Atomic layer deposited Al2O3passivation layer for few-layer WS2field effect transistors.

We have investigated the effect of an Al2O3passivation layer on the performance of few-layer WS2FETs. While the performance of WS2FETs is often limited by a substantial decrease in carrier mobility owing to charged impurities and a Schottky barrier between the WS2and metal electrodes, the introduction of an Al2O3overlayer by atomic layer deposition (ALD) suppressed the influence of charged impurities by high-κdielectric screening effect and reduced the effective Schottky barrier height. We argue that n-doping of WS2, induced by positive fixed charges formed at Al2O3/WS2interface during the ALD process, is responsible for the reduction of the effective Schottky barrier height in the devices. In addition, the Al2O3passivation layer protected the device from oxidation, and maintained stable electrical performance of the WS2FETs over 57 d. Thus, the ALD of Al2O3overlayer provides a facile method to enhance the performance of WS2FETs and to ensure ambient stability.

Structural configurations and Raman spectra of carbon nanoscrolls.

Three types of carbon nanoscroll (CNS) structures that are formed when scrolling up graphene sheets are investigated using Raman spectroscopy and atomic force microscopy (AFM). The CNSs were produced from exfoliated monolayer graphene deposited on a Si chip by applying a droplet of isopropyl alcohol (IPA) solution. The three types of CNS are classified as single-elliptical-core, double-elliptical-core (both with large internal volumes) and collapsed ribbon-like, based on AFM surface profile measurements. We discuss the structure and formation of CNS with much larger hollow cores than is commonly assumed and relate this to the large effective 2D bending stiffness of graphene in the IPA solution. The large elliptical core structures show Raman spectra similar to those previously reported for CNS and indicate little interaction between the scrolled layers. The Raman spectra from ribbon-like structures show additional features that are similar to that of folded graphene. These new features can be related to layer breathing modes combined with some resonance enhancement at specific regions of the ribbon-like CNSs that are due to specific twist angles produced when the structure folds/collapses.

Angle-resolved photoelectron spectroscopy and scanning tunnelling spectroscopy studies of the endohedral fullerene Li@C60.

Gas phase photoelectron spectroscopy (Rydberg Fingerprint Spectroscopy), TDDFT calculations and low temperature STM studies are combined to provide detailed information on the properties of the diffuse, low-lying Rydberg-like SAMO states of isolated Li@C60 endohedral fullerenes. The presence of the encapsulated Li is shown by the calculations to produce a significant distortion of the lowest-lying S- and P-SAMOs that is dependent on the position of the Li inside the fullerene cage. Under the high temperature conditions of the gas phase experiments, the Li is mobile and able to access different positions within the cage. This is accounted for in the comparison with theory that shows a very good agreement of the photoelectron angular distributions, allowing the symmetry of the observed SAMO states to be identified. When adsorbed on a metal substrate at low temperature, a strong interaction between the low-lying SAMOs and the metal substrate moves these states to energies much closer to the Fermi energy compared to the situation for empty C60 while the Li remains frozen in an off-centre position.

Blister-based-laser-induced-forward-transfer: a non-contact, dry laser-based transfer method for nanomaterials.

We show that blister-based-laser-induced forward-transfer can be used to cleanly desorb and transfer nano- and micro-scale particles between substrates without exposing the particles to the laser radiation or to any chemical treatment that could damage the intrinsic electronic and optical properties of the materials. The technique uses laser pulses to induce the rapid formation of a blister on a thin metal layer deposited on glass via ablation at the metal/glass interface. Femtosecond laser pulses are advantageous for forming beams of molecules or small nanoparticles with well-defined velocity and narrow angular distributions. Both fs and ns laser pulses can be used to cleanly transfer larger nanoparticles including relatively fragile monolayer 2D transition metal dichalcogenide crystals and for direct transfer of nanoparticles from chemical vapour deposition growth substrates, although the mechanisms for inducing blister formation are different.

Low-lying, Rydberg states of polycyclic aromatic hydrocarbons (PAHs) and cyclic alkanes.

