Improvement of the mechanical properties of single-walled carbon nanotube networks by carbon plasma coatings

Carbon vacuum arc was used to deposit 5–25 nm thick carbon coatings on single-walled carbon nanotube (SWCNT) networks. The SWCNT bundles thus embedded in conformal coatings maintained their optical transparency and electrical conductivity. Sheet resistances of the networks were measured during the vacuum arc deposition, revealing initially a 100-fold increase, followed by significant recovery after exposing the samples to an ambient atmosphere. Nanoindentation measurements revealed improved elasticity of the network after applying the carbon coating. Pristine SWCNT networks were easily deformed permanently, but a 20 nm carbon coating strengthened the nanostructure, resulting in a fully elastic recovery from a 20 μN load applied with a Berkovich tip. In nano-wear tests on selected areas, the coated SWCNT maintained its networking integrity after two passes raster scan at loads up to 25 μN. On the other hand, the pristine networks were badly damaged under a 10 μN scan load and completely displaced under 25 μN. Raman and electron energy loss spectroscopies indicated the carbon coating on bundles to be mainly sp² bonded. Finite element modeling suggests that the low content of sp³ bonds may be due to heating by the intense ion flux during the plasma pulse.     

Thermal grafting of organic monolayers on amorphous carbon and silicon (111) surfaces: A comparative study

Thermally-assisted (160 °C) liquid phase grafting of linear alkene molecules has been performed simultaneously on amorphous carbon (a-C) and hydrogen passivated crystalline silicon Si(111):H surfaces. Atomically flat a-C films with a high sp³ average surface hybridization, sp³ / (sp² + sp³) = 0.62, were grown using pulsed laser deposition (PLD). Quantitative analysis of X-ray photoelectron spectroscopy, X-ray reflectometry and spectroscopic ellipsometry data show the immobilization of a densely packed (> 3 × 10¹⁴ cm^? 2) single layer of organic molecules. In contrast with crystalline Si(111):H and other forms of carbon films, no surface preparation is required for the thermal grafting of alkene molecules on PLD amorphous carbon. The molecular grafted a-C surface is stable against ambient oxidation, in contrast with the grafted crystalline silicon surface.     

X-ray photoemission spectroscopy of nitrogen-doped UNCD/a-C:H films prepared by pulsed laser deposition

Nitrogen-doped ultrananocrystalline diamond (UNCD)/hydrogenated amorphous carbon (a-C:H) films were deposited by pulsed laser deposition (PLD). Nitrogen contents in the films were controlled by varying a ratio in the inflow amount between nitrogen and hydrogen gases. The film doped with a nitrogen content of 7.9 at.% possessed n-type conduction with an electrical conductivity of 18 Ω^? 1 cm^? 1 at 300 K. X-ray photoemission spectra, which were measured using synchrotron radiation, were decomposed into four component spectra due to sp², sp³ hybridized carbons, C=N and C–N. A full-width at half-maximum of the sp³ peak was 0.91 eV. This small value is specific to UNCD/a-C:H films. The sp²/(sp³ + sp²) value was enhanced from 32 to 40% with an increase in the nitrogen content from 0 to 7.9 at.%. This increment probably originates from the nitrogen incorporation into an a-C:H matrix and grain boundaries of UNCD crystallites. Since an electrical conductivity of a-C:H does not dramatically enhance for this doping amount according to previous reports, we believe that the electrical conductivity enhancement is predominantly due to the nitrogen incorporation into grain boundaries.     

Fluidized-bed synthesis of sub-millimeter-long single walled carbon nanotube arrays

The rapid growth method for vertically aligned, single walled carbon nanotube (SWCNT) arrays on flat substrates was applied to a fluidized-bed, using ceramic beads as catalyst supports as a means to mass produce sub-millimeter-long SWCNT arrays. Fe/Al₂O_x catalysts were deposited on the surface of Al₂O₃ beads by sputtering and SWCNTs were grown on the beads by chemical vapor deposition (CVD) using C₂H₂ as a feedstock. Scanning electron microscopy and transmission electron microscopy showed that SWCNTs of 2–4 nm in diameter grew and formed vertically aligned arrays of 0.5 mm in height. Thermogravimetric analysis showed that the SWCNTs had a catalyst impurity level below 1 wt.%. Furthermore, they were synthesized at a carbon yield as high as 65 at.% with a gas residence time as short as <0.2 s. Our fluidized-bed CVD, which efficiently utilizes the three-dimensional space of the reactor volume while retaining the characteristics of SWCNTs on substrates, is a promising option for mass-production of high-purity, sub-millimeter-long SWCNT arrays.     

