Zirconia–hafnia (ZrO2–HfO2) nanolaminate structures were grown using the atomic layer deposition (ALD) technique with different stacking sequences and layer thickness layer thicknesses. The microstructural evolution and surface roughness were compared with those of single-layer ZrO2 or HfO2 films using transmission electron microscopy and atomic force microscopy. Thin single-layer ALD-ZrO2 films were polycrystalline and composed of the tetragonal ZrO2 phase as-deposited, whereas thicker (>14 nm) films were composed mainly of the monoclinic phase. HfO2 films were amorphous as-deposited and crystallized into primarily monoclinic during subsequent anneals at temperatures over 500 °C. All the nanolaminate structures having individual layer thicknesses greater than approximately 2 nm were crystalline (mixture of tetragonal and monoclinic phases) independent of layer sequence and also exhibited a layer-to-layer epitaxy relationship within each grain. However, the identity of the starting layer determined the final grain size and surface roughness of the nanolaminates. A qualitative model for the observed microstructure evolution of the laminate films is proposed.

A structural and morphological study of nanostructured gold thin films prepared by pulsed laser deposition in the presence of several inert background gases (Ar, He, and N2) and at various pressures (from 10 mTorr to 1 Torr) and target-to-substrate distances (from 1 to 10 cm) is presented. Structural and morphological analyses were undertaken using semiquantitative x-ray diffraction, scanning tunneling microscopy, and transmission electron microscopy. For each set of deposition conditions, the kinetic energy of the neutral gold species [Au(I)] present in the plasma plume was determined by time-of-flight emission spectroscopy and used to characterize the plasma dynamics. It is shown that all films exhibit a transition from highly [111] oriented to polycrystalline as the Au(I) kinetic energy decreases. The polycrystalline phase ratio is close to 0% for Au(I) kinetic energy larger than approximately 3.0 eV/atom and approximately 86 ± 10% for Au(I) kinetic energy smaller than approximately 0.30 eV/atom, irrespective of the background gas atmosphere. The mean crystallite size of both phases and the mean roughness of the films also follow a unique relation with the Au(I) kinetic energy, independently of the nature of the background gas, and nanocrystalline films with crystallite size as small as 12 nm are obtained for Au(I) kinetic energy smaller than 0.3 eV/atom.

Nix and Gao established an important relation between microindentation hardnessand indentation depth. Such a relation has been verified by many microindentation experiments (indentation depths in the micrometer range), but it does not always hold in nanoindentation experiments (indentation depths approaching the nanometer range). We have developed a unified computational model for both micro- and nanoindentation in an effort to understand the breakdown of the Nix–Gao relation at indentation depths approaching the nanometer scale. The unified computational model for indentation accounts for various indenter shapes, including a sharp, conical indenter, a spherical indenter, and a conical indenter with a spherical tip. It is based on the conventional theory of mechanism-based strain gradient plasticity established from the Taylor dislocation model to account for the effect of geometrically necessary dislocations. The unified computational model for indentation indeed shows that the Nix–Gao relation holds in microindentation with a sharp indenter, but it does not hold in nanoindentation due to the indenter tip radius effect.

Simple equations are proposed for determining elastic modulus and hardness properties of thin films on substrates from nanoindentation experiments. An empirical formulation relates the modulus E and hardness H of the film/substrate bilayer to corresponding material properties of the constituent materials via a power-law relation. Geometrical dependence of E and H is wholly contained in the power-law exponents, expressed here as sigmoidal functions of indenter penetration relative to film thickness. The formulation may be inverted to enable deconvolution of film properties from data on the film/substrate bilayers. Berkovich nanoindentation data for dense oxide and nitride films on silicon substrates are used to validate the equations and to demonstrate the film property deconvolution. Additional data for less dense nitride films are used to illustrate the extent to which film properties may depend on the method of fabrication.

Nanocrystalline ZnO particle–polymer hybrid was synthesized by controlled polymerization and hydrolysis of zinc acrylate (ZA). 13C nuclear magnetic resonance spectra revealed the polymerization of ZA during hydrolysis in the presence of hydrazine at 65 °C for 24 h. Nanocrystalline ZnO particles were dispersed in the organic matrix through the polymerization–hydrolysis reaction of ZA using hydrazine or methylhydrazine. ZnO particles increased in crystallinity with increasing amount of water for hydrolysis in the system using hydrazine. Methylhydrazine was found to yield ZnO with higher crystallinity than that obtained using hydrazine. The nanocrystalline particles were identified to be ZnO by electron diffraction. ZnO particle–polymer hybrid was workable by mild heating into transparent films between silica plates. The absorption edge of the transparent ZnO particle–polymer hybrid film was blue-shifted depending on the size of ZnO particles.

