Ultra-low-edge-defect graphene nanoribbons patterned by neutral beam

Top-down process, comprising lithography and plasma etching is widely used in very-large-scale integration due to its scalability, has the greatest potential to fabricate graphene nanoribbon based nanoelectronic devices for large-scale intergraded circuits. However, conventional plasma etching inevitably introduces plenty of damage or defects to the etched materials, which drastically degrades the performance of nano materials. In this study, extremely low-damage neutral beam etching (NBE) is applied to fabricate ultra-low-defect graphene nanoribbon array (GNR). The ultra-low-edge-defect GNRs are fabricated by E-beam lithography followed by oxygen NBE from large-scale chemical-vapor-deposition-grown graphene. AFM images clearly shows the GNRs patterned by NBE and E-beam lithography, and Raman spectroscopy exhibits extremely low I_D/I_G of GNRs, which indicate that high-quality GNRs can be successfully fabricated by neutral beam. We also demonstrated bottom-gated field-effect transistor with the high-quality GNR and observed a high carrier mobility (>200 cm² V⁻¹ s⁻¹) at room temperature.     

Tubular graphene nanoribbons with attached manganese oxide nanoparticles for use as electrodes in high-performance supercapacitors

Graphene nanoribbons (GNRs) with tubular shaped thin graphene layers were prepared by partially longitudinal unzipping of vapor-grown carbon nanofibers (VGCFs) using a simple solution-based oxidative process. The GNR sample has a similar layered structure to graphene oxide (GO), which could be readily dispersed in isopropyl alcohol to facilitate electrophoretic deposition (EPD). GO could be converted to graphene after heat treatment at 300 °C. The multilayer GNR electrode pillared with open-ended graphene tubes showed a higher capacitance than graphene flake and pristine VGCF electrodes, primarily due to the significantly increased surface area accessible to electrolyte ions. A GNR electrode with attached MnO₂ nanoparticles was prepared by EPD method in the presence of hydrated manganese nitrate. The specific capacitance of GNR electrode with attached MnO₂ could reach 266 F g⁻¹, much higher than that of GNR electrode (88 F g⁻¹) at a discharge current of 1 A g⁻¹. The hydrophilic MnO₂ nanoparticles attached to GNRs could act as a redox center and nanospacer to allow the storage of extra capacitance.     

Graphene etching controlled by atomic structures on the substrate surface

We etched graphene on a sapphire (1 ?1 0 2) surface using the reaction between graphene and hydrogen catalyzed by metal nanoparticles. To investigate effects of the atomic structure of the sapphire substrate on graphene etching, we used sapphire substrate with as-polished, air-annealed, and step-ordered surfaces. We investigated the relationship between the atomic arrangement of sapphire and graphene etching and found that graphene is selectively etched in the [1 ?1 0 ?1] direction of sapphire. This indicates that atomic structure of the sapphire surface can be used as a template to control graphene etching. By combining the transfer method for graphene sheets grown on metal substrates with the present etching technique, graphene nanoribbons can be fabricated at a wafer level.     

Electronic thermal conductivity and thermopower of armchair graphene nanoribbons

A theoretical investigation of the diffusion contribution to thermopower, S_d, and the electronic thermal conductivity, κ_e, of semiconducting armchair graphene nanoribbons (GNRs) is made for T ⩽ 300 K. Considering the electrons to be scattered by edge roughness, impurities and deformation-potential coupled acoustic phonons and optical phonons, expressions for S_d and κ_e are obtained. Numerical calculations of S_d and κ_e, as functions of temperature and linear carrier density, bring out the relative importance of the contributing scattering mechanisms. A GNR of width 5 nm, supporting an electron density 2 × 10⁸ m⁻¹, is found to exhibit room temperature values of S_d and κ_e as 42 μV/K and 26.5 W/mK, respectively. A decrease in armchair GNR width, is found to enhance S_d and reduce κ_e. The effect of varying the electron density is to increase their magnitude when Fermi energy moves into the second subband. An analysis of thermopower and thermal conductivity data in clean armchair GNR samples will enable better understanding of the electron–phonon interaction.     

