Adelina Ilie

Effect of sp2-phase nanostructure on field emission from amorphous carbons

Electron field emission from amorphous carbon is found to depend on the clustering of the sp2 phase. The size of the sp2 phase is varied by thermal annealing and it dominates the effect of other parameters, such as chemical composition, surface termination, sp3 content, or conductivity. The optimum size of the sp2 phase is determined by Raman spectroscopy and is of the order of 1 nm. The field emission originates from the sp2 regions and is facilitated by the large field enhancement from more conductive sp2 clusters in an insulating sp3 matrix.

Raman Spectra of Monolayer, Few-Layer, and Bulk ReSe2: An Anisotropic Layered Semiconductor

Rhenium diselenide (ReSe2) is a layered indirect gap semiconductor for which micromechanical cleavage can produce monolayers consisting of a plane of rhenium atoms with selenium atoms above and below. ReSe2 is unusual among the transition-metal dichalcogenides in having a low symmetry; it is triclinic, with four formula units per unit cell, and has the bulk space group P1̅. Experimental studies of Raman scattering in monolayer, few-layer, and bulk ReSe2 show a rich spectrum consisting of up to 16 of the 18 expected lines with good signal strength, pronounced in-plane anisotropy of the intensities, and no evidence of degradation of the sample during typical measurements. No changes in the frequencies of the Raman bands with layer thickness down to one monolayer are observed, but significant changes in relative intensity of the bands allow the determination of crystal orientation and of monolayer regions. Supporting theory includes calculations of the electronic band structure and Brillouin zone center phonon modes of bulk and monolayer ReSe2 as well as the Raman tensors determining the scattering intensity of each mode. It is found that, as for other transition-metal dichalcogenides, Raman scattering provides a powerful diagnostic tool for studying layer thickness and also layer orientation in few-layer ReSe2.

Effect of work function and surface microstructure on field emission of tetrahedral amorphous carbon

The work function of tetrahedral amorphous carbon (ta-C) has been measured by Kelvin probe to lie in the range 4–5 eV, irrespective of its sp3 content or nitrogen addition. This implies that the surface barrier to emission is dominant and that emission changes caused by sp3 bonding or nitrogen addition are not directly due to changes in work function. Hydrogen, oxygen, and argon plasma treatments are all found to increase the emission of a-C, but hydrogen and argon treatments are found to reduce the work function while oxygen treatment increases it. Detailed studies of the surface with varying plasma treatment conditions suggest that the changes in emission arise mainly from changes in the surface microstructure, such as the formation of sp2 regions within the sp3 bulk. The need for local field enhancement mechanisms to account for emission over the sizeable barrier is emphasized, which may arise from local chemical nonhomogeneity, or formation of nanometer-size sp2 clusters embedded in an sp3 matrix.

Role of sp2 phase in field emission from nanostructured carbons

It is shown that sp2 phase organization plays an important role in the field emission from nanostructured carbons. Emission is found to depend on the cluster size, anisotropy, and mesoscale bonding of the sp2 phase, and the electronic disorder. It is found by Raman spectroscopy that increasing the size of sp2 clusters in the 1–10 nm range improves emission. Anisotropy in the sp2 phase orientation can help or inhibit the emission. sp2 clusters embedded in the sp3 matrix or electronic disorder induced by localized defects oriented in the field direction can provide a local field enhancement to facilitate the emission.

Reduction in defect density by annealing in hydrogenated tetrahedral amorphous carbon

Electronic applications of diamond-like carbon have been limited by its relatively high disorder and defect density. We find that the density of paramagnetic defects in hydrogenated tetrahedral amorphous carbon and the Urbach slope of the optical absorption edge can be reduced by annealing at 300 °C, with little effect on the optical gap. This leads to a reduction in the dark conductivity and an increase in the photosensitivity. The effect is attributed to the migration of hydrogen through the C–C network, to allow better passivation of dangling bonds and a modification of the more weakly bonded sp2 clusters with narrower local band gaps.

Electrical and optical properties of boronated tetrahedrally bonded amorphous carbon (ta-C:B)

Tetrahedrally bonded amorphous carbon (ta-C) is a predominately sp3-bonded semiconductor with a band gap of order 2 eV. It can be doped n-type using nitrogen but no successful p-type doping has been reported until now. On the other hand, it has recently been shown that the incorporation of boron reduces the intrinsic compressive stress of ta-C, while still maintaining its high fraction of sp3 sites. This paper reports a detailed study of the electrical properties of boron-doped ta-C (ta-C:B). The ta-C:B films are deposited in a filtered cathodic vacuum arc system using a pressed cathode of graphite and boron powder. The composition and structure of the films are examined by electron energy loss spectroscopy. We find that the room temperature conductivity of the films increases by five orders of magnitude with a boron concentration from 0 to 8%. The conductivity activation energy decreases for the same boron concentration, while the E04 gap remains constant. N-type silicon/ta-C:B heterojunctions show a rectifying behaviour as a function of the boron concentration of the films. The films show photo-conductivity. The combined results indicate p-type doping of ta-C.

