Self-assembled monolayers (SAMs) bearing sulfonate (-SO3H) surface functional groups, on single-crystal Si wafers, were used as substrates for the deposition of TiO2 thin films from aqueous solutions. Polycrystalline TiO2 thin films over 50 nm thick formed in 2 h by hydrolysis of TiCl4 in aqueous HCI solutions at 80 °C. The films were pore-free, showed excellent adherence and uniformity, and consisted of anatase crystallites 2–4 nm in diameter. Annealing at temperatures up to 600 °C caused coarsening of the anatase grains, but no loss of adherence or structural integrity.

Diamond windows were heated at 700-900 °C in air for short times to better define the limits of application at high temperature. The infrared (IR) transmission of polished chemical vapor deposition (CVD) diamond windows was reduced after heating in a furnace at 800 °C for 75 s, while heating at 700 °C for 75 s produced little change. The 800 °C heating caused increased visible light scatter, and increased scatter appears to be mainly responsible for the reduced IR transmission. The forward scatter at 10.6 μm for the CVD diamond samples was 0.8% before heating, 2.8% after heating at 800 °C for 75 s, and 6.2% after heating at 800 °C for 255 s. Single crystal (110) type IIa diamond exhibited little change in IR transmission when heated at 800 °C in air for 255 s, while heating for 555 s at 800 °C caused a significant drop in IR transmittance (6-12%). A slight drop in IR transmittance (1-5%) occurred for a type IIa diamond when heated at 900 °C for 45 s. The etched surfaces were characterized by differential interference contrast optical microscopy, scanning electron microscopy, and Talystep surface profiles. Etched features are concentrated at grain boundaries (for the CVD samples) and at sites with residual damage from mechanical polishing that could not be seen before the heat treatment. Deep etch pits formed at grain boundaries that extend into the bulk of samples.

Pt/Ti/SiO2/Si structures have been studied to investigate the structural, chemical, and microstructural changes that occur during annealing. Grain growth of the as-deposited Pt columns was observed after annealing at 650 °C, and extensive changes in the Pt microstructure were apparent following a 750 °C anneal for 20 min. In addition, two types of defects were identified on the surfaces of annealed substrates. Defect formation was retarded when the surface was covered with a ferroelectric film. Concurrent with the annealing-induced Pt microstructure changes, Ti from the adhesion layer between the Pt and the SiO2 migrated into the Pt layer and oxidized. It was shown with spectroscopic ellipsometry and Auger electron spectroscopy that for long annealing times, the titanium oxide layer can reach the Pt surface. Consequently, at the processing temperatures utilized in preparing many ferroelectric thin films, the substrate is not completely inert or immobile. The changes associated with Ti migration could be especially problematic in techniques that require the substrate to be heated prior to film deposition.

Polycarbonate (LexanTM) (PC) was implanted with 2 MeV B+ and O+ ions separately to fluences of 5 × 1017, 1 × 1018, and 5 × 1018 ions/m2, and characterized for changes in surface hardness and tribological properties. Results of tests showed that hardness values of all implanted specimens increased over those of the unirradiated material, and the O+ implantation was more effective in improving hardness for a given fluence than the B+ implantation. Reciprocating sliding wear tests using a nylon ball counterface yielded significant improvements for all implanted specimens except for the 5 × 1017 ions/m2 B+-implanted PC. Wear tests conducted with a 52100 steel ball yielded significant improvements for the highest fluence of 5 × 1018 ions/m2 for both ions, but not for the two lower fluences. The improvements in properties were related to Linear Energy Transfer (LET) mechanisms, where it was shown that the O+ implantation caused greater ionization, thereby greater cross-linking at the surface corresponding to much better improvements in properties. The results were also compared with a previous study on PC using 200 keV B+ ions. The present study indicates that high energy ion irradiation produces thicker, more cross-linked, harder, and more wear-resistant surfaces on polymers and thereby improves properties to a greater extent and more efficiently than lower energy ion implantation.

