Optical Kerr effect exhibited by carbon nanotubes and carbon/metal nanohybrid materials

Structural modification of carbon nanotubes in combination with metallic nanoparticles is reported. An enhancement in the nonlinear optical refraction of multi-wall carbon nanotubes by the incorporation of platinum nanoparticles was observed. Comparative results were analyzed taking into account the participation of single-wall carbon nanotubes that originate a decrease in the nonlinear optical response of the multi-wall carbon nanotubes integrating a thin film. A Nd:YAG laser system featuring 532 nm wavelength with 4 ns pulse duration in a two-wave mixing experiment was employed for exploring the studied optical nonlinearities of the samples. The contribution of optical processes to mechanical characteristics dependent on high optical irradiance in carbon nanotubes was described. A variation in the mass density associated to the optically irradiated tubes allowed us to calculate the change in Young's modulus in a thin film configuration. The estimation of an opto-mechanical phenomenon was based on the evaluation of the nonlinearity of index responsible for the optical Kerr effect. According to Raman and optical evaluations, the inclusion of metallic nanoparticles in carbon structures results in a modification of surface that also gives origin to noticeable optical Kerr nonlinearities. Potential applications for developing laser-induced controlled opto-mechanical nanohybrid systems can be contemplated.     

Detailed profiling of CNTs arrays along the growth window in a floating catalyst reactor

We report a detailed longitudinal and depth profiles of multi-wall carbon nanotubes (CNTs) arrays synthesized using xylene and ferrocene in a floating catalyst reactor. Point to point analyses of the CNTs grown in a “growth window” with CNTs arrays longer than 0.5 mm were performed using optical microscopy, Raman spectroscopy, FESEM, high-resolution TGA/DTA, and TEM techniques. The heights of the CNTs arrays show a maximum at a mid point of the growth window, while a reverse trend of minimum is observed for iron-to-CNTs atomic ratios. The ratio of amorphous carbon to CNTs sharply increases along the growth window and from the bottom to top of CNTs arrays. The CNTs diameter also increases along the growth window, due to deposition of the amorphous carbon, which can be almost removed by temperature programmed oxidation up to around 500 °C. A base growth mechanism, the variations of catalyst content, residence time and temperature profile along the growth window, the adsorption and decomposition of polycyclic aromatic hydrocarbons to amorphous carbon, and a limited diffusion of hydrocarbon species through the arrays covered by excessive amorphous carbon may explain the results.     

Carbon nanotubes formed in graphite after mechanical grinding and thermal annealing

Multi-walled carbon nanotubes with cylindrical and bamboo-type structures are produced in a graphite sample after mechanical milling at ambient temperature and subsequent thermal annealing up to 1400 °C. The ball milling produces a precursor structure and the thermal annealing activates the nanotube growth. Different nanotubular structures indicate different formation mechanisms: multi-wall cylindrical carbon nanotubes are probably formed upon micropores and the bamboo tubes are produced because of the metal catalysts. A two-dimensional growth governed by surface diffusion is believed to be one important factor for the nanotube growth. A potential industrial production method is demonstrated with advantages of large production quantity and low cost. Received: 17 May 2002 / Accepted: 12 September 2002 / Published online: 4 December 2002 RID="*" ID="*"Corresponding author. Fax: +61-2/6125-8338, E-mail: ying.chen@anu.edu.au     

Characterization of fluorinated multiwalled carbon nanotubes with X-ray absorption,photoelectron and emission spectroscopies

The combined investigation of the chemical bond formation in fluorinated multiwalled carbon nanotubes with 15 wt.% fluorine concentrations (MWCNTs + F 15 wt.%) using X-ray absorption, emission and photoelectron spectroscopy at C 1s and F 1s thresholds is presented. All measurements were performed at BESSY II. The analysis of the soft X-ray and photoelectron spectra point to the formation of covalent chemical bonding between fluorine and carbon atoms in the fluorinated nanotubes. Based on results of this combined study the depth dependent effects are discussed.     

