The hardnesses of electropolished, polycrystalline α-brass, and aluminum were measured as functions of load using Vickers microindentation, and Berkovich nanoindentation. Data were compared with literature data for silver, copper, and tungsten. In all cases, the hardness was observed to increase with decreasing size. Theories in the literature based on strain gradient plasticity and the addition of statistically stored and geometrically stored dislocation densities predict that the square of the hardness should increase linearly with inverse size of the indent. Our data and the literature data agree with this prediction over a limited range of indent diameters represented by microhardness and deep nanohardness data, whereas for the shallow nanohardness data, a second linear behavior is observed. The linear behavior of the microhardness and deep nanohardness data together with the second linear behavior generated by the shallow nanohardness data constituted what we designate a bilinear behavior. An algorithm is developed to calculate the induced shear stresses in a circular Volterra dislocation loop from a line integral of the Peach–Koehler equation using dislocation mechanics and isotropic elasticity. The computed induced shear stresses when plotted versus depth of indentation produced curves that exhibited a bilinear behavior identical to the bilinear behavior resulted from experiments, and the curves collapsed to a single curve for the different materials simulated.

Austenite–ferrite transformation at different isothermal temperatures in low carbon steel was investigated by a two-dimensional cellular automaton approach, which provides a simple solution for the difficult moving boundary problem that governs the ferrite grain growth. In this paper, a classical model for ferrite nucleation at austenite grain boundaries is adopted, and the kinetics of ferrite grain growth is numerically resolved by coupling carbon diffusion process in austenite and austenite–ferrite (γ–α) interface dynamics. The simulated morphology of ferrite grains shows that the γ–α interface is stable. In this cellular automaton model, the γ–α interface mobility and carbon diffusion rate at austenite grain boundaries are assumed to be higher than those in austenite grain interiors. This has influence on the morphology of ferrite grains. Finally, the modeled ferrite transformation kinetics at different isothermal temperatures is compared with the experiments in the literature and the grid size effects of simulated results are investigated by changing the cell length of cellular automaton model in a set of calculations.

Phase equilibria of the Ag–Sn–Cu ternary system have been determined experimentally as well as using the calculation of phase diagram (CALPHAD) method. Various Ag–Sn–Cu alloys were prepared to study the isothermal sections of the Ag–Sn–Cu ternary system at 240 and 450 °C. No ternary compounds were found and all the binary compounds had only limited ternary solubility. The ∈1–Cu3Sn phase is a very stable phase. It is in equilibrium with the Ag, ζ–Ag4Sn, ∈2–Ag3Sn, η–Cu6Sn5, and Cu phases at 240 °C, and is in equilibrium with the Ag, ζ, ∈2, L, and δ–Cu4Sn phases at 450 °C. Thermodynamic models of the Ag–Sn–Cu ternary system were developed based on available thermodynamic models of the constituent binary systems without introducing ternary interaction parameters. The isothermal sections at 240 and 450 °C were calculated, and the results were in good agreement with those determined experimentally. In addition to the isothermal sections, stability diagrams of Sn and Cu were calculated as well.

During the manufacturing and the service life of Au–Al wire bonded electronic packages, the ball bonds experience elevated temperatures and hence accelerated interdiffusion reactions that promote the transformation of the Au–Al phases and the growth of creep cavities. In the current study, these service conditions were simulated by thermally exposing Au–Al ball bonds at 175 and 250 °C for up to 1000 h. The Au–Al phase transformations and the growth of cavities were characterized by scanning electron microscopy. The volume changes associated with the transformation of the intermetallic phases were theoretically calculated, and the effect of the phase transformations on the growth of cavities was studied. The as-bonded microstructure of a Au–Al ball bond typically consisted of an alloyed zone and a line of discontinuous voids (void line) between the Au bump and the bonded Al metallization. Thermal exposure resulted in the nucleation, growth, and the transformation of the Au–Al phases and the growth of cavities along the void line. Theoretical analysis showed that the phase transformations across and lateral to the ball bond result in significant volumetric shrinkage. The volumetric shrinkage results in tensile stresses and promotes the growth of creep cavities at the void line. Cavity growth is higher at the crack front due to stress concentration, which was initially at the edge of the void line. The crack propagation occurs laterally by the coalescence of sufficiently grown cavities at the void line resulting in the failure of the Au–Al ball bonds.

