Scanning tunneling microscopy of carbon nanotubes

This article reports on the application of scanning tunneling microscopy for the study of surface structures and electronic properties of carbon nanotubes. Geometric effects resulting from the cylindrical shape of the tubes as well as the particular band structure of the graphitic crystal lattice can lead to a variety of contrast patterns. On the atomic scale, it is sometimes possible to see the full honeycomb lattice structure but often different structures are observed. Besides distortions caused by tip–sample interactions, we find that a complex superstructure superimposed on the simple atomic contrast pattern arises from elastic scattering of the Fermi states at defects or impurities. From a careful analysis of high-resolution images it is possible to extract information about elastic strain of individual tubes. A new combination of scanning tunneling and scanning force microscopy enables near-atomic point resolution of the force signal the tubes can be identified without the need of a conducting substrate. This imaging mode is a crucial step for the characterization of electronic devices based on individual single-wall tubes. This mode can be further enhanced by the use of single-walled tubes as probe tips. Received: 17 May 1999 / Accepted: 18 May 1999 / Published online: 4 August 1999     

Mechanical properties of carbon nanotubes

A variety of outstanding experimental results on the elucidation of the elastic properties of carbon nanotubes are fast appearing. These are based mainly on the techniques of high-resolution transmission electron microscopy (HRTEM) and atomic force microscopy (AFM) to determine the Young’s moduli of single-wall nanotube bundles and multi-walled nanotubes, prepared by a number of methods. These results are confirming the theoretical predictions that carbon nanotubes have high strength plus extraordinary flexibility and resilience. As well as summarising the most notable achievements of theory and experiment in the last few years, this paper explains the properties of nanotubes in the wider context of materials science and highlights the contribution of our research group in this rapidly expanding field. A deeper understanding of the relationship between the structural order of the nanotubes and their mechanical properties will be necessary for the development of carbon-nanotube-based composites. Our research to date illustrates a qualitative relationship between the Young’s modulus of a nanotube and the amount of disorder in the atomic structure of the walls. Other exciting results indicate that composites will benefit from the exceptional mechanical properties of carbon nanotubes, but that the major outstanding problem of load transfer efficiency must be overcome before suitable engineering materials can be produced. Received: 17 May 1999 / Accepted: 18 May 1999 / Published online: 29 July 1999     

Towards processing of carbon nanotubes for technical applications

Production methods for carbon nanotubes are now well established and allow their synthesis on a scale of grams per day. For many potential applications of this unique material, its purification still remains a crucial problem. In this article various purification methods for single- and multi-wall carbon nanotubes are reviewed. These methods are compared in terms of their capacity, efficiency, and effects on the tubes. In addition, the use of Raman spectroscopy for monitoring the chromatographic purification of single-wall nanotubes is described. Received: 17 May 1999 / Accepted: 18 May 1999 / Published online: 29 July 1999     

Y-branching of single walled carbon nanotubes

Y-branching was observed by scanning tunnelling microscopy (STM) in single wall carbon nanotubes grown by thermal decomposition of C₆₀ fullerene in the presence of transition metals. These novel carbon nanostructures may play an important role in carbon-based nanoelectronics. Received: 18 November 1999 / Accepted: 20 January 2000 / Published online: 8 March 2000     

Phase-contrast scanning force microscopy and chemical heterogeneity of GR polysulfone ultrafiltration membranes

The surfaces of three commercial urea formaldehyde polysulfone membranes from Dow Denmark^TM (GR51, GR61 and GR81) are characterised both topographically and chemically. Their topography is studied by scanning force microscopy to obtain the corresponding pore-size distributions, which are in fair agreement with nominal molecular weight cut-offs. The composition of the surfaces of the membranes is analysed by X-ray photoelectron spectroscopy. The resulting percentage content of nitrogen, which could be attributed probably to an additive used in the manufacturing process, is shown to correlate with the portion of the total surface with different viscoelastic properties as investigated by using phase-contrast scanning force microscopy. Both parameters are increasing for membranes with decreasing molecular weight cut-off. Also, the additive seems to be more sparsely distributed for the membranes with bigger pores, according to fractal analysis. Finally, all the membranes are very similarly wettable. Received: 22 May 2001 / Accepted: 30 May 2001 / Published online: 25 July 2001     