Effect of graphene nanosheets on electrochemical performance of Li4Ti5O12 in lithium-ion capacitors

In order to improve the electrochemical performance of lithium titanium oxide, Li₄Ti₅O₁₂ (LTO), for the use in the lithium-ion capacitors (LICs) application, LTO/graphene composites were synthesized through a solid state reaction. The composite exhibited an interwoven structure with LTO particles dispersed into graphene nanosheets network rather than an agglomerated state pristine LTO particles. It was found that there is an optimum percentage of graphene additives for the formation of pure LTO phase during the solid state synthesis of LTO/graphene composite. The effect of graphene nanosheets addition on electrochemical performance of LTO was investigated by a systemic characterization of galvanostatic cycling in lithium and lithium-ion cell configuration. The optimized composite exhibited a decreased polarization upon cycling and delivered a specific capacity of 173 mA h g⁻¹ at 0.1 C and a well maintained capacity of 65 mA h g⁻¹ even at 20 C. The energy density of 14 Wh kg⁻¹ at a power density of 2700 W kg⁻¹ was exhibited by a LIC full cell with a balanced mass ratio of anode to cathode along with a superior capacitance retention of 97% after 3000 cycles at a current density of 0.4 A g⁻¹. This boost in reversible capacity, rate capability and cycling performance was attributed to a synergistic effect of graphene nanosheets, which provided a short lithium ion diffusion path as well as facile electron conduction channels.     

Easy synthesis of porous graphene nanosheets and their use in supercapacitors

We report the easy synthesis of porous graphene nanosheets (PGNs) using the etching of graphene sheets by MnO₂. An electrode made from PGNs exhibits a specific capacitance of 154 F g^?1 at 500 mV s^?1 in 6 M KOH compared to a value of 67 F g^?1 for graphene nanosheets, and a low capacitance loss of 12% after 5000 cycles. Interestingly, PGN electrode material shows an excellent rate capability due to its open layered and mesopore structures that facilitate the efficient access of electrolytes to the electrode material and shorten the ion diffusion pathway through the porous sheets. This approach offers the potential for cost-effective, environmentally friendly and large-scale production of PGNs.     

Monolayer graphene as ultimate chemical passivation layer for arbitrarily shaped metal surfaces

Monolayer graphene was grown on polycrystalline Ru thin films on patterned fused silica. The Ru films grow with columnar structure with strongly aligned grains exposing flat (0 0 0 1) surface facets within the 3D geometric patterns and on the adjacent planar silica surface. The monolayer graphene was found to completely and uniformly cover the Ru films on the complex engineered substrates. In addition, we demonstrate that the single atomic layer graphene protects the underlying metal surface against reaction with ambient gases of particular importance for applications such as concave focusing mirrors, non-planar microelectrode arrays, etc.     

Non-metal catalytic synthesis of graphene from a polythiophene monolayer on silicon dioxide

Direct synthesis of graphene without metal catalysts on a dielectric substrate is a major goal in graphene-based electronics and is an increasingly popular nanotechnology alternative to metal oxide semiconductor technology. However, current methods for the synthesis of these graphenes have many limitations, including the use of metal catalyst. Herein, we report a facile approach to the direct synthesis of graphene sheets based on the self-assembled monolayers (SAMs) technique. The new method for metal catalyst-free direct synthesis of a graphene sheet is through a solution-processable, inexpensive, easy, and reproducible cross-linked polythiophene self-assembled monolayer (SAM) that is formed via the [4 + 2] π cycloaddition reaction of π-electron conjugated thiophene layer self-assembled on the dielectric silicon dioxide substrate. The bifunctional molecules were carefully designed to create an SAM via silanization of alkoxy silane groups on the SiO₂ substrate, and at the other end, a thin cross-linked polythiophene layer via a [4 + 2] π-electron cycloaddition reaction of π-electron conjugated thiophene SAM. By heating the cross-linked polythiophene SAM up to 1000 °C under a high vacuum, single-layered or few-layered graphene sheets were successfully prepared on the dielectric silicon oxide substrate.     

Synthesis of cross-linked graphene aerogel/Fe2O3 nanocomposite with enhanced supercapacitive performance

In this work, cross-linked graphene aerogel (CL-GA) and its composite with Fe₂O₃ nanoparticles (NPs) were synthesized through a one-step hydrothermal procedure by using p-phenylenediamine (PPD). Structural characterizations revealed that in the preparation of the composite PPD acts as a cross-liker and provides high surface area by decreasing restacking of graphene sheets and functions as nitrogen source simultaneously. The electrochemical characteristics of the nanocomposite were investigated by cyclic voltammetry (CV), galvanostatic charge/discharge, electrochemical impedance spectroscopy (EIS) and Fast Fourier transform continues cyclic voltammetry (FFTCCV). The results show that cross-linked graphene aerogel/Fe₂O₃ (CL-GA/Fe₂O₃) nanocomposite displays enhanced supercapacitive performance, where it has capacitance of 445 at 1 A g⁻¹, high energy density of 63 W h Kg⁻¹, and 89% capacitance retention after 5000 cycles in 3 M KOH. Presence of PPD considerably improved supercapacitive performance of nanocomposite as a result it could be promising material in synthesis of efficient graphene/metal oxide-based electrode material for high performance supercapacitors.     