Single-walled carbon nanotube/silicone rubber composites for compliant electrodes

Single-walled carbon nanotube (SWCNT)/silicone rubber composites that can be used in fabricating compliant electrodes are prepared by spraying a mixed solution of ionic-liquid-based SWCNT gel and silicone rubber onto an elastic substrate. Subsequently, the composites are exposed to nitric acid vapor. Scanning electron microscopy and atomic force microscopy images of the composites show that the SWCNTs are finely dispersed in the polymer matrix due to the addition of the ionic liquid. Doping of the SWCNTs by nitric acid can significantly lower the sheet resistance (R_s) of the composites; samples with 4 wt% of SWCNT content exhibit the lowest R_s value (50 Ω sq^?1). This sheet resistance corresponds to a conductivity value of 63 S cm^?1. In addition, the composites retain a high conductivity after several tensile strains are applied. Stretching the composite sample to 300% of the original length increased the R_s value to 320 Ω sq^?1 (19 S cm^?1). Even after 20th stretch/release/stretch cycle, the conductivity remains constant at a value of 18 S cm^?1. These results provide a scalable route for preparing highly stretchable and conductive SWCNT composites with relatively low SWCNT concentrations.     

Preparation of tetrahedral amorphous carbon films by filtered cathodic vacuum arc deposition

Tetrahedrally bonded amorphous carbon (ta-C) and nitrogen doped (ta-C:N) films were obtained at room temperature in a filtered cathodic vacuum arc (FCVA) system incorporating an off-plane double bend (S-bend) magnetic filter. The influence of the negative bias voltage applied to substrates (from −20 to −350 V) and the nitrogen background pressure (up to 10⁻³ Torr) on film properties was studied by scanning electron microscopy (SEM), electron energy loss spectroscopy (EELS), Raman spectroscopy, X-ray photoemission spectroscopy (XPS), secondary ion mass spectroscopy (SIMS) and X-ray reflectivity (XRR). The ta-C films showed sp³ fractions between 84% and 88%, and mass densities around 3.2 g/cm³ in the wide range of bias voltage studied. In contrast, the compressive stress showed a maximum value of 11 GPa for bias voltages around −90 V, whereas for lower and higher bias voltages the stress decreased to 6 GPa. As for the ta-C:N films grown at bias voltages below −200 V and with N contents up to 7%, it has been found that the N atoms were preferentially sp³ bonded to the carbon network with a reduction in stress below 8 GPa. Further increase in bias voltage or N content increased the sp² fraction, leading to a reduction in film density to 2.7 g/cm³.     

Thermal and electrical conductivity of array-spun multi-walled carbon nanotube yarns

The electrical resistivity of CNT yarns of diameters 10–34 μm, spun from multi-walled carbon nanotube arrays, have been determined from 2 to 300 K in magnetic fields up to 9 T. The magnetoresistance is large and negative at low temperatures. The thermal conductivity also has been determined, by parallel thermal conductance, from 5 to 300 K. The room-temperature thermal conductivity of the 10 μm yarn is (60 ± 20) W m^?1 K^?1, the highest measured result for a CNT yarn to date. The thermal and electrical conductivities both decrease with increasing yarn diameter, which is attributed to structural differences that vary with the yarn diameter.     

Fabrication and characterization of single-walled carbon nanotube fiber for electronics applications

We present a customized technique to spin fiber from unique single-wall carbon nanotube (SWCNT) films utilizing a motorized pulling/twisting stage. The manufactured SWCNT fibers’ diameter ranged from 30 to 130 μm. Electrical measurements show fusing current of 1–200 mA – depending on the spun fiber’s diameter – which is close to the values known for copper wires with similar diameter. These results reveal that the fiber spinning process could retain most of the advantageous electrical properties of original nanotubes, and also indicate a good possibility for using these low cost, sustainable SWCNT fibers in electrical wiring applications.     