TD-DFT calculations of low-lying, Rydberg states of a series of polycyclic hydrocarbons and cyclic alkanes are presented. Systematic variations in binding energies and photoelectron angular distributions for the first members of the s, p and d Rydberg series are predicted for increasing molecular complexity. Calculated binding energies are found to be in very good agreement with literature values where they exist for comparison. Experimental angle-resolved photoelectron spectroscopy results are presented for coronene, again showing very good agreement with theoretical predictions of binding energies and also for photoelectron angular distributions. The Dyson orbitals for the small "hollow" carbon structures, cubane, adamantane and dodecahedrane, are shown to have close similarities to atomic s, p and d orbitals, similar to the superatom molecular orbitals (SAMOs) reported for fullerenes, indicating that these low-lying, diffuse states are not restricted to π-conjugated molecules.

In situ studies of growth of carbon nanotubes on a local metal microheater.

Using electron microscopy and in situ Raman spectroscopy we investigate carbon nanotube growth from ethylene on iron catalyst islands patterned on top of Mo electrodes, using a highly localized resistive on-chip-heating technique. A clear transition is observed between multi-walled and single-walled nanotube growth as the local temperature of the heater is increased. This can be rationalized in terms of the balance between incoming carbon flux and diffusion through the catalyst particle. The observed changes in heater performance on exposure to the hydrocarbon gas are explored and related to the formation of molybdenum carbide, leading to a rapid change in resistivity and heating power that increases the local temperature of the heater by up to 100 °C. This provides optimum conditions for nanotube growth after an incubation time that depends on the carbon flux.

Anisotropic hot electron emission from fullerenes.

Photoelectron spectra for fullerenes C(60) and C(70) ionized using 800 nm laser pulses with pulse durations from 120 to 1000 fs show thermal electron kinetic energy distributions but they also exhibit angular anisotropy with respect to the laser light polarization. The effective temperature of electrons, measured along the laser polarization direction, is significantly higher than in the perpendicular direction. We explain this observation by considering that the emission of the thermal electrons is uncorrelated with the phase of the laser pulse, unlike directly ionized electrons, and, depending on the time of emission, they may experience an additional "kick" from the vector potential of the laser field when they are emitted from the molecule.

Diffraction from carbon nanofiber arrays.

A square planar photonic crystal composed of carbon nanofibers was fabricated using e-beam lithography and chemical vapor deposition. The diffraction properties of the system were characterized experimentally and compared with theory and numerical simulations. The intensities of the (-1,0) and (-1,-1) diffraction beams were measured as functions of the angles of incidence for both s and p-polarization. The obtained radiation patterns can be explained using a simple ray interference model, but finite-difference time-domain (FDTD) calculations are necessary to reproduce the observed dependence of the scattered radiation intensity on incident laser polarization. We explain this in terms of the aspect ratio of the nanofibers and the excitation of surface plasmon polaritons at the substrate interface.

Optical properties of carbon nanofiber photonic crystals.

Carbon nanofibers (CNFs) are used as components of planar photonic crystals. Square and rectangular lattices and random patterns of vertically aligned CNFs were fabricated and their properties studied using ellipsometry. We show that detailed information such as symmetry directions and the band structure of these novel materials can be extracted from considerations of the polarization state in the specular beam. The refractive index of the individual nanofibers was found to be n(CNF) = 4.1.

Growth of aligned MWNT arrays using a micrometer scale local-heater at low ambient temperature.

Ambient room temperature growth of aligned multi-walled carbon nanotube arrays on micrometer scale local heaters is demonstrated. High growth rates of up to 8.8 microm per second have been achieved and the growth has been monitored in situ using optical microscopy. The growth starts and ends abruptly over the length of the local heater. The terminal length of the nanotubes shows a clear dependence on growth temperature and small inhomogeneities in temperature across the heater are seen to lead to interesting microstructure of the arrays. The activation energy for growth was seen to be consistent with earlier reports for acetylene growth of nanotubes on iron catalysts.

A carbon nanotube gated carbon nanotube transistor with 5 ps gate delay.