Adsorption separation of vinyl chloride and acetylene on activated carbon modified by metal ions

This work mainly involved the adsorption separation of vinyl chloride and acetylene on modified activated carbons. Six metal ions with different hardness were loaded on activated carbon respectively. The effect of metal ions on the adsorption separation performance of vinyl chloride and acetylene was investigated. The experimental results shown that the separation factor of C₂H₃Cl to C₂H₂ over modified activated carbon followed the order: Al(III)/AC > Mg(II)/AC > Fe(III)/AC > AC > Zn(II)/AC ≈ Cu(II)/AC > Ag(I)/AC. The effect of the hardness of metal ions on the adsorption capacity of C₂H₂ was more remarkable than that of C₂H₃Cl, thus the separation factor of C₂H₃Cl to C₂H₂ increased with the rising of absolute hardness of the metal ions.     

Synthesis of bimetallic PtPd nanocubes on graphene with N,N-dimethylformamide and their direct use for methanol electrocatalytic oxidation

Bimetallic PtPd nanocubes supported on graphene nanosheets (PtPdNCs/GNs) were prepared by a rapid, one-pot and surfactant-free method, in which N,N-dimethylformamide (DMF) was used as a bi-functional solvent for the reduction of both metal precursors and graphene oxide (GO) and for the surface confining growth of PtPdNCs. The morphology, structure and composition of the thus-prepared PtPdNCs/GNs were characterized by transmission electron microscopy (TEM), high resolution TEM, energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. Because no surfactant or halide ions were involved in the proposed synthesis, the prepared PtPdNCs/GNs were directly modified onto a glassy carbon electrode and showed high electrocatalytic activity for methanol oxidation in cyclic voltammetry without any pretreatments. Moreover, with the synergetic effects of Pt and Pd and the enhanced electron transfer by graphene, the PtPdNCs/GNs composites exhibited higher electrocatalytic activity (j_p = 0.48 A mg⁻¹) and better tolerance to carbon monoxide poisoning (I_f/I_b = 1.27) compared with PtPd nanoparticles supported on carbon black (PtPdNPs/C) (j_p = 0.28 A mg⁻¹; I_f/I_b = 1.01) and PtNPs/GNs (j_p = 0.33 A mg⁻¹; I_f/I_b = 0.95). This approach demonstrates that the use of DMF as a solvent with heating is really useful for reducing GO and metal precursors concurrently for preparing clean metal–graphene composites.     

Synthesis of graphene-CoS electro-catalytic electrodes for dye sensitized solar cells

A large CoS-implanted graphene (G-CoS) film electrode was prepared using chemical vapor deposition followed by successive ionic layer absorption and reaction. HRTEM and AFM show that CoS nanoparticles are uniformly implanted on the graphene film. Furthermore, the G-CoS electro-catalytic electrode is characterized in a dye sensitized solar cells (DSSC) and is found to be highly electro-catalytic towards iodine reduction with low charge transfer resistance (R_ct ～5.05 Ω cm²) and high exchange current density (J₀～2.50 mA cm^?2). The improved performance compared to the pristine graphene is attributed to the increased number of active catalytic sites of G-CoS and highly conducting path of graphene. The comprehensive G-CoS synthesis process is a simple and scalable process which can easily adapt for large scale electro-catalytic film fabrication for several other electro-chemical energy harvesting and storage applications.     