Interference and Interaction in multi-wall carbon nanotubes

We report equilibrium electric resistance R and tunneling spectroscopy (dI/dV)measurements obtained on single multi-wall nanotubes contacted by four metallic Au fingers from above. At low temperature quantum interference phenomena dominate the magnetoresistance. The phase-coherence (l_φ)and elastic-scattering lengths (l_e)are deduced. Because l_e is of order of the circumference of the nanotubes, transport is quasi-ballistic. This result is supported by a dI/dV spectrum which is in good agreement with the density of states (DOS) due to the one-dimensional subbands expected for a perfect single-wall tube. As a function of temperature T the resistance increases on decreasing T and saturates at ≈1–10 Kfor all measured nanotubes. R(T) cannot be related to the energy-dependent DOS of graphene but is mainly caused by interaction and interference effects. On a relatively small voltage scale of the order ≈10 meV, a pseudogap is observed in dI/dV which agrees with Luttinger-liquid theories for nanotubes. Because we have used quantum diffusion based on Fermi-liquid as well as Luttinger-liquid theory in trying to understand our results, a large fraction of this paper is devoted to a careful discussion of all our results. Received: 17 May 1999 / Accepted: 18 May 1999 / Published online: 4 August 1999     

Chemical, morphological and accumulation phenomena in ultrashort-pulse laser ablation of TiN in air

Ultrashort-pulse laser ablation (τ=130 fs, λ=800 nm, repetition rate 2–20 Hz) of titanium nitride was investigated for laser fluences between 0.3 and 4.5 J/cm² using the direct focusing technique in air. The influence of the laser pulse number and the peak fluence was investigated by means of several surface analytical techniques (optical microscopy, dynamic friction atomic force microscopy, scanning Auger electron microscopy and small-spot electron spectroscopy for chemical analysis). The correlation of the results about optical, physical and chemical properties of the irradiated areas allows us to propose a simple oxidation model, which explains different observed phenomena associated with surface damage such as mound formation and crater widening and clarifies the incubation behavior reported earlier for this material. Received: 8 May 2000 / Accepted: 9 May 2000 / Published online: 13 September 2000     

Molecular beam epitaxy of GaN on a substrate of MoS2 layered compound

The feasibility of MoS₂ layered compound as a substrate for GaN growth was investigated. GaN films were successfully grown on MoS₂ by plasma-enhanced molecular beam epitaxy and the crystal quality of GaN on MoS₂ was compared with that on Al₂O₃. For GaN grown on MoS₂ substrate, it was found that the surface flatness observed by atomic force microscopy, stress in the film measured by Raman spectroscopy, optical properties measured by photoluminescence spectroscopy, and threading dislocation density observed by transmission electron microscopy show superior properties compared with that grown on Al₂O₃. These results suggest the layered compound such as MoS₂, which has no dangling bonds on the surface and has lattice mismatching of 0.9% to GaN, has high potential for a substrate of GaN growth. Received: 1 March 1999 / Accepted: 8 March 1999 / Published online: 26 May 1999     

Electrical transport measurements on single-walled carbon nanotubes

We review transport measurements on single-walled carbon nanotubes contacted by metal electrodes. At room temperature some devices show transistor action similar to that of p-channel field effect transistors, while others behave as gate-voltage independent wires. At low temperatures transport is usually dominated by Coulomb blockade. In this regime the quantum eigenstates of the finite-length tubes can be studied. At higher temperatures power law behaviour is observed for the temperature and bias dependence of the conductance. This is consistent with tunneling into a one-dimensional Luttinger liquid in a nanotube. We also discuss recent developments in contacting nanotubes which should soon allow study of their intrinsic transport properties. Received: 17 May 1999 / Accepted 18 May 1999 / Published online: 4 August 1999     

Spatio-temporal imaging of voltage pulses with a laser-gated photoconductive sampling probe

We report on the fabrication process of a scanning force microscopy (SFM) cantilever probe suitable for the investigation of ultrafast transient signals in microwave integrated circuits. High temporal resolution is achieved by integrating a laser-gated photoconductive switch within a coplanar waveguide structure onto a low-temperature GaAs cantilever. This is demonstrated by temporal and spatio-temporal measurements performed on a coplanar strip line. Received: 17 February 1999 / Revised version: 22 April 1999 / Published online: 29 July 1999     

