ISIF 2011

ISIF 2011
International Symposium on Integrated Functionalities
July 31 August 4 University of Cambridge, UK

Technical Program Chairs James F. Scott and Sandwip K. Dey Chairs, Local Committee Neil Mathur and Ekhard Salje ISIF 2010 Chair Ram S. Katiyar ISIF General Chairs Carlos Paz de Araujo, University of Colorado and Symetrix Corp Orlando Auciello, Argonne National Laboratory Sandwip Dey, Arizona State University Rudy Panholzer, Naval Postgraduate School
www.isif.net
ISIF 2011 Location of venues
The conference will take place on the Downing Site in Cambridge city centre. Our base is at: Department of Earth Sciences University of Cambridge Downing Street Cambridge CB2 3EQ One of the parallel sessions will take place in Earth Sciences in the Tilley Lecture Theatre (17 on the map of the Downing Site). The other two parallel sessions will take place in the department of Plant Sciences (16 on the map), and the department of Physiology (see the long arrow), both of which are also located on the Downing Site. All plenary talks will take place in Physiology. Registration on Monday 1 August between 8.00 and 10.00 and coffee are in Earth Sciences (5 on the map). Late registrations will be at the Department of Materials Science and Metallurgy on the New Museums Site on the other side of Downing Street. Accommodation booked through the website and the Conference Dinner are in King's College and everything else (registration, tutorials, posters, talks, coffee, lunch) is on the Downing Site. Posters are displayed on the second floor of the Department of Earth Sciences.
Teas and coffees are in the Common Room just inside the main entrance. Exhibitions from PI-KEM Ltd, Asylum Research, Radiant Technologies Inc, aixACCT Systems GmbH and attocube systems AG are in the Oxburgh Room on the second floor. The EPL exhibition is near the tea/coffee area. Tutorials are in Harker 1 on the second floor. Lifts to the second floor are marked in red on the plan above.
Tutorials
Tutorials will take place Sunday 31 July from 2pm - 5.30pm in Harker 1 in the Department of Earth Sciences: 2.00 - 3.15 Finlay Morrison - Electrical Characterisation of Materials: ac Impedance Spectroscopy The talk will focus on the application of impedance spectroscopy for electrical characterisation of functional materials. Topics covered will include: Benefits of ac spectroscopic measurements over dc and fixed frequency measurements Introduction to ac impedance and ac circuits Immittance formalisms Data representation and analysis using equivalent circuits Some case studies including bulk ferroelectrics, high permittivity materials, integrated FeRAM devices. The talk should be of interest to anyone who uses any type of dielectric constant or conductivity measurements to investigate structure property relationships in ferroelectric, piezoelectric or multiferroic materials.
3.15 - 4.30 Alexi Gruverman: piezoforce microscopy (pfm) 4.30 - 5.30 Asylum Research: pfm demonstration Delegates are encouraged to bring samples for pfm, and make appointments with the Asylum representative for testing during the conference. The Asylum stand will be in Earth Sciences.
Exhibitors
The ISIF 2001 conference is pleased to welcome the following exhibitors: aixACCT Systems GmbH - www.aixacct.com
Asylum Research - www.asylumresearch.co.uk
attocube systems AG - www.attocube.com
EPL - epljournal.edpsciences.org
PI-KEM Ltd - www.pi-kem.com
Radiant Technologies Inc - www.ferrodevices.com
Monday 1 August
Plant Sciences Lecture Theatre
9:00 9:05
9:00
Physiology Lecture Theatre
Earth Sciences Lecture Theatre
Welcome - Jim Scott
9:05
Spintronics and electrical devices Plenary - Chair Stuart Parkin
Manuel Bibes - FERROELECTRIC TUNNEL JUNCTIONS FOR LOWPOWER NON-VOLATILE CHARGE- AND SPIN-BASED DATA STORAGE (189) 9:50 10:00
9:50 10:00
Chair - Manuel Bibes and Moon-Ho Jo

