Bismuth embrittlement of copper is an atomic size effect

Embrittlement by the segregation of impurity elements to grain boundaries is one of a small number of phenomena that can lead to metallurgical failure by fast fracture(1). Here we settle a question that has been debated for over a hundred years(2): how can minute traces of bismuth in copper cause this ductile metal to fail in a brittle manner? Three hypotheses for Bi embrittlement of Cu exist: two assign an electronic effect to either a strengthening(3) or weakening(4) of bonds, the third postulates a simple atomic size effect(5). Here we report first principles quantum mechanical calculations that allow us to reject the electronic hypotheses, while supporting a size effect. We show that upon segregation to the grain boundary, the large Bi atoms weaken the interatomic bonding by pushing apart the Cu atoms at the interface. The resolution of the mechanism underlying grain boundary weakening should be relevant for all cases of embrittlement by oversize impurities.

Thickness independence of true phase transition temperatures in barium strontium titanate films

The functional properties of two types of barium strontium titanate (BST) thin film capacitor structures were studied: one set of structures was made using pulsed-laser deposition (PLD) and the other using chemical solution deposition. While initial observations on PLD films looking at the behavior of T-m (the temperature at which the maximum dielectric constant was observed) and T-c(*) (from Curie-Weiss analysis) suggested that the paraelectric-ferroelectric phase transition was progressively depressed in temperature as BST film thickness was reduced, further work suggested that this was not the case. Rather, it appears that the temperatures at which phase transitions occur in the thin films are independent of film thickness. Further, the fact that in many cases three transitions are observable, suggests that the sequence of symmetry transitions that occur in the thin films are the same as in bulk single crystals. This new observation could have implications for the validity of the theoretically produced thin film phase diagrams derived by Pertsev [Phys. Rev. Lett. 80, 1988 (1998)] and extended by Ban and Alpay [J. Appl. Phys. 91, 9288 (2002)]. In addition, the fact that T-m measured for virgin films does not correlate well with the inherent phase transition behavior, suggests that the use of T-m alone to infer information about the thermodynamics of thin film capacitor behavior, may not be sufficient. (C) 2004 American Institute of Physics.

Perovskite lead zirconium titanate nanorings: Towards nanoscale ferroelectric

Rings of perovskite lead zirconium titanate (PZT) with internal diameters down to similar to 5 nm and ring thicknesses of similar to 5-10 nm have been fabricated and structurally, crystallographically, and chemically characterized using an analytical transmission electron microscope. Ring fabrication involved conformal solution deposition of a thin layer of PZT on the inside of a thin film of anodized aluminum oxide nanopores, and subsequent sectioning of the coated pores perpendicular to their cylinder axes. Although the starting solution used for the solution deposition was made from morphotropic phase boundary PZT, the nanorings were found to be on the zirconium-rich side of the PZT phase diagram. Nevertheless, coatings were found to be of perovskite crystallography. The dimensions of these nanorings are such that they have the potential to demonstrate polarization vortices, as modeled by Naumov [Nature (London) 432, 737 (2004)], and moreover represent the perfect morphology to allow vortex alignment and the creation of the ferroelectric "solenoid" as modeled by Gorbatsevich and Kopaev [Ferroelectrics 161, 321 (1994)].

Ordered arrays of lead zirconium titanate nanorings

Periodic arrays of nanorings of morphotropic phase boundary lead zirconium titanate ( PZT) have been successfully fabricated using a novel self-assembly technique: close-packed monolayers of latex nanospheres were deposited onto Pt-coated silicon substrates, and then plasma cleaned to form ordered arrays of isolated nanospheres, not in contact with each other. Subsequent pulsed laser deposition of PZT, high angle argon ion etching and thermal annealing created the arrays of isolated nanorings, with diameters of similar to 100 nm and wall thicknesses of similar to 10 nm. Energy dispersive x-ray analysis confirms that the rings are compositionally morphotropic phase boundary PZT, and high resolution transmission electron microscopy imaging of lattice fringes demonstrates some periodicities consistent with perovskite rather than pyrochlore material. The dimensions of these nanorings, and the expected 'soft' behaviour of the ferroelectric material from which they are made, means that they offer the most likely opportunity to date for observing whether or not vortex arrangements of electrical dipoles, analogous to those seen in ferromagnetic nanostructures, actually exist.