Synthesis, integration, and electrical properties of individual single-walled carbon nanotubes

High-quality single-walled carbon nanotubes (SWNTs) are synthesized by chemical vapor deposition (CVD) of methane on silicon-dioxide substrates at controlled locations using patterned catalytic islands. With the synthesized nanotube chips, microfabrication techniques are used to reliably contact individual SWNTs and obtain low contact resistance. The combined chemical synthesis and microfabrication approaches enable systematic characterization of electron transport properties of a large number of individual SWNTs. Results of electrical properties of representative semiconducting and metallic SWNTs are presented. The lowest two-terminal resistance for individual metallic SWNTs (≈5 μm long) is ≈16.5 kΩ measured at 4.2 K. Received: 17 May 1999 / Accepted: 18 May 1999 / Published online: 14 July 1999     

Internal reflection mode scanning near-field optical microscopy with the tetrahedral tip on metallic samples

An internal reflection mode is introduced for scanning near-field optical microscopy (SNOM) with the tetrahedral tip. A beam of light is coupled into the tip and the light specularly reflected out of the tip is detected as a photosignal for SNOM. An auxiliary STM mode is used to control the distance during the scanning process and to record the topography of the sample simultaneously with the SNOM image. Images were obtained of different metallic samples which show a contrast in the order of 10% of the total reflected photosignal. In images of metallic samples an inverted contrast is consistently obtained compared to images previously obtained of comparable samples in a transmission mode. The contrast shows a pronounced dependence on the polarization of the incident beam with respect to the orientation of the edges of the tip. In the case of gold surfaces, the photosignal as a function of distance between the tip and the surface shows a pronounced peak in the near-field range of 0–20 nm which is tentatively attributed to the excitation of surface plasmons on the gold surface. The pronounced near-field effects and the strong contrast in the near-field images and the resolution well below 50 nm are an indication of a highly efficient coupling of the incident beam to a local excitation of the tip apex which is essential for the function of the tip as a probe for SNOM. Received: 17 May 1999 / Accepted: 18 May 1999 / Published online: 21 October 1999     

Field emission from carbon nanotubes: perspectives for applications and clues to the emission mechanism

We report on the extensive characterization of carbon nanotube electron field emitters. We studied the emission behavior of single-wall, closed and opened arc-discharge multi-wall, and catalytically grown multi-wall nanotubes, as single emitters and in film form. The nanotube field emitters show excellent field emission properties, but significant differences were observed between the different types of nanotubes. To obtain good performances as well as long emitter lifetimes, the nanotubes should be multi-walled and have closed, well-ordered tips. Complementary results such as energy distribution and luminescence induced by the field emission give further precious indications on the field emission mechanism. The large field amplification factor, arising from the small radius of curvature of the nanotube tips, is partly responsible for the good emission characteristics. Additional evidence however shows that the density of states at the tip is non-metallic, appearing in the form of localized states with well-defined energy levels. Received: 15 May 1999 / Accepted: 18 May 1999 / Published online: 29 July 1999     

Characterization of thiol-functionalized carbon nanotubes on gold surfaces

Multi-walled carbon nanotubes were functionalized with thiol groups by chemical route. Exploiting the chemical affinity between thiol and gold an assembly of carbon nanotubes was obtained by spontaneous chemical adsorption to gold using Au–S bonds. The multi-walled carbon nanotubes were first chemically cut by acid treatment and then functionalized with short chain thiol (2-aminoethanethiol). Substrate dipping in a suspension of functionalized carbon nanotubes allows them to bond to the gold surface. The resultant products, as well as the intermediate were characterized by means of X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, visible spectroscopy, scanning electron microscopy and atomic force microscopy.     