Michael Woerner - PHOTOELASTIC, FERROELECTRIC, AND FERROMAGNETIC PROPERTIES OF PEROVSKITE SUPERLATTICES STUDIED BY FEMTOSECOND X-RAY DIFFRACTION (169) R. A. Cowley - SOFT MODES AND STRUCTURAL PHASE TRANSITIONS (38)
Stuart Parkin - RACETRACK MEMORY: A CURRENT CONTROLLED DOMAIN-WALL SHIFT REGISTER (245)
Superlattices Chair - J.-M. Triscone and M. Dawber
Ferroelectrics theory Chair - A. J. Bell and R. A. Cowley
10:30
10:30
Tea/coffee
Paul G. Evans - STRUCTURE AND NANOSECOND DYNAMICS OF FERROELECTRIC-DIELECTRIC SUPERLATTICES IN APPLIED ELECTRIC FIELDS (45)
Tea/coffee
Tea/coffee
Jirka Hlinka - HEISENBERG-LIKE SWITCHING IN FERROELECTRICS (58) 11:00
11:00
Lee Phillips -GRAPHENE SPINTRONIC DEVICES WITH HIGHLY SPIN-POLARIZED OXIDE ELECTRODES (119)
11:15
Xavier Marti - SPIN-VALVE-LIKE MAGNETORESISTANCE OF AN ANTIFERROMAGNET-BASED TUNNEL JUNCTION (218)
11:15
11:30
11:30
11:45
Bui Nguyen Quoc Trinh - SUB-MICRON FERROELECTRIC-GATE Ram Katiyar - DEPENDENCE OF THE STRUCTURAL, DIELECTRIC, Nicole A. Benedek - HYBRID IMPROPER FERROELECTRICITY: A THIN FILM TRANSISTOR USING SOL-GEL ITO CHANNEL AND AND FERROELECTRIC PROPERTIES WITH PERIODICITY AND MECHANISM FOR CONTROLLABLE POLARIZATIONSTACKED (BLT/PZT) INSULATOR (90) COMPOSITION IN ARTIFICIAL BaTiO3/ (Ba,Sr)TiO3 MAGNETIZATION COUPLING (29) SUPERLATTICES (19) Daniel Pantel - ELECTRORESISTANCE AND TUNNEL MAGNETORESISTANCE IN FERROELECTRIC Pb(Zr0.2Ti0.8)O3 BARRIERS (139)
11:45
12:00
12:00
Lunch
Lunch
Javier Junquera - FIRST-PRINCIPLES SIMULATIONS ON PbTiO3/SrTiO3 SUPERLATTICES (229)
Lunch
Nick Bristowe - MODELLING SCREENING MECHANISMS IN POLAR OXIDE THIN FILMS (30) 13:30
13:30
BiFeO3 and Multiferroics Chair - J. Fontcuberta & G. Catalan
Josep Fontcuberta - MAGNETOELECTRIC COUPLING IN EXCHANGE-BIASED MULTIFERROIC HETEROSTRUCTURES (233) 14:00
Abstracts can be located by their abstract number, shown in brackets in the programme as (n)
14:00
14:00
Massimo Ghidini - REVERSIBLE CONTROL OF PERPENDICULAR MAGNETIC ANISOTROPY IN FERROMAGNETIC FILMS VIA THERMAL AND ELECTRICAL TREATMENTS OF THE FERROELECTRIC SUBSTRATE (49) Jaichan Lee - METAL-INSULATOR TRANSITION IN TUNABLE 2D/3DEG SrTiO3/(Sr1-x,Lax)TiO3 SUPERLATTICES (65) Vladimir Zelezny - INFRARED SPECTROSCOPY OF NANOSCOPIC Igor Luk'yanchuk - STRAIN-INDUCED FERROELASTIC DOMAINS EPITAXIAL BaTiO3/SrTiO3 SUPERLATTICES (93) AT METAL-INSULATOR PHASE TRANSITIONS IN VO2 (72) Gijsbert Rispens - GROWTH AND CHARACTERISATION OF BIFEO3-LAFEO3 SUPERLATTICES (188) 14:45 14:30 14:15
Peter Sushko - EFFECT OF THE CATION INTERMIXING AND SURFACE DEFECTS ON THE ELECTRONIC STRUCTURE OF THE LaAlO3/SrTiO3 (001) HETEROJUNCTION (160)
Serge M. Nakhmanson - A CASE IN DEFENCE OF PEROVSKITE SnTiO3 AS A STRONG, LEAD-FREE FERROELECTRIC MATERIAL; A FIRST-PRINCIPLES INVESTIGATION (156)
14:00
14:15
14:30
Sebastiaan van Dijken - PATTERN TRANSFER AND ELECTRICFIELD INDUCED MAGNETIC DOMAIN FORMATION IN MULTIFERROIC HETEROSTRUCTURES (16)
14:45
Helen Chan - MODIFICATION OF THE STRAIN AND MAGNETORESISTANCE OF La0.7(Ca1-xSrx)0.3MnO3 THIN FLIMS USING FERROELECTRIC POLING AND MAGNETOSTRICTION (56) Claude Ederer - MECHANISMS FOR FERROELECTRIC DISPLACEMENTS FROM FIRST PRINCIPLES (105) 15:00
15:00
15:15
15:30
Andreas Ruediger - DIRECT EVIDENCE OF CATIONIC B-SITE Marta Gibert - LaNiO3/LaMnO3 SUPERLATTICES: TRANSPORT ORDERING IN MULTIFERROIC Bi2FeCrO6 NANOSTRUCTURES BY AND MAGNETIC PROPERTIES (202) MAGNETIC CIRCULAR DICHROISM (7) Tatiana Correia - LEAD-FREE FERROELECTRIC HETEROSTRUCTURES FOR ENERGY STORAGE TECHNOLOGIES (162)
15:15
15:30
Tea/coffee
Tea/coffee
Tea/coffee
16:00
16:00
Plenary - Chair I. Dzyaloshinskii
I. Dzyaloshinskii - MAGNETOELECTRICITY: HISTORICAL REMARKS(240) 16:15 ` 17:00 Jean-Marc Triscone - INTERLAYER COUPLING AND UNIT-CELL SCALE SPECTROSCOPIC MAPPING OF LOCAL DISTORTIONS IN FERROELECTRIC SUPERLATTICES (140) Herbert Kliem - A MODEL FOR TRANSIENT POLARIZATION SWITCHING IN FERROELECTRICS (114) Laurent Baudry - FORMATION AND EVOLUTION OF EXOTIC POLARIZATION TEXTURES IN NANOFERROELECTRICS (118) Matt Dawber - ARTIFICIALLY LAYERED SUPERLATTICES BASED ON PBTIO3 (204) 17:15
16:15
R. Ramesh - COUPLING MAGNETISM TO ELECTRICITY IN MULTIFERROIC HETEROSTRUCTURES (231)
17:00
Chair - J. Fontcuberta & G. Catalan
17:15
Jan Seidel - PHOTOVOLTAIC AND ELECTROCHROMIC PROPERTIES OF BiFeO3 (228)
17:30
R. Blinc - CREATION OF POLAR NANOCLUSTERS IN RELAXORS (238)
17:30
17:45
17:45 Bahruz Gadjiev - INFLUENCE OF DEFECT DISTRIBUTION ON PHYSICAL PROPERTIES OF LAYERED FERROELECTRIC SEMICONDUCTORS WITH AN INCOMMENSURATE PHASE (247) 18:00
18:00 Pavlo Zubko - FERROELECTRIC DOMAINS IN LEAD TITANATE/STRONTIUM TITANATE SUPERLATTICES (173)
18:15
18:15
18:30
18:30
Tuesday 2 August
Nanodomains and nanocrystals Chair - J.M.Gregg and A. Gruverman
J. M. Gregg - DOMAIN PATTERNS IN NANOSCALE FERROELECTRICS (106) 9:15 9:30 9:45 10:00 Markys Cain - ENERGY LOSS IN PIEZOELECTRIC ENERGY HARVESTING CANTILEVERS (168)

Energy harvesting Chair - Qi Zhang & S. Kar-Narayan
9:00
9:00
M. Kenzelmann - MAGNETICALLY-DRIVEN ELECTRIC POLARIZATION IN MAGNETO-ELECTRICS AND MULTIFERROICS (237)
9:15
9:30
9:45
Eric Bousquet - UNEXPECTEDLY LARGE ELECTRONIC CONTRIBUTION TO MAGNETOELECTRICITY (9)
10:00
Moon-Ho Jo - SPATIALLY RESOLVED PHOTODETECTION IN BISMUTH FERRITE (235) Sushma Kotru - EFFECT OF TOP ELECTRODE ON THE PHOTO-VOLTAIC PROPERTIES OF PLZT THIN FILM CAPACITORS (75) 10:30 10:15
Jonathan A. Bock - TUNGSTEN BRONZE STRUCTURED RELAXOR FERROELECTRICS FOR THERMOELECTRIC APPLICATIONS (108) Alexei Gruverman - SWITCHING BEHAVIOR AND ELECTRONIC PROPERTIES Feng Yan - THE APPLICATION OF BISMUTH-BASED OXIDES IN HYBRID OF ULTRATHIN FERROELECTRIC HETEROSTRUCTURES (21) PHOTOVOLTAIC DEVICES (17) Hongbin Yu - NANOSTRUCTURED ZnO AND ZnTe FOR ENERGY HARVESTING APPLICATIONS (59) Marin Alexe - DOMAIN AND DOMAIN WALL ROLE IN PHOTOVOLTAIC Andrew M. Rappe - THE BULK PHOTOVOLTAIC EFFECT: COMPUTATIONAL EFFFECT IN BiFeO3 (192) MATERIALS DESIGN FOR ENERGY APPLICATIONS (226)
10:15
10:30
Tea/coffee
Venkatraman Gopalan - LOCAL STRUCTURE AND DYNAMICS OF A SINGLE FERROELECTRIC DOMAIN WALL (179)
Tea/coffee
Tea/coffee
11:00
Lang Chen - NANOSCALE PHASE SEPARATION IN QUASI-UNIAXIAL STRAINED MULTIFERROIC EPITAXIAL THIN FILMS (103)
11:15
Electrocalorics Chair - Qi Zhang & S. Kar-Narayan

Q. M. Zhang - GIANT ELECTROCALORIC EFFECT IN FERROELECTRIC POLYMERS AND THEIR DEVICE DEMONSTRATIONS (178)
11:00
Huajun Liu - TETRAGONAL BiFeO3 PHASE WITH GIANT C/A RATIO ON SrTiO3 SUBSTRATES (18)
11:15
11:30 Zdravko Kutnjak - ENHANCEMENT OF THE ELECTROCALORIC AND ELECTROMECHANICAL EFFECTS NEAR THE CRITICAL POINT IN FERROELECTRIC RELAXOR MATERIALS (171)
11:30
B. Andrzejewski - MAGNETIC PROPERTIES OF BiFeO3 CERAMICS OBTAINED Russell Cowburn - DOMAIN WALLS IN MAGNETIC NANOSTRUCTURES (236) BY HOT-PRESSING OF NANOPOWERS (23)
11:45
11:45
Meghdad Palizdar - INFLUENCE OF SECONDARY PHASE ON MULTIFERROIEC PROPERTIES OF Bi5Co0.5Fe0.5Ti3O15 CERAMICS MADE FROM MOLTEN SALT METHOD (135)
12:00
Lunch Lunch Poster sesssion A