High-quality Ta2O5 thin films for high-density memory devices were prepared at low temperatures by electron cyclotron resonance plasma-enhanced chemical vapor depostion (ECR-PECVD) without postannealing treatment. The effects of deposition temperature on the microstructure, composition, and electrical properties of the dielectric films were studied. The increase in deposition temperature from 145 °C to 205 °C improved the stoichiometry of the Ta2O5 thin films. As a consequence, EBD increased from 3.3 MV/cm to 4.4 MV/cm, and ∊Ta2O5, increased from 14 to 25. Interfacial SiO2 layer was observed by cross-sectional TEM, and its effects on the electrical properties of the overall dielectric film were also studied. The incubation period in which interfacial SiO2 grows was discussed with regard to reactivity between oxygen and Si substrate.

The microstructure and composition of TiN films, formed by ion beam enhanced deposition (IBED) with different energy (40 keV and 90 keV) xenon ion bombardment and by simple physical vapor deposition (hereafter S-PVD) without any ion beam enhancement, and the interfaces between TiN films and Si substrates have been studied by cross-sectional view analytical electron microscopy in this work. Both the IBED TiN films prepared by Xe+ bombardment with either 40 keV or 90 keV energy ions and the S-PVD TiN film consist of nanocrystals. The TEM observations in the S-PVD case reveal an amorphous layer and a mixed layer of TiN grains and amorphous material at the TiN/Si interface. The thicknesses of the amorphous layer and the mixed layer are about 210 nm and at least 40 nm, respectively. Upon 40 keV Xe+ bombardment, an amorphous Si transition layer of about 50 nm thickness is found at the TiN/Si interface, and the TiN grains close to the TiN/Si interface are of weak preferred orientation. Upon 90 keV Xe+ bombardment, amorphous TiN and Si layers are found with a total thickness of 80 nm at the TiN/Si interface, and the TiN grains near the TiN/Si interface are of preferred orientation [111]TiN ‖ [001]Si. The energy of xenon ion bombardment has a strong effect on the microstructural characteristics of TiN films and the interfaces between the TiN films and the Si substrates, as well as the size and the preferred orientation of TiN grains.

For crystal structures of oxides with tetrahedral coordination polyhedra, the average number of tetrahedra participating in the sharing of a corner, i.e., Zoltai's tetrahedral sharing coefficient, provides a measure of the degree of polymerization of the tetrahedra. By contouring oxide phase diagrams with Zoltai's tetrahedral sharing coefficient, crystal structure systematics can be conveniently displayed and correlated with other physical and thermochemical properties. The advantages of this analysis are (i) a structural map guides exploration for new compounds, (ii) possible structures for existing compounds that are not known are suggested, (iii) the internal consistency of the chemistry of specific compounds is tested by structural constraints, (iv) the physical behavior and properties of a family of compounds in a chemical system can be correlated with the degree of polymerization of the tetrahedra, and (v) the analysis lends itself to computer programming, in that contour templates of tetrahedral sharing coefficients for different types of oxide systems can be easily determined and overlaid on traditional phase diagrams. Shortcomings to this approach are that the tetrahedral sharing coefficient does not define a unique tetrahedral anion topology, ambiguities arise if some of the oxygen atoms are not part of the tetrahedral anion, and many chemical systems contain oxides where one or more of the tetrahedral cations adopt other coordination geometries.

