Effect of epitaxial strain on ferroelectric polarization in multiferroic BiFeO3 films

Multiferroic BiFeO3 epitaxial films with thickness ranging from 40 nm to 960 nm were grown by pulsed laser deposition on SrTiO3 (001) substrates with SrRuO3 bottom electrodes. X-ray characterization shows that the structure evolves from angularly-distorted tetragonal with c/a ~ 1.04 to more bulk-like distorted rhombohedral (c/a ~ 1.01) as the strain relaxes with increasing thickness. Despite this significant structural evolution, the ferroelectric polarization along the body diagonal of the distorted pseudo-cubic unit cells, as calculated from measurements along the normal direction, barely changes.Comment: Legend in Fig.3 corrected and et

Antiferromagnetic transitions in `T-like' BiFeO3

Recent studies have reported the existence of an epitaxially-stabilized tetragonal-like ('T-like') monoclinic phase in BiFeO3 thin-films with high levels of compressive strain. While their structural and ferroelectric properties are different than those of rhombohedral-like ('R-like') films with lower levels of strain, little information exists on magnetic properties. Here, we report a detailed neutron scattering study of a nearly phase-pure film of T-like BiFeO3. By tracking the temperature dependence and relative intensity of several superstructure peaks in the reciprocal lattice cell, we confirm antiferromagnetism with largely G-type character and TN = 324 K, significantly below a structural phase transition at 375 K, contrary to previous reports. Evidence for a second transition, possibly a minority magnetic phase with C-type character is also reported with TN = 260 K. The co-existence of the two magnetic phases in T-like BiFeO3 and the difference in ordering temperatures between R-like and T-like systems is explained through simple Fe-O-Fe bond distance considerations.Comment: 9 pages, 7 figures. Slight modifications to introductory text and presentation of data. Supplementary Material section adde

Development of boron calibration via hybrid comparator method in prompt gamma activation analysis

The prompt gamma activation analysis (PGAA) facility at the Nuclear Engineering Teaching Laboratory at The University of Texas at Austin was utilized to quantify boron concentrations in boron carbide semiconductor films deposited on silicon substrates. Calibration was complicated by the unique and varying sample geometries analyzed. In addition, there was a dearth of solid materials available with quantified boron concentrations having comparable or readily modifiable dimensions to exploit for calibration purposes. Therefore, a novel hybrid comparator method was developed for the quantification of boron utilizing aluminum as an inexpensive and easily machinable reference material. Aluminum samples were manufactured with high tolerances to match the geometry of each sample of interest. Each boron carbide film sample and its congruent aluminum sample were measured in the PGAA system. The measured aluminum responses and relevant nuclear parameters were used to standardize the measurements. A boron standard was created using a procedure derived from a similar approach used by the National Institute of Standards and Technology. Quality control measurements using this standard show that the method provided accuracy to within 5% for boron quantification

Temperature Driven Structural Phase Transition in Tetragonal-Like BiFeO3

Highly-strained BiFeO3 exhibits a "tetragonal-like, monoclinic" crystal structure found only in epitaxial films (with an out-of-plane lattice parameter exceeding the in-plane value by >20%). Previous work has shown that this phase is properly described as a M$_{C}$ monoclinic structure at room temperature [with a (010)$_{pc}$ symmetry plane, which contains the ferroelectric polarization]. Here we show detailed temperature-dependent x-ray diffraction data that evidence a structural phase transition at ~100C to a high-temperature M$_{A}$ phase ["tetragonal-like" but with a (1-10)$_{pc}$ symmetry plane]. These results indicate that the ferroelectric properties and domain structures of strained BiFeO$_3$ will be strongly temperature dependent.Comment: 10 pages, 3 figure

The pursuit of isotopic and molecular fire tracers in the polar atmosphere and cryosphere