Ionela Vrejoiu - EPITAXIAL SUBMICRON-SIZED HETEROSTRUCTURES OF FERROELECTRIC AND FERROMAGNETIC/FERRIMAGNETIC OXIDES (167)
Lunch Poster session A

S. Kar-Narayan - SCANNING THERMAL MICROSCOPY STUDIES OF ELECTROCALORIC FILMS AND DEVICES (111)
12:00 12:30
12:30
Poster Session A
13:30
Chuanwei Huang - SHEAR STRAIN EFFECT ON THE PHASE TRANSITIONS AND ANOMALOUS DIELECTRIC/PIEZOELECTRIC PROPERTIES FOR BiFeO3 THIN FILMS (200)
13:30
13:45 Gil Rosenman - BIOINSPIRED PEPTIDE SUPRAMOLECULAR STRUCTURES: FERROELECTRICITY AT NANOSCALE (152)
13:45 Emmanuel Defay - PREDICTED COEFFICIENT OF PERFORMANCE FOR ELECTROCALORIC MATERIALS IN AN IDEAL REFRIGERATION CYCLE (61) 14:00
14:00
Daniel Sando - BiFeO3 HETEROSTRUCTURES FOR ELECTO-OPTIC MODULATORS (203) Wataru Sakamoto - Mn DOPING EFFECT ON ELECTRICAL AND MAGNETIC PROPERTIES OF BiFeO3-BaTiO3 THIN FILMS PREPARED BY CHEMICAL SOLUTION DEPOSITION (154)
14:15
14:15
14:30
Zuhuang Chen - STRAIN-INDUCED LOW SYMMETRY FERROELECTRIC PHASES IN EPITAXIAL BiFeO3 (104) Florian Johann - FABRICATION OF EPITAXIAL BISMUTH FERRITE NANOSTRUCTURES BY CHEMICAL ETCHING (107)
Nanodomains and nanocrystals: Continuous media

D. Saranya - STUDIES ON FIELD DEPENDENT DOMAIN STRUCTURES IN MULTI- GRAINED 0.85PbMg1/3Nb2/3O3-0.15PbTiO3 THIN FILMS BY DYNAMIC CONTACT FORCE MICROSCOPY (39)
Rami N. Chukka - INVESTIGATIONS OF ELECTROCALORIC COOLING EFFICIENCIES IN FERROELECTRIC THIN-FILMS BY SOLID STATE MODEL (117)
14:30
14:45
14:45
14:45
Xavier Marti - SKIN LAYER OF BiFeO3 SINGLE CRYSTALS (219)
Li-Wu Chang - COMPLEX DOMAIN STRUCTURES INDUCED-BY CLAMPING EFFECT IN RELAXOR FERROELECTRIC 88%Pb(Zn1/3Nb2/3)O3-12%PbTiO3 (001) SINGLE CRYSTAL THIN FILMS (116) Valanoor Nagarajan - EXPLORING TOPOLOGICAL DEFECTS IN EPITAXIAL BiFeO3 THIN FILMS (101) 15:15 15:30 Xavier Moya - CALORIMETRIC STUDY OF GIANT ELECTROCALORIC EFFECTS IN BaTiO3 SINGLE CRYSTALS (10) 15:00
Q. Zhang - MOVING TOWARDS ELECTROCALORIC REFRIGERATION (146)
14:45
15:00
15:15 E. Simon - PFM IMAGING AND FAR-INFRARED SPECTROSCOPIC STUDY OF POLYDOMAIN PbTiO3 THIN FILM ON LaAlO3 (44)
Faye Bygrave - BiFeO3-PbTiO3 THIN FILMS AROUND THE MPB: A STRUCTURAL STUDY(32)
15:30
15:45
Tea/coffee
15:45 16:00
Tea/coffee Tea/coffee
16:00
RRAM Plenary - Chair Sandwip Dey

16:40 16:45
16:40 16:45 Donald Evans - NOVEL ELECTRODE GEOMETRY TO INDUCE EXOTIC DOMAIN STATES (40)
Rainer Waser - REDOX-BASED MEMRISTIVE SWITCHING - SCALING BEYOND FLASH? (232)
Hermann Kohlstedt - TUNNEL JUNCTIONS FOR MEMORY APPLICATIONS (63)

Neil Mathur - GIANT AND REVERSIBLE STRAIN-MEDIATED MAGNETOCALORIC EFFECTS IN FERROMAGNETIC-FERROELECTRIC HETEROSTRUCTURES (15)
17:00 L. J. McGilly - DOMAIN BUNDLE BOUNDARIES IN SINGLE CRYSTAL BaTiO3 LAMELLAE: SEARCHING FOR NATURALLY FORMING DIPOLE FLUX-CLOSURE / QUADRUPOLE CHAINS (121)
Anna Ggor - MAGNETO-ELASTIC EFFECT IN CuCrSe2 ANTIFERROMAGNET (48)
17:00
17:15 J.Y. Dai - STUDY OF LUFE2O4 THIN FILM GROWTH AND ITS STRUCTURAL AND MULTIFERROIC PROPERTIES (4)
17:15
Cheol Seong Hwang - KINETIC STUDY ON THE FORMATION AND RUPTURE Ivan Gregora - STUDY OF LOCAL DOMAIN STRUCTURE IN LiTaxNb1xO3 AND OF CONDUCTING NANO-FILAMENTS IN RRAM (74) VTE-TREATED LiTaO3 CRYSTALS BY BIREFINGENCE IMAGING, RAMAN SPECTROSCOPY AND PIEZO FORCE MICROSCOPY (27)
17:30
Nanodomains and nanocrystals: Nanopatterned media

Alessio Morelli - SWITCHING PROPERTIES OF NANOSTRUCTURES OF EPITAXIAL BISMUTH FERRITE (131) Takshi Nishida - FABRICATION OF PbTiO3 AND Pt SELF-ORGANIZED NANOCRYSTAL ARRAY STRUCTURE FOR HIGH DENSITY FERROELECTRIC MEMORIES (97) Raymond McQuaid - IMAGING DOMAIN SWITCHING AND FLUX-CLOSURE QUADRANT FORMATION IN SINGLE CRYSTAL BaTiO3 LAMELLAE (148) Jonathan Spanier - FERROELECTRIC CYLINDRICAL NANO-SHELLS: MATERIALS, PROPERTIES AND DEVICES (201) S. G. Shivareddy - FUNCTIONAL CARBON NANOTUBE ARRAYS FOR 3D FERROELECTRICS (197)
Haidong Lu - ELECTRIC MODULATION OF MAGNETIZATION IN FERROELECTRIC-FERROMAGNETIC HETEROJUNCTIONS (54)
17:30
17:45
Anquan Jiang - FERROELECTRIC POLARIZATION MODULATION OF BIPOLAR DIODE CURRENT IN A FERRORESISTIVE MEMORY WITH A HIGH INTEGRATION DENSITY (98)
Zdravko Kutnjak - NEW SOFT MAGNETOELECTRICS: MIXTURES OF THE FERROELECTRIC LIQUID CRYSTAL AND MAGNETIC NANOPARTICLES (87) Ingrid Caero Infante - NEAR ROOM TEMPERATURE MULTIFERROIC TRANSITIONS IN BIFEO3 FILMS (246) Ignasi Fina - EFFECTS OF STRAIN ON THE MAGNETOELECTRIC BEHAVIOUR OF ORTHORHOMBIC YMnO3 THIN FILMS (176)
17:45
18:00
18:00
18:15
18:15
18:30
18:30 18:45 19:30
18:45
Reception in King's College at 18:45 - dinner ticket holders only. Dinner at 19.30
19:30
Wednesday 3 August
High-K dielectrics and polymers Chair - C. Hobbs and S. Stemmer
Susanne Stemmer - SCALING AND INTERFACE CONTROL OF HIGH-K/III-V INTERFACES (180) Ho Nyung Lee - BAND GAP NARROWING IN EPITAXIAL FERROELECTRICS BY A MOTT INSULATOR (5) 9:15 9:30
9:00