Liquid-phase oxidation of benzene to phenol by molecular oxygen over transition metal substituted polyoxometalate compounds

Transition metal substituted polyoxometalate (TMSP) compounds were used as catalysts for the liquid-phase oxidation of benzene to phenol by molecular oxygen with ascorbic acid as a reducing agent in an acetone/sulfolane/water mixed solvent. [(C₄H₉)₄N]₅[PW₁₁CuO₃₉(H₂O)] is the best catalyst tested in this study. It showed 9.2% benzene conversion (TON = 25.8) and 91.8% selectivity to phenol for the oxidation of benzene at 323 K for 12 h. The effect of the substituted transition metal in the TMSP compounds on the benzene conversion is in the order: Cu > V > Fe ≫ Mn > Ti > Cr > Co > Ni > Zn. The effect of the central atom in the TMSP compounds on the benzene conversion is in the order: P ≈ Si > Ge > B. [SiW₁₁O₃₉]⁸⁻ is a good polyoxometalate ligand for transition metal ions as [PW₁₁O₃₉]⁷⁻ for the oxidation of benzene. The selectivity to phenol was dramatically improved by adding the sulfolane solvent, but the benzene conversion decreased when a large amount of sulfolane was used in the mixed solvent. Ascorbic acid is indispensable for forming phenol from benzene oxidation by O₂ over TMSP compounds. Higher O₂ pressure in the catalytic system ensured more oxygen molecules solving in the solvent, and promoted the benzene conversion.     

Carbon nanotube and nanofiber syntheses by the decomposition of methane on group 8–10 metal-loaded MgO catalysts

We have found that several precious metal-loaded MgO catalysts are active in the formation of carbon nanotube (CNT) by the chemical vapor deposition (CVD) of methane. The catalysts were prepared with nine metals (Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt) by impregnation onto a high surface area MgO. CNT synthesis was carried out in the temperature range from 600 °C to 1000 °C after reduction with H₂ at 800 °C.The amount of carbon deposited and crystallinity in the produced CNT on nine metals showed interesting tendencies: (i) The amount of carbon formed increased in the following transition series metals: first < second < third row transition elements, and (ii) the index of crystallinity I_G/I_D in Raman-bands of the CNTs decreased in the following order: 8 > 9 > 10 in the Periodic Table. Group 8 and 9 metals produced tube type fibers composed of the graphite layers arranged parallel to the fiber axis. On the other hand, carbon nanofibers (CNFs) grown on group 10 metals had herringbone type graphene sheets.     

The effects of pulse repetition rate on the structural,surface morphological and UV photodetection properties of pulsed laser deposited Mg-doped ZnO nanorods

The Mg_0.05Zn_0.95O (MZO) nanorod array (NRA) films have been successfully grown onto SiO₂/ n-Si substrates by pulsed laser deposition (PLD) without any template or seed layer and the influence of pulse repetition rate (3 to 15 Hz) of a 248 nm KrF excimer laser on their crystallinity, surface morphology and UV photodetection properties were systematically investigated. All the samples show the hexagonal wurtzite phase with a preferential c-axis orientation and the optimum crystallization of the MZO NRAs occurs at 5 Hz. FE-SEM analysis revealed that the growth of MZO NRAs is strongly influenced by the pulse repetition rate. It was observed that the average film thickness increases almost linearly with the pulse repetition rate and the MZO nanorod arrays grown at 5 Hz exhibits best surface area. Moreover, the room temperature UV photodetection properties of the samples were investigated in metal–semiconductor–metal (MSM) planar configurations and are found to be strongly driven by the pulse repetition rate dependent crystalline and surface morphological features. The device current–voltage (I–V) characteristics were measured under dark and UV light conditions. Then, the photocurrent and responsivity were measured with the variation of optical power density and applied voltage, respectively. Transient photoresponse studies show an exceedingly stable and fast switching UV photoresponse for the photodetector having MZO nanorods grown at 5 Hz, which demonstrates highest responsivity of 17 mA/W upon 2 mW/cm² UV illumination (365 nm), at 5 V bias.     

Numerical experiments on phonon properties of isotope and vacancy-type disordered graphene