Photoconductivity and electronic transport in tetrahedral amorphous carbon and hydrogenated tetrahedral amorphous carbon

The photoconductivity of tetrahedral amorphous carbon (ta-C) and hydrogenated tetrahedral amorphous carbon (ta-C:H) has been studied as a function of temperature, photon energy, and light intensity in order to understand the transport and recombination processes. ta-C and ta-C:H are found to be low mobility solids with μτ products of order 10−11–10−12 cm2/V at room temperature because of their relatively high defect densities. Deep defects tend to be the dominant recombination centers, but at high and moderate temperatures only a fraction of these centers or even tail states can act as recombination centers because the carrier demarcation levels do not always span the gap. For excitation by high energy UV photons, a peak in the photoconductivity is found at 200 K, similar to the thermal quenching effect found in a-Si:H, and attributed to competitive recombination between two classes of centers with very different capture cross sections.

Photoconductivity of nitrogen-modified hydrogenated tetrahedral amorphous carbon

The changes in the photoconductivity of hydrogenated tetrahedral amorphous carbon (ta-C:H) with nitrogen incorporation were studied. Low level nitrogen incorporation improves the photoconductivity, by shifting the Fermi level upwards in the band gap. Films with a photosensitivity of about 200 at room temperature under white light illumination of 35 mW/cm2 were obtained; thus is the highest value so far reported for diamond-like carbons. At high temperatures, photoconductivity is controlled by nonradiative recombination through gap states, whereas at low temperatures it occurs by energy-loss hopping in the band tails. Nitrogen addition does not create extra charge defect recombination centers. Low temperature photoconductivity allows the direct determination of the localization radius of the band tail states. This radius varies from 2–3 A in ta-C:H to 9 A in ta-C. This illustrates how hydrogen can increase state localization and the photoluminescence efficiency in amorphous carbons.

Field emission from nano-cluster carbon films

Abstract Field emission has been reported to occur at much lower fields in carbon based thin film systems than from any other material systems. The emission has been shown to depend on the various material parameters, but whichever carbon based system is used, it is found that emission occurs at localised sites rather than uniformly over the entire surface. Carbon films with mixed sp 3 /sp 2 bonding, like nanocrystalline diamond and nanocluster graphitic films emit at lower fields with a higher emission site density than single-phase films. The sp 2 cluster size in any carbon film can be altered during deposition, but it is easier to control nanocluster size by post-deposition annealing. Annealing increases the sp 2 cluster size embedded in a sp 3 matrix until the sp 3 matrix disappears completely and the film transforms into nanocrystalline graphite. To distinguish the effects of the sp 2 cluster size from other material parameters, a series of different carbon films were annealed post-deposition and the sp 2 cluster size was measured using visible Raman. Field emission was then measured at a vacuum of 10 −8 mbar on all films using a parallel plate configuration. It was found that the field emission for all films tested depended upon the clustering of the sp 2 phase and this effect dominates the effects of the other parameters, such as chemical composition, surface termination, sp 3 content or conductivity. The optimum size of the sp 2 was of the order of 1 nm for all systems tested. We believe that field emission occurs form the localised conducting, predominantly sp 2 bonded regions, which provideds the large field enhancement required for effective emission.

Encapsulated inorganic nanostructures: a route to sizable modulated, noncovalent, on-tube potentials in carbon nanotubes.

The large variety of hybrid carbon nanotube systems synthesized to date (e.g., by encapsulation, wrapping, or stacking) has provided a body of interactions with which to modify the host nanotubes to produce new functionalities and control their behavior. Each, however, has limitations: hybridization can strongly degrade desirable nanotube properties; noncovalent interactions with molecular systems are generally weak; and interlayer interactions in layered nanotubes are strongly dependent upon the precise stacking sequence. Here we show that the electrostatic/polarization interaction provides a generic route to designing unprecedented, sizable and highly modulated (1 eV range), noncovalent on-tube potentials via encapsulation of inorganic partially ionic phases where charge anisotropy is maximized. Focusing on silver iodide (AgI) nanowires inside single-walled carbon nanotubes, we exploit the polymorphism of AgI, which creates a variety of different charge distributions and, consequently, interactions of varying strength and symmetry. Combined ab initio calculations, high-resolution transmission electron microscopy, and scanning tunneling microscopy and spectroscopy are used to demonstrate symmetry breaking of the nanotube wave functions and novel electronic superstructure formation, which we then correlate with the modulated, noncovalent electrostatic/polarization potentials from the AgI filling. These on-tube potentials are markedly stronger than those due to other noncovalent interactions known in carbon nanotube systems and lead to significant redistribution of the wave function around the nanotube, with implications for conceptually new single-nanotube electronic devices and molecular assembly. Principles derived can translate more broadly to relating graphene systems, for designing/controlling potentials and superstructures.