Optical emission spectroscopy of the plasma during sputter deposition of YBCO films for microwave applications

YBCO thin films are currently used in several HTS-based electronics applications. The performance of devices, which may include microwave passive components (filters, resonators), grain boundary junctions or spintronic multilayer structures, is determined by film quality, which in turn depends on the deposition technology used and growth parameters. We report on results from nonintrusive Optical Emission Spectroscopy of the plasma during YBCO thin film deposition in a high-pressure on-axis sputtering system under different conditions, including small trace gas additions to the sputtering gas. We correlate these results with the compositional and structural changes which affect the DC and microwave properties of YBCO films. Film morphology, composition, structure and in- and out-of-plane orientation were assessed; T, and microwave surface resistance measurements were made using inductive and resonator techniques. Comparison was made with films sputtered in an off-axis 2-opposing magnetron system.

Tailoring the morphology of carbon nanotube assemblies using microgradients in the catalyst thickness

In addition to the structural control of individual carbon nanotubes (CNTs), the morphological control of their assemblies is crucial to realize miniaturized CNT devices. Microgradients in the thickness of catalyst are used to enrich the variety of available self-organized morphologies of CNTs. Microtrenches were fabricated in gate/spacer/cathode trilayers using a conventional self-aligned top-down process and catalyst exhibiting a microgradient in its thickness was formed on the cathode by sputter deposition through gate slits. CNTs, including single-walled CNTs, of up to 1μm in length were grown within 5-15 s by chemical vapor deposition. The tendency of thin CNTs to aggregate caused interactions between CNTs with different growth rates, yielding various morphologies dependent on the thickness of the catalyst. The field emission properties of several types of CNT assemblies were evaluated. The ability to produce CNTs with tailored morphologies by engineering the spatial distribution of catalysts will enhance their performance in devices. © 2011 The Japan Society of Applied Physics.

Chemical sputtering of ta-C: Implications for the deposition of carbon nitride

The majority of attempts to synthesize the theoretically predicted superhard phase β-C3N4 have been driven towards the use of techniques which maximize both the carbon sp3 levels and the amount of nitrogen incorporated within the film. However, as yet no attempt has been made to understand the mechanism behind the resultant chemical sputter process and its obvious effect upon film growth. In this work, however, the chemical sputtering process has been investigated through the use of an as-deposited tetrahedrally bonded amorphous carbon film with a high density nitrogen plasma produced using an rf-based electron cyclotron wave resonance source. The results obtained suggested the presence of two distinct ion energy dependent regimes. The first, below 100 eV, involves the chemical sputtering of carbon from the surface, whereas the second at ion energies in excess of 100 eV exhibits a drop in sputter rate associated with the subplantation of nitrogen within the carbon matrix. Furthermore, as the sample temperature is increased there is a concomitant decrease in sputter rate suggesting that the rate is controlled by the adsorption and desorption of additional precursor species rather than the thermal desorption of CN. A simple empirical model has been developed in order to elucidate some of the primary reactions involved in the sputter process. Through the incorporation of various previously determined experimental parameters including electron temperature, ion current density, and nitrogen partial pressure the results indicated that molecular nitrogen physisorbed at the ta-C surface was the dominant precursor involved in the chemical sputter process. However, as the physisorption enthalpy of molecular nitrogen is low this suggests that activation of this molecular species takes place only through ion impact at the surface. The obtained results therefore provide important information for the modeling and growth of high density carbon nitride. © 2001 American Institute of Physics.

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.

Low-temperature growth of carbon nanotubes by plasma-enhanced chemical vapor deposition

Vertically aligned carbon nanotubes were grown at temperatures as low as 120degreesC by plasma-enhanced chemical vapor deposition. A systematic study of the temperature dependence of the growth rate and the structure of the as-grown nanotubes is presented using a C2H2/NH3 system and nickel as the catalyst. The activation energy for the growth rate was found to be 0.23 eV, much less than for thermal chemical vapor deposition (1.2-1.5 eV). This suggests growth occurs by surface diffusion of carbon on nickel. The result could allow direct growth of nanotubes onto low-temperature substrates like plastics, and facilitate the integration in sensitive nanoelectronic devices. (C) 2003 American Institute of Physics.

Effects of pre-treatment and plasma enhancement on chemical vapor deposition of carbon nanotubes from ultra-thin catalyst films

We report a detailed study of surface-bound chemical vapor deposition of carbon nanotubes and nanofibers from evaporated transition metal catalysts exposed to ammonia diluted acetylene. We show that a reduction of the Fe/Co catalyst film thickness below 3 nm results into a transition from large diameter (> 40 nm), bamboo-like nanofibers to small diameter (similar to 5 nm) multi-walled carbon nanotubes. The nanostructuring of ultrathin catalyst films critically depends on the gas atmosphere, with the resulting island distribution initiating the carbon nucleation. Compared to purely thermal chemical vapor deposition, we find that, for small diameter nanotube growth, DC plasma assistance is detrimental to graphitization and sample homogeneity and cannot prevent an early catalyst poisoning. (c) 2006 Elsevier B.V. All rights reserved.

The role of the catalytic particle in the growth of carbon nanotubes by plasma enhanced chemical vapor deposition

Vertically aligned carbon nanotubes were synthesized by plasma enhanced chemical vapor deposition using nickel as a metal catalyst. High resolution transmission electron microscopy analysis of the particle found at the tip of the tubes reveals the presence of a metastable carbide Ni3C. Since the carbide is found to decompose upon annealing at 600 degreesC, we suggest that Ni3C is formed after the growth is stopped due to the rapid cooling of the Ni-C interstitial solid solution. A detailed description of the tip growth mechanism is given, that accounts for the composite structure of the tube walls. The shape and size of the catalytic particle determine the concentration gradient that drives the diffusion of C atoms across and though the metal. (C) 2004 American Institute of Physics.