Depth-sensing indentation at ultramicroscopic and macroscopic contacts (“nanoindentation” and “macroindentation,” respectively) was performed on four brittle materials (soda-lime glass, alumina titanium carbide, sapphire, and silicon) and the resulting load–displacement traces examined to provide insight to the elastic and plastic deformation scaling with contact size. The load–displacement traces are examined in terms of the unloading stiffness, the energies deposited during loading and recovered on unloading, and the effect of the indenter tip radius on the loading curve. The results of the analyses show that the elastic and plastic deformation during loading and unloading is invariant with the scale of the contact, and the unloading curve is best described by neither a conical tip nor a paraboloid of revolution, but of some compromise.

Poly (vinyl alcohol)–mediated synthesis of monodisperse, self-assembled, superparamagnetic maghemite particles was carried out through a magnetic field–induced biomimetic route. Modifying the kinetics of precipitation, the magnetic field promoted the nucleation of the maghemite phase over magnetite and also induced a self-assembly–assisted shape anisotropy during the precipitation of the particles in the polymer matrix.

When lead-free solder alloys mix with lead-free component and board metallizations during reflow soldering, the solder interconnections become multicomponent alloy systems whose microstructures cannot be predicted on the basis of the SnPb metallurgy. To better understand the influences of these microstructures on the reliability of lead-free electronics assemblies, SnAgCu-bumped components were reflow-soldered with near-eutectic SnAgCu solder pastes on Ni(P)|m.Au- and organic solderability preservative (OSP)-coated printed wiring boards and tested under cyclic thermal shock loading conditions. The reliability performance under thermomechanical loading was found to be controlled by the kinetics of recrystallization. Because ductile fracturing of the as-soldered tin-rich colonies would require a great amount of plastic work, the formation of continuous network of grain boundaries by recrystallization is needed for cracks to nucleate and propagate intergranularly through the solder interconnections. Detailed microstructural observations revealed that cracks nucleate and grow along the grain boundaries especially between the recrystallized part and the non-recrystallized part of the interconnections. The thermal cycling test data were analyzed statistically by combining the Weibull statistics and the analysis of variance. The interconnections on Ni(P)|m.Au were found out to be more reliable than those on Cu|m.OSP. This is due to the extensive dissolution of Cu conductor, in the case of the Cu|m.OSP assemblies, into molten solder that makes the microstructure to differ noticeably from that of the Ni(P)|m.Au interconnections. Because of large primary Cu6Sn5 particles, the Cu-enriched interconnections enhance the onset of recrystallization, and cracking of the interconnections is therefore faster. The solder paste composition had no statistically significant effect on the reliability performance.

Organic semiconductors on single-crystalline metal surfaces are model systems for injection contacts in organic field-effect transistors (OFET) and light-emitting diodes. They allow us to classify possible metal–organic interaction scenarios and to elucidate general tendencies, which most likely will also be found at metal–organic interfaces in real devices. In this contribution, we report a comprehensive investigation of the interface of perylene, a promising material for OFETs, with the close-packed noble metal surface Ag(111), using high-resolution electron energy loss spectroscopy, low-energy electron diffraction, and scanning tunneling microscopy as surface analytical techniques. The most important findings are: In the monolayer, molecules are oriented flat and form an incommensurate, most probably fluid overlayer. The molecules interact electronically with the substrate and become weakly metallic. Scanning tunneling microscopy reveals a propensity of perylene molecules toward a specific adsorption site on Ag(111), if the influence of intermolecular interactions is inhibited. Film growth at room temperature is similar to Stranski–Krastanov type. Finally, co-planar adsorption of perylene on Ag(111) is metastable, and annealing the monolayer at 420 K leads to a structural transformation of the film. The perylene–Ag(111) interface can therefore be classified as weakly interacting.