Semiconducting carbon nanotubes (CNTs) are attractive as channel material for field-effect transistors due to their high carrier mobility. In this paper we show that a local CNT gate can provide a significant improvement in the subthreshold slope of a CNT transistor compared to back gate switching and provide gate delays as low as 5 ps. The CNT gated CNT transistor devices are fabricated using a two-step chemical vapour deposition technique. The measured transfer characteristics are in very good agreement with theoretical modelling results that provide confirmation of the operating principle of the transistors. Gate delays below 2 ps should be readily achievable by reducing the thickness of the gate dielectric.

Conductance and polarisability of C60 films.

Thin films of C60 deposited in vacuum are studied using current-voltage (I-V) measurements and atomic force microscopy (AFM). In situ electrical measurements give an average resistivity of ca. 30 Mn cm for the as-deposited films at room temperature. The I-V dependences are found to correspond to ohmic behaviour but they have a hysteresis shape attributed to remnant polarisation due to the domain structure of the films. AFM images show a grainy surface morphology for the deposited C60. Temperature dependent measurements in the range 290-365 K provide evidence for a variable range hopping mechanism of conductance with an activation energy of 0.8-1.0 eV. With further temperature increase the C60 films restructure leading to an increase in grain size and a change of the electrical properties with I-V dependences showing Schottky barrier formation. The effect of oxygen on the conductance of the C60 films under their exposure to an ambient atmosphere is considered and discussed.

Fabrication and mechanical properties of suspended one-dimensional polymer nanostructures: polypyrrole nanotube and helical polyacetylene nanofibre.

Mechanical properties of suspended quasi-one-dimensional polymer nanostructures were investigated using atomic force microscopy (AFM). A recently developed new acid-free etch method combined with electron beam lithography was used to fabricate suspended polypyrrole (PPy) nanotubes and helical polyacetylene (HPA) nanofibres. The elastic modulus of each suspended structure was obtained by AFM force-distance measurements. The estimated modulus value of the PPy nanotube (HPA nanofibre) was 0.96 GPa (0.5 GPa). Using this acid-free method, all-organic flexible NEMS devices can be fabricated in the future.

Surface entropy of rare-gas clusters.

Abundances of ArN+ and XeN+ clusters produced in a supersonic expansion source are inverted to find relative dissociation energies. The values around the shell and subshell closings at N=55, 71, and 147 differ from theoretical values derived from ground-state energies of Lennard-Jones clusters. A significant part of the difference can be accounted for by the conformational entropies of surface atoms and vacancies.

Thermal radiation from C(N)+ and La@C(N)+.

The radiative cooling of positively charged fullerene and endohedral fullerene fragments of C60, C70, C84, and La@C82 has been measured in a time-of-flight mass spectrometer. The radiative cooling is measured via its influence on the metastable decay. The emissivity extracted from the data is between 4x10(-4) and 13x10(-4). These values agree fairly well with the emissivity calculated from considering the low-energy tail of the surface plasmon. No major difference is found in the emission behavior of empty and endohedral fullerenes.

Energy distributions in multiple photon absorption experiments.

Photofragmentation experiments on molecules and clusters often involve multiple photon absorption. The distributions of the absorbed number of photons are frequently approximated by Poisson distributions. For realistic laser beam profiles, this approximation fails seriously due to the spatial variation of the mean number of absorbed photons across the laser beam. We calculate the distribution of absorbed energy for various laser and molecular-beam parameters. For a Gaussian laser beam, the spatially averaged distributions have a power-law behavior for low energy with a cutoff at an energy which is proportional to fluence. The power varies between -1 for an almost parallel laser beam and -5/2 for a divergent beam (on the scale of the molecular beam). We show that the experimental abundance spectra of fullerenes and small carbon clusters can be used to reconstruct the distribution of internal energy in the excited C60 molecule prior to fragmentation and find good agreement with the calculated curves.

Surface charging and impulsive ion ejection during ultrashort pulsed laser ablation.

We report time-resolved studies using femtosecond laser pulses, accompanied by model calculations, that illuminate the difference in the dynamics of ultrashort pulsed laser ablation of different materials. Dielectrics are strongly charged at the surface on the femtosecond time scale and undergo an impulsive Coulomb explosion. This is not seen from metals and semiconductors where the surface charge is effectively quenched.