Ferroelectrics Experimental Chair - F. Morrison
9:00
RRAM Chair - H. Kohlstedt and A. Jiang
Doo Seok Jeong - Pt/Ti/Al2O3/Al TUNNEL JUNCTIONS SHOWING ELECTROFORMING-FREE BIPOLAR RESISTIVE SWITCHING BEHAVIOR (91)
9:15
9:30
9:45
9:45
10:00
10:00
10:15
Jung Ho Yoon - ROLE OF Ru NANO-DOTS EMBEDDED IN TIO2 THIN FILMS FOR IMPROVING THE RESISTIVE SWITCHING BEHAVIOR (73) Myung Soo Lee - RESISTIVE SWITCHING CHARACTERISTICS OF ALD-HfO2 Qiu Xiaoyan - WEAK FERROMAGNETISM OF HfO2 FILM ON COMPRESSIVELY Gustau Catalan - FLEXOELECTRICITY IN THIN FILMS AND SINGLE CRYSTALS FILMS ANNEALED IN OXYGEN AND UV-IRRADIATED OXYGEN AMBIENT STRAINED Si83Ge17/Si SUBSTRATE (96) (34) (132) R. Soni - BREAKDOWN ANALYSIS OF Cu DOPED Ge0.3Se0.7 BASED RRAM Hyo Kyeom Kim - THE INFLUENCE OF DIFFERENT TYPES OF LaDEVICES TO UNDERSTAND THE STOCHASTIC NATURE OF THE RESISTIVE INCORPORATED TiN METAL GATE STACKS ON HfO2 ; TiN/La/TiN AND TiLaN SWITCHING PROCESS (158) (79) Marie-Paule Besland - GaV4S8: A MATERIAL IN THE RACE TOWARDS RRAM Hyung-suk Jung - THE IMPACT OF ALD GROWN SiOxNy AND AlOxNy Stephen Ducharme - APPLICATIONS OF FERROELECTRIC POLYMER THIN MEMORIES (224) PASSIVATION LAYERS ON THE ELECTRICAL PROPERTIES OF METAL FILMS AND NANOSTRUCTURES (225) GATE/HIGH-k Ge MOS CAPACITORS (84) Aidong Li - COMPARISON OF THE INTERFACIAL AND ELECTRICAL PROPERTIES OF HfAlO FILMS ON Ge WITH S AND GeO2 PASSIVATION (207)
10:15
10:30
10:30
Tea/coffee
Tea/coffee
Tea/coffee
11:00
11:00
Graphene Plenary - Chair Neil Mathur
11:30
Roman Gorbachev - COULOMB DRAG IN GRAPHENE / BORON NITRIDE HETEROSTRUCTURES (151)
12:00
Leonid Ponomarenko - CONTRALABLE METAL-INSULATOR TRANSITION AND VERTICAL TRANSPORT IN GRAPHENE BASED HETEROSTRUCTURES (244)
11:30
Lunch Lunch Poster sesssion B
12:00
Lunch
12:30
12:30
Poster Session B
Poster session B
13:30
13:30
rf and high frequency devices Plenary - Chair J. Banys
Guru Subramanyam - BARIUM-STRONTIUM-TITANATE THIN FILM BASED VARACTORS FOR MICROWAVE APPLICATIONS (190) 14:10 14:15
14:10 14:15
Chair - J. Banys and E. Rocas
Eduard Rocas - THERMAL AND INTRINSIC NONLINEARITIES OF FERROELECTRIC-BASED MICROWAVE DEVICES (150)
Kui Yao - VINYLIDENE FLUORIDE-BASED POLYMER AND OLIGOMER THIN FILMS ON SUBSTRATES (115)
Chair - G. Catalan
Finlay D. Morrison - DIELECTRICS BY DESIGN: CHEMICAL CONTROL OF DIPOLE BEHAVIOUR IN TETRAGONAL TUNGSTEN BRONZES AND BISMUTH FERRITE (184)
14:45
14:45
14:45 Xiao-Bing Liu - THE INTRINSIC COERCIVE FIELD FOR P(VDF-TrFE) THIN-FILMS WITH DIFFERENT THICKNESS (86) Pankaj Sharma - INVESTIGATION OF LOCAL SWITCHING BEHAVIOR IN NANOSTRUCTURED ULTRATHIN FERROELECTRIC POLYMERS (138) 15:30 James F. Scott - COMPARISON OF ZnO FILMS DEPOSITED VIA PLD, PE-CVD, SPUTTERING,AND MISTED CVD (222) 15:15 15:00
Manfang Mai - POLARIZATION RELAXATION AND CHARGE INJECTION IN THIN FILMS OF P(VDF-TrFE) COPOLYMERS (124)
Andrew J Bell - IMPEDANCE SPECTROSCOPY AND DIELECTRIC MODELLING OF (KxNa1-x)1/2Bi1/2TiO3 (28)
14:45
15:00
Anthony Roberts - IMPLEMENTING A PIEZOELECTRIC TRANSFORMER FOR A FERROELECTRIC PHASE SHIFTER CIRCUIT (8)
15:15
Robert Dorey - GREEN NANO-ENABLED SOLUTIONS FOR LOCAL ENERGY NETWORKS (53)
15:30
Tea/coffee
Hiroshi Uchida - PREFERENTIAL CRYSTAL GROWTH OF MBi4Ti4O15 (M = Ca, Sr) FILMS USING NANOSHEET TEMPLATE (1)
Tea/coffee
Tea/coffee
16:00
Juras Banys - INVESTIGATION OF 0.4Na1/2Bi1/2TiO3- (0.6-x)SrTiO3xPbTiO3 SOLID SOLUTIONS (109)
Chair - S. Ducharme and A. J. Bell
16:00
16:15
16:15 16:30
16:30
Jianhua Hao - CHARACTERISTICS OF FERROELECTRIC TITANATE/III-V SEMICONDUCTOR HETEROSTRUCTURE (100) Hiroshi Funakubo - HIGH TEMPERATURE DIELECTRIC PROPERTIES OF CAXIS ORIENTED EPITAXIAL BISMUTH LAYER-STRUCTURED DIELECTRIC THIN FILMS (47)
16:45
Paul W. M. Blom - ORGANIC FERROELECTRICS FOR MEMORY AND DISPLAY APPLICATIONS (175) Ahmad Mukifza Harun - A CASE STUDY OF LiNbO3 PVDF COMPOSITE THIN FILM (22) Hartmut Gundel - FERROELECTRIC THIN FLMS FOR MOBILE Catherine Dubourdieu - TETRAGONAL BaTiO3 EPITAXIAL FILMS WITH OUTCOMMUNICATION APPLICATIONS (62) OF-PLANE C-AXIS ORIENTATION ON SrTiO3 BUFFERED-Si(001): STRUCTURE AND ELECTRICAL PROPERTIES (42)
Wontae Chang - FERROELECTRICALLY ACTIVE ACOUSTIC WAVE PROPAGATION (69)
16:45
17:00
Paul Kirby - OPTIMIZATION OF BOTTOM ELECTRODE STRUCTURE FOR THIN FILM FERROELECTRIC RF DEVICES (46)
Devices Chair - Joe Evans and MacLeod

