The Fourteenth International Meeting on Ferroelectricity
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Ceramic Mineral Waste-Forms for Nuclear Waste Immobilization
materials Review Ceramic Mineral Waste-Forms for Nuclear Waste Immobilization Albina I. Orlova 1 and Michael I. Ojovan 2,3,* 1 Lobachevsky State University of Nizhny Novgorod, 23 Gagarina av., 603950 Nizhny Novgorod, Russian Federation 2 Department of Radiochemistry, Lomonosov Moscow State University, Moscow 119991, Russia 3 Imperial College London, South Kensington Campus, Exhibition Road, London SW7 2AZ, UK * Correspondence: [email protected] Received: 31 May 2019; Accepted: 12 August 2019; Published: 19 August 2019 Abstract: Crystalline ceramics are intensively investigated as effective materials in various nuclear energy applications, such as inert matrix and accident tolerant fuels and nuclear waste immobilization. This paper presents an analysis of the current status of work in this field of material sciences. We have considered inorganic materials characterized by different structures, including simple oxides with fluorite structure, complex oxides (pyrochlore, murataite, zirconolite, perovskite, hollandite, garnet, crichtonite, freudenbergite, and P-pollucite), simple silicates (zircon/thorite/coffinite, titanite (sphen), britholite), framework silicates (zeolite, pollucite, nepheline /leucite, sodalite, cancrinite, micas structures), phosphates (monazite, xenotime, apatite, kosnarite (NZP), langbeinite, thorium phosphate diphosphate, struvite, meta-ankoleite), and aluminates with a magnetoplumbite structure. These materials can contain in their composition various cations in different combinations and ratios: Li–Cs, Tl, Ag, Be–Ba, Pb, Mn, Co, Ni, Cu, Cd, B, Al, Fe, Ga, Sc, Cr, V, Sb, Nb, Ta, La, Ce, rare-earth elements (REEs), Si, Ti, Zr, Hf, Sn, Bi, Nb, Th, U, Np, Pu, Am and Cm. They can be prepared in the form of powders, including nano-powders, as well as in form of monolith (bulk) ceramics. -
Surface Plasmons and Gain Media
Chapter 5 Surface plasmons and gain media by M.A. Noginov, G. Zhu Center for Materials Research, Norfolk State University, Norfolk, VA, 23504 V.P. Drachev, V.M. Shalaev School of Electrical & Computer Engineering and Birck Nanotechnology Center, Purdue University, West Lafayette, IN 47907 Nanophotonics with Surface Plasmons V.M. Shalaev & S. Kawata (Editors) Advances in Nano-Optics and Nano-Photonics r 2007 Published by Elsevier B.V. ISSN: 1871-0018 DOI: 10.1016/S1871-0018(06)02005-X 141 Contents Page y 1. Introduction . ...................................143 y 2. Estimation of the critical gain ........................148 y 3. Experimental samples and setups . ....................149 y 4. Experimental results and discussion....................149 y 5. Summary . ...................................164 Acknowledgments ................................... 165 References . ....................................... 165 142 § 1. Introduction The technique of coloring stain glasses by gold and silver nanoparticles was known to Romans. The British Museum has a famous Lycurgus Cup (4th Century A.D.), which changes its color depending on the illumination (fig. 1). When viewed in reflected light, for example, in daylight, it appears green. However, when a light is shone into the cup and transmitted through the glass, it appears red. Nowadays it is known that the colora- tion of the Cup is determined by the frequency of localized surface plasmon (SP) resonance in metallic nanoparticles embedded into the glass. Localized SP is the oscillation of free electrons in a metallic particle (driven by an external electromagnetic wave), whose resonance frequency is the plasma frequency adjusted by the size and, mainly, the shape of the particle. A phenomenon relevant to localized SPs is a surface plasmon polariton (SPP) or a surface electromagnetic wave propagating along the interface between two media possessing permittivities with opposite signs, such as metal–dielectric interface. -
Electronic Ferroelectricity in Carbon Based Materials