Low-temperature resistivity, Seebeck coefficient, thermal conductivity, and heat-capacity measurements were performed on Ba8Ga16Sn30. This compound crystallizes in a cubic type-VIII clathrate phase, space group I¯43m, with the Baatoms residing inside voids created by a tetrahedrally bonded network of Ga andSn atoms. Ba8Ga16Sn30 exhibits semiconducting behavior above 150 K with a low thermal conductivity and thus may hold potential for thermoelectric applications.

Transmittance loops upon thermal cycling of VO2 thin films were found to change among films with different fabrication conditions that lead to different transition temperatures (Tts) from that of a strain-free VO2 single crystal, 68 °C. The residual stresses in the films quantitatively determined from x-ray diffractometry were used to explain this variation. Electron spectroscopy for chemical analysis spectra showed that the difference in the binding energy of core electrons 2p1/2 and 2p3/2 of the vanadium atom are affected by residual stress and proportional to Tts of the films. The bond length between vanadium and oxygen atoms at room temperature varies with different residual stresses and, furthermore, affects the movements of both atoms during phase change (and hence the Tt of VO2 thin films). Residual stresses also affect the hysteresis span of the transmittance loop. The relationship between the residual stress of as-deposited VO2 films and the relative positions between vanadium and oxygen atoms are also delineated in detail.

Materials in nanocrystalline forms are well known to possess unusual and interesting properties when compared to the bulk conditions, and these open up an exciting range of novel applications. The key step involved in the systematic exploitation of nanocrystals for real applications lies in the development of reliable methods to synthesize nanocrystals of arbitrary chemical compositions in a range of crystal sizes. In particular, metallic alloy nanocrystals pose a special challenge. We demonstrate that nano-to-micro-sized crystals of intermetallic nickel–aluminide (Ni3Al) ranging from approximately 3 nm to over 100 nm in size can be synthesized by co-sputtering from elemental Ni and Al onto unheated, incompatible organic substrates, followed by controlled postdeposition heat treatment at mild temperatures. The crystal size of approximately 3 nm here is the smallest ever reported for monolithic ordered Ni3Al.

The effect of the density and in-plane distribution of interfacial interactions on crack initiation in an epoxy-silicon joint was studied in nominally pure shear loading. Well-defined combinations of strong (specific) and weak (nonspecific) interactions were created using self-assembling monolayers. The in-plane distribution of strong and weak interactions was varied by employing two deposition methods: depositing mixtures of molecules with different terminal groups resulting in a nominally random distribution, and depositing methyl-terminated molecules in domains defined lithographically with the remaining area interacting through strong acid-base interactions. The two distributions lead to very different fracture behavior. For the case of the methyl-terminated domains (50 μm on a side) fabricated lithographically, the joint shear strength varies almost linearly with the area fraction of strongly interacting sites. From this we infer that cracks nucleate on or near the interface over nearly the entire range of bonded area fraction and do so at nearly the same value of local stress (load/bonded area). We postulate that the imposed heterogeneity in interfacial interactions results in heterogeneous stress and strain fields within the epoxy in close proximity to the interface. Simply, the bonded areas carry load while the methyl terminated domains carry negligible load. Stress is amplified adjacent to the well-bonded regions (and reduced adjacent to the poorly bonded regions), and this leads to crack initiation by plastic deformation and chain scission within the epoxy near the interface. For the case of mixed monolayers, the dependence is entirely different. At low areal density of strongly interacting sites, the joint shear strength is below the detection limit of our transducer for a significant range of mixed monolayer composition. With increasing density of strongly interacting sites, a sharp increase in joint shear strength occurs at a methyl terminated area fraction of roughly 0.90. We postulate that this coincides with the onset of yielding in the epoxy. For methyl-terminated area fractions less than 0.85, the joint shear strength becomes independent of the interfacial interactions. This indicates that fracture no longer initiates on the interface but away from the interface by a competing mechanism, likely plastic deformation and chain scission within the bulk epoxy. The data demonstrate that the in-plane distribution of interaction sites alone can affect the location of crack nucleation and the far-field stress required.

