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At least 145 records · Page 8

Carbon Nanotubes/Nanofibers by Plasma Enhanced Chemical Vapour Deposition

Plasma enhanced chemical vapour deposition (PECVD) has been recently used for the production of vertically aligned carbon nanotubedfibers (CN) directly on substrates. These structures are potentially important technologically as electron field emitters (e.g. microguns, microwave amplifiers, displays), nanoelectrodes for sensors, filter media, superhydrophobic surfaces and thermal interface materials for microelectronics. A parametric study on the growth of CN grown by glow discharge dc-PECVD is presented. In this technique, a substrate containing thin film Ni catalyst is exposed to C2H2 and NH3 gases at 700 C. Without plasma, this process is essentially thermal CVD which produces curly spaghetti-like CN as seen in Fig. 1 (a). With the plasma generated by biasing the substrate at -6OOV, we observed that the CN align vertically during growth as shown in Fig. l(b), and that the magnitude of the applied substrate bias affects the degree of alignment. The thickness of the thin film Ni catalyst was found to determine the average diameter and inversely the length of the CN. The yield and density of the CN were controlled by the use of different diffusion barrier materials under the Ni catalyst. Patterned CN growth [Fig. l(c)], with la variation in CN diameter of 4.1% and 6.3% respectively, is achieved by lithographically defining the Ni thin film prior to growth. The shape of the structures could be varied from very straight nanotube-like to conical tip-like nanofibers by increasing the ratio of C2H2 in the gas flow. Due to the plasma decomposition of C2H2, amorphous carbon (a-C) is an undesirable byproduct which could coat the substrate during CN growth. Using a combination of depth profiled Auger electron spectroscopy to study the substrate and in-situ mass spectroscopy to examine gas phase neutrals and ions, the optimal conditions for a-C free growth of CN is determined.

Teo, K. B. K.↗

Epitaxially Grown Single-Crystalline SrTiO 3 Membranes Using a Solution-Processed, Amorphous SrCa 2 Al 2 O 6 Sacrificial Layer

Water-soluble sacrificial layers based on epitaxially-grown, single crystalline (Ca, Sr, Ba) 3 Al 2 O 6 layer are widely used for creating free-standing perovskite oxide membranes. However, obtaining these sacrificial layers with intricate stoichiometry remains a challenge, especially for molecular beam epitaxy (MBE). In this study, we demonstrate the hybrid MBE growth of epitaxial, single crystalline SrTiO 3 films using a solution processed, amorphous SrCa 2 Al 2 O 6 sacrificial layer onto SrTiO 3 (001) substrates. Prior to the growth, the oxygen plasma exposure was used to first create the crystalline SrCa 2 Al 2 O 6 layer with well-defined surface crystallinity. Utilizing reflection high energy electron diffraction, x-ray diffraction, and atomic force microscopy, we observe an atomic layer-by-layer growth of epitaxial, single crystalline SrTiO 3 film on the SrCa 2 Al 2 O 6 layer with atomically smooth surfaces. The SrCa 2 Al 2 O6 layer was subsequently dissolved in de-ionized water to create free-standing SrTiO3 membranes that were transferred onto a metal-coated Si wafer. Membranes created with Sr-deficiency revealed ferroelectric-like behavior measured using piezo force microscopy whereas stoichiometric films remained paraelectric-like. Furthermore, these findings underscore the viability of using ex-situ deposited amorphous SrCa2Al2O6 for epitaxial, single crystalline growth, as well as the importance of point defects in determining the ferroic properties in membranes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Amorphous metallic films in silicon metallization systems

Diffusion barrier research was focussed on lowering the chemical reactivity of amorphous thin films on silicon. An additional area of concern is the reaction with metal overlays such as aluminum, silver, and gold. Gold was included to allow for technology transfer to gallium arsenide PV cells. Amorphous tungsten nitride films have shown much promise. Stability to annealing temperatures of 700, 800, and 550 C were achieved for overlays of silver, gold, and aluminum, respectively. The lower results for aluminum were not surprising because there is an eutectic that can form at a lower temperature. It seems that titanium and zirconium will remove the nitrogen from a tungsten nitride amorphous film and render it unstable. Other variables of research interest were substrate bias and base pressure during sputtering.

