Calculation of the electronic structure of carbon films using electron energy loss spectroscopy.

The detailed understanding of the electronic properties of carbon-based materials requires the determination of their electronic structure and more precisely the calculation of their joint density of states (JDOS) and dielectric constant. Low electron energy loss spectroscopy (EELS) provides a continuous spectrum which represents all the excitations of the electrons within the material with energies ranging between zero and about 100 eV. Therefore, EELS is potentially more powerful than conventional optical spectroscopy which has an intrinsic upper information limit of about 6 eV due to absorption of light from the optical components of the system or the ambient. However, when analysing EELS data, the extraction of the single scattered data needed for Kramers Kronig calculations is subject to the deconvolution of the zero loss peak from the raw data. This procedure is particularly critical when attempting to study the near-bandgap region of materials with a bandgap below 1.5 eV. In this paper, we have calculated the electronic properties of three widely studied carbon materials; namely amorphous carbon (a-C), tetrahedral amorphous carbon (ta-C) and C60 fullerite crystal. The JDOS curve starts from zero for energy values below the bandgap and then starts to rise with a rate depending on whether the material has a direct or an indirect bandgap. Extrapolating a fit to the data immediately above the bandgap in the stronger energy loss region was used to get an accurate value for the bandgap energy and to determine whether the bandgap is direct or indirect in character. Particular problems relating to the extraction of the single scattered data for these materials are also addressed. The ta-C and C60 fullerite materials are found to be direct bandgap-like semiconductors having a bandgaps of 2.63 and 1.59eV, respectively. On the other hand, the electronic structure of a-C was unobtainable because it had such a small bandgap that most of the information is contained in the first 1.2 eV of the spectrum, which is a region removed during the zero loss deconvolution.

Tetrahedral amorphous carbon-silicon heterojunction band energy offsets

Non-hydrogenated tetrahedral amorphous carbon (ta-C) has shown superior field emission characteristics. The understanding of the emission mechanism has been hindered by the lack of any directly measured data on the band offsets between ta-C and Si. In this paper results from direct in situ X-ray photoemission spectroscopy (XPS) measurements of the band-offset between ta-C and Si are reported. The measurements were carried out using a filtered cathodic vacuum arc (FCVA) deposition system attached directly to an ultra-high vacuum (UHV) XPS chamber via a load lock chamber. Repeated XPS measurements were carried out after monolayer depositions on in situ cleaned Si substrates. The total film thickness for each set of measurements was approximately 5 nm. Analysis of the data from undoped ta-C on n and p Si show the unexpected result that the conduction band barrier between Si and ta-C remains around 1.0 eV, but that the valence band barrier changes from 0.7 to 0.0 eV. The band line up derived from these barriers suggests that the Fermi level in the ta-C lies 0.3 eV above the valence band on both p and n+Si. The heterojunction barriers when ta-C is doped with nitrogen are also presented. The implications of the heterojunction energy barrier heights for field emission from ta-C are discussed.

Encapsluation of Co and Pd multi-metal nanowires inside multiwalled carbon nanotubes by microwave plasma chemical vapor deposition

We report the synthesis of multiwalled carbon nanotubes (MWCNTs) encapsulated with Co/Pd magnetic and nonmagnetic multi-metal nanowires using Co and Pd thin-layers deposited on Si substrate by microwave plasma enhanced chemical vapor deposition using a bias-enhanced growth method. Detailed structural and compositional investigations of these metal nanowires inside MWCNTs were carried out by scanning electron microscopy and transmission electron microscopy to elucidate the growth mechanisms. Energy dispersive X-ray spectroscopy revealed that MWCNTs were encapsulated with Co and Pd nanowires, separately, at the tube top and the bottom of Co nanowire, respectively. The face-centered-cubic (fcc) structure of Co nanowires was confirmed by a selected area diffraction pattern. We proposed a fruitful description for the encapsulating mechanisms of both Co and Pd multi-metal nanowires. © 2006 Elsevier B.V. All rights reserved.

Smooth thin film C/diamond membranes with controllable optical band gaps

Mixed phase carbon-diamond films which consist of small grain diamond in an a:C matrix were deposited on polished Si using a radio frequency CH4 Ar plasma CVD deposition process. Ellipsometry, surface profilometry, scanning electron microscopy (SEM) and spectrophotometry were used to analyse these films. Film thicknesses were typically 50-100 nm with a surface roughness of ± 30 A ̊ over centimetre length scans. SEM analysis showed the films were smooth and pinhole free. The Si substrate was etched using backside masking and a directional etch to give taut carbon-diamond membranes on a Si grid. Spectrophotometry was used to analyse the optical properties of these membranes. Band gap control was achieved by varying the dc bias of the deposition process. Band gaps of 1.2 eV to 4.0 eV were achieved in these membranes. A technique for controlling the compressive stress in the films, which can range from 0.02 to 7.5 GPa has been employed. This has allowed the fabrication of thin, low stress, high band gap membranes that are extremely tough and chemically inert. Such carbon-diamond membranes seem promising for applications as windows in analytical instruments. © 1992.