Electronic ferroelectricity in carbon based materials Natasha Kirova1,3* and Serguei Brazovskii2,3 1LPS, CNRS, Univ Paris-Sud, Université Paris-Saclay, 91405 Orsay Cedex, France 2LPTMS, CNRS, Univ Paris-Sud, Université Paris-Saclay, 91405 Orsay Cedex, France 3Moscow Institute for Steel and Alloys, Leninskii av. 4, 119049 Moscow, Russia. We review existing manifestations and prospects for ferroelectricity in electronically and optically active carbon-based materials. The focus point is the proposal for the electronic ferroelectricity in conjugated polymers from the family of substituted polyacetylenes. The attractive feature of synthetic organic ferroelectrics is a very high polarizability coming from redistribution of the electronic density, rather than from conventional displacements of ions. Next fortunate peculiarity is the symmetry determined predictable design of perspective materials. The macroscopic electric polarization follows ultimately from combination of two types of a microscopic symmetry breaking which are ubiquitous to qusi-1D electronic systems. The state supports anomalous quasi-particles - microscopic solitons, carrying non-integer electric charges, which here play the role of nano-scale nucleus of ferroelectric domain walls. Their spectroscopic features in optics can interfere with low-frequency ferroelectric repolarization providing new accesses and applications. In addition to already existing electronic ferroelectricity in organic crystals and donor-acceptor chains, we point to a class of conducting polymers and may be also to nano-ribbons of the graphene where such a state can be found. These proposals may lead to potential applications in modern intensive searches of carbon ferroelectrics. Keywords: ferroelectricity, organic conductor, conjugated polymers, polyacetylene, graphene, soliton, non- integer charge, domain wall 1. Introduction Ferroelectricity is a phenomenon of spontaneous controllable electric polarizations in some, usually crystalline, solids [1]. -
Zirconolite, Chevkinite and Other Rare Earth Minerals from Nepheline Syenites and Peralkaline Granites and Syenites of the Chilwa Alkaline Province, Malawi
Zirconolite, chevkinite and other rare earth minerals from nepheline syenites and peralkaline granites and syenites of the Chilwa Alkaline Province, Malawi R. G. PLATT Dept. of Geology, Lakehead University, Thunder Bay, Ontario, Canada F. WALL, C. T. WILLIAMS AND A. R. WOOLLEY Dept. of Mineralogy, British Museum (Natural History), Cromwell Road, London SW7 5BD, U.K. Abstract Five rare earth-bearing minerals found in rocks of the Chilwa Alkaline Province, Malawi, are described. Zirconolite, occurring in nepheline syenite, is unusual in being optically zoned, and microprobe analyses indicate a correlation of this zoning with variations in Si, Ca, Sr, Th, U, Fe, Nb and probably water; it is argued that this zoning is a hydration effect. A second compositional zoning pattern, neither detectable optically nor affected by the hydration, is indicated by variations in Th, Ce and Y such that, although total REE abundances are similar throughout, there appears to have been REE fractionation during zirconolite growth from relatively heavy-REE and Th-enrichment in crystal cores to light-REE enrichment in crystal rims. Chevkinite is an abundant mineral in the large granite quartz syenite complexes of Zomba and Mulanje, and analyses are given of chevkinites from these localities. There is little variation in composition within each complex, and only slight differences between them; they are all typically light-REE-enriched. The Mulanje material was shown by X-ray diffraction to be chevkinite and not the dimorph perrierite, but chemical arguments are used in considering the Zomba material to be the same species. Other rare earth minerals identified are monazite, fluocerite and bastn/isite. -
Electrical Properties of Cati03
The University of New South Wales Faculty of Science and Technology School of Materials Science and Engineering Electrical Properties of CaTi03 A Thesis in Ceramic Engineering by Mei-Fang Zhou Submitted in Partial Fulfilment of the Requirements for the Degree of Doctor of Philosophy March 2004 U N b W 2 7 JAN 2005 LIBRARY CERTIFICATE OF ORIGINALITY I hereby declare that this submission is my own work and to the best of my knowledge it contains no materials previously published or written by another person, nor material which to a substantial extent has been accepted for the award of any other degree or diploma at UNSW or any other educational institution, except where due acknowledgement is made in the thesis. Any contribution made to the research by others, with whom I have worked at UNSW or elsewhere, is explicitly acknowledged in the thesis. I also declare that the intellectual content of this thesis is the