So, F.↗

Plasma deposition of amorphous hydrogenated carbon films on III-V semiconductors

Amorphous hydrogenated carbon films were grown on GaAs, InP and fused silica substrates using plasmas generated from hydrocarbon gases. Methane and n-butane sources were utilized. The effects of flow rate and power density on film growth were investigated. Carbon was the major constituent in the films. The degree of asymmetry at the carbon-semiconductor interface was approximately independent of the power density. Different H-C bonding configurations were detected by the technique of secondary-ion mass spectrometry. Band gaps up to 3 eV were obtained from optical absorption studies. Breakdown strengths as high as 600 MV/m were measured.

Pouch, John J.↗

Shape-memory properties in Ni-Ti sputter-deposited film

A Ni-Ti alloy, generically called nitinol, was prepared from sputtering targets of two different compositions on glass substrates using a dc magnetron source. The as-deposited films were amorphous in structure and did not exhibit a shape memory. The amorphous films were crystallized with a suitable annealing process, and the transformation properties were measured using differential scanning calorimetry. The annealed films demonstrated a strong shape-memory effect. Stress/strain measurements and physical manipulation were used to evaluate the shape recovery. These tests demonstrated sustained tensile stresses of up to 480 MPa in the high-temperature phase, and a characteristic plastic deformation in the low-temperature phase.

Busch, J. D.↗

Orientation-tunable local crystallization of Si films enabled by atomic imprint crystallization

Here, in this paper, we demonstrate area-selective crystallization of amorphous Si into tunable crystal orientations enabled by atomic imprint crystallization (AIC), where an amorphous Si layer is crystallized by solid phase epitaxy (SPE) from an externally impressed single-crystalline Si template. Using micro-patterned single-crystalline Si templates, a limited area of an amorphous Si film, where the film surface and patterned template surface are in contact, is crystallized via SPE to create an array of crystallographically aligned dots embedded in amorphous matrix. Combining AIC from the top surface and conventional SPE from the substrate, we demonstrate the fabrication of an array of crystalline dots embedded in single-crystalline matrix with tunable in-plane rotation angle. The results indicate the high tunability of the crystallization process enabled by AIC, allowing precise control of crystallographic properties of thin films with area-selectivity; such capability opens opportunities for the design of new materials for a wide range of applications in materials science.

Amorphous↗

Irradiation-Driven Restructuring of UO 2 Thin Films: Amorphization and Crystallization

Combustion synthesis in uranyl nitrate–acetylacetone–2-methoxyethanol solutions was used to deposit thin UO 2 films on aluminum substrates to investigate the irradiation-induced restructuring processes. Thermal analysis revealed that the combustion reactions in these solutions are initiated at ~160 °C. The heat released during the process and the subsequent brief annealing at 400 °C allow the deposition of polycrystalline films with 5–10 nm UO 2 grains. The use of multiple deposition cycles enables tuning of the film thicknesses in the 35–260 nm range. Irradiation with Ar 2+ ions (1.7 MeV energy and a fluence of up to 1 × 10 17 ions/cm 2 ) is utilized to generate a uniform distribution of atomic displacements within the films. X-ray fluorescence (XRF) and alpha-particle emission spectroscopy showed that the films were stable under irradiation and did not undergo sputtering degradation. X-ray photoelectron spectroscopy (XPS) showed that the stoichiometry and uranium ionic concentrations remain stable during irradiation. The high-resolution electron microscopy imaging and electron diffraction analysis demonstrated that at the early stages of irradiation (below 1 × 10 16 ion/cm 2 ) UO 2 films show complete amorphization and beam-induced densification (sintering), resulting in a pore-free disordered film. Prolonged irradiation (5 × 10 16 ion/cm 2 ) is shown to trigger a crystallization process at the surface of the films that moves toward the UO 2 /Al interface, converting the entire amorphous material into a highly crystalline film. This work reports on an entirely different radiation-induced restructuring of the nanoscale UO 2 compared to the coarse-grained counterpart. The preparation of thin UO 2 films deposited on Al substrates fills an area of national need within the stockpile stewardship program of the National Nuclear Security Administration and fundamental research with actinides. Here, the method reported in this work produces pure, robust, and uniform thin-film actinide targets for nuclear science measurements

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

GaAs Substrate Recycling Using in-situ Deposited NaCl Layers via Molecular Beam Epitaxy