Studies of switching kinetics in ferroelectric thin films

Experimental studies are reported concerning the importance of interfacial capacitance (including electrode screening, space-charge layers, and/or chemically discrete dead layers). on domain switching behaviour in thin films of ferroelectric lead zirconate-titanate (PZT), strontium bismuth tantalate (SBT), and barium strontium titanate (BST). Emphasis is placed upon studies at applied field values very near the coercive field E, asymmetry in fatigue for positive and negative polarity coercive fields, and in the case of BST, of the coexistence of ferroelectric and paraelectric phases Studies of dielectric loss show important correlations between tan 6 and fatigue (polarization decrease) as a function of bipolar switching cycles N. This is a priori not obvious, since the former is a linear response and the latter, a nonlinear response. Modelling of enlarged interfacial,space-charge layers in PZT films and chemically distinct dead (paraelectric) layers in BST films shows contradictory tendencies of coercive-voltage changes with the growth of passive layers.

Electrode field penetration: A new interpretation of tunneling currents in barium strontium titanate (BST) thin films

This paper shows that penetration of the applied electric field into the electrodes of a ferroelectric thin film capacitor produces both an interfacial capacitance and an effective mechanism for electron tunneling. The model predictions are compared with experimental results on Au-BST-SrRuO3 capacitors of varying thicknesses, and the agreement is excellent.

Switching dynamics in ferroelectric thin films: An experimental survey

We have conducted a broad survey of switching behavior in thin films of a range of ferroelectric materials, including some materials that are not typically considered for FeRAM applications, and are hence less studied. The materials studied include: strontium bismuth tantalate (SBT), barium strontium titanate (BST), lead zicronate titanate (PZT), and potassium nitrate (KNO3). Switching in ferroelectric thin films is typically considered to occur by domain nucleation and growth. We discuss two models of frequency dependence of coercive field, the Ishisbashi-Orihara theory where the limiting step is domain growth and the model of Du and Chen where the limiting step is nucleation. While both models fit the data fairly well the temperature dependence of our results on PZT and BST suggest that the nucleation model of Du and Chen is more appropriate for the experimental results that we have obtained.

Low-temperature catalytic decomposition of N2O on platinum and bismuth-modified platinum: identification of active sites

Classification of the active surface sites of platinum catalysts responsible for low temperature N2O decomposition, in terms of steps, kinks and terraces, has been achieved by controlled addition of bismuth to as-received platinum/graphite catalysts.

Epitaxial Magnetic Oxide Nanocrystals Via Phase Decomposition of Bismuth Perovskite Precursors

The phase instability of bismuth perovskite (BiMO₃), where M is a ferromagnetic cation, is exploited to create self-assembled magnetic oxide nanocrystal arrays on oxide supports. Conditions during pulsed laser deposition are tuned so as to induce complete breakdown of the perovskite precursor into bismuth oxide (Bi₂ O₃ ) and metal oxide (M-O_x ) pockets. Subsequent cooling in vacuum volatizes the Bi₂ O₃ leaving behind an array of monodisperse nanocrystals. In situ reflective high energy electron diffraction beam is exploited to monitor the synthesis in real-time. Analysis of the patterns confi rms the phase separation and volatization process. Successful synthesis of M-O_x, where M = Mn, Fe, Co, and Cr, is shown using this template-free facile approach. Detailed magnetic characterization of nanocrystals is carried out to reveal the functionalities such as magnetic anisotropy as well as larger than bulk moments, as expected in these oxide nanostructures.