Robert Dorey - NON-SILICON PIEZOELECTRIC MICROSYSTEMS (134)
A. V. Kimmel - CAN OXYGEN VACANCIES SWITCH POLARIZATION AXIS IN FERROELECTRICS? EXAMPLES FOR BaTiO3 AND KNbO3 (92)
17:00
17:15
Andrei Vorobiev - MICROWAVE RESPONSE OF BiFeO3 FILMS IN PARALLEL- Noah T. Jafferis - TRAVELING WAVE-INDUCED AERODYNAMIC PROPULSIVE Masamichi Nishide - LATERAL SIZE DEPENDENCE OF CRYSTAL STRUCTURE PLATE CAPACITORS (2) FORCE USING ACTIVE CONTROL OF THE DYNAMIC SHAPE OF IN THE Pb(Zr,Ti)O3 THICK FILM AT THE MORPHOTROPIC PHASE BOUNDARY PIEZOELECTRICALLY-DEFORMED PLASTIC SUBSTRATES (80) (94)
17:15
17:30 Hiroaki Watanabe - IMPROVEMENT AND EVALUATION ON SORTING ALGORITHM WITH FUNCTIONAL MEMORY BASED ON FeRAM (78)
Karsten Rachut - BOTTOM ELECTRODE MATERIALS FOR BST THIN FILM VARACTORS (12)
17:45
Noriyuki Inoue - TSDC (THERMALLY STIMULATED DEPOLARIZATION CURRENT) STUDY OF THE RARE EARTH AND MAGNESIUM CO-DOPED BaTiO3 (82) Jessie Zhu - BiScO3 DOPED (Na0.5K0.5)NbO3 LiTaO3 PIEZOELECTRIC CERAMICS (172) A. Al-Zein - THE SOFT MODE OF PbMg1/3Nb2/3O3 INVESTIGATED BY HYPERRAMAN SCATTERING (55)
17:30
17:45
18:00
18:15
Markys G Cain - IN-SITU REAL TIME STRUCTURAL RESPONSE OF A FERROELECTRIC TO AN APPLIED EXTERNAL ELECTRIC FIELD OF VARYING FREQUENCY (31) Choong Hyo Park - INCREASE OF GENERATING POWER OF CANTILEVER TYPE PIEZOELECTRIC GENERATORS BY INTERCONNECTING THE GENERATORS (36)
18:00
18:15 Glenn J. T. Leighton - ORIENTATION DEPENDANT ELASTIC PROPERTIES OF FERROELECTRIC THIN FILMS (50) Kaynts Diana - FORMATION OF FERROELECTRIC INCLUSIONS IN THE MATRIX (Sb2S3)100-x(AsSI)x AND (As2S3)100-y(SbSI)y GLASSES (112) 18:30 18:45
18:30
18:45
Thursday 4 August
Plant Sciences Lecture Theatre Earth Sciences Lecture Theatre
9:00
9:00
Medical applications Plenary - Chair M. Goryll
Susan Trolier-McKinstry - MEDICAL APPLICATIONS OF PIEZOELECTRIC MICROELECTROMECHANICAL SYSTEMS (159) 9:45
9:45
Medical applications Plenary - Chair M. Goryll
M. Klee - PIEZOELECTRIC THIN FILMS A TECHNOLOGY PLATFORM FOR INNOVATIVE DEVICES (234)
10:30
Tea/coffee
Tea/coffee
Tea/coffee
10:30 11:00
11:00
Chair - D. Chrisey and M. Goryll

Todd C. MacLeod - INITIAL RESULTS FROM ON-ORBIT TESTING OF THE FRAM MEMORY TEST EXPERIMENT ON THE FASTSAT MICRO-SATELLITE (163)
Hedi Mattoussi- COLLOIDAL INORGANIC NANOCRYSTALS AS FLEXIBLE PLATFORMS FOR IMAGING AND SENSING (230)
Devices Chair - Joe Evans and MacLeod
Ferroelectrics Experimental Chair - H. N. Lee

Keisuke Kobayashi - STUDY OF DEFECTS AND DOMAIN STRUCTURE FOR CONTROLLING PIEZOELECTRIC RESPONSE IN (Na,K)NbO3 (95) Pintilie Lucian - COMPARISON BETWEEN THE ELECTRICAL PROPERTIES OF TETRAGONAL Pb(Zr,Ti)O3 AND BaTiO3 EPITAXIAL THIN FILMS (20)
11:15
11:15
11:30 Joe Evans - AN AUTONOMOUS NON-VOLATILE MEMORY LATCH (77)
Orlando Auciello - OXIDE AND ULTRANANOCRYSTALLINE DIAMOND FILMS AS PLATFORM MATERIALS FOR A NEW GENERATION OF MULTIFUNCTIONAL BIOMEDICAL DEVICES AND BIOSENSORS (199)
Ricardo Jimnez Riobo - ADVANCED CHEMICAL SOLUTION DEPOSITION METHODS FOR THE LOW TEMPERATURE PROCESSING OF FERROELECTRIC THIN FILMS (149) Andreas Klein - VARIATION OF FERMI LEVEL POSITION IN FERROELECTRIC MATERIALS: BARRIER HEIGHTS AT ELECTRODE INTERFACES AND ELECTRICAL CONDUCTIVITY (174)
11:30
11:45
11:45
12:00
Michael Goryll -TRANSPORT THROUGH BIOGENIC SILICA NANOPORE MEMBRANES ON SILICON SUBSTRATES (52)
Mitsue Takahashi - NAND FLASH MEMORY BY FERROELECTRIC-GATE FIELD- A. Roy - EFFECT OF ERBIUM DOPANT ON THE BAND GAP ENERGIES OF RF EFFECT-TRANSISTOR INTEGRATION (205) SPUTTERED Ba0.8Sr0.2TiO3 THIN FILMS (24)
12:00
12:15
12:15
ISIF 2011 Poster Session A - Tuesday 2 August, 12:20 - 13:30

RRAMs
Kyung Jean Yoon Pawan K. Sharma R. Soni Gleb Cheglakov Bach Thang Phan Chanwoo Park Memristive Switching utilizing the electronic bipolar resistive switching Titanium dioxide (81) Ferromagnetic Ordering in Lanthanum Substituted Nano-Cobalt Ferrite at Room Temperature (141) RANDOM TELEGRAPH NOISE IN Cu DOPED Ge0.3Se0.7 BASED RESISTIVE SWITCHING MEMORY CELLS (157) CHARACTERISATION OF NiO EPITAXIAL FILMS DEPOSITED BY MOLECULAR BEAM EPITAXY (241) COPPER IONS INDUCED RESISTANCE SWITCHING IN ZnO THIN FILMS (251) Resistive switching characteristics and different forming states of Ti/ Pr0.48Ca0.52MnO3 junctions (255)
BiFeO3 and Multiferroics

