Publications

Nanostructural characterization of amorphous diamondlike carbon (a-C) films grown on silicon using pulsed-laser deposition (PLD) is correlated to both growth energetic and film thickness. Raman spectroscopy and x-ray reflectivity probe both the topological nature of 3- and 4-fold coordinated carbon atom bonding and the topographical clustering of their distributions within a given film. In general, increasing the energetic of PLD growth results in films becoming more ``diamondlike'', i.e. increasing mass density and decreasing optical absorbance. However, these same properties decrease appreciably with thickness. The topology of carbon atom bonding is different for material near the substrate interface compared to material within the bulk portion of an a-C film. A simple model balancing the energy of residual stress and the free energies of resulting carbon topologies is proposed to provide an explanation of the evolution of topographical bonding clusters in a growing a-C film.

The carbon ion energy used during filtered cathodic vacuum arc deposition determines the bonding topologies of amorphous-carbon (a-C) films. Regions of relatively low density occur near the substrate/film and film/surface interfaces and their thicknesses increase with increasing deposition energy. The ion subplantation growth results in mass density gradients in the bulk portion of a-C in the growth direction; density decreases with distance from the substrate for films grown using ion energies < 60 eV and increases for films grown using ion energies > 160 eV. Films grown between these energies are the most diamondlike with relatively uniform bulk density and the highest optical transparencies. Bonding topologies evolve with increasing growth energy consistent with the propagation of subplanted carbon ions inducing a partial transformation of 4-fold to 3-fold coordinated carbon atoms.

We demonstrate high critical current density superconducting films of YBa{sub 2}Cu{sub 3}O{sub 7{minus}{delta}} (YBCO) and Tl{sub 2}Ba{sub 2}CaCu{sub 2}O{sub 8{minus}{delta}} (Tl-2212) using LaNiO{sub 3} (LNO) buffer layers. YBCO films grown on an LNO buffer layer have only a slightly lower J{sub c} (5K, H=0) than films grown directly on a bare LaAlO{sub 3} substrate. It is noteworthy that YBCO films grown on LNO buffer layers exhibit minor microstructural disorder and enhanced flux pinning. LNO-buffered Tl-2212 samples show large reductions in J{sub c} at all temperatures and fields compared to those grown on bare LaAlO{sub 3}, correlating to both a-axis grain and nonsuperconducting phase formation. With additional optimization, LNO could be a promising buffer layer for both YBCO and Tl-based superconducting films, perhaps ideally suited for coated conductor applications.

Epitaxial thin films of the Tl cuprate superconductors Tl{sub 2}Ba{sub 2}CaCu{sub 2}O{sub 8}, Tl{sub 2}Ba{sub 2}Ca{sub 2}Cu{sub 3}O{sub 10}, and TL{sub 0.78}Bi{sub 0.22}Ba{sub 0.4}Sr{sub 1.6}Ca{sub 2}Cu{sub 3}O{sub 9{minus}{delta}} are studied with x-ray photoemission spectroscopy. These data, together with previous measurements in this lab of Tl{sub 2}Ba{sub 2}CuO{sub 6+{delta}} and TlBa{sub 2}CaCu{sub 2}O{sub 7{minus}{delta}}, comprise a comprehensive data set for a comparative study of Tl cuprates with a range of chemical and electronic properties. In the Cu 2p spectra, a larger energy separation between the satellite and main peaks (E{sub s}-E{sub m}) and a lower intensity ratio (I{sub s}/I{sub m}) are found to correlate with higher values of T{sub c}. Analysis of these spectra within a simple configuration interaction model suggests that higher values of T{sub c} are related to low values of the O 2p {r_arrow} Cu 3d charge transfer energy. In the O 1s region, a smaller bond length between Ba and Cu-O planar oxygen is found to correlate with a lower binding energy for the signal associated with Cu-O bonding, most likely resulting from the increased polarization screening by Ba{sup 2+} ions. For samples near optimum doping, maximum T{sub c} is observed to occur when the Tl 4f{sub 7/2} binding energy is near 117.9 eV, which is near the middle of the range of values observed for Tl cuprates. Higher Tl 4f{sub 7/2} binding energies, corresponding to formal oxidation states nearer Tl{sup 1+}, are also found to correlate with longer bond lengths between Ba and Tl-O planar oxygen, and with higher binding energies of the O 1s signal associated with Tl-O bonding.