Diamond-coated silicon wires for supercapacitor applications in ionic liquids

For a long time sp² carbon has been the dominating material for supercapacitor applications. In this paper a new concept of using boron-doped diamond for supercapacitors is proposed. Diamond surface enlargement is realized via bottom-up template-growth. In this method, silicon nanowire electrodes are coated with a thin (~ 100 nm) layer of nanocrystalline diamond (NCD) by microwave enhanced chemical vapor deposition (MWCVD). The quality of overgrowth is characterized by high resolution scanning electron microscopy which reveals a homogeneous coverage of diamond on Si nanowire surface. To enhance the potential window to 4 V, a room temperature ionic liquid is used as electrolyte. The dilution of the ionic liquid is investigated in terms of conductivity and specific capacitance. The capacitance as measured via cyclic voltammetry reaches 105 μF/cm². An energy density of 84 μJ/cm² and a high power density of 0.94 mW/cm² are obtained in combination with good stability of over 10,000 charging/discharging cycles.     

Bi-level surface modification of hard disk media by carbon using filtered cathodic vacuum arc: Reduced overcoat thickness without reduced corrosion performance

The corrosion performance of commercial hard disk media which was subjected to bi-level surface modification has been reported. The surface treatment was carried out by bombarding the surface of the magnetic media with C⁺ ions at 350 eV followed by 90 eV using filtered cathodic vacuum arc (FCVA). The energy and embedment depth of the impinging C⁺ ions were adjusted by applying an optimized bias to the substrate and simulated by a Stopping and Range of Ions in Matter (SRIM) code which predicted the formation of a graded atomically mixed layer at the carbon-media interface. Cross-section transmission electron microscopy (TEM) revealed the formation of a 1.8 nm dense nano-layered carbon overcoat structure on the surface of the media. Despite an ~ 33% reduction in the thickness, the bi-level surface modified disk showed corrosion performance similar to that of a commercially manufactured disk with a thicker carbon overcoat of 2.7 nm. This improvement in the corrosion/oxidation resistance per unit thickness can be attributed to the formation of a dense and highly sp³ bonded carbon layer, as revealed by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. This study demonstrates the effectiveness of the bi-level surface modification technique in forming an ultra-thin yet protective overcoat for future hard disks with high areal densities.     

Localized DLC etching by a non-thermal atmospheric-pressure helium plasma jet in ambient air

Using a versatile atmospheric-pressure helium plasma jet, diamond-like carbon (DLC) films were etched in ambient air. We observed that the DLC films are etched at a nominal rate of around 60 nm/min in the treated area (230 μm in diameter) during a 20-min exposure. The etching rate increased after the initial 10-min exposure. During this period, the flat DLC surface was structurally modified to produce carbon nanostructures with a density of ~ 2.4 × 10¹¹ cm^− 2. With this increase in surface area, the etching rate increased. After 20 min, the DLC film had a circular pattern etched into it down to the substrate where silicon nanostructures were observed with sizes varying from 10 nm to 1 μm. The initial carbon nanostructure formation is believed to involve selective removal of the sp²-bonded carbon domains. The carbon etching results from the formation of reactive oxygen species in the plasma.     

Resist-assisted assembly of single-walled carbon nanotube devices with nanoscale precision

We report a novel resist-assisted dielectrophoresis method for single-walled carbon nanotube (SWCNT) assembly. It provides nanoscale control of the location, density, orientation and shape of individual SWCNTs. Sub-50 nm accuracy and a yield higher than 85% have been achieved. Using the method, we demonstrate suspended-body SWCNT field-effect transistors (FETs) with back-gate and sub-100 nm air-gap lateral-gate configurations. The suspended-body SWCNT FETs show excellent electrical characteristics with I_on/I_off ～ 10⁷, ultra-low off currents ～10^?14 A and small subthreshold swings. The technique contributes to the ultimate solution for bottom-up fabrication of a broad field of CNT-based devices, such as: complementary metal–oxide-semiconductor and nano-electrical–mechanical-system devices for sensing and radio-frequency applications. Moreover, the versatile method could be applied to the assembly of many other promising materials, such as: nanowires and graphene flakes.     