Jim Bennett Jinsong Zhu Meghdad Palizdar Meghdad Palizdar R.Muralidharan Kai Chen Maria Polomska Clare Cambridge Danyang Wang Lourdes Fbrega S. G. Shivareddy Ignasi Fina Ryan Cherifi Xiaobing Chen J. W. Kim Dalhyun Do STRUCTURE AND FERROELECTRIC PROPERTIES IN THE (1-X)BIFEO3-X(K0.5BI0.5)TIO3 PIEZOELECTRIC CERAMIC SYSTEM (70) Dielectric, Magnetic, Multiferroicic Properties in Garnet Re3Fe5O12 ceramics (71) REACTIVE TEMPLATE GRAIN GROWTH OF BiFeO3-PbTiO3 BY USING Bi4Ti3O 12 AND PbBi4Ti4O15 AS TEMPLATE (136) SYNTHESIS OF ORIENTED BiFeO3-PbTiO3 BY MOLTEN SALT METHOD (137) EFFECT OF SUBSTRATE INDUCED STRAIN ON THE MORPHOTROPIC PHASE BOUNDARY OF BiFeO3-PbTiO3 EPITAXIAL THIN FILMS (147) 2D Multiferroic Photonic-Band-Gap Materials for Tunable and Absolute Electromagnetic Vacuum (110) SOLID-SOLID SOLUTIONS OF BiFeO3: MECHANOCHEMICAL SYNTHESIS AND RAMAN STUDIES (143) GROWTH AND CHARACTERIZATION OF HIGH QUALITY BiFeO3-PbTiO3 SINGLE CRYSTALS (37) STRUCTURAL, ELECTRICAL AND MAGNETIC PROPERTIES OF (La, Mn) COSUBSTITUTED BiFeO3 THIN FILMS (11) FERROELECTRIC SWITCHING AND CYCLOIDAL ORDER IN o-YMnO3 THIN FILMS (177) PFM STUDIES OF Bi1-xPrxFe0.95Co0.05O3 THIN FILMS DERIVED BY CHEMICAL SOLUTION DEPOSITION METHOD (182) TAILORING FERROELECTRICITY IN CoFe2O4-BaTiO3 BILAYERS (185) NOVEL PHASES INDUCED AT INTERFACES WITH FERROELECTRICS (187) STUDY OF STRUCTURAL, MAGNETIC AND FERROELECTRIC ON Bi5FeTi3O15 AND Bi5Fe0.5Co0.5Ti3O15 CERAMICS (212) EFFECTS OF ANNEALING ATMOSPHERE ON STRUCTURE AND ELECTRICAL PROPERTIES OF (Bi0.9Eu0.1)(Fe0.9Mn0.1)O3- THIN FILMS (215) STRUCTURE AND ELECTRICAL PROPERTIES OF RARE-EARTH SUBSTITUTED Bi(Fe0.975Cu0.025)O3- THIN FILMS PREPARED BY CHEMICAL SOLUTION DEPOSITION (216) ENHANCEMENT OF FERROELECTRICITY IN RARE EARTH AND MANGANESE IONS CODOPED BiFeO3 THIN FILMS VIA CHEMICAL SOLUTION DEPOSITION METHOD (217) FABRICATION AND PROPERTIES OF BaTiO3-CuFe2O4 BI-LAYER THIN FILMS (252) COMPARATIVE STUDY ON STRUCTURE AND FERROELECTRIC PROPERTIES OF DIFFERENT RARE-EARTH SUBSTITUTED MULTIFERROIC BiFeO3 (249) RARE EARTH SUBSTITUTED MULTIFERROIC BiFeO3 (257)
C. M. Raghavan
Dong-Jin Yoon Zhangjian Zhou Christopher Kavanagh
Energy harvesting
Susanne Stemmer PEROVSKITE-BASED OXIDE THERMOELECTRICS (181)
High-K dielectrics and polymers

Catherine Dubourdieu Aidong Li Caroline Borderon MICROSTRUCTURE AND MOS CAPACITOR PROPERTIES OF Bi2Fe4O9 FILMS GROWN ON Si(001) (43) CHARACTERISTICS OF Gd2-xLaxO3 HIGH-K FILMS BY METAL-ORGANIC CHEMICAL VAPOR DEPOSITION (206) THE EFFECT OF MN DOPING ON THE DIELECTRIC PROPERTIES AND DOMAIN WALL MOBILITY OF (Ba0.8Sr0.2)TiO3 THIN FILMS (76) TEMPERATURE CONTROL OF P(VDF-TRFE) COPOLYMER THIN FILMS DERIVED BY SOLGEL PROCESS (250)
Zhangjian Zhou
Spintronics and electronic devices

H.Z. Zeng TRAPPING PROPERTIES OF LiNbO3 /AlGaN/GaN METAL-FERROELECTRICSEMICONDUCTOR HETEROSTRUCTURE CAPACITORS BY CONDUCTANCE MEASUREMENTS (209) LIGHT CONTROLLED RESISTIVE SWITCHING IN AMORPHOUS AL2O3 FILMS (239) FABRICATION AND CHARACTERISATION OF Fe/GaAs ELECTRICAL SPIN INJECTION DEVICE (242) CO ADSORBATE INDUCED SPIN-REORIENTATION TRANSITION OF Co/Cu(110) (243) CHARACTERIZATION OF A COMMON-GATE AMPLIFIER USING FERROELECTRIC TRANSISTORS (130) ELECTRICAL PROPERTIES OF ZnO THIN FILMS ON DIFFERENT SUBSTRATES (259)
Mariana Ungurean Jun-Young Kim Shin Liang Chin Fat D. Ho M. Echizen
ISIF 2011 Poster Session B - Wednesday 3 August, 12:20 - 13:30

Ferroelectrics Theory
Pavel Marton Lang Chen Rhodri Lewis LARGE PIEZOELECTRIC RESPONSE IN NANOTWINNED BATIO3 REVISITED (126) Stability and crossover of 109 and 71 domains influenced by thickness and depolarization field in rhombohedral ferroelectric thin films (102) ROLE OF SINGLE-CRYSTAL PILLARS IN FORMING THE EFFECTIVE PROPERTIES AND FIGURES OF MERIT OF NOVEL 13 PIEZOCOMPOSITES (153)
Devices
Ying Dai Longhai Wang Cody Mitchell Caroline S. John Tom Phillips Alexis Borowiak ADDRESSABLE METAL-FERROELECTRIC-METAL NANOCAPACITOR ARRAYS FABRICATED BY FOCUSED ION BEAM MILLING (122) LEAKAGE CURRENT AND DIELECTRIC PROPERTIES OF INTEGRATED FERROELECTRIC CAPACITOR ETCHED IN NON-CRYSTALLINE PHASE (123) CHARACTERISTICS OF A NONVOLATILE SRAM MEMORY CELL UTILIZING A FERROELECTRIC TRANSISTOR (88) CHARACTERIZATION OF AN AUTONOMOUS NON-VOLATILE FERROELECTRIC MEMORY LATCH (83) Modeling of SONOS Memory Cell Erase Cycle (164) PULSED LASER DEPOSITION OF EPITAXIAL PZT FILMS ON STO AND SI SUBSTRATES FOR NON-VOLATILE MEMORY APPLICATIONS (254)
Superlattices
Won-Jeong Kim LEAKAGE CURRENT BEHAVIORS OF SrTiO3/BiFeO3 MULTI-LAYERS FABRICATED BY PLUSED LASER DEPOSITION (113)
Nanodomains and nanocrystals

