Search

Nanothermite NiO–Al is a promising material system for low gas emission heat sources; yet, its reactive properties are highly dependent on material processing conditions. In the current study, sputter deposition is used to fabricate highly controlled nanolaminates comprised of alternating NiO and Al layers. Films having an overall stoichiometry of 2Al to 3NiO were produced with different bilayer thicknesses to investigate how ignition and self-sustained, high temperature reactions vary with changes to nanometer-scale periodicity and preheat conditions. Ignition studies were carried out with both hot plate and laser irradiation and compared to slow heating studies in hot-stage x-ray diffraction. Ignition behavior has bilayer thickness and heating rate dependencies. The 2Al/3NiO with λ ≤ 300 nm ignited via solid/solid diffusion mixing (activation energy, Ea = 49 ± 3 kJ/mole). Multilayers having λ≥ 500 nm required a more favorable mixing kinetics of solid/liquid dissolution into molten Al (Ea = 30 ± 4 kJ/mole). This solid/liquid dissolution Ea is a factor of 5 lower than that of the previously reported powder compacts due to the elimination of a passivating Al oxide layer present on the powder. The reactant mixing mechanism between 300 and 500 nm bilayer thicknesses was dependent on the ignition source's heating rate. The self-propagating reaction velocities of 2Al/3NiO multilayers varied from 0.4 to 2.5 m/s. Pre-heating nanolaminates to temperatures below the onset reaction temperatures associated with forming intermediate nickel aluminides at multilayer interfaces led to increased propagation velocities, whereas pre-heating samples above the onset temperatures inhibited subsequent attempts at laser ignition. [ABSTRACT FROM AUTHOR]

Solution deposition is widely used for the fabrication of lead zirconate titanate (PZT) thin films on platinized silicon substrates. However, phase and texture evolution during the crystallization process is not well understood, particularly due to the difficulty in tracking changes in the thin films in situ during heating. In this work, we characterized phase and texture evolution in situ during heating and crystallization of PZT thin films using high-energy X-ray diffraction. Films were pyrolyzed at either 300 °C or 400 °C and heated at various rates between 0.5 °C/s and ∼150 °C/s. For films that were pyrolyzed at 300 °C, the most rapid heating rates first induced strong intensities from a transient Pt3Pb phase. The Pt3Pb phase inherited the texture of the pre-existing platinum layer. Combined with other observations, the results suggest the conversion of the platinum to the intermetallic phase near the interface due to the interdiffusion of lead. In all experimental variations, the pyrochlore phase was observed to form concurrently with the disappearance of the Pt3Pb phase after which the perovskite phase ultimately crystallized. For films that were pyrolyzed at 400 °C, the Pt3Pb phase was not observed at any of the heating rates; instead, the pyrochlore phase was first observed, followed by the perovskite phase. Independent of the pyrolysis temperature or observation of Pt3Pb, a 111-dominant crystallographic texture formed in the perovskite phase when crystallized using fast heating rates. These results demonstrate that 111 textures in solution-derived PZT thin films are not correlated with the observation of Pt3Pb or other intermetallic or transient phases. [ABSTRACT FROM AUTHOR]

Presents information on a study wherein single-phase aluminum nitride thin films with preferred crystallographic orientations have been grown on single-crystal sapphire by pulsed-laser ablation. Methods; Results; Discussion.

The effects of chemistry, substrate, and processing conditions on through-thickness cation distributions are explored in solution-derived morphotropic composition lead zirconate titanate (PZT) films. Films prepared from chelate-based and conventional sol-gel chemistries were spin cast onto Pt/ZnO/SiO2/Si and Pt/Ti/SiO2/Si substrates and pyrolyzed at 300°C, 350°C, and 400°C prior to crystallization at 700°C either in a preheated furnace or via rapid thermal processing. For films crystallized within a conventional furnace on Pt/ZnO/SiO2/Si substrates no chemical gradients were observed. All films prepared on Pt/Ti/SiO2/Si substrates had increased titanium concentrations near the PZT/Pt interfaces, and the source is shown to be titanium diffusing from the substrate metallization stack. The effect of heating method and rate was explored in films prepared on Pt/ZnO/SiO2/Si substrates with 15°C, 50°C, and 100°C/s heating rates within a rapid thermal annealer. Only one solution chemistry-heating rate combination resulted in the formation of a chemical gradient: a conventional sol-gel chemistry and a 50°C/s heating rate. Infrared spectroscopy of pyrolyzed gel films showed absorption spectra differences in the bonding structure between the two chemistries with the conventional sol-gel-derived films exhibiting a signature more similar to that of a PbTiO3 gel, suggestive of a gel-structure source of gradient formation during crystallization. [ABSTRACT FROM AUTHOR]

Atom probe tomography ( APT) is a powerful materials characterization technique capable of ppm chemical resolution and near atomic scale spatial resolution. However, owing to a number of factors, the technique has not been widely applied to insulating materials and even less to complex oxides. In this study, we outline the methodology necessary to obtain high-quality results on a technologically relevant complex oxide Pb(Zr,Ti)O3 (or PZT) using laser-assisted APT on both bulk and thin film specimens. We show how, with optimized and well-controlled conditions, APT complements conventional techniques such as STEM- EDS. The correlative information can be used to obtain the nanoscale 3-D chemical information and investigate the nanoscale distribution of cations. Using nearest-neighbor cluster analysis routines, 5-10 nm segregation of B-site cations was detected in bulk sintered PZT 53/47 from chemically prepared powders. No statistically significant segregation of B-site cations was observed in thin film specimens. This work opens new avenues toward understanding the process-structure properties in complex materials at length scales heretofore unachievable. [ABSTRACT FROM AUTHOR]