This work presents an alternative method to conventional III-V substrate recycling methods via growth of NaCl on nearly-lattice matched GaAs (001) substrates. Reflection high energy electron diffraction and transmission electron microscopy confirm an epitaxial relationship between the NaCl layers and the underlying GaAs. If the sample is heated too much prior to GaAs deposition, the NaCl fully desorbs from the surface. The quality of the deposition of GaAs on NaCl ranges from amorphous at low temperature to polycrystalline at intermediate temperatures. Exposure to electron beams during growth results in larger and (001) textured grains. The substrate is separated from the GaAs film in seconds via submersion in water, revealing a substrate surface comparable to the original.

electron beams↗

Crystallization kinetics of amorphous acetonitrile nanoscale films

We measure the isothermal crystallization kinetics of amorphous acetonitrile films using molecular beam dosing and reflection adsorption infrared spectroscopy RAIRS techniques. Experiments on a graphene covered Pt(111) substrate revealed that the crystallization rate slows dramatically at long times and that the overall kinetics cannot be described by a simple application of the Avrami equation. The crystallization kinetics also have a thickness dependence with the thinner films crystallizing much slower than thicker ones. Additional experiments showed that decane layers at both the substrate and vacuum interfaces can also affect the crystallization rates. A comparison of the crystallization rates for CH 3 CN and CD 3 CN films showed only an isotope effect of ~1.09. When amorphous films were deposited on a crystalline film, the crystalline layer did not act as a template for the formation of a crystalline growth front. Finally, these overall results suggest that the crystallization kinetics complicated indicating the possibility of multiple nucleation mechanisms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Compact Plasma Deposition Chamber

Contamination and nonuniformity are reduced. Substrates serve as walls of deposition chamber in configuration for plasma deposition of amorphous silicon. New chamber intended for production of amorphous silicon solar cells. Design reduces requirements on chamber size and expected to increase product quality.

Bickler, D. B.↗

Electrochemical patterning of amorphous carbon on diamond

The ability to pattern ion-implantation damaged or other nondiamond carbon on a diamond substrate is useful for fabricating a variety of devices. We accomplished such patterning by an unmasked implantation into a diamond substrate followed by photolithography and a selective electrochemical etch. The use of a high resistivity medium coupled with applied biases over 50 V permitted etching without requiring contact between the substrate and an electrode. Many electrolytes gave etches that exhibit high selectivity for nondiamond carbon over both diamond and dielectrics such as photoresist. Optical, electrical, and Raman spectroscopic measurements elucidate the effects of the etch on the implanted diamond surface.

Marchywka, Mike↗

Zwitterion Moieties in Polypeptides Synergistically Enhance the Release of Cellulose and Amorphous Polysaccharides from Plant Cell Walls

This study demonstrated that covalently localized zwitterionic moieties in zwitterionic polypeptides (ZIPs) effectively disrupt hydrogen bonds in cellulosic substrates, including filter paper and plant cell wall materials, without significant cytotoxicity. ZIPs with varying densities of zwitterionic side chains were synthesized via the postpolymerization modification of histidinecontaining oligopeptides. The newly developed ZIPs predominantly comprised repeating units with zwitterionically converted side chains. Such ZIPs can cleave multiple hydrogen bonds by anchoring the zwitterionic structure at specific sites, thereby partially dissociating the polysaccharide chains in the cell wall. They are especially effective in dissolving amorphous cellulose, even at low concentrations in aqueous solutions. Importantly, this effect was achieved with minimal cellular toxicity, harnessing the advantages of ionic liquid-like properties while mitigating their high-toxicity limitations. This biofriendly approach to cell wall denaturation highlights a novel method for controlling hydrogen bond networks in polysaccharides and cell walls. These findings indicate a new approach for reducing biomass recalcitrance and developing next-generation biobased materials and fuels derived from plant cell walls.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optimized oxygen deprived low temperature sputtered WO3 thin films for crystalline structures

In this work, we report a detailed analysis on the effects of processing parameters for sputtered tungsten trioxide (WO 3 ) thin nanoscale films on their structural, vibrational and electrical properties. The research aims to understand the fundamental aspects of WO3 sputtering at relatively low temperatures and in an oxygen deprived environment targeting applications of temperature and oxygen sensitive substrates. Structural analysis indicates that films deposited at room temperature, or substrate temperatures at or below 400 degrees C with low oxygen partial pressure are amorphous. Furthermore, crystallization of the films was observed with distinct Raman peaks when the films were annealed at 300 degrees C or above using rapid thermal annealing for 10 min. Films revealed monoclinic phases of WO 3 with the presence of W-O-W stretching, bending and lattice vibrational modes in the Raman spectra. Interestingly, a change of transport behavior from insulating to semiconducting was observed for as deposited films on post annealing. Annealed films revealed stoichiometric WO 3 phases with no external defects detected. The present study adopts a route to intercalate WO 3 in a variety of applications from electrochromic coloration to a nanocrystalline thin film for electronic devices sensitive to higher temperatures and gas flow in the sputtering system.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Rapid thermal annealing of Amorphous Hydrogenated Carbon (a-C:H) films