We report the stability of TlBa2CaCu2O7 and Tl2Ba2CaCu2O8 on LaAlO3(100) epitaxial thin films, under a variety of conditions. All films are stable in acetone and methanol and with repeated thermal cycling to cryogenic temperatures. Moisture, especially vapor, degrades film quality rapidly. These materials are stable to high temperatures in either N2 or O2 ambients. While total degradation, resulting from Tl depletion, occurs at the same temperatures for both phases, 600 °C in N2 and 700 °C in O2, the onset of degradation occurs at somewhat lower temperatures for TlBa2CaCu2O7 than for Tl2Ba2CaCu2O8.

Free-standing aligned carbon nanotubes have previously been grown above 7000C on mesoporous silica embedded with iron nanoparticles. Here, carbon nanotubes aligned over areas up to several square centimeters were grown on nickel-coated glass below 666oC by plasma-enhanced hot filament chemical vapor deposition. Acetylene (C2H2) gas was used as the carbon source and ammonia (NH3) gas was used as a catalyst and dilution gas. Nanotubes with controllable diameters from 20 to 400 nanometers and lengths from 0.1 to 50 micrometers were obtained. Using this method, large panels of aligned carbon nanotubes can be made under conditions that are suitable for device fabrication.

Highly-oriented, multi-walled carbon nanotubes were grown on polished polycrystalline and single crystal nickel substrates by plasma enhanced hot filament chemical vapor deposition at temperatures below 666"C. The carbon nanotubes range from 10 to 500 nm in diameter and 0.1 to 50 pm in length depending on growth conditions. Acetylene is used as the carbon source for the growth of the carbon nanotubes and ammonia is used for dilution gas and catalysis. The plasma intensity, acetylene to ammonia gas ratio and their flow rates, etc. affect the diameters and uniformity of the carbon nanotubes. In summary, we synthesized large-area highly-oriented carbon nanotubes at temperatures below 666C by plasma-enhanced hot filament chemical vapor deposition. Acetylene gas is used to provide carbon for nanotube growth and ammonia gas is used for dilution and catalysis. Plasma intensity is critical in determining the nanotube aspect ratios (diameter and length), and range of both site and height distributions within a given film.

Amorphous carbon (a-C) films grow via energetic processes such as pulsed-laser deposition (PLD). The cold-cathode electron emission properties of a-C are promising for flat-panel display and vacuum microelectronics technologies. These ultrahard films consist of a mixture of 3-fold and 4-fold coordinated carbon atoms, resulting in an amorphous material with diamond-like properties. The authors study the structures of a-C films grown at room temperature as a function of PLD energetics using x-ray reflectivity, Raman spectroscopy, high-resolution transmission electron microscopy, and Rutherford backscattering spectrometry. While an understanding of the electron emission mechanism in a-C films remains elusive, the onset of emission is typically preceded by conditioning where the material is stressed by an applied electric field. To simulate conditioning and assess its effect, the authors use the spatially-localized field and current of a scanning tunneling microscope tip. Scanning force microscopy shows that conditioning alters surface morphology and electronic structure. Spatially-resolved electron energy loss spectroscopy indicates that the predominant bonding configuration changes from predominantly 4-fold to 3-fold coordination.