We present a supercritical CO2 (SCCO2) process for the preparation of nanoporous organosilicate thin films for ultralow dielectric constant materials. The porous structure was generated by SCCO2 extraction of a sacrificial poly(propylene glycol) (PPG) from a nanohybrid film, where the nanoscopic domains of PPG porogen are entrapped within the crosslinked poly(methylsilsesquioxane) (PMSSQ) matrix. As a comparison, porous structures generated by both the usual thermal decomposition (at approximately 450 °C) and by a SCCO2 process for 25 and 55 wt% porogen loadings were evaluated. It is found that the SCCO2 process is effective in removing the porogen phase at relatively low temperatures (<200 °C) through diffusion of the supercritical fluid into the phase-separated nanohybrids and selective extraction of the porogen phase. Pore morphologies generated from the two methods are compared from representative three-dimensional (3D) images built from small-angle x-ray scattering (SAXS) data.

The microstructure of Ba(Cd1/3Ta2/3)O3 ceramics with boron additive was investigated by high-resolution and analytical electron microscopy. Superlattice reflections were present at positions of (h ± 1/3, k ± 1/3, l ± 1/3) away from the fundamental reflections in the [110] zone diffraction pattern for the pseudocubic perovskite unit cell. Lattice images showed a well-ordered structure with hexagonal symmetry. No boron segregation and amorphous phase was observed along grain boundaries. An amorphous phase rich in boron-oxide was observed to form pockets partially penetrating along multiple grain junctions.

The influence of tricalcium aluminate (3CaO·Al2O3) phase doping on in vitro biocompatibility and bioactivity of calcium aluminate (CaO·Al2O3) based bone cement has been investigated. It is demonstrated that the presence of approximately 25% tricalcium aluminate in the bone cement remarkably improves the bioactivity, yet still retains desirable mechanical strength and biocompatibility. An intermediary compound layer such as Ca3Al2(OH)12 was formed on the surface of the doped sample onto which hydroxyapatite (HAp) began to form soon, after only 2 days of immersion in a simulated body fluid solution. This is about seven-fold acceleration in the HAp formation over undoped calcium aluminate cement on which it took approximately15 days to nucleate the HAp phase. The depth of the HAp-containing layer after60 days of soaking was as much as 85 μm, about an order of magnitude more than the undoped calcium aluminate cement. The dramatically accelerated nucleation and growth of hydroxyapatite caused by the presence of tricalcium aluminate is attributed to the occurrence of intermediate layer materials such as Ca3Al2(OH)12, which most likely acts as the nuclei for HAp formation. This doped bone cement can be useful for injectable orthopedic applications, as the setting time for hardening has also been significantly reduced (by a factor of at least 4) to a practical regime of tens of minutes.

Nanoindentation experiments were carried out on a columnar ∼1.5-μm-thick TiN film on steel using a conical indenter with a 5-μm tip radius. Microstructural examination of the contact zone indicates that after initial elastic deformation, the deformation mechanism of the TiN is dominated by shear fracture at inter-columnar grain boundaries of the TiN film. A simple model is proposed whereby the applied load is partitioned between a deforming TiN annulus and a central expanding cavity in the steel substrate. It is possible to obtain a good fit to the experimental load–displacement curves with only one adjustable parameter, namely the inter-columnar shear fracture stress of the TiN film. The implication of results in the context of the performance of TiN films in service is also discussed.

We studied the polarity-induced changes in the nanoindentation response of GaAs{111}. The nanoindentations were made under a large range of loads (Fmax between 0.2 mN and 50 mN) at room temperature on {111} faces of A (Ga) or B (As) character. The loading–unloading curves were compared first, with special attention addressed to pop-in events and hardness values (reported previously for microindentation). Transmission electron microscopy was used to observe the nanoindentation structures generated at the two polar surfaces. The size of the dense plastic zone generated around the indent site was found to increase linearly with √Fmax and similarly for both polar surfaces. The indentation rosettes possess a threefold symmetry with arms developed along the <110> directions parallel to the surface. Sizes were found to be very close for both polar surfaces and the entire load range. For an A-polar face, the rosette arms are constituted by two arms: a long arm (LA, α dislocations) and a short arm (β dislocations). At the B surface, only the LA (β dislocations) are formed. Furthermore, microtwinning was observed only for an A-polar face, similar to previous observations of anisotropic microtwinning at GaAs(001) surfaces.