Using the nonconventional sintering technique, such as microwave sintering, it is observed to enhance the densification rate of SrTiO3 materials as effectively as employing the highly active powders prepared by the chemical route. Although the chemically derived powders demonstrate better sinterability than the mixed oxide powders, the thermal analysis indicates that the segregation of Ti4+-containing clusters during decomposition of precursors in the direct pyrolysis (DP) process induces the occurrence of TiO2 particles (anatase phase) prior to the formation of SrTiO3 phase. These particles retard the necking process required to sinter the materials. The spray pyrolysis (SP) process can circumvent the preferential nucleation of TiO2 phase and, therefore, produce powders exhibiting superior sintering behavior to the DP-derived powders. The microwave sintering technique, on the other hand, substantially enhances the rate of diffusion of the ions in the materials such that even the mixed oxide powders can be sintered at a temperature about 200 °C lower than that needed to achieve the same density in a conventional sintering process. Fine grain (∼4 μm) microstructure is obtained for the materials microwave sintered at 1220 °C for 10 min. The migration of grain boundaries requires higher temperature to initiate than the formation of neckings between the grains. The grain growth occurs only when the material was sintered at temperatures higher than 1250 °C.

A scanning laser crack detection technique has been developed for use in corrosion fatigue testing of fine metallic wires. The technique has been integrated into a computerized data acquisition and control system allowing the unattended operation of extended fatigue tests. The system is capable of detecting cracks with surface lengths as small as 100 μm, with crack opening displacements as low as 1 μm. Detection schemes of light loss and light scattering have been successfully used to monitor crack initiation in air and in 0.9% sodium chloride solution. The present scanning laser system has been used for crack initiation detection in over 50 fatigue experiments and has the potential for use in crack growth monitoring. The method can provide information concerning other surface phenomena in addition to the study of cracks. The technique has potential applications beyond metallic wires, including fibers used in optics and ceramic reinforcement fibers used in structural composites.

We demonstrate the use of a synchrotron radiation source for in situ x-ray diffraction analysis during rapid thermal annealing (RTA) of 0.35 μm Salicide (self-aligned silicide) and 0.4 μm Polycide (silicided polysilicon) TiSi2 Complementary Metal Oxide Semiconductor (CMOS) gate structures. It is shown that the transformation from the C49 to C54 phase of TiSi2 occurs at higher temperatures in submicron gate structures than in unpatterned blanket films. In addition, the C54 that forms in submicron structures is (040) oriented, while the C54 that forms in unpatterned Salicide films is randomly oriented. Although the preferred oreintation of the initial C49 phase was different in the Salicide and Polycide gate structures, the final orientation of the C54 phase formed was the same. An incomplete conversion of C49 into C54-TiSi2 during the RTA of Polycide gate structures was observed and is attributed to the retarding effects of phosphorus on the transition.

The model proposed by Harris et al. [J. Mater. Res. 5, 1763–1773 (1990)], describing planar inversion domain boundaries in aluminum nitride, consists of a basal plane of aluminum atoms octahedrally coordinated with respect to oxygen, and with a translation of R = 1/3〈1011〉. This thin sandwich is inserted onto the basal plane of the wurtzite structure of aluminum nitride. This model does not take into consideration any interfacial relaxation phenomena, and is arguably electrically unstable. Therefore, this paper presents a refinement of the model of Harris et al., by incorporating the structural relaxations arising from modifications in local chemistry. The interfacial structure was investigated through the use of conventional transmission electron microscopy, convergent electron diffraction, high resolution transmission electron microscopy, analytical electron microscopy, and atomistic computer simulations. The refined planar inversion domain boundary model is closely based on the original model of Harris et al.; however, the local chemistry is changed, with every fourth oxygen being replaced by a nitrogen. Atomistic computer simulation of these defects, using a classical Born model of ionic solids, verified the stability of these defects as arising from the adjustment in the local chemistry. The resulting structural relaxations take the form of a 0.3 mrad twist parallel to the interface, a contraction of the basal planes adjacent to the planar inversion domain boundary, and an expansion of the c-axis component of the displacement vector; the new displacement vector across the interface is R = 1.3〈1010〉 + ∊〈0001〉, where ∊meas = 0.387 and ∊calc = 0.394.