Synthesis and electrochemical properties of nickel oxide/carbon nanofiber composites

The electrospinning of polyacrylonitrile (PAN) with a polyaniline and graphene sol–gel mixture produced uniform, smooth fibers with an average diameter of 0.3 μm. These electrospun fibers were stabilized for 2 h at 200 °C and then carbonized at 800 °C for 5 h. Composites were prepared by depositing Ni(OH)₂ on the carbon nanofibers (CNFs) and calcining them at different temperatures. The composites were characterized with X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The effect of the calcination temperatures on the electrochemical properties was studied using cyclic voltammetry and electrochemical impedance spectroscopy. The specific capacitance (SC) was found to be highest (738 F g⁻¹) at a calcination temperature of 400 °C. The charge transfer resistance (R_p) decreased as the calcination temperature was increased. However, the electrical double layer capacitance (EDLC) increased with an increase in the calcination temperature. The EDLC increased from 0.144 F g⁻¹ at a calcination temperature of 100 °C to 485 F g⁻¹ at a calcination temperature of 500 °C.     

Long-term H-release of hard and intermediate between hard and soft amorphous carbon evidenced by in situ Raman microscopy under isothermal heating

We study the kinetics of the H release from plasma-deposited hydrogenated amorphous carbon films under isothermal heating at 450, 500 and 600 °C for long times up to several days using in situ Raman microscopy. Four Raman parameters are analyzed. They allow the identification of different processes such as the carbon network reorganization and the H release from sp³ or sp² carbon atoms and the corresponding timescales. Carbon reorganization with aromatization and loss of sp³ hybridization occurs first in 100 min at 500 °C. The final organization is similar at all investigated temperatures. Full H release from sp³ carbon occurs on a longer timescale of about 10 h while H release from sp² carbon atoms is only partial, even after several days. All these processes occur more rapidly with higher initial H content, in agreement with what is known about the stability of these types of films. A quantitative analysis of these kinetics studies gives valuable information about the microscopic processes at the origin of the H release through the determination of activation energies.     

Carbon nanotube capacitors arrays using high-k dielectrics

The electrical characteristics and fabrication process of nanocapacitor arrays using metal-high-k dielectric-carbon nanotube-metal layers (MICntM) were studied. MWCNTs arrays were fabricated using an electron beam lithography based lift-off process for catalyst definition and the high-k dielectric layer, hafnium oxide (HfO₂), was deposited using rf magnetron sputtering. The MICntM structures show high capacitance and the compatibility with high-k dielectric material and its deposition processes. MICntM capacitors arrays with sputtered HfO₂ show specific capacitance of 0.62 μF/cm². The leakage current density at 1 V is less than 5 μA/cm². The high aspect ratio of MWCNTs increases the effective electrode area and HfO₂ allows higher permittivity, hence, higher capacitance structures are realized.     

Microstructure and optical band gap control of DLC film deposited by pulsed discharge plasma CVD

DLC films were deposited on silicon and quartz glass substrates by pulsed discharge plasma chemical vapor deposition (CVD), where the plasma was generated by pulsed DC discharge in H₂–CH₄ gas mixture at about 90 Torr in pressure, and the substrates were located near the plasma. The repetition frequency and duty ratio of the pulse were 800 Hz and 20%, respectively. When CH₄ / (CH₄ + H₂) ratio, i.e. methane concentration (Cm), increased from 3 to 40%, C₂ species in the plasma was increased, and corresponding to the increase of C₂, deposition rate of the film was increased from about 0.2 to 2.4 μm/h. The absorption peaks of sp³C–H and sp²C–H structures were observed in the FT-IR spectra, and the peak of sp²C–H structure was increased with increasing Cm, showing that sp² to sp³ bonding ratio was increased when Cm was increased. Corresponding to these structural changes due to the increase of Cm, optical band gap (Eg) was decreased from 3 to 0.5 eV continuously when Cm was increased from 3 to 40%.     

Substrate temperature effects on the microhardness and adhesion of diamond-like thin films

Diamond-like films were deposited on silicon substrates by r.f. plasma-enhanced chemical vapor deposition from gas methane. In this study, the substrate temperature, T_S, was varied in a wide range from 20 to 370°C while maintaining fixed other important process parameters such as r.f. power (70 W) or pressure (2.5 Pa). The increase of T_S causes an increase of the sp²/(sp²+sp³) bonded carbon ratio and a decrease of the hydrogen content. These changes produce a great modification of the mechanical properties: microhardness, friction coefficient and adhesion. The variations of mechanical properties with T_S correlate well with the sp²/(sp²+sp³) bonded carbon ratio and the hydrogen content in the films showing a gradual transformation of the diamond-like structure into a more sp²-rich one.     

