peak intensities in Raman spectra, which show good correspondence with their carrier mobility obtained by Hall measurements. Also, a progressive shift of neutrality points to a more negative gate voltage is observed with the increase in defect density. Both the connections of carrier mobility and the shift of neutrality points to a negative direction in relation to the defect density in graphene are observed for the first time in CVD-grown graphene films. With the best growth conditions, a cm-scaled graphene film with carrier mobility of ～ 1350 cm(2) V(-1) s(-1) (p-type in air) can be obtained.     

Graphene edge lithography

Fabrication of graphene nanostructures is of importance for both investigating their intrinsic physical properties and applying them into various functional devices. In this paper, we report a scalable fabrication approach for graphene nanostructures. Compared with conventional lithographic fabrication techniques, this new approach uses graphene edges as the templates or masks and offers advantage in technological simplicity and capability of creating small features below 10 nm scale. Moreover, mask layers used in the fabrication process could be simultaneously used as the dielectric layers for top-gated devices. The as-fabricated graphene nanoribbons (GNRs) are of high quality with the carrier mobility ～400 cm(2)/(V s) for typical 15 nm wide ribbons. Our technique allows easy and reproducible fabrication of various graphene nanostructures, such as ribbons and rings, and can be potentially extended to other materials and systems by use of their edges or facets as templates.     

Intracellular pH sensing using p-aminothiophenol functionalized gold nanorods with low cytotoxicity

We report an intracellular pH sensor based on surface enhanced Raman scattering (SERS) using the hydrochloric acid (HCl) treated gold nanorods (GNRs) as the SERS substrates and p-aminothiophenol (pATP) as the Raman reporter. Using the HCl treated GNRs previously reported by us, the biocompatibility and the SERS performance of GNRs have been greatly improved. Meanwhile, the adsorbed reporters are allowed to be directly exposed to the surrounding environments, which is very important for biosensors. It is found that the SERS spectrum of pATP is strongly dependent on the pH value. The intensities of SERS bands at 1142 cm(-1), 1390 cm(-1), and 1432 cm(-1) increased obviously with the pH value varying from 3.0 to 8.0. This pH-dependent SERS performance of pATP-functionalized HCl treated GNRs was well retained after the incorporation of the GNRs into living HeLa cells. Our experimental results indicate that such pATP-functionalized HCl treated GNRs can be used as an effective intracellular pH sensor. Thus, we show a good example that the bioapplications of the normal CTAB-stabilized GNRs can be expanded after the simple HCl treatment.     

Large-scale graphene transistors with enhanced performance and reliability based on interface engineering by phenylsilane self-assembled monolayers

In this letter, we report the dielectric/graphene interface physics and engineering of large-scale, chemical vapor deposited (CVD) graphene transistors by self-assembling a molecular-scale organosilane monolayer onto the dielectric surface. We show that phenyl-alkyl-terminated self-assembled monolayers (SAM) at the dielectric/graphene interface consistently improve the graphene device performance and reliability. The extrinsic field-effect mobility of large-scale CVD graphene transistors on the phenyl-SAM engineered dielectric is currently up to 2500 cm(2)/(V s) at room temperature, considerably higher than the counterparts without the SAM. In addition, significant reduction on the bias stress instability and hysteresis is achieved by the SAM-based interface engineering. Further analysis reveals that charge injection from graphene to the dielectric/graphene interface dominates the observed hysteresis behavior. For both graphene transistors with and without SAMs, the bias stress stability, that is, Dirac point shift under bias stress, is well described by the stretched exponential model with its fitting parameters clearly indicating different interface properties.