Perovskite-structured solid solutions intended for use as microwave dielectric resonators were studied by Raman spectroscopy. Two distinct categories were investigated: (i) simple perovskite–simple perovskite solid solutions, that is, CaTiO3–SrTiO3 (CTST), CaTiO3–CaZrO3 (CTCZ), CaTiO3–NdAlO3 (CTNA), and CaTiO3–LaGaO3 (CTLG); and (ii) simple perovskite–complex perovskite solid solutions, such as CaTiO3–SrMg1/3Nb2/3O3 (CTSMN). In the latter category, the influence of A-site ion radius was also addressed by examining 0.5CaTiO3– 0.5LaMg1/2Ti1/2O3 (0.5CT–0.5LMT), 0.5SrTiO3 (ST)–0.5LMT, and 0.5BaTiO3 (BT)–0.5LMT. Raman data from the end members and solid solutions are compared, paying particular attention to F2g and A1g mode bands, often associated with ordering of B-site species.

Sn–9Zn and Sn–8Zn–3Bi solder balls were bonded to Cu or electroless Au/Ni(P)pads, and the effect of aging on joint reliability, including impact reliability, was investigated. For the purpose of quantitatively evaluating the impact toughness ofthe solder joints, a test similar to the classic Charpy impact test was performed.The interfacial compounds formed in the solder/Cu joint during soldering wereCu–Zn intermetallic compounds (IMCs), not Cu–Sn IMCs. One of the Cu–Zn IMCs, γ–Cu5Zn8, thickened remarkably with aging, and eventually its morphology changed from layer-type into discontinuous. The rapid growth of the γ–Cu5Zn8 and void formation at the bond interface led to the significant degradation of the joint reliability due to a ductile-to-brittle transition of the joint. Meanwhile, the compound formed in the solder/Au/Ni(P) joint during soldering was a Au–Zn IMC, above which Zn redeposited during aging. Both the dissolution and diffusion of Ni into the solders were extremely slow, which contributes to negligible void formation at the bond interface. As a result, the solder bumps on the Au/Ni(P) pads were able to maintain the high joint strength and impact toughness even after prolonged aging.

Thin films of the perfluorinated phthalocyanines F16PcVO and F16PcCu were grown on insulator substrates by physical vapor deposition under high vacuum conditions to study their growth and electrical properties, analyzing them as possible candidates for n-type channel materials in organic field effect transistors. As insulator substrates, mica, amorphous SiO2, poly(styrene), poly(vinylchloride), poly(vinylcarbazole), poly(methylmetacrylate) and poly(vinylidenefluoride) were chosen, offering chemically different interactions with the molecules, degrees of order, and tribological characteristics. Optical absorption spectroscopy was used to analyze the alignment of the molecules relative to the substrates and the electronic coupling to adjacent molecules in the films. Electrical conduction measurements served to analyze the electronic coupling of the molecules parallel to the insulating substrates and to discuss the growth mode of films. Atomic force microscopy and scanning electron microscopy were chosen to study the morphology of the films. An inclined orientation at an average surface angle between 58° and 86° dependent on the different substrates was found for both F16Pc. In particular, on mica, thin conductive channels of the organic n-semiconductors could be formed at an average film thickness well below 10 nm at conductivities of up to 1.3 × 10-2 S cm-1. Conductive channels could also be formed on the different polymer substrates at, however, at least an order of magnitude smaller conductivity. Before these layers were formed on the polymers, semiconductor material diffused into the polymer substrates, dependent upon the substrate temperature during deposition relative to the glass transition temperature of the polymers. An influence of the viscous state of the polymer substrates was also seen on the intermolecular coupling detected in optical spectra. Based on these results, implications for the applicability of F16Pc as organic n-channels in organic field effect transistors are discussed.