Abstract: In this paper, we demonstrate the fabrication of electrostatically loaded, free-standing Al–0.5wt.%Cu thin-film samples, realizing a near-zero compliance support post. We measure Young’s modulus E =74GPa using cantilevers, in good agreement with grain texture measurements. We measure residual stress σ R ranging from 30 to 60MPa using fixed–fixed beams and find that processing induces significant plastic straining, which leads to residual stress values significantly less than the as-deposited value. Strength of this alloy is at least 172MPa if the film is not severely strained, and the material exhibits no room-temperature fatigue up to 1 billion cycles at this stress level. Notched devices that have been subjected to process-induced plastic straining of ∼4% are weaker and fatigue logarithmically with the number of cycles. We compare deformation processes on the samples using ex situ TEM. The mechanism for the high strength value is attributed to the grain size and the thin surface oxide which constrain dislocation glide, while fatigue of the highly strained material is associated with the appearance of persistent slip bands. [Copyright &y& Elsevier]

Abstract The thickening behavior of aluminum scandium nitride (Al 0.88 Sc 0.12 N) films grown on Si(111) substrates has been investigated experimentally using X-ray diffraction (XRD), transmission electron microscopy (TEM), atomic force microscopy, and residual stress measurement. Al 0.88 Sc 0.12 N films were grown with thicknesses spanning 14 nm to 1.1 μm. TEM analysis shows that the argon sputter etch used to remove the native oxide prior to deposition produced an amorphous, oxygen-rich surface, preventing epitaxial growth. XRD analysis of the films show that the AlScN(002) orientation improves as the films thicken and the XRD AlScN(002) rocking curve full width half maximum decreases to 1.34° for the 1.1 μm thick film. XRD analysis shows that the unit cell is expanded in both the a- and c-axes by Sc doping; the a-axis lattice parameter was measured to be 3.172 ± 0.007 Å and the c-axis lattice parameter was measured to be 5.000 ± 0.001 Å, representing 1.96% and 0.44% expansions over aluminum nitride lattice parameters, respectively. The grain size and roughness increase as the film thickness increases. A stress gradient forms through the film; the residual stress grows more tensile as the film thickens, from −1.24 GPa to +8.5 MPa. Highlights • Al 0.88 Sc 0.12 N films of varied thicknesses (14 nm – 1.1 μm) were deposited on silicon. • The argon sputter etch amorphized the substrate surface, preventing epitaxial growth. • As the films thicken the film texture improves and the films coarsen. • The unit cell is expanded due to scandium substitution within the host lattice. [ABSTRACT FROM AUTHOR]

Black TiO2 nanoparticles with a crystalline core and amorphous-shell structure exhibit superior optoelectronic properties in comparison with pristine TiO2. The fundamental mechanisms underlying these enhancements, however, remain unclear, largely due to the inherent complexities and limitations of powder materials. Here, we fabricate TiO2 homojunction films consisting of an oxygen-deficient amorphous layer on top of a highly crystalline layer, to simulate the structural/functional configuration of black TiO2 nanoparticles. Metallic conduction is achieved at the crystalline-amorphous homointerface via electronic interface reconstruction, which we show to be the main reason for the enhanced electron transport of black TiO2. This work not only achieves an unprecedented understanding of black TiO2 but also provides a new perspective for investigating carrier generation and transport behavior at oxide interfaces, which are of tremendous fundamental and technological interest. [ABSTRACT FROM AUTHOR]

The formation of Al 3 Sc, in 100 nm Al 0.8 Sc 0.2 films, is found to be driven by exposure to high temperature through higher deposition temperature or annealing. High film resistivity was observed in films with lower deposition temperature that exhibited a lack of crystallinity, which is anticipated to cause more electron scattering. An increase in deposition temperature allows for the nucleation and growth of crystalline Al 3 Sc regions that were verified by electron diffraction. The increase in crystallinity reduces electron scattering, which results in lower film resistivity. Annealing Al 0.8 Sc 0.2 films at 600 °C in an Ar vacuum environment also allows for the formation and recrystallization of Al 3 Sc and Al and yields saturated resistivity values between 9.58 and 10.5 μΩ-cm regardless of sputter conditions. Al 3 Sc was found to nucleate and grow in a random orientation when deposited on SiO 2 , and highly {111} textured when deposited on 100 nm Ti and AlN films that were used as template layers. The rocking curve of the Al 3 Sc 111 reflection for the as-deposited films on Ti and AlN at 450 °C was 1.79° and 1.68°, respectively. Annealing the film deposited on the AlN template reduced the rocking curve substantially to 1.01° due to recrystallization of Al 3 Sc and Al within the film. [Display omitted] • The formation of Al 3 Sc is found to be driven by exposure to high temperatures. • Low deposition temperatures lead to low crystallinity films with high resistivity. • {111} textured Al 3 Sc achieved by leveraging temperature and a template layer. • Annealing Al 0.8 Sc 0.2 films reduces resistivity regardless of sputter conditions. • Strong recrystallization effect seen in annealed films with {111} textured Al 3 Sc. [ABSTRACT FROM AUTHOR]