Pulsed laser CVD investigations of single-wall carbon nanotube growth dynamics

The nucleation and rapid growth of single-wall carbon nanotubes (SWNTs) were explored by pulsed-laser assisted chemical vapor deposition (PLA-CVD). A special high-power, Nd:YAG laser system with tunable pulse width (>0.5 ms) was implemented to rapidly heat (>3×10⁴°C/s) metal catalyst-covered substrates to different growth temperatures for very brief (sub-second) and controlled time periods as measured by in situ optical pyrometry. Utilizing growth directly on transmission electron microscopy grids, exclusively SWNTs were found to grow under rapid heating conditions, with a minimum nucleation time of >0.1 s. By measuring the length of nanotubes grown by single laser pulses, extremely fast growth rates (up to 100 microns/s) were found to result from the rapid heating and cooling induced by the laser treatment. Subsequent laser pulses were found not to incrementally continue the growth of these nanotubes, but instead activate previously inactive catalyst nanoparticles to grow new nanotubes. Localized growth of nanotubes with variable density was demonstrated through this process and was applied for the reliable direct-write synthesis of SWNTs onto pre-patterned, catalyst-covered metal electrodes for the synthesis of SWNT field-effect transistors.     

Formation and structure of circular-disc assemblies of double-walled carbon nanotubes from a catalytic CVD reaction

A large-size circular-disc (CD) assembly of carbon nanotubes (CNTs) was formed from injection catalytic chemical vapor deposition (CVD) reactions. The CNT-CD assembly, which has an outer diameter of 830 nm, consists of closely packed rings of double-walled carbon nanotubes (DWNTs), in twenty-eight circles, and stacked in five layers. A structural interpretation suggests that the CNT-CD assembly is coiled from a “tape-like” bundle of DWNTs, whose coiling to form the CNT-CD resembles the rolling up of tape to form a disc. The large CD assembly was formed within milliseconds in the transient gas flow reactions, and the coiling of nanotubes or “nucleation” of the circular assembly was associated with shears generated by gas disturbances in the vapor phase.     

Vertically aligned carbon nanotubes from natural precursors by spray pyrolysis method and their field electron emission properties

Vertically aligned carbon nanotubes have been synthesized from botanical hydrocarbons: Turpentine oil and Eucalyptus oil on Si(100) substrate using Fe catalyst by simple spray pyrolysis method at 700°C and at atmospheric pressure. The as-grown carbon nanotubes were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), thermogravimetric analysis (TGA), differential thermal analysis (DTA), and Raman spectroscopy. It was observed that nanotubes grown from turpentine oil have better degree of graphitization and field emission performance than eucalyptus oil grown carbon nanotubes. The turpentine oil and eucalyptus oil grown carbon nanotubes indicated that the turn-on field of about 1.7 and 1.93 V/μm, respectively, at 10 μA/cm². The threshold field was observed to be about 2.13 and 2.9 V/μm at 1 mA/cm² of nanotubes grown from turpentine oil and eucalyptus oil respectively. Moreover, turpentine oil grown carbon nanotubes show higher current density in relative to eucalyptus oil grown carbon nanotubes. The maximum current density of 15.3 mA/cm² was obtained for ∼3 V/μm corresponding to the nanotubes grown from turpentine oil. The improved field emission performance was attributed to the enhanced crystallinity, fewer defects, and greater length of turpentine oil grown carbon nanotubes.     

Radial breathing modes of single-walled carbon nanotubes in resonance Raman spectra at high temperature and their chiral index assignment

Radial breathing modes (RBMs) in resonance Raman spectra from single-walled carbon nanotubes (SWCNTs) on a SiO₂/Si (0 0 1) substrate are studied between 25 and 720 °C. A change in the relative intensity of each RBM peak with temperature is observed, which originates from the temperature dependence of the resonance condition of nanotubes. For 25 °C, each RBM peak is reasonably assigned on the basis of data in the literature [J. Maultzsch, H. Telg, S. Reich, F. Hennrich, C. Thomsen, Phys. Rev. B 72 (2005) 205438]. By taking into account the temperature-dependent behavior of the relative intensity of the RBM peaks, each RBM peak is successfully assigned even for 720 °C. It is found that most of the observed RBM peaks for a laser excitation energy of E_exc = 1.96 eV are from chiral SWCNTs. These results make it possible to discuss further details of the chirality-dependent growth behavior observed for in situ Raman spectroscopy.     