We used nanoindentation coupled with finite element modeling to determine the mechanical properties of amorphous Si layers formed by self-ion implantation of crystalline Si at approximately 100 K. When the effects of the harder substrate on the response of the layers to indentation were accounted for, the amorphous phase was found to have a Young’s modulus of 136 ± 9 GPa and a hardness of 10.9 ± 0.9 GPa, which were 19% and 10% lower than the corresponding values for crystalline Si. The hardness agrees well with the pressure known to induce a phase transition in amorphous Si to the denser β–Sn-type structure of Si. This transition controls the yielding of amorphous Si under compressive stress during indentation, just as it does in crystalline Si. After annealing 1 h at 500 °C to relax the amorphous structure, the corresponding values increase slightly to 146 ± 9 GPa and 11.6 ± 1.0 GPa. Because hardness and elastic modulus are only moderately reduced with respect to crystalline Si, amorphous Si may be a useful alternative material for components in Si-based microelectromechanical systems if other improved properties are needed, such as increased fracture toughness.

We synthesized ultrafine TiO2 nanoparticles by pulsed laser ablation of a titanium target immersed in an aqueous solution of surfactant sodium dodecyl sulfate (SDS) or deionized water. The surfactant concentration dependence of TiO2 nanocrystal formation was systematically investigated by various characterization techniques. The maximum amount of ultrafine anatase nanocrystalline particles (with mean size of 3 nm in diameter) was obtained in an aqueous solution of 0.01 M SDS. A probable formation process was proposed based on the laser-induced reactive quenching and surfactant-mediated growth. The phase transformation and particle growth of as-prepared products were also investigated by heat treatment up to 500 °C. Single-phase anatase nanoparticles with a mean size of 8 nm were obtained by heat treatment of samples prepared in water or in a 0.01 M SDS solution. Particle size did not substantially increase through annealing, probably due to the relatively homogeneous size distribution and crystallinity of as-prepared titania nanoparticles.

Lutetium nitride (LuN), an end member of a new quaternary system Si3N4–SiO2–Lu2O3–LuN, was synthesized by direct nitridation of a lutetium metal. The nitridation extent of the lutetium ingot (10 × 5 × 2 mm) reached about 97% by heating at 1600 °C for 8 h with an applied N2 pressure of 0.92 MPa; the initial shape of the bulk metal was maintained in the course of nitridation. The resulting nitrided lutetium possessed a moderately low oxygen content (∼0.7 wt%), which enables the preparation of uncharacterized high nitrogen-containing phases in the Lu–Si–O–N system.

A viscous-elastic-plastic indentation model was extended to a thin-film system, including the effect of stiffening due to a substrate of greater modulus. The system model includes a total of five material parameters: three for the film response (modulus, hardness, and time constant), one for the substrate response (modulus), and one representing the length-scale associated with the film-substrate interface. The substrate influence is incorporated into the elastic response of the film through a depth-weighted elastic modulus (based on a series sum of film and substrate contributions). Constant loading- and unloading-rate depth-sensing indentation tests were performed on polymer films on glass or metal substrates. Evidence of substrate influence was examined by normalization of the load-displacement traces. Comparisons were made between the model and experiments for indentation tests at different peak load levels and with varying degrees of substrate influence. A single set of five parameters was sufficient to characterize and predict the experimental load-displacement data over a large range of peak load levels and corresponding degrees of substrate influence.

Ni-Ti surface alloy was prepared by ion-implanting Ni into Ti. The surface film was amorphous having a Ni surface content of 10–40 at.%. The material was compared with a Ni-Ti bulk alloy (44.08:55.9) regarding their redox and electrocatalytic behavior in NaOH by cyclic voltammetry. The surface was characterized by x-ray photoelectron spectroscopy, x-ray and electron diffraction, transmission electron microscopy, and atomic force microscopy. The ion-implanted material revealed an enhanced activity toward the redox conversion of Ni(OH)2 ↔ NiOOH and the anodic oxidation of glucose. The effect is discussed considering the enhanced generation of active Ni surface sites from amorphous Ni and the stabilization of higher valence Ni by Ti.