We present an overview of recent multidisciplinary, multi-institutional efforts to identify and date major sources of combustion aerosol in the current and paleoatmospheres. The work was stimulated, in part, by an atmospheric particle \u27sample of opportunity\u27 collected at Summit, Greenland in August 1994, that bore the 14C imprint of biomass burning. During the summer field seasons of 1995 and 1996, we collected air filter, surface snow and snowpit samples to investigate chemical and isotopic evidence of combustion particles that had been transported from distant fires. Among the chemical tracers employed for source identification are organic acids, potassium and ammonium ions, and elemental and organic components of carbonaceous particles. Ion chromatography, performed by members of the Climate Change Research Center (University of New Hampshire), has been especially valuable in indicating periods at Summit that were likely to have been affected by the long range transport of biomass burning aerosol. Univariate and multivariate patterns of the ion concentrations in the snow and ice pinpointed surface and snowpit samples for the direct analysis of particulate (soot) carbon and carbon isotopes. The research at NIST is focusing on graphitic and polycyclic aromatic carbon, which serve as almost certain indicators of fire, and measurements of carbon isotopes, especially 14C, to distinguish fossil and biomass combustion sources. Complementing the chemical and isotopic record, are direct \u27visual\u27 (satellite imagery) records and less direct backtrajectory records, to indicate geographic source regions and transport paths. In this paper we illustrate the unique way in which the synthesis of the chemical, isotopic, satellite and trajectory data enhances our ability to develop the recent history of the formation and transport of soot deposited in the polar snow and ice

Phase transition close to room temperature in BiFeO3 thin films

BiFeO3 (BFO) multiferroic oxide has a complex phase diagram that can be mapped by appropriately substrate-induced strain in epitaxial films. By using Raman spectroscopy, we conclusively show that films of the so-called supertetragonal T-BFO phase, stabilized under compressive strain, displays a reversible temperature-induced phase transition at about 100\circ, thus close to room temperature.Comment: accepted in J. Phys.: Condens. Matter (Fast Track Communication

Si-compatible candidates for high-K dielectrics with the Pbnm perovskite structure

We analyze both experimentally (where possible) and theoretically from first-principles the dielectric tensor components and crystal structure of five classes of Pbnm perovskites. All of these materials are believed to be stable on silicon and are therefore promising candidates for high-K dielectrics. We also analyze the structure of these materials with various simple models, decompose the lattice contribution to the dielectric tensor into force constant matrix eigenmode contributions, explore a peculiar correlation between structural and dielectric anisotropies in these compounds and give phonon frequencies and infrared activities of those modes that are infrared-active. We find that CaZrO_3, SrZrO_3, LaHoO_3, and LaYO_3 are among the most promising candidates for high-K dielectrics among the compounds we considered.Comment: 17 pages, 9 figures, 4 tables. Supplementary information: http://link.aps.org/supplemental/10.1103/PhysRevB.82.064101 or http://www.physics.rutgers.edu/~sinisa/highk/supp.pd

Reactivity of Perovskites with Water: Role of Hydroxylation in Wetting and Implications for Oxygen Electrocatalysis

Oxides are instrumental to applications such as catalysis, sensing, and wetting, where the reactivity with water can greatly influence their functionalities. We find that the coverage of hydroxyls (*OH) measured at fixed relative humidity trends with the electron-donor (basic) character of wetted perovskite oxide surfaces. Using ambient pressure X-ray photoelectron spectroscopy, we report that the affinity toward hydroxylation, coincident with strong adsorption energies calculated for dissociated water and hydroxyl groups, leads to strong H bonding that is favorable for wetting while detrimental to catalysis of the oxygen reduction reaction (ORR). Our findings provide novel insights into the coupling between wetting and catalytic activity and suggest that catalyst hydrophobicity should be considered in aqueous oxygen electrocatalysis.National Science Foundation (U.S.). Materials Research Science and Engineering Centers (Program) (Award DMR-0819762)National Science Foundation (U.S.). Graduate Research Fellowship (Grant DGE-1122374)National Science Foundation (U.S.) (Career Award (0952564