Combustion synthesis of titanium borides from Ti and B binary powder mixtures having molar ratios B/Ti of 1.9 to 2.4 resulted in the formation of TiB2 as the primary phase and TiB as the secondary phase. The amount of TiB decreased when the particle size of the Ti in the powder mixtures became small and when the B content was increased. The results are discussed in terms of the homogeneity of reactant powder mixtures and the degree of boron saturation of the Ti-B melt. The burning rate increased from 11 to 15 mm/s as the titanium particle size decreased from −100 to −325 mesh with the same boron particle size of –325 mesh.

Extraordinary adhesion of a Nb-based/Au-Sn metallization structure on a SiO2/Si substrate has been observed by a tensile pull test. The metallization bond fails mostly via fracture through either the Si substrate or epoxy adhesive. The intrinsic adhesion pull strength of the metallization scheme is concluded to be greater than 10 kpsi, and the adhesion exceeds the Si-Si cohesive strength. The Nb-Si and Nb-O bonds at the interface are thermodynamically stable.

Film growth and microstructural evolution were investigated for sol-gel derived LiNbO3 thin films deposited on lattice-matched single-crystal substrates. Epitaxial LiNbO3 films of about 100 nm nominal thickness were prepared by spin coating a solution of the lithium niobium ethoxide on sapphire (0001) substrates and annealing at 400 °C or 700 °C in a humidified oxygen atmosphere. These films exhibited an epitaxial relationship with the substrate of the type LiNbO3 (0001) || α-Al2O3 (0001) and LiNbO3 [100] || α-Al2O3 [100] as determined by x-ray pole figure analysis. Transmission electron microscopy indicated the epitaxial films annealed at 400 °C consisted of slightly misoriented ∼5 nm subgrains and of numerous ∼10 nm enclosed pores. The microstructure and orientation development of these films was consistent with a heteroepitaxial nucleation and growth mechanism, in which epitaxial nuclei form at the substrate surface and grow upward into an amorphous and porous intermediate film: Epitaxial films annealed at 700 °C contained larger 150-200 nm subgrains and pinholes. Misorientations between adjacent subgrains appeared to be significantly smaller in films annealed at 700 °C than those in films annealed at 400 °C. Hydrolysis of the alkoxide precursor solution prior to spin coating promoted the development of polycrystalline films on single-crystal sapphire substrates. Infrared spectra and thermal analysis indicated that, independent of the degree of the solution hydrolysis, nucleation of LiNbO3 was immediately preceded by decomposition of an amorphous carbonate intermediate phase.

Internal damage in metal matrix composite (MMC) under static tensile loading was observed by in situ x-ray computed tomography based on synchrotron radiation (SR-CT). A tensile testing sample stage was developed to investigate the fracture process during the tensile test. Aluminum alloy matrix composites reinforced by long or short SiC fibers were used. The projection images obtained under tensile loading showed good performance of the sample stage, and matrix deformation and breaks of the long SiC fibers could be observed. In the CT images taken at the maximum stress just before failure, debondings of the short SiC fibers to the matrix, many pullouts of the fibers, and matrix cracking could be clearly observed. The in situ SR-CT allowed the observation of generation and growth of such defects under different tensile stress levels. The results from the nondestructive observation revealed that the MMC was broken by propagation of the matrix cracks which might be caused by stress concentration at the ends of the short fibers. A three-dimensional CT image reconstructed from many CT images provided easy understanding of the fiber arrangement, crack shape, and form of the void caused by fiber pullout. In situ SR-CT is a useful method for understanding failure mechanisms in advanced materials.

A node-bond percolation model is presented for the gas permeability and pore surface area of the coarse porosity in woven fiber structures during densification by chemical vapor infiltration (CVI). Model parameters include the number of nodes per unit volume and their spatial distribution, and the node and bond radii and their variability. These parameters relate directly to structural features of the weave. Some uncertainty exists in the proper partition of the porosity between “node” and “bond” and between intra-tow and inter-tow, although the total is constrained by the known fiber loading in the structure. Applied to cloth layup preforms the model gives good agreement with the limited number of available measurements.