Raman spectroscopy on single- and multi-walled nanotubes under high pressure

The pressure dependence of the high-energy Raman modes in single- and multi-walled carbon nanotubes was measured in the range 0–10 GPa. We found the pressure coefficient to be linear in both materials but 25% smaller in MWNT. Given that the curvature effects on vibrational properties of the rolled-up graphene sheets are small, we can explain this difference simply with elasticity theory. Received: 17 May 1999 / Accepted 18 May 1999 / Published online: 4 August 1999     

Formation of gold nanowires through self-assembly during scanning force microscopy

Gold films with a nominal thickness of 5–40 monolayers were grown on dielectric substrates and imaged by scanning force microscopy (SFM). The films originally consisted of well-separated or densely packed clusters. During imaging in contact mode, the morphology of the films changed drastically. At low coverage, i.e. Θ<10 monolayers, the well-known stripes originating from mobile clusters, eventually accumulated into larger aggregates, were observed. In contrast, at larger coverage, highly ordered structures consisting of one-dimensional wires evolved during scanning. They often were parallel with equal separation, i.e. well-defined periodicity, over distances of several μm. Typically, the wires were 5–10 nm high and 50–100 nm wide. Investigations of Au films prepared at varying temperature on different dielectric substrates allow us to suggest a self-assembling mechanism for wire formation in which gold is periodically collected by the SFM tip and redeposited as soon as a critical amount is reached. Received: 22 February 1999 / Accepted: 2 March 1999 / Published online: 7 April 1999     

Dynamics of gold cluster systems

x surface of Si(111) wafers was studied as a function of annealing time at relatively low annealing temperatures (50 and 100 °C) by application of scanning force microscopy. A fast increase in cluster diameter and height as a function of annealing time was detected. After more than 3 h of annealing depletion zones and nucleation exclusion zones were observed. Received: 13 August 1998 / Published online: 10 February 1999     

Time-resolved current response of a nanosecond laser pulse illuminated STM tip

Time-resolved dependence of the transient current through a ns laser pulse illuminated scanning tunneling microscope (STM) tip/sample gap in tunneling mode and out of tunneling range is presented. A self-designed fast STM-preamplifier (bandwidth 35 MHz) allows one to resolve the fine structure of the transient signal as well as the observation of some effects that are undetectable by using conventional low-band preamplifiers. The dependence of the threshold laser pulse intensity, which corresponds to the beginning of electron emission from tip (in non-tunneling mode), as a function of the tip/sample distance was investigated. At tip/sample distances from tunnel contact up to approximately 1 μm a linear dependence is found. This behavior is in good agreement with the theory for field enhancement in a STM tip/sample system. In tunneling mode a ns (fast component) as well as a μs (slow component) current response was found as a result of the laser pulse illumination. These data suggest the tip bending to be an important factor in clarifying the thermal/mechanical mechanism of laser-assisted surface nanomodification. Received: 4 May 1998 / Accepted: 29 January 1999 / Published online: 28 April 1999     

Scanning force microscopy of ion-irradiated organic single crystals of benzoyl glycine

Single crystals of the amino acid benzoyl glycine (hippuric acid) are irradiated normal to the as-grown surface by highly charged Bi ions with a kinetic energy of 2.38 GeV and a fluence of 1×10¹⁰ ions/cm². The projectiles create circular craters with a mean diameter of 40 (10) nm on the surface of the crystal as observed by scanning force microscopy (SFM). The mean depth amounts to 4 (1) nm, this value being considered as a lower limit due to the finite radius of curvature of the force cantilever tip. Thus, on the average, each single-ion projectile seems to eject about 10⁴ molecules. On the surface of non-irradiated crystals, SFM reveals terraces of a few monolayers in height. In water, it was possible to visualize the lattice periodicity. Terraces were also observed on the irradiated crystal surface in the presence of the craters, indicating that the crystal is still intact at the given dose. Received: 25 May 2000 / Accepted: 26 May 2000 / Published online: 13 July 2000     

Investigation of the thermal conductivity of diamond film on aluminum nitride ceramic

Diamond films were successfully synthesized on aluminum nitride(AlN) ceramic substrates by hot-filament chemical vapor deposition (HFCVD) method. The thermal conductivity of the diamond film/aluminum nitride ceramic (DF/AlN) composites was studied by photothermal deflection (PTD) technique. It has reached 2.04 W/cm K, 73% greater than that of AlN ceramic. Compared with the measurement of scanning electron microscopy (SEM) and Raman spectroscopy, the influence of diamond films on the thermal conductivity of the composites was pointed out. The adhesion and the stresses were also studied. The unusual stability and very good adhesion of the diamond film on AlN ceramic substrate obtained is attributed to the formation of aluminum carbide. Received: 24 March 1998 / Accepted: 8 March 1999 / Published online: 5 May 1999