An analytical model was developed in a previous work to relate the normalized indenter displacement to both the coating-to-substrate Young's modulus ratio and the coating-thickness-to-contact-radius ratio for Hertzian indentation on coating/substrate systems. However, application of this model is contingent upon the determination of the contact radius during indentation. Using the data from finite element analyses, an empirical equation is proposed in this paper to determine the normalized contact radius. Combining this empirical equation with the previous analytical equation, both the contact radius and the indenter displacement for Hertzian indentation on coating/substrate systems are predicted. The predictions obtained by this combined empirical–analytical method are shown to agree with the finite element results in general although the indenter displacement is over-estimated when the coating is stiffer than the substrate. Finally, the potential applications of this method to determine the elastic properties of coatings from the indentation data are envisaged.

A thin layer of SrTiO3 (STO) has successfully been used as a buffer layer to grow high-quality superconducting YBa2Cu3O7-δ(YBCO) thick films on polycrystalline metal substrates with a biaxially oriented MgO template produced by ion-beam-assisted deposition. Using this architecture, 1.5-μm-thick YBCO films with an in-plane mosaic spread in the range of 2.5° to 3.5° in full width at half-maximum and critical current density over 2 × 10 6A/cm2 in self-field at 75 K have routinely been achieved. It is interesting to note that the pulsed laser deposition growth conditions of SrTiO3 buffer layers, such as growth temperature and oxygen pressure, have strong effects on the superconducting properties of YBCO. Detailed studies using transmission electron microscopy, scanning electron microscopy, and atomic force microscopy were used to explore the microstructures of STO deposited at different conditions and to understand further their effects on the growth and properties of YBCO films.

The influence of mechanical activation on the characteristics and mechanism of ignition of self-propagating high-temperature synthesis processes of different silicides in the systems Me–Si (Me =Ti, Nb, Mo) was investigated. The results show that mechanical activation does not alter the mechanism involved but influences significantly the ignition characteristics. The influence, however, strongly depends on the stoichiometry of the mixtures. The composition Ti:Si = 1:2 shows the largest influence, with the ignition temperatures decreasing from 1400 °C for unmilled powders to about 600 °C for powders milled for several hours. The compositionsTi:Si = 5:3, Nb:Si = 1:2 show less pronounced decreases, while the compositionMo:Si = 1:2 shows no decrease. These differences are discussed in terms of the role of microstructure in the reaction mechanism and the different response of the systems to contamination, particularly from oxygen. The results suggest that for these systems self-ignition processes during milling cannot be explained only on the basis of the decrease in the ignition temperature.

The curvature of the loading curve, the initial slope of the unloading curve, and the ratio of the residual depth to maximum indentation depth are three main quantitiesthat can be established from an indentation load-displacement curve. A relationship among these three quantities was analytically derived. This relationship is valid for elasto-plastic material with power law strain hardening and indented by conical indenters of any geometry. The validity of this relationship is numerically verified through large strain, large deformation finite element analyses. The existence of an intrinsic relationship among the three quantities implies that only two independent quantities can be obtained from the load-displacement curve of a single conical indenter. The reverse analysis of a single load-displacement curve will yield non-unique combinations of elasto-plastic material properties due to the availability of only two independent quantities to solve for the three unknown material properties.

This paper describes the growth kinetics of an interfacial MgO layer as well as those of an MgB2 layer during ex situ annealing of the evaporated amorphous boron (a-B) film under Mg vapor overpressure. A thin MgO layer is formed at the interface between a-B and Al2O3 substrate before the formation of crystalline MgB2 layer and the interfacial layer is epitaxially related with Al2O3 substrate (MgO (111)[110] // Al2O3 (0001)[1100]). The interfacial MgO layer continues to grow during the annealing, and its apparent growth rate is about 0.1 nm/min. The analysis of MgB2 layer growth kinetics using cross-sectional transmission electron microscopy reveals that there exist two distinct growth fronts at both sides of an MgB2 layer. The growth kinetics of the lower MgB2 layer obeys the parabolic rate law during the entire annealing time. The growth of the upper MgB2 layer is controlled by the surface reaction between out-diffused boron and Mg vapor up to 10 min, resulting in a rough surface morphology of MgB2 layer. By considering the mass balance of Mg and boron during ex situ annealing, we obtained the diffusivities of Mg and boron in MgB2 layer which were in the same order range of approximately 10−12 cm2/s.