product of my own work, except to the extent that assistance from others in the project’s design and conception or in style, presentation and linguistic expression is acknowledged. (Signed) ACKNOWLEDGMENTS The author would like to express her thanks to the following people for their contributions to the completion of this work: Prof. J. Nowotny, my supervisor, for sparking my interest in this thesis project and for providing valuable advice on various aspects of the project. I am grateful for his constant encouragement and great assistance with the research plan, thesis corrections and valuable discussion. In particular, he contributed exceptional expertise in the defect chemistry of amphoteric semiconducting oxides. -
Ferroelectricity and Piezoelectricity Batio3
Ferroelectricity and Piezoelectricity BaTiO3 cubic (contains i = > no spontaneous P) Can be used to make nonvolatile memory BaTiO3 r 1 Can be used to make ultracapacitors Paraelectric state Above Tc, BaTiO3 is paraelectric. The susceptibility (and dielectric constant) diverge like a Curie-Weiss law. 1 1 0 TT c This causes a big peak in the dielectric constant at Tc. Ferroelectric Paraelectric PbTiO3 Dielectric constant 1 TT c Pyroelectric constant Polarization Specific heat Antiferroelectricity PbZrO3 Polarization aligns antiparallel. Associated with a structural phase transition. Large susceptibility and dielectric constant near the transition. Phase transition is observed in the specific heat, x-ray diffraction. Applied field T > Tc T < Tc T < Tc Piezoelectricity Many piezoelectric materials are ferroelectric. Electric field couples to polarization, polarization couples to structure. lead zirconate titanate (Pb[ZrxTi1−x]O3 0<x<1) —more commonly known as PZT barium titanate (BaTiO3) Tc = 408 K lead titanate (PbTiO3) Tc = 765 K potassium niobate (KNbO3) Tc = 708 K lithium niobate (LiNbO3) Tc = 1480 K lithium tantalate (LiTaO3) Tc = 938 K quartz (SiO2), GaAs, GaN Gallium Orthophosphate (GaPO4) Tc = 970 K Third rank tensor, No inversion symmetry Piezoelectric crystal classes: 1, 2, m, 222, mm2, 4, -4, 422, 4mm, -42m, 3, 32, 3m, 6, -6, 622, 6mm, -62m, 23, -43m Piezoelectricity When you apply a voltage across certain crystals, they get longer. AFM's, STM's Quartz crystal oscillators Surface acoustic wave generators Pressure sensors - Epcos Fuel injectors - Bosch Inkjet printers PZT (Pb[ZrxTi1−x]O3 0<x<1) Antiferroelectric Large piezoelectric response near the rhombohedral-tetragonal transition. Electric field induces a structural phase transition. -
4Utpo3so UM-P-88/125
4utpo3So UM-P-88/125 The Incorporation of Transuranic Elements in Titanatc Nuclear Waste Ceramics by Hj. Matzke1, B.W. Seatonberry2, I.L.F. Ray1, H. Thiele1, H. Trisoglio1, C.T. Walker1, and T.J. White3'4'5 1 Commission of the European Communities, Joint Research Centre, i Karlsruhe Establishment, ' \ 'I European Institute for Transuranium Elements, Postfach 2340, D-7500 Karlsruhe, Federal Republic of Germany. 2 Advanced Materials Program, Australian Nuclear Science and Technology Organization, Private Mail Bag No. 1, Menai, N.S.W., 2234, Australia. 3 National Advanced Materials Analytical Centre, School of Physics, The University of Melbourne, Parkville, Vic, 3052, Australia. Supported by the Australian Natio-al Energy Research, Development and Demonstration Programme. 4 Member, The American Ceramic Society 5 Author to whom correspondence whould oe addressed 2 The incorporation of actinide elements and their rare earth element analogues in titanatc nuclear waste forms are reviewed. New partitioning data are presented for three waste forms contining Purex waste simulant in combination with either NpC^, PuC>2 or An^Oo. The greater proportion of transuranics partition between perovskitc and ztrconoiite, while some americium may enter loveringite. Autoradiography revealed clusters of plutonium atoms which have been interpreted as unrcacted dioxide or scsquioxide. It is concluded that the solid state behavior of transaranic elements in titanate waste forms is poorly understood; certainly inadequate to tailor a ceramic for the incorporation of fast breeder reactor wastes. A number of experiments are proposed that will provide an adequate, data base for the formulation and fabrication of transuranic-bearing jj [i waste forms. ' ' 1 ~> I. -
Coupled Electricity and Magnetism: Multiferroics and Beyond