We have studied phonon properties of graphene theoretically with different concentrations of ¹³C isotope and vacancy-type defects. The forced vibrational method, which is based on the mechanical resonance to extract the pure vibrational eigenmodes by numerical simulation, has been employed to compute the phonon density of states (PDOSs) and mode pattern of isotope-disordered graphene as well as a combined isotope and vacancy-type defective graphene structure. We observe a linear reduction of the E_2g mode frequencies with an increase in ¹³C concentration due to the reduced mass variation of the isotope mixture. We find a downshift of the E_2g mode of 65 cm^− 1, which is a very good agreement with the experimental results, and the phonon frequencies described by the simple harmonic oscillator model. The vacancy-type defects break down the phonon degeneracy at the Г point of the LO and TO modes, distort and shift down the phonon density of states significantly. The PDOS peaks for the combined isotope and vacancy-type defects show the remarkable increase in the low-frequency region induced by their defect formations. Due to phonon scattering by ¹³C isotope or vacancies, some graphene phonon wave functions become localized in the real space. Our numerical experiments reveal that the lattice vibrations in the defective graphene show the remarkably different properties such as spatial localization of lattice vibrations due to their random structures from those in the perfect graphene. The calculated typical mode patterns for in-plane K point optical phonon modes indicate that the features of strongly localized state depend on the defect density, and the phonon is localized strongly within a region of several nanometers in the random percolation network structures. In particular, for in-plane K point optical phonon modes, a typical localization length is on the order of ≈ 7 nm for isotope impurities, ≈ 5 nm for vacancy-type defects and ≈ 6 nm for mixed-type defects at high defect concentrations of 30%. Our findings can be useful for the interpretation of experiments on infrared, Raman, and neutron-diffraction spectra of defective graphene, as well as in the study of a wide variety of other physical properties such as thermal conductivity, specific heat capacity, and electron–phonon interaction.     

Metal-catalyzed etching of graphene governed by metal–carbon interactions: A comparison of Fe and Cu

We present a comparative investigation on the etching of graphene catalyzed by Fe and Cu. When Fe or Cu thin film deposited on graphene is rapidly annealed in either N₂ or forming gas (10% H₂/90% N₂), particles are produced due to the dewetting of thin films. Low-voltage scanning electron microscopy reveals different morphology for Fe and Cu particles and their strikingly different catalytic etching behaviors. For the Fe thin film on graphene annealed at 950 °C in either gas environment, graphene is severely damaged, suggesting that the etching could occur through catalytic carbon hydrogenation or carbon dissolution into Fe due to the strong Fe–C interactions. In contrast, while no etching takes place for Cu particles on graphene at 1050 °C in N₂, Cu particles catalytically etch channels in graphene in forming gas through carbon hydrogenation, and the width of the channel is much narrower than the diameter of Cu particle due to the non-wetting behavior of Cu on graphene. The weak interactions between Cu and graphene, along with the low solubility of carbon in Cu, make Cu particles ideal for tracking their etching paths on graphene. This work provides new insights into the metal-catalyzed etching of graphene.     

Spectral phonon thermal properties in graphene nanoribbons

This work provides a comprehensive investigation on the spectral phonon properties in graphene nanoribbons (GNRs) by the normal mode decomposition (NMD) method, considering the effects of edge chirality, width, and temperature. We find that the edge chirality has no significant effect on the phonon relaxation time but has a large influence to the phonon group velocity. As a result, the thermal conductivity of around 707 W/(m K) in the 4.26 nm-wide zigzag GNR at room temperature is higher than that of 467 W/(m K) in the armchair GNR with the same width. As the width decreases or the temperature increases, the thermal conductivity reduces significantly due to the decreasing relaxation times. Good agreement is achieved between the thermal conductivities predicted from the Green–Kubo method and the NMD method. We find that optical phonons dominate the thermal transport in the GNRs while the relative contribution of acoustic phonons to the thermal conductivity is only 10.1% and 13% in the zigzag GNR and the armchair GNR, respectively. Interestingly, the ZA mode is found to contribute only 1–5% to the total thermal transport in GNRs, being much lower than that of 30–70% in single layer graphene.     

Mesoporous nitrogen-doped graphene aerogels with enhanced rate capability towards high performance supercapacitors

In this work, a novel preparation method and architecture of mesoporous nitrogen-doped graphene aerogels (GAs) using electrostatic attraction are reported. The sacrificial template, positively charged SiO₂ nanoparticles by using (3-Animopropyl) triethoxysilane (3-APTS), can significantly decrease the spacing between graphene oxide sheets, due to the strong electrostatic attraction between the graphene oxide and SiO₂. After the etching of templates, the ratio of mesopores is greatly increased, and the electrochemical performances of electrodes are enhanced. The mesoporous GAs yield an enhanced specific capacitance of 203 F/g at a current density of 1 A/g, and a capacitance fade of only 8.95% at a high current density of 20 A/g, indicating improved ion transport in mesoporous architecture. The controllable synthesized method can be further applied to prepare other mesoporous materials and such mesoporous nitrogen-doped GAs have great potential in high rate performance supercapacitors.