BiFeO3 is perhaps the only material that is both magnetic and a strong ferroelectric at room temperature. As a result, it has had an impact on the field of multiferroics that is comparable to that of yttrium barium copper oxide (YBCO) on superconductors, with hundreds of publications devoted to it in the past few years. In this Review, we try to summarize both the basic physics and unresolved aspects of BiFeO3 (which are still being discovered with several new phase transitions reported in the past few months) and device applications, which center on spintronics and memory devices that can be addressed both electrically and magnetically.

Physics and Applications of Bismuth Ferrite

Lanthanide ions possess fascinating optical properties and their discovery, first industrial uses and present high technological applications are largely governed by their interaction with light. Lighting devices (economical luminescent lamps, light emitting diodes), television and computer displays, optical fibres, optical amplifiers, lasers, as well as responsive luminescent stains for biomedical analysis, medical diagnosis, and cell imaging rely heavily on lanthanide ions. This critical review has been tailored for a broad audience of chemists, biochemists and materials scientists; the basics of lanthanide photophysics are highlighted together with the synthetic strategies used to insert these ions into mono- and polymetallic molecular edifices. Recent advances in NIR-emitting materials, including liquid crystals, and in the control of luminescent properties in polymetallic assemblies are also presented. (210 references.)

Taking advantage of luminescent lanthanide ions

The molecular origin of standard metabolic rate and thermogenesis in mammals is examined. It is pointed out that there are important differences and distinctions between the cellular reactions that 1) couple to oxygen consumption, 2) uncouple metabolism, 3) hydrolyze ATP, 4) control metabolic rate, 5) regulate metabolic rate, 6) produce heat, and 7) dissipate free energy. The quantitative contribution of different cellular reactions to these processes is assessed in mammals. We estimate that approximately 90% of mammalian oxygen consumption in the standard state is mitochondrial, of which approximately 20% is uncoupled by the mitochondrial proton leak and 80% is coupled to ATP synthesis. The consequences of the significant contribution of proton leak to standard metabolic rate for tissue P-to-O ratio, heat production, and free energy dissipation by oxidative phosphorylation and the estimated contribution of ATP-consuming processes to tissue oxygen consumption rate are discussed. Of the 80% of oxygen consumption coupled to ATP synthesis, approximately 25-30% is used by protein synthesis, 19-28% by the Na(+)-K(+)-ATPase, 4-8% by the Ca2(+)-ATPase, 2-8% by the actinomyosin ATPase, 7-10% by gluconeogenesis, and 3% by ureagenesis, with mRNA synthesis and substrate cycling also making significant contributions. The main cellular reactions that uncouple standard energy metabolism are the Na+, K+, H+, and Ca2+ channels and leaks of cell membranes and protein breakdown. Cellular metabolic rate is controlled by a number of processes including metabolic demand and substrate supply. The differences in standard metabolic rate between animals of different body mass and phylogeny appear to be due to proportionate changes in the whole of energy metabolism. Heat is produced by some reactions and taken up by others but is mainly produced by the reactions of mitochondrial respiration, oxidative phosphorylation, and proton leak on the inner mitochondrial membrane. Free energy is dissipated by all cellular reactions, but the major contributions are by the ATP-utilizing reactions and the uncoupling reactions. The functions and evolutionary significance of standard metabolic rate are discussed.

Cellular energy utilization and molecular origin of standard metabolic rate in mammals

Ionic liquid crystals.

Domains in ferroelectrics were considered to be well understood by the middle of the last century: They were generally rectilinear, and their walls were Ising-like. Their simplicity stood in stark contrast to the more complex Bloch walls or N\'eel walls in magnets. Only within the past decade and with the introduction of atomic-resolution studies via transmission electron microscopy, electron holography, and atomic force microscopy with polarization sensitivity has their real complexity been revealed. Additional phenomena appear in recent studies, especially of magnetoelectric materials, where functional properties inside domain walls are being directly measured. In this paper these studies are reviewed, focusing attention on ferroelectrics and multiferroics but making comparisons where possible with magnetic domains and domain walls. An important part of this review will concern device applications, with the spotlight on a new paradigm of ferroic devices where the domain walls, rather than the domains, are the active element. Here magnetic wall microelectronics is already in full swing, owing largely to the work of Cowburn and of Parkin and their colleagues. These devices exploit the high domain wall mobilities in magnets and their resulting high velocities, which can be supersonic, as shown by Kreines' and co-workers 30 years ago. By comparison, nanoelectronic devices employing ferroelectric domain walls often have slower domain wall speeds, but may exploit their smaller size as well as their different functional properties. These include domain wall conductivity (metallic or even superconducting in bulk insulating or semiconducting oxides) and the fact that domain walls can be ferromagnetic while the surrounding domains are not.

/pdf/domain-wall-nanoelectronics-3iwxoy7x89.pdf

Domain wall nanoelectronics

We report on extensive experimental studies on thin film, single crystal, and ceramics of multiferroic bismuth ferrite BiFeO3 using differential thermal analysis, high-temperature polarized light microscopy, high-temperature and polarized Raman spectroscopy, high-temperature x-ray diffraction, dc conductivity, optical absorption and reflectivity, and domain imaging, and show that epitaxial (001) thin films of BiFeO3 are clearly monoclinic at room temperature, in agreement with recent synchrotron studies but in disagreement with all other earlier reported results. We report an orthorhombic order-disorder beta phase between 820 and 925 (±5) °C, and establish the existence range of the cubic gamma phase between 925 (±5) and 933 (±5) °C, contrary to all recent reports. We also report the refined Bi2O3-Fe2O3 phase diagram. The phase transition sequence rhombohedral-orthorhombic-cubic in bulk [monoclinic-orthorhombic-cubic in (001)BiFeO3 thin film] differs distinctly from that of BaTiO3. The transition to the cubic gamma phase causes an abrupt collapse of the band gap toward zero (insulator-metal transition) at the orthorhombic-cubic beta-gamma transition around 930 °C. Our band structure models, high-temperature dc resistivity, and light absorption and reflectivity measurements are consistent with this metal-insulator transition.