The effect of grain size on the elimination of an isolated pore was investigated both by the Monte Carlo simulations and by a scaling analysis. The Monte Carlo statistical mechanics model for sintering was constructed by mapping microstructures onto domains of vectors of different orientations as grains and domains of vacancies as pores. The most distinctive feature of the simulations is that we allow the vacancies to move. By incorporating the outer surfaces of the sample in the simulations, sintering takes place via vacancy diffusion from the pores to the outer sample surfaces. The simulations were performed in two dimensions. The results showed that the model is capable of displaying various sintering phenomena such as evaporation and condensation, rounding of a sharp corner, pore coalescence, thermal etching, neck formation, grain growth, and growth of large pores. For the elimination of an isolated pore, the most salient result is that the scaling law of the pore elimination time tp with respect to the pore diameter dp changes as pore size changes from larger than the grains to smaller than the grains. For example, in sample-size-fixed simulations, tp ∼ d3p for dp < G and tp ∼ d2p for dp > G with the crossover pore diameter dc increasing linearly with G where G is the average grain diameter. For sample-size-scaled simulations, tp ∼ d4p for dp < G and tp ∼ d3p for dp > G. That tp has different scaling laws in different grain-size regimes is a result of grain boundaries serving as diffusion channels in a fine-grain microstructure such as those considered in the simulations. A scaling analysis is provided to explain the scaling relationships among tp, dp, and G obtained in the simulations. The scaling analysis also shows that these scaling relationships are independent of the dimensionality. Thus, the results of the two-dimensional simulations should also apply in three dimensions.

Effects of thermal annealing on the dielectric/piezoelectric properties of Pb(Zn,Mg)1/3Nb2/3O3-PbTiO3 ceramics (PZMN-PT with Zn/Mg = 6/4) were examined across the rhombohedral/tetragonal morphotropic phase boundary (MPB). Examination of the lattice parameters and the rhombohedral angle indicated that the MPB is in the vicinity of 24 mol% PbTiO3. Both the relative dielectric permittivity (∊r) and the piezoelectric constant (d33)/electromechanical coupling constant (kp) were increased by thermal annealing (800–900 °C) after sintering at 1150 °C for 1 h. The observed improvements in the dielectric and piezoelectric properties were attributed to the elimination of PbO-rich amorphous intergranular layers (about 1 nm thickness) induced by thermal annealing. Both the dielectric analysis using the series mixing model and the microscopic examination by transmission electron microscopy supported this conclusion.

Crystalline, uniform, adherent, ultrathin films of TiO2 were deposited onto OH-functionalized organic self-assembled monolayers (SAMs) on single-crystalline Si at low-temperature (<100 °C) from anhydrous ethanolic solutions of titanium isopropoxide. The films were identified as TiO2 by x-ray photoelectron spectroscopy, electron diffraction, and energy-dispersive x-ray microanalysis. Transmission electron microscopy showed the films to be uniform in thickness (2 ± 0.5 nm) and continuous. On bare Si, in contrast, there was no evidence of TiO2 deposition under identical conditions. Unlike the anatase films deposited on SAMs from aqueous solutions (described in the preceding paper), the electron diffraction patterns of the films deposited from alkoxide solutions suggest that they were the rutile phase. It is suggested that the functionalized SAMs enable the anchoring of the Ti alkoxide and initiate the formation of an adherent oxide film, and that they are sufficiently uniform that the resulting film is continuous and uniform in thickness.

Tin oxide (SnO2) thin films were deposited on sapphire (0001) substrate by metal-organic chemical vapor deposition (MOCVD) at temperatures of 600 and 700 °C. The microstructure of the deposited films was characterized by x-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM). At the growth conditions studied, films were single-phase rutile and epitaxial, but showed variant structures. Three distinct in-plane epitaxial relationships were observed between the films and the substrate. A crystallographic model is proposed to explain the film morphology. This model can successfully predict the ratio of the width to the length of an averaged grain size based upon the lattice mismatch of the film-substrate interface.