Sp3/sp2 character of the carbon and hydrogen configuration in micro- and nanocrystalline diamond

Hot filament and microwave plasma CVD micro- nanocrystalline diamond films are analysed by visible and ultra-violet excitation source Raman spectroscopy. The sample grain size varies from 20 nm to 2 μm. The hydrogen concentration in samples is measured by SIMS and compared to the grain size, and to the ratio of sp² carbon bonds determined by Raman spectroscopy from the 1332 cm^− 1 diamond peak and the sp² 1550 cm^− 1 G band. Hydrogen concentration appears to be proportional to the sp² bonds ratio. The 3000 cm^− 1 CH_x stretching mode band intensity observed on the Raman spectra is decreasing with the G band intensity. Thermal annealing modifies the sp² phase structure and concentration, as hydrogen outdiffuses.     

Thermal stability and surface modifications of detonation diamond nanoparticles studied with X-ray photoelectron spectroscopy

Detonation nanodiamond (ND) particles were dispersed on silicon nitride (SiN_x) coated sc-Si substrates by spin-coating technique. Their surface density was in the 10¹⁰–10¹¹ cm^?2 range. Thermal stability and surface modifications of ND particles were studied by combined use of X-ray Photoelectron Spectroscopy (XPS) and Field Emission Gun Scanning Electron Microscopy (FEG SEM). Different oxygen-containing functional groups could be identified by XPS and their evolution versus UHV annealing temperature (400–1085 °C) could be monitored in situ. The increase of annealing temperature led to a decrease of oxygen bound to carbon. In particular, functional groups where carbon was bound to oxygen via one σ bond (C–OH, C–O–C) started decomposing first. At 970 °C carbon–oxygen components decreased further. However, the sp²/sp³ carbon ratio did not increase, thus confirming that the graphitization of ND requires higher temperatures. XPS analyses also revealed that no interaction of ND particles with the silicon nitride substrate occurred at temperatures up to about 1000 °C. However, at 1050 °C silicon nitride coated substrates started showing patch-like damaged areas attributable to interaction of silicon nitride with the underlying substrate. Nevertheless ND particles were preserved in undamaged areas, with surface densities exceeding 10¹⁰ cm^?2. These nanoparticles acted as sp³-carbon seeds in a subsequent 15 min Chemical Vapour Deposition run that allowed growing a 60–80 nm diamond film. Our previous study on Si(100) showed that detonation ND particles reacted with silicon between 800 and 900 °C and, as a consequence, no diamond film could be grown after Chemical Vapour Deposition (CVD). These findings demonstrated that the use of a thin silicon nitride buffer layer is preferable insofar as the growth of thin diamond films on silicon devices via nanoseeding is concerned.     

Production of hydrogen and MWCNTs by methane decomposition over catalysts originated from LaNiO3 perovskite

LaNiO₃ type perovskite was prepared by the “self-combustion” method and was used as catalyst precursor for the methane decomposition reaction at 600 and 700 °C. CH₄ conversion reaches 80% at 700 °C and 65% at 600 °C using pure CH₄. The yield of CNT and H₂ were 2.2 g_CNT g^?1 h^?1 and 8.2 L g^?1 h^?1 at 700 °C respectively after 4 h of reaction. When the reaction is prolonged to 22 h the catalytic activity decreases but the catalyst is still active, the production of hydrogen reaches 63.5 L (STP) per gram of catalyst and the production of MWCNT was equal to 17 g per gram of catalyst.Multi-wall carbon nanotubes were characterized by X-ray diffraction (XRD), surface area (BET), transmission electron microscopy (TEM), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and Raman spectroscopy. TEM micrographs showed that MWCNT longer than 20 μm were formed with inner diameters ranging from 5 to 16 nm and outer diameters up to about 40 nm.The results obtained here clearly show that the use of the perovskite LaNiO₃ as catalytic precursor is very effective for the simultaneous production of carbon nanotubes and hydrogen.