Coupled electricity and magnetism: multiferroics and beyond Daniel Khomskii Cologne University, Germany JMMM 306, 1 (2006) Physics (Trends) 2, 20 (2009) Degrees of freedom charge Charge ordering Ferroelectricity Qαβ ρ(r) (monopole) P or D (dipole) (quadrupole) Spin Orbital ordering Magnetic ordering Lattice Maxwell's equations Magnetoelectric effect In Cr2O3 inversion is broken --- it is linear magnetoelectric In Fe2O3 – inversion is not broken, it is not ME (but it has weak ferromagnetism) Magnetoelectric coefficient αij can have both symmetric and antisymmetric parts Pi = αij Hi ; Symmetric: Then along main axes P║H , M║E For antisymmetric tensor αij one can introduce a dual vector T is the toroidal moment (both P and T-odd). Then P ┴ H, M ┴ E, P = [T x H], M = - [T x E] For localized spins For example, toroidal moment exists in magnetic vortex Coupling of electric polarization to magnetism Time reversal symmetry P → +P t → −t M → −M Inversion symmetry E ∝ αHE P → −P r → −r M → +M MULTIFERROICS Materials combining ferroelectricity, (ferro)magnetism and (ferro)elasticity If successful – a lot of possible applications (e.g. electrically controlling magnetic memory, etc) Field active in 60-th – 70-th, mostly in the Soviet Union Revival of the interest starting from ~2000 • Perovskites: either – or; why? • The ways out: Type-I multiferroics: Independent FE and magnetic subsystems 1) “Mixed” systems 2) Lone pairs 3) “Geometric” FE 4) FE due to charge ordering Type-II multiferroics:FE due to magnetic ordering 1) Magnetic spirals (spin-orbit interaction) 2) Exchange striction mechanism 3) Electronic mechanism Two general sets of problems: Phenomenological treatment of coupling of M and P; symmetry requirements, etc. -
Electrical Characterisation of Ferroelectric Field Effect Transistors Based On
Technische Universität Dresden Electrical Characterisation of Ferroelectric Field Effect Transistors based on Ferroelectric HfO2 Thin Films Dipl.-Ing. Ekaterina Yurchuk von der Fakultät Elektrotechnik und Informationstechnik der Technischen Universität Dresden zur Erlangung des akademischen Grades Doktoringenieur (Dr.-Ing.) genehmigte Dissertation Vorsitzender: Prof. Dr.-Ing. habil. R. Schüffny Gutachter: Prof. Dr.-Ing. T. Mikolajick Tag der Einreichung: 23.07.2014 Prof. Dr. K. Dörr Tag der Verteidigung: 06.02.2015 Abstract The ferroelectric field effect transistors (FeFETs) are considered as promising candidates for future non-volatile memory applications due to their attractive features, such as non-volatile data storage, program/erase times in the range of nanoseconds, low operation voltages, almost unlimited endurance, non-destructive read-out and a compact one-transistor cell structure without any additional access device needed. Despite the efforts of many research groups an industrial implementation of the FeFET concept is still missing. The main obstacles originate from the conventional perovskite ferroelectric materials (lead zirconium titanate (PZT) and strontium bismuth tantalate (SBT)), in particular their integration and scaling issues. The recently discovered ferroelectric behaviour of HfO2-based dielectrics yields the potential to overcome these limitations. The decisive advantages of these materials are their full compatibility with the standard CMOS process and improved scaling potential. Utilisation of the Si:HfO2 ferroelectric thin films allows to fabricate FeFETs in a state-of-the- art CMOS technology node of 28 nm. The ferroelectricity in HfO2 has been discovered only several years ago. Therefore, there are still a lot of uncertainties about the origin of the ferroelectric behaviour as well as the impact of different fabrication conditions on its emergence. -
Evidence for Ferroelectricity in Iv-Vi Compounds G
EVIDENCE FOR FERROELECTRICITY IN IV-VI COMPOUNDS G. Pawley To cite this version: G. Pawley. EVIDENCE FOR FERROELECTRICITY IN IV-VI COMPOUNDS. Journal de Physique Colloques, 1968, 29 (C4), pp.C4-145-C4-150. 10.1051/jphyscol:1968423. jpa-00213627 HAL Id: jpa-00213627 https://hal.archives-ouvertes.fr/jpa-00213627 Submitted on 1 Jan 1968 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. JOURNAL DE PHYSIQUE Colloque C 4, supplkment au no 11-12, Tome 29, Novembre-Dkcembre 1968, page C 4 - 145 EVIDENCE FOR FERROELECTRICITY IN IV-VI COMPOUNDS Department of Natural Philosophy - The University, Edinburgh, Scotland Rbum6. - Parce que les mkthodes habituelles servant h ktablir le caractkre ferroklectrique des cristaux ne sont pas applicables au cas de corps de haute conductivitk, on doit alors introduire d'autres moyens basks sur d'autres propriktks ferroklectriques. L'analyse de la structure cristalline peut fournir un modile montrant la possibilitk de polarisation reversible, mais une preuve plus convaincante peut venir de l'ktude de la dynamique du cristal. La diffusion inklastique cohbente des neutrons donne les frkquences des modes normaux du cristal et la variation en tempkrature de certains modes peut indiquer la ferroklectricite ou I'antiferrokkctricite. -