The aim of this laboratory-directed research and development project was to study amorphous carbon (a-C) thin films for eventual cold-cathode electron emitter applications. The development of robust, cold-cathode emitters are likely to have significant implications for modern technology and possibly launch a new industry: vacuum micro-electronics (VME). The potential impact of VME on Sandia`s National Security missions, such as defense against military threats and economic challenges, is profound. VME enables new microsensors and intrinsically radiation-hard electronics compatible with MOSFET and IMEM technologies. Furthermore, VME is expected to result in a breakthrough technology for the development of high-visibility, low-power flat-panel displays. This work covers four important research areas. First, the authors studied the nature of the C-C bonding structures within these a-C thin films. Second, they determined the changes in the film structures resulting from thermal annealing to simulate the effects of device processing on a-C properties. Third, they performed detailed electrical transport measurements as a function of annealing temperature to correlate changes in transport properties with structural changes and to propose a model for transport in these a-C materials with implications on the nature of electron emission. Finally, they used scanning atom probes to determine important aspects on the nature of emission in a-C.

Aim of this laboratory-directed research and development (LDRD) project was to develop diamond and/or diamond-like carbon (DLC) films for electronic applications. Quality of diamond and DLC films grown by chemical vapor deposition (CVD) is not adequate for electronic applications. Nucleation of diamond grains during growth typically results in coarse films that must be very thick in order to be physically continuous. DLC films grown by CVD are heavily hydrogenated and are stable to temperatures {le} 400{degrees}C. However, diamond and DLC`s exceptional electronic properties make them candidates for integration into a variety of microelectronic structures. This work studied new techniques for the growth of both materials. Template layers have been developed for the growth of CVD diamond films resulting in a significantly higher nucleation density on unscratched or unprepared Si surfaces. Hydrogen-free DLC with temperature stability {le} 800{degrees}C has been developed using energetic growth methods such as high-energy pulsed-laser deposition. Applications with the largest system impact include electron-emitting materials for flat-panel displays, dielectrics for interconnects, diffusion barriers, encapsulants, and nonvolatile memories, and tribological coatings that reduce wear and friction in integrated micro-electro-mechanical devices.

Highly tetrahedral-coordinated-amorphous-carbon (a-tC) films deposited by pulsed-laser deposition (PLD) on silicon substrates are studied. These films are grown at room-temperatures in a high-vacuum ambient. a-tC films grown in this manner have demonstrated stability to temperatures in excess of T = 1000 °C, more than sufficient for any post-processing treatment or application. Film surfaces are optically smooth as determined both visually and by atomic-force microscopy. PLD growth parameters can be controlled to produce films with a range of sp2 - sp3 carbon-carbon bond ratios. Films with the highest yield of sp3 C-C bonds have high resistivity, with a dielectric permittivity constant ε to approximately 4, measured capacitively at low frequencies (1 - 100 kHz). These a-tC films are p-type semiconductors as grown. Schottky barrier diode structures have been fabricated.

Epitaxial films of Ba{sub 2}YCu{sub 3}O{sub 7-{delta}} (BYCO) as thin as 250 {Angstrom} and with J{sub c}`s approaching those of the best in situ grown films can be formed by co-evaporating BaF{sub 2}, Y, and Cu followed by a two-stage anneal. High quality films of these thicknesses become possible if low oxygen partial pressure [p(O{sub 2}) = 4.3 Torr] is used during the high temperature portion of the anneal (T{sub a}). The BYCO melt line is the upper limit for T{sub a}. The use of low p(O{sub 2}) shifts the window for stable BYCO film growth to lower temperature, which allows the formation of smooth films with greater microstructural disorder than is found in films grown in p(O{sub 2}) = 740 Torr at higher T{sub a}. The best films annealed in p(O{sub 2}) = 4.3 Torr have J{sub c} values a factor of four higher than do comparable films annealed in p(O{sub 2}) = 740 Torr. The relationship between the T{sub a} required to grow films with the strongest pinning force and p(O{sub 2}) is log [p(O{sub 2})] {proportional_to} T{sub a}{minus}{sup 1a} independent of growth method (in situ or ex situ) over a range of five orders of magnitude of p(O{sub 2}).