L. J. McGilly Jess Ricote DOMAIN CONFIGURATIONS IN MORPHOTROPIC PHASE BOUNDARY PbZr(1-x)Ti(x)O3 (120) CO IMPLANTATION OF Pb(Mg1/3Nb2/3)O3-PbTiO3 SINGLE CRYSTALS: EFFECT ON THE FERROELECTRIC DOMAIN CONFIGURATION (13)
Ferroelectrics Experimental
Vitaly Yu. Topolov Robert Dorey Zdravko Kutnjak Yoshiaki Yoshida Raphal Renoud Oleksandr Gomonnai Maksim Ivanov M. Lourdes Calzada Thorsten Bayer Jianhua Hao Juras Banys Emmanuel Le Boulbar M. H. Kim M. H. Kim Tsuyoshi Osumi. Hyunwoo Choi Choon-Ho Lee Do-Woo Kim D.J. Keeble Zhangjian Zhou Sarah Turp NOVEL HIGH-SENSITIVE COMPOSITES BASED ON FERROELECTRIC CERAMICS (165) INTEGRATED THICK FILM ACOUSTIC EMISSION SENSOR FOR STRUCTURAL HEALTH MONITORING (60) Improvement of piezoelectric response in (Pb(Mg1/3Nb2/3)O3)0,74-(PbTiO3)0,26 ferroelectric relaxor near the morphotropic phase boundary (133) Dry etching properties of Piezoelectric MEMS (170) Dielectric properties of PZT thin films under a low ac-electric field at different bias fields (64) HYDROSTATIC PRESSURE EFFECT ON PHASE TRANSITIONS IN TlIn(S0.97Se0.3)2 FERROELECTRIC (51) DIELECTRIC SPECTROSCOPY OF NANOGRAIN PSN CERAMICS (125) FERROELECTRIC AND PIEZOELECTRIC PROPERTIES OF MULTILAYER COMPOSITE THIN FILMS BASED ON MPB Pb(Mg1/2Nb2/3)O3PbTiO3 (33) Temperature dependent electric and dielectric analysis of BST films with blocking and injecting electrodes (14) REVISIBLE MODIFICATION OF PHOTOLUMINESCENCE IN FERROELECTRICS (99) TWO DIMENSIONAL DISTRIBUTION OF THE RELAXATION TIMES OF RELAXORS (25) HIGH TEMPERATURE MEASUREMENT OF ELASTIC MODULI OF BULK (0001) FREESTANDING GaN AND RELATED SUBSTRATES (128) Effects of Additives on Dielectric and Piezoelectric Properties of (Na0.53K0.47)(Nb0.55Ta0.45)O3 Ceramics (144) Effects of A-site Non-Stoichiometry on Dielectric and Piezoelectric Properties of (Na0.50+xK0.50+y)(Nb0.55Ta0.45)O3 Ceramics (145) Preparation and characterization of BaTiO3 thin films using reactive sputtering method (166) Effects of surface morphology on the retention loss of ferroelectric domains in P(VDF-TrFE) thin films (191) Characteristics of BaNb2O6 Thin Films made by MOCVD using Ultrasonic Nebulization (195) Preparation of Ba6Ti2Nb8O30 Thin Films by MOCVD using Ultrasonic Nebulization (196) VACANCY DEFECTS IN UNDOPED AND IRON DOPED STRONTIUM TITANATE THIN FILMS OBSERVED BY POSITRON ANNIHILATION LIFETIME SPECTROSCOPY (214) Zhangjian Zhou - TEMPERATURE DEPENDENCE OF OPTICAL PROPERTIES OF NDDOPED BISMUTH TITANATE THIN FILM FOR OPTICAL APPLICATION (248) BaTiO3-BASED LEAD-FREE PIEZOELECTRICS (256)
rf and high-frequency devices