Analogies and Differences Between Ferroelectrics and Ferromagnets
Analogies and Differences between Ferroelectrics and Ferromagnets Nicola A. Spaldin Materials Department, University of California, Santa Barbara, CA 93106-5050, USA [email protected] ferro Fer"ro A prefix, or combining form, indicating ferrous iron as an ingredient; as, ferrocyanide. [From Latin ferrum, iron.] Source: Webster’s Revised Unabridged Dictionary, (c) 1996, 1998 MICRA, Inc. Abstract. We describe the similarities and differences between ferromagnets – materials that have a spontaneous magnetization that is switchable by an applied magnetic field – and ferroelectrics, which have an analogous electric-field switch- able electric polarization. After comparing the driving force for ion off-centering that causes the polarization in ferroelectrics with the physics of spin polariza- tion that causes the magnetization of ferromagnets, we analyze the mechanisms of domain formation and resulting domain structures in both material classes. We describe the emerging technologies of ferroelectric and magnetoresistive random access memories, and discuss the behavior of magnetoelecric multiferroics, which combine ferromagnetism and ferroelectricity in the same phase. The “ferro” part in the name “ferroelectric” is something of a misnomer, since it does not refer to the presence of iron in ferroelectric materials. Rather it arises from the many similarities in behavior between ferroelectrics, with their spontaneous electric polarization, and ferromagnets, with their sponta- neous magnetization. Indeed one of the earliest observations of ferroelectric- ity ([1]) describes the electric hysteresis in Rochelle salt as “analogous to the magnetic hysteresis in the case of iron.” A systematic comparison between the behavior of ferromagnets and ferroelectrics, does not, to our knowledge, exist in the literature. The purpose of this chapter is to outline the sim- ilarities in behavior between ferromagnets and ferroelectrics, and, perhaps more importantly, to point out the differences in their fundamental physics and consequent applications. -
Quantum Ferroelectricity in Charge-Transfer Complex Crystals
ARTICLE Received 13 Jan 2015 | Accepted 12 May 2015 | Published 16 Jun 2015 DOI: 10.1038/ncomms8469 OPEN Quantum ferroelectricity in charge-transfer complex crystals Sachio Horiuchi1,2, Kensuke Kobayashi3, Reiji Kumai2,3, Nao Minami4, Fumitaka Kagawa2,5 & Yoshinori Tokura4,5 Quantum phase transition achieved by fine tuning the continuous phase transition down to zero kelvin is a challenge for solid state science. Critical phenomena distinct from the effects of thermal fluctuations can materialize when the electronic, structural or magnetic long-range order is perturbed by quantum fluctuations between degenerate ground states. Here we have developed chemically pure tetrahalo-p-benzoquinones of n iodine and 4–n bromine sub- stituents (QBr4–nIn, n ¼ 0–4) to search for ferroelectric charge-transfer complexes with tet- rathiafulvalene (TTF). Among them, TTF–QBr2I2 exhibits a ferroelectric neutral–ionic phase transition, which is continuously controlled over a wide temperature range from near-zero kelvin to room temperature under hydrostatic pressure. Quantum critical behaviour is accompanied by a much larger permittivity than those of other neutral–ionic transition compounds, such as well-known ferroelectric complex of TTF–QCl4 and quantum antiferro- electric of dimethyl–TTF–QBr4. By contrast, TTF–QBr3I complex, another member of this compound family, shows complete suppression of the ferroelectric spin-Peierls-type phase transition. 1 National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba 305-8562, Japan. 2 CREST, Japan Science and Technology Agency (JST), Tokyo 102-0076, Japan. 3 Condensed Matter Research Center (CMRC) and Photon Factory, Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK), Tsukuba 305-0801, Japan.