Effect of deposition conditions on the chemical bonding in sputtered carbon nitride films

A balanced planar r.f. powered magnetron sputter source has been used to deposit carbon nitride films from a graphite target under various conditions. Sample temperature, bias voltage and nitrogen content in the gas mixture were varied. The effects of oxygen, methane and ammonia on the film growth were also studied. Special attention was paid to the effects of the deposition parameters on the structure of the films, in particular the hybridisation of the carbon and nitrogen bonding. The chemical bonding of the carbon and nitrogen atoms was studied by electron energy loss spectroscopy (EELS). The chemical composition was evaluated by Rutherford back-scattering. The intensity of transitions to π antibonding orbitals, as revealed by EELS, was found to increase with the nitrogen content in the films. Ion bombardment of the films during growth and the addition of oxygen or hydrogen-rich gases further increased the proportion of π bonds of both the carbon and nitrogen atoms. It is suggested that the increase in the transitions to μ antibond orbitals is to be explained by increased sp2 or possibly sp hybridisation of the carbon and nitrogen. Also, the effect of annealing on the bonding of nitrogen rich films after deposition was tested. The changes caused by nitrogen and deposition conditions are consistent with previous reports on the formation of paracyanogen structures.

Carbon based bottom gate thin film transistor

This paper describes the fabrication and characterization of a carbon based, bottom gate, thin film transistor (TFT). The active layer is formed from highly sp2 bonded nitrogenated amorphous carbon (a-C:N) which is deposited at room temperature using a filtered cathodic vacuum arc technique. The TFT shows p-channel operation. The device exhibits a threshold voltage of 15 V and a field effect mobility of 10-4 cm2 V-1 s-1 . The valence band tail of a-C:N is observed to be much shallower than that of a-Si:H, but does not appear to severely impede the shift of the Fermi level. This may indicate that a significant proportion of the a-C tail states can still contribute to conduction.

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.

Low field electron emission from nanoclustered carbon grown by cathodic arc

Nanocluster carbon films grown using a cathodic arc process at room temperature in the presence of background gases such as helium are found to be good electron emitters. The variation in the surface morphology and the corresponding emission characteristics of the films with change in helium partial pressure (5×10-4 to 50 Torr) during film growth are reported. The effect of helium partial pressure on clustering was studied for films grown at nitrogen partial pressures of 10-4 and 10-3 Torr. The surface morphology of the films varied from smooth through clusters (with sizes 50-200 nm) to fibrous films. The threshold field varied from 1 to 10 V/μm for an emission current density 1 μA/cm2.

Optical gap in carbon nitride films

In this paper we study the effect of introducing nitrogen into different carbon networks. Two kinds of carbon nitride films were deposited: (a) Using a DC-magnetron sputtering system sp2 bonded carbon nitride (a-CN) films were deposited and (b) Using a combination of filtered cathodic vacuum arc and a low-pressure N2 plasma source, N was introduced into sp3 carbon networks (ta-C), leading to the formation of a more dense CN film named ta-CN. For ta-CN films we found that the optical gap initially decreases as the N content and the sp2 fraction rises, but above a certain N quantity there is a level-off of the value, and the gap then remains constant despite further increases in the fraction and clustering of the sp2 phase. However, for a-CN films the optical gap increases with the nitrogen content. These two different trends are not easily explained using the same framework as that for carbon films, in which any decrease in the band gap is associated to an increase in the sp2 fraction or its clustering. Here we discuss the conditions that lead to high optical gap in sp2-bonded carbon nitride samples, which are clearly not associated to the presence of any crystalline super-hard phase. We also compared other differences in properties observed between the two films, such as deposition rate, infrared and Raman spectra. © 2003 Elsevier Science B.V. All rights reserved.

X-ray propagation in carbon nanotubes

The maintenance of the growth of the multibillion-dollar semiconductor industry requires the development of techniques for the fabrication and characterisation of nanoscale devices. Consequently, there is great interest in photolithography techniques such as extreme UV and x-ray. Both of these techniques are extremely expensive and technologically very demanding. In this paper we describe research on the feasibility of exploiting x-ray propagation within carbon nanotubes (CNT's) for the fabrication and characterisation of nanoscale devices. This work discusses the parameters determining the design space available. To demonstrate experimentally the feasibility of x-ray propagation, arrays of carbon nanotubes have been grown on silicon membranes. The latter are required to provide structural support for the CNT's while minimising energy loss. To form a waveguide metal is deposited between the nanotubes to block x-ray transmission in this region at the same time as cladding the CNT's. The major challenge has been to fill the spaces between the CNT's with material of sufficient thickness to block x-ray transmission while maintaining the structural integrity of the CNT's. Various techniques have been employed to fill the gaps between the nanotubes including electroplating, sputtering and evaporation. This work highlights challenges encountered in optimising the process.

Vertically aligned carbon nanotubes growth using self-assembled Ni nanoparticles produced by ion implantation

An alternative method for seeding catalyst nanoparticles for carbon nanotubes and nanowires growth is presented. Ni nanoparticles are formed inside a 450 nm SiO2 film on (100) Si wafers through the implantation of Ni ions at fluences of 7.5×1015 and 1.7×1016 ions.cm-2 and post-annealing treatments at 700, 900 and 1100°C. After exposed to the surface by HF dip etching, the Ni nanoparticles are used as catalyst for the growth of vertically aligned carbon nanotubes by direct current plasma enhanced chemical vapor deposition. © 2007 Materials Research Society.