The kinetics for the crystallization of amorphous Ni(P) films and the formation of intermetallic compounds in Sn/Ni(P) films during isothermal aging treatment were studied with in situ intrinsic stress measurements. The intrinsic stress changes from crystallization were about 200 and 150 MPa for Ni(14P) and Ni(11.7P) films, respectively, and according to Johnson–Mehl–Avrami analysis, the Avrami exponents were about 3.6 ± 0.46 and 4.2 ± 0.39, and the activation energies were 242 and240 kJ/mol, respectively, for the crystallization of Ni(14P) and Ni(11.7P) films. The stress due to the formation of intermetallic compounds such as Ni3Sn4 and Ni3P in Sn/Ni(11.7P) films was about 320 MPa. Application of in situ stress measurementsto the empirical growth model during isothermal phase transformation of Sn/Ni(P) showed that the intermetallic compounds growth was interface reaction-controlled (n = 0.91 ± 0.08) in the early stage and then became diffusion-controlled (n =0.38 ± 0.01), and the activation energy was about 35.9 kJ/mol.

Calcium phosphate [single-phase hydroxyapatite (HA), single-phase tricalcium phosphate (TCP), and biphasic HA-TCP] nanowhiskers and/or powders were produced by using a novel microwave-assisted “combustion synthesis (auto ignition)/molten salt synthesis” hybrid route. This work is an example of our “synergistic processing” philosophy combining these three technologies while taking advantage of their useful aspects. Aqueous solutions containing NaNO3, Ca(NO3)2·4H2O and KH2PO4 (with or without urea) were irradiated in a household microwave oven for 5 min at 600 watts of power. The as-synthesized precursors were then simply stirred in water at room temperature for 1 h to obtain the nanowhiskers or powders of the desired calcium phosphate bioceramics.

Silicon is a principal material in submicrometer-scale devices. Components in such devices are subject to intense local stress concentrations from nanoscale contacts during function. Questions arise as to the fundamental nature and extent of any strength-degrading damage incurred at such contacts on otherwise pristine surfaces. Here, a simple bilayer test procedure is adapted to probe the strengths of selected areas of silicon surfaces after nanoindentation with a Berkovich diamond. Analogous tests on silicate glass surfaces are used as a control. The strengths increase with diminishing contact penetration in both materials, even below thresholds for visible cracking at the impression corners. However, the strength levels in the subthreshold region are much lower in the silicon, indicating exceptionally high brittleness and vulnerability to small-scale damage in this material. The results have important implications in the design of devices with silicon components.

Nanoindentation was performed to evaluate the matrix strength of the ultra-fine grained steel produced by accumulative roll-bonding and subsequently annealed. The nanohardness, associated with the matrix strength, decreases with increasing annealing temperature. Because the matrix strength corresponds to the first term σ0 of the Hall–Petch relation, this result suggests that the σ0 might not be constant for these steels between various grain sizes. Therefore, it is suggested that the change of the macroscopic strength during annealing is dominated by not only the grain coarsening leading to a reduction of grain refinement strengthening, but also the softening of the matrix strength.

We investigated the discrepancy between the significant 18O isotope motion observed after bipolar voltage cycling used to induce ferroelectric fatigue in unannealed Pt/Pb(Zr,Ti)O3/Ir (PZT) capacitors and the lack of any observable oxygen tracer motion in annealed capacitors. We found that while unannealed Pt electrodes are permeable to oxygen, annealed Pt electrodes are oxygen impermeable. Further, when the initial oxygen tracer profile does not vary strongly with depth, the ability to detect oxygen motion during fatigue voltage cycling depends critically on the oxygen permeability of the capacitor’s top electrode. Our results indicate that oxygen exchange between the PZT film and external oxygen sources and sinks during voltage cycling is not necessary for ferroelectric fatigue to be manifest. In addition, studies of the dependence of ferroelectric materials properties on ambient gases should be accompanied by analysis of the permeability of exposed surfaces to the gases of interest.