Amorphous hydrogenated carbon (a-C:H) films were deposited on silicon and quartz substrates by a 30 kHz plasma discharge technique using methane. Rapid thermal processing of the films was accomplished in nitrogen gas using tungsten halogen light. The rapid thermal processing was done at several fixed temperatures (up to 600 C), as a function of time (up to 1800 sec). The films were characterized by optical absorption and by ellipsometry in the near UV and the visible. The bandgap, estimated from extrapolation of the linear part of a Tauc plot, decreases both with the annealing temperature and the annealing time, with the temperature dependence being the dominating factor. The density of states parameter increases up to 25 percent and the refractive index changes up to 20 percent with temperature increase. Possible explanations of the mechanisms involved in these processes are discussed.

Alterovitz, Samuel A.↗

Friction and wear of plasma-deposited amorphous hydrogenated films on silicon nitride

An investigation was conducted to examine the friction and wear behavior of amorphous hydrogenated carbon (a-C:H) films in sliding contact with silicon nitride pins in both dry nitrogen and humid air environments. Amorphous hydrogenated carbon films approximately 0.06 micron thick were deposited on silicon nitride flat substrates by using the 30 kHz ac glow discharge of a planar plasma reactor. The results indicate that an increase in plasma deposition power gives an increase in film density and hardness. The high-density a-C:H films deposited behaved tribologically much like bulk diamond. In the dry nitrogen environment, a tribochemical reaction produced a substance, probably a hydrocarbon-rich layer, that decreased the coefficient of friction. In the humid air environment, tribochemical interactions drastically reduced the wear life of a-C:H films and water vapor greatly increased the friction. Even in humid air, effective lubrication is possible with vacuum-annealed a-C:H films. The vacuum-annealed high-density a-C:H film formed an outermost superficial graphitic layer, which behaved like graphite, on the bulk a-C:H film. Like graphite, the annealed a-C:H film with the superficial graphitic layer showed low friction when adsorbed water vapor was present.

Miyoshi, Kazuhisa↗

Magnetic order in nanogranular iron germanium (Fe 0.53 Ge 0.47 ) films

We study the effect of strain on the magnetic properties and magnetization configurations in nanogranular Fe x Ge 1-x films (x = 0.53 ± 0.05) with and without B20 FeGe nanocrystals surrounded by an amorphous structure. Relaxed films on amorphous silicon nitride membranes reveal a disordered skyrmion phase while films near and on top of a rigid substrate favor ferromagnetism and an anisotropic hybridization of Fe d levels and spin-polarized Ge sp band states. The weakly coupled topological states emerge at room temperature and become more abundant at cryogenic temperatures without showing indications of pinning at defects or confinement to individual grains. These results demonstrate the possibility to control magnetic exchange and topological magnetism by strain and inform magnetoelasticity-mediated voltage control of topological phases in amorphous quantum materials.

36 MATERIALS SCIENCE↗

Impact of Interfacial Structure on Heterogeneous Nucleation of Amorphous Carbonates

For this work, classical molecular dynamics simulations were performed to provide physical insight into the impact of interfacial structure on the heterogeneous nucleation of amorphous calcium carbonate (ACC, CaCO 3 ·H 2 O) and amorphous magnesium carbonate (AMC, MgCO 3 ·H 2 O) by using α-quartz as a model substrate. Interfacial structure and energies were computed for ACC and AMC in contact with the (100), (001), and (101) α-quartz surfaces. The simulations showed α-quartz surfaces drew water molecules out of the carbonate nuclei to form a partial hydration layer. The formation of a partial hydration layer and its disruption to the ACC/AMC structure meant the α-quartz–ACC/AMC interfaces were not energetically favored relative to separate α-quartz–water and ACC/AMC–water interfaces and, thus, homogeneous ACC/AMC nucleation was favored over heterogeneous nucleation. The CMD simulations hence provided an atomic-level explanation for a reported nonclassical growth mechanism whereby carbonate minerals grow via homogeneous nucleation and subsequent surface attachment of amorphous intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