/pdf/b-phase-and-g-b-metal-insulator-transition-in-multiferroic-22dclxpseq.pdf

β phase and γ-β metal-insulator transition in multiferroic BiFeO3

We report on extensive experimental studies on thin film, single crystal, and ceramics of multiferroic bismuth ferrite $\mathrm{Bi}\mathrm{Fe}{\mathrm{O}}_{3}$ using differential thermal analysis, high-temperature polarized light microscopy, high-temperature and polarized Raman spectroscopy, high-temperature x-ray diffraction, dc conductivity, optical absorption and reflectivity, and domain imaging, and show that epitaxial (001) thin films of $\mathrm{Bi}\mathrm{Fe}{\mathrm{O}}_{3}$ are clearly monoclinic at room temperature, in agreement with recent synchrotron studies but in disagreement with all other earlier reported results. We report an orthorhombic order-disorder $\ensuremath{\beta}$ phase between 820 and 925 $(\ifmmode\pm\else\textpm\fi{}5)\phantom{\rule{0.2em}{0ex}}\ifmmode^\circ\else\textdegree\fi{}\mathrm{C}$, and establish the existence range of the cubic $\ensuremath{\gamma}$ phase between 925 $(\ifmmode\pm\else\textpm\fi{}5)$ and 933 $(\ifmmode\pm\else\textpm\fi{}5)\phantom{\rule{0.2em}{0ex}}\ifmmode^\circ\else\textdegree\fi{}\mathrm{C}$, contrary to all recent reports. We also report the refined ${\mathrm{Bi}}_{2}{\mathrm{O}}_{3}\text{\ensuremath{-}}{\mathrm{Fe}}_{2}{\mathrm{O}}_{3}$ phase diagram. The phase transition sequence rhombohedral-orthorhombic-cubic in bulk [monoclinic-orthorhombic-cubic in $(001)\mathrm{Bi}\mathrm{Fe}{\mathrm{O}}_{3}$ thin film] differs distinctly from that of $\mathrm{Ba}\mathrm{Ti}{\mathrm{O}}_{3}$. The transition to the cubic $\ensuremath{\gamma}$ phase causes an abrupt collapse of the band gap toward zero (insulator-metal transition) at the orthorhombic-cubic $\ensuremath{\beta}\text{\ensuremath{-}}\ensuremath{\gamma}$ transition around $930\phantom{\rule{0.2em}{0ex}}\ifmmode^\circ\else\textdegree\fi{}\mathrm{C}$. Our band structure models, high-temperature dc resistivity, and light absorption and reflectivity measurements are consistent with this metal-insulator transition.

/pdf/bphase-andg-bmetal-insulator-transition-in-1725oz7b8r.pdf

βphase andγ−βmetal-insulator transition in multiferroicBiFeO3

Thermodynamic considerations in constructing energy balances for cellular growth

Pseudo-binary phase diagram and crystal growth of [PMN]

A new synthetic strategy has been developed to introduce bent and rigid tridentate 2,6-bis(benzimidazol-2‘-yl)pyridine cores into rodlike ligands L11-17. The crystal structure of the nonmesogenic ligand L13 (C39H37N5O4, triclinic, P, Z = 2) shows the expected trans−trans conformation of the tridentate binding unit, which provides a linear arrangement of the semirigid aromatic sidearms. The crystal structure of the related mesogenic ligand L16 (C61H81N5O4, triclinic, P, Z = 2) demonstrates the fully extended conformation adopted by the lipophilic side chains, leading to a slightly helically twisted I-shaped molecule. A rich and varied mesomorphism results which can be combined with the simultaneous tuning of electronic and photophysical properties via a judicious choice of the spacers between the rigid central core and the semirigid lipophilic sidearms. Ligands L13,14 react with Ln(NO3)3·xH2O to give quantitatively and selectively the neutral 1:1 complexes [Ln(Li)(NO3)3] (Ln = La to Lu), which are stable in the solid state at room temperature but partially dissociate in acetonitrile to give the cationic species [Ln(Li)(NO3)2]+. The crystal structure of [Lu(L13)(NO3)3]·3CH3CN (30, LuC45H46N11O13, monoclinic, C2/c, Z = 8) reveals a U-shaped arrangement of the ligand strand arising from the cis−cis conformation of the coordinated tridentate binding unit. This drastic geometric change strongly affects the thermal behavior and the photophysical and electronic properties of the lipophilic complexes [Ln(L14)(NO3)3]. Particular attention has been focused on structure−properties relationships, which can be modulated by the size of the lanthanide metal ions.

/pdf/bent-tridentate-receptors-in-calamitic-mesophases-with-3y8nde8vkg.pdf

Paul Tissot

Papers

β phase and γ-β metal-insulator transition in multiferroic BiFeO3

βphase andγ−βmetal-insulator transition in multiferroicBiFeO3

Thermodynamic considerations in constructing energy balances for cellular growth

Pseudo-binary phase diagram and crystal growth of [PMN]

Bent Tridentate Receptors in Calamitic Mesophases with Predetermined Photophysical Properties: New Luminescent Lanthanide-Containing Materials