Andrei Vorobiev Spartak Gevorgian Hartmut Gundel High Q-factor Ba0.25Sr0.75TiO3 thin film bulk acoustic wave resonators: growth conditions and correlations with microstructure (3) MODEL OF FERROELECTRIC FBARs INCLUDING LONGITUDINAL AND SHEAR WAVES (198) WET CHEMICAL ETCHING OF BaSrTiO3 FERROELECTRIC THIN FILMS FOR INTELLIGENT ANTENNA APPLICATION (253)
PREFERENTIAL CRYSTAL GROWTH OF MBi4Ti4O15 (M = Ca, Sr) FILMS USING NANOSHEET TEMPLATE
HIROSHI UCHIDA1), YOUTA KONDO1), JUNICHI KIMURA2), ITARU TAKUWA2) AND HIROSHI FUNAKUBO2) 1) SOPHIA UNIVERSITY AND 2) TOKYO INSTITUTE OF TECHNOLOGY
Contact address: uchidah@sophia.ac.jp Thin films of bismuth layer-structured dielectric (BLSD), CaBi4Ti4O15 and SrBi4Ti4O15, were prepared on nanosheet template of Ca2Nb5O10 for assembling the crystal orientation and the dielectric properties of the BLSD crystals on silicon wafer. One-axis oriented BLSD films were designed for the application of high-end dielectric capacitors driving under high-temperature region because BLSD crystals possess small temperature coefficient of capacitance (TCC) as well as excellent dielectric permittivity with little size effect and high electrical resistivity along to the c-axis direction. The BLSD films were synthesized by chemical solution deposition technique on platinized silicon wafer with Ca2Nb5O10 nanosheet templates which was supported by chemical treatment followed by dip coating . The Ca2Nb5O10 nanosheets were supported on the substrate surface with (00l) preferential crystal orientation. The films consisted of BLSD crystal with preferential orientation of (00l) plane normal to the substrate surface with nanosheet templates, whereas random oriented BLSD crystals with poor crystallinity were only obtained on the substrate without template layers. Anisotropic crystal growth of BLSD occurred by the lattice matching between perovskite blocks in BLSD crystal and crystal lattices of nanosheet templates with pseudo-perovskite structure.
MICROWAVE RESPONSE OF BiFeO3 FILMS IN PARALLEL-PLATE CAPACITORS A. Vorobiev, T. Ahmed, S. Gevorgian, Chalmers University of Technology, SE-41296 Gothenburg, Sweden
BiFeO3 (BFO) is extensively considered for its multiferroic and multifunctional properties. Non-volatile memory and sensors are only some of the applications to mention. Its relatively high piezoelectric constant makes BFO attractive for applications in thin film bulk acoustic wave resonators (FBARs). Low permittivity is beneficial for high power applications, and the high Curie temperature ensures low temperature dependence of its parameters. In this work the dielectric and piezoelectric properties BFO films in parallelplate configuration are studied at microwave frequencies in a view of their applications in tunable FBARs. The 150 nm thick BFO films are grown by pulsed laser deposition on platinum bottom electrodes. Fused silica is used as the substrates. X-ray diffraction analysis indicates that the BFO films are strongly (111)pseudocubic oriented as a result of growth facilitated by the Pt(111) texture. The dielectric response of the BFO films is measured at 1 MHz and in the frequency range 1-30 GHz under different dc electric fields. The dc bias is changed from zero (non-poled state) up to 33 V/m and then reversed down to zero. The measured break down field, ca. 500 kV/cm, is sufficiently high to ignore any effects associated with leakage current. The 1 MHz permittivity and loss tangent correspond to those measured in the microwave range. Their frequency dependences (only permittivity is shown in Fig. 1) reveal no remarkable relaxation phenomena which may be considered as evidence that non-180 domain wall processes are strongly limited as it should be in (111) oriented BFO films. The permittivity is higher than that reported for BFO ceramics (ca. 30), most likely, due to compressive out-of-plane strain caused by large difference in thermal expansion coefficients of the BFO film and silica substrate. Additionally, we assume that vibrations of the domain walls may contribute to the total permittivity since irreversible polarization behaviour is detected in the whole frequency range (Fig. 1). As an example of the irreversible polarization response, Fig. 2 shows the permittivity and loss tangent at 10 GHz versus electric field varying in the arrow directions starting from a non-poled state. Fig. 3 shows frequency dependences of the loss tangent of a BFO film at different dc electric fields. Increase of loss tangent with frequency in the whole range confirms negligible contribution of the leakage current. The dependences reveal resonant peaks due to both intrinsic (field independent) and field induced (at 3.2 GHz and 5.5 GHz) piezoeffects. The resonances arise at different frequencies due to reflections of acoustic waves from different interfaces of the multilayer test structure. The rather intensive field induced resonance at ca. 3.3 GHz indicates that electrostrictive coefficient of the BFO films is high enough for its application in the tunable FBARs.
Fig. 1. Permittivity of a BFO film vs. frequency at different dc electric fields.
Fig. 2. Permittivity (circles) and loss tangent (squares) of a BFO film at 10 GHz vs. dc electric fields.
Fig. 3. Loss tangent of a BFO film vs. frequency at different dc electric fields.
STUDY OF LUFE2O4 THIN FILM GROWTH AND ITS STRUCTURAL AND MULTIFERROIC PROPERTIES J.Y. Dai Department of Applied Physics, The Hong Kong Polytechnic University, Hong Kong, P.R. China.
LuFe2O4 has attracted extensive research interest due to its novel electronic ferroelectricity and multiferroic properties. In particular, its giant dielectric tunability under magnetic field and electric fields suggests that this material has great potential in application of a variety of electronic devices such as multiferroic memory and tunable microwave and optical devices. The successful growth of LuFe2O4 film is essential for applying this material to integrated electronic devices, and the thin film form of LuFe2O4 may present some unique characteristics which do not exist in its bulk. However, due to the difficulty in forming LuFe2O4 phase in grown film, the report on the study of LuFe2O4 film is rare [1]. In this paper, we report the growth of the LuFe2O4 film as well as structural and multiferroic properties of the film. LuFe2O4 thin films are epitaxially deposited on sapphire substrate by pulsed-laser deposition. Different growth conditions are tackled and it is found that substrate temperature is the most critical condition for the film growth (should be 750oC above); while below 750 oC the films crystallization is poor. The Lu:Fe ratio is also found to be important in forming the LuFe2O4 phase in the film; while higher content of Fe oxide in the target is favorable for the formation of LuFe2O4 phase. However, impurity phases such as Fe3O4 and Fe2O3 are induced in the film with a Fe oxide enriched target. A large dielectric tunability under electric field is revealed in the film; while the dielectric tunability decreases as the frequency increases, and eventually the dielectric tunability disappears above 500 MHz. Nonlinear I-V loop characteristic of the LuFe2O4 thin film is revealed, and electric field induced phase transition is observed at the Neel temperature (250 K) and charge order transition temperature (340 K) of the LuFe2O4 film, respectively. An insulator-to-metal phase transition is also observed at 340 K in the temperaturedependent dielectric curve of the LuFe2O4 film. Presence of very large dielectric tunability under both magnetic and electric fields reveals strong magnetoelectric coupling in the LuFe2O4 thin film. [1] J. Liu, Y. Wang and J.Y. Dai, Structural and dielectric properties of LuFe2O4 thin films grown by pulsed-laser deposition, Thin Solid Films 518 (2010) 6909. Corresponding contact: apdaijy@inet.polyu.edu.hk
ISIF 2011 Multiferroics and Magnetoelectrics: Theory & Experiments (2)
The authors gratefully acknowledge financial support from the Hong Kong Research Grant Council (No. PolyU 500609).
BAND GAP NARROWING IN EPITAXIAL FERROELECTRICS BY A MOTT INSULATOR
H. N. Lee, W. S. Choi, M. F. Chisholm, G. E. Jellison, Jr., and D. J. Singh Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA
The effort to search for highly efficient photovoltaic materials has recently been extended to the field of transition metal oxides, where the strong correlation of electrons gives us extra degrees of freedom. Here, we present a novel route to modifying the band gap of a ferroelectric oxide with a Mott insulator. Single crystalline Bi4Ti3O12 thin films atomically doped with LaCoO3 are studied as a possible candidate for a small band gap ferroelectric. Bi4Ti3O12 is composed of alternating two Bi-Ti-O perovskite blocks and a Bi-O layer, making a highly anisotropic structure. Thus, we have attempted by pulsed laser epitaxy to modify the local structure of Bi4Ti3O12 by precise mixing of LaCoO3. We could successfully intercalate the LaCoO3 layers within the Bi4Ti3O12 layers, forming a layered composite oxide structure. Spectroscopic ellipsometry results indicated that the optical gap of Bi4Ti3O12 (Eg=3.5 eV) could be reduced to Eg=2.6 eV, i.e., a 30% reduction, by intercalating two unit cell layers of LaCoO3 to a unit cell of Bi4Ti3O12 layer. Moreover, between 2 and 3 eV, the optical conductivity was as large as 1100 1 cm-1, indicating considerable absorption in the visible wavelength range. As a result. the photocurrent measurement showed a significant increase in photo-induced charges. In this talk, therefore, the underlying mechanism of band gap lowering will be discussed in terms of modified crystal structure and chemical environment based on results from density-functional theory and electron energy loss spectroscopy studies. Research sponsored by the Materials Sciences and Engineering Division, Office of Basic Energy Sciences, U.S. Department of Energy and by the Laboratory Directed Research and Development Program of Oak Ridge National Laboratory.
DIRECTEVIDENCEOFCATIONICBSITEORDERINGINMULTIFERROICBi2FeCrO6 NANOSTRUCTURESBYMAGNETICCIRCULARDICHROISM R.Nechache1,C.Nauenheim2,U.Lanke3,A.Pignolet2,F.Rosei2,A.Ruediger2

1
NASTCenter&DepartmentofChemicalScienceandTechnology,UniversityofRomeTor Vergata,ViadellaRicercaScientifica1,00133Rome(Italy) Centrenergie,MatriauxetTlcommunications,INRS,1650,boulevardLionelBoulet, Varennes,QubecJ3X1S2,Canada.

3
CanadianLightSourceInc.101PerimeterRoadSaskatoon,SKS7N0X4,Canada.
We report on recent findings on magnetic ordering in cationic sublattices of nanostructured doubleperovskiteBi2FeCrO6asinvestigatedbyxraycircularmagneticdichroismatthesoftx ray beam line at the Canadian Light Source [1]. Our results indicate a high degree of antiferromagnetic ordering between the iron and chromium sublattices resulting in room temperatureferrimagnetism.Thisresultpavesthewayfordifferentfascinatingfieldsoffurther research including a tunable band gap by variation of the degree of cationic ordering, room temperaturemagnetoelectriccouplingandspinvalveapplications.
Figure 2. XPEEM at RT and zero magnetic field obtained for both Fe and Cr cations: Left circular polarization (LCP) for (a) Fe and (d) Cr; Right circular polarization(RCP) for (b) Fe and (e) Cr. (c) and (f) XMCD images for