Pulsed laser deposition of multiwalled carbon nanotubes thin films

The physical/chemical properties of multiwalled carbon nanotubes have attracted much interest for applications in different fields, from micro-electronic to coating technology due, in particular, to their peculiar conductivity properties, to their hardness and high resistance to thermal stress. The technology to produce carbon nanotubes thin films with the desired properties, however, is still under development. In this work, we report on multiwalled carbon nanotubes thin films deposited by pulsed laser deposition techniques ablating commercially polystyrene-nanotubes pellets on alumina substrates. MicroRaman spectroscopy and high resolution Transmission Electron Microscopy provide the experimental confirmation that carbon nanotubes-like structures are present on the alumina surface with both minimal morphological damage of the tubes and structural changes induced by laser beam.     

Raman spectroscopy of SWNTs produced by a XeCl excimer laser ablation at high temperatures

Synthesis of single-wall carbon nanotubes (SWNTs) was carried out by an ablation method using a XeCl excimer laser. It was irradiated onto a graphite target containing Co and Ni at the temperatures of 1073, 1173, 1273, 1373, 1473, 1523 and 1623 K under the atmosphere (0.1 MPa) of Ar gas with the flow rate of 12 ml/min. The measurement by a scanning/transmission electron microscope and Raman spectroscopy found the formation of SWNTs with the diameter of about 1.3 nm and the length of about 2 μm in ablated carbonaceous soot. The ratio of peak intensity of 1590 cm⁻¹ (G band) to that of 1335 cm⁻¹ (D band) in the high frequency Raman spectra increased with increasing the ambient temperature. The radial breathing mode (RBM) in the low frequency Raman spectra shows that the mean diameter of SWNTs increased with increasing the ambient temperature.     

Structures of water molecular nanotube induced by axial tensile strains

Five well-ordered nano-ice structures embedded in carbon nanotubes are obtained in this study. These five nano-ice phases all exhibit single walled tubular morphologies, including the pentagon, hexagon ice nanotubes whose structures are quite different from bulk ice. Our simulation results indicate that water molecules tend to rearrange into surface ring structures to reduce the number of free OH groups. The structural behavior of these ice nanotubes inside CNTs subject to axial stress is also investigated. The ice nanotubes tend to be drawn to ice nanorings or ice nanospring during the mechanical stretching. The distribution function exhibits typical order-to-disorder transition of the water network confined in carbon nanotube during the stretching. By analysis, we suggest that it is unlikely that additional water molecules will enter the tubes because of the increased volume available if the tubes are stretched at contact with a water reservoir.     

Carbon nanotube grease with enhanced thermal and electrical conductivities

A stable and homogeneous grease based on carbon nanotubes (CNTs, single-wall and multi-wall) in polyalphaolefin oil has been produced without using a chemical surfactant. For example, for a 11 wt% (7 vol%) single-wall CNT (diameter 1–2 nm, length 0.5–40 μm) loading, the thermal conductivity (TC) of the grease shows a 60–70% increase compared to that for no nanotube loading. In addition, the grease is electrically conductive, has a high dropping point, good temperature resistance, and does not react with copper at temperatures up to 177 °C. The performance of carbon nanotube grease could be much better with the improvement of nanotube quality and purity. A possible explanation for these results is that of a high loading of CNTs (>10 wt%), they become associated with each other by van der Waals forces in the grease to form three-dimensional percolation networks. Time-dependent magnetic results demonstrate that, even under the influence of a strong outside magnetic field, the TC value remains constant. This phenomenon can be attributed to the existence of networks that makes magnetic alignment of nanotubes impossible.     

High power ultrafast Nd:YVO<Subscript>4</Subscript> laser mode locked by single wall carbon nanotube absorber

We use a single walled carbon nanotubes (SWCNTs) absorber to demonstrate a high power mode locking for Nd:YVO₄ lasers. Under the pump power of 12 W, continuous wave mode-locked (CWML) pulse were generated with the maximum average output power of 3.6 W and the pulse duration of 7.6 ps. The peak power and the single pulse energy of the mode-locked laser were up to 4.9 kW and 37.5 nJ, respectively. To our knowledge, this is the highest average output power of the CWML laser with the SWCNTs absorber reported.     

Electrophoresis and orientation of multiple wall carbon nanotubes in polymer solution

This paper contains an in-depth analysis of the electrophoresis of multi-wall carbon nanotubes (MWNTs) in liquid epoxy where electrophoresis experiments under DC and AC fields were carried out for five different types of multi-wall carbon nanotubes (MWNTs). DC electrophoresis and particle image velocimetry were used to determine the electrophoretic particle mobility and zeta potential, where the MWNTs with the largest outer diameter and length led to the highest mobility values. The orientation and agglomeration of MWNTs into “striation” lines under AC electrophoresis were investigated by analysing the hue, saturation and intensity of the transmitted polarised light under microscope, following a schedule of step-wise applied voltage in the range of 0 to 100 V. Plots of hue and saturation as a function of the applied voltage were used to assess the degree of orientation and density of orientated MWNT structures, respectively, and to determine an optimum AC electric field value for the orientation of a specific MWNT type by electrophoresis.     

Critical role of laser wavelength on carbon films grown by PLD of graphite

The structure of thin films deposited by pulsed laser ablation (PLD) is strongly dependent on experimental conditions, like laser wavelength and fluence, substrate temperature and pressure. Depending on these parameters we obtained various kinds of carbon materials varying from dense, mainly tetrahedral amorphous carbon (ta-C), to less compact vertically oriented graphene nano-particles. Thin carbon films were grown by PLD on n-Si 〈100〉 substrates, at temperatures ranging from RT to 800°C, from a rotating graphite target operating in vacuum. The laser ablation of the graphite target was performed by a UV pulsed ArF excimer laser (λ=193 nm) and a pulsed Nd:YAG laser, operating in the near IR (λ=1064 nm). The film structure and texturing, characterised by X-ray diffraction analysis, performed at grazing incidence (GI-XRD), and the film density, evaluated by X-ray reflectivity measurements, are strongly affected both by laser wavelength and fluence and by substrate temperature. Micro-Raman and GI-XRD analysis established the progressive formation of aromatic clusters and cluster condensation into vertically oriented nano-sized graphene structures as a direct function of increasing laser wavelength and deposition temperature. The film density, negatively affected by substrate temperature and laser wavelength and fluence, in turn, results in a porous bulk configuration and a high macroscopic surface roughness as shown by SEM characterisation. These structural property modifications induce a relevant variation also on the emission properties of carbon nano-structures, as evidenced by field emission measurements. This work is dedicated to our friend Giorgio who passed away 20th August.     

Altering the catalytic activity of thin metal catalyst films for controlled growth of chemical vapor deposited vertically aligned carbon nanotube arrays

The growth rate and terminal length of vertically aligned carbon nanotube arrays (VANTAs) grown by chemical vapor deposition have been dramatically improved through pulsed KrF excimer laser pretreatments of multilayer metal catalyst films. Silicon wafers coated with Al, Mo, and Fe layers were laser processed in air with single laser shots of varying fluence through circular apertures, then heated to ∼750°C and exposed to acetylene and ferrocene containing gas mixtures typically used to grow vertically aligned nanotube arrays. In situ videography was used to record the growth kinetics of the nanotube arrays in both patterned and unpatterned regions to understand the changes in catalytic activity, growth rates, and termination of growth. The height of the patterned regions varied with fluence, with the most successful treatment resulting in 1.4 cm tall posts of nanotubes embedded in a 0.4 cm tall nanotube carpet. High-resolution transmission electron microscopy images from the nanotubes in the posts revealed fewer walls, smaller diameters, and a much narrower distribution of diameters compared to the nanotubes grown in the carpet. This information, along with data obtained from weighing the material from each region, suggests that pulsed laser processing can also significantly increase the areal density of VANTAs. Research sponsored by the Division of Materials Sciences and Engineering, U.S. Department of Energy.     

Cumulative and continuous laser vaporization synthesis of single wall carbon nanotubes and nanohorns

The conditions for the scaled synthesis of single wall carbon nanotubes (SWNTs) and single wall carbon nanohorns (SWNHs) by laser vaporization at high temperatures are investigated and compared using in situ diagnostics. An industrial Nd:YAG laser (600 W, 1–500 Hz repetition rate) with tunable pulse widths (0.5–50 ms) is utilized to explore conditions for high-yield production. High-speed videography (50000 frames/s) of the laser plume and pyrometry of the target surface are correlated with ex situ high resolution transmission electron microscopy analysis of the products for pure carbon targets and carbon/catalyst targets to understand the effects of the processing conditions on the resulting nanostructures. Carbon is shown to self-assemble into single-wall nanohorn structures at rates of ∼1 nm/ms, which is comparable to the catalyst-assisted SWNT growth rates. Two regimes of laser ablation, cumulative ablation by multiple pulses and continuous ablation by individual pulses, were explored. Cumulative ablation with spatially overlapping 0.5-ms pulses is favorable for the high yield and production rate of SWNTs at ∼6 g/h while continuous ablation by individual long laser pulses (∼20 ms) at high temperatures results in the highest yield of SWNHs at ∼10 g/h. Adjustment of the laser pulse width is shown to control SWNH morphology.     

Growth of single-wall carbon nanotubes dependent on laser power density and ambient gas pressure during room-temperature CO2 laser vaporization

Single-wall carbon nanotubes (SWNTs) were synthesized by the irradiation of 20-ms CO₂ laser pulses onto a graphite–Co/Ni target at room temperature. We investigated the effect of laser power density (10–150 kW/cm²) and ambient Ar gas pressure (150–760 Torr) on the abundance of SWNTs with lengths of up to about 200 nm in soot-like carbonaceous deposits. For a constant power density (30 kW/cm²), depending on the Ar gas pressure, SWNTs with diameters of 1.2–1.4 nm were synthesized. Expansion behavior and temperature-fall rates of clusters and/or particles in laser plumes were also analyzed by high-speed video imaging and temporally and spatially resolved emission spectroscopy. The temperature-fall rates were estimated to be 171–427 K/ms. The SWNT growth on the time scale of a few milliseconds appeared to be related to some features of condensing clusters and/or particles, including resident densities, collision frequencies and temperatures. Received: 16 July 2001 / Accepted: 23 July 2001 / Published online: 30 August 2001     

Formation of Y-junction carbon nanotubes by catalytic CVD of methane

Y-junction carbon nanotubes were grown by catalytic CVD of methane at 700 ^°C on NiO-CuO-MoO(7:2:1) (w/w/w)/SiO₂ catalyst. For comparison, NiO-CuO(8:2) (w/w)/SiO₂ and NiO-MoO(8:2) (w/w)/SiO₂ catalysts were tested for carbon nanotube formation. TEM analysis indicates that no Y-junction structures were formed with the latter two catalysts. This finding elucidates why the addition of a small amount of MoO to NiO-CuO/SiO₂ catalyst is crucial for enhancing the formation of Y-junction carbon nanotubes.     

Atomistic Failure Mechanism of Single Wall Carbon Nanotubes with Small Diameters

Single wall carbon nanotubes with small diameters （〈 5.0 A） subjected to bending deformation are simulated by orthogonal tight-binding molecular dynamics approach. Based on the calculations of C-C bond stretching and breaking in the bending nanotubes, we elucidate the atomistic failure mechanisms of nanotube with small diameters. In the folding zone of bending nanotube, a large elongation of C-C bonds occurs, accounting for the superelastic behaviour. The C-C bonds parallel to the axis direction of nanotube are broken firstly due to the sustained longitudinal stretching strain, giving rising to forming one-notch or two-notch bond-breaking mode depending on nanotube chirMities. The direct bond-breaking mechanism is responsible for the brittle fracture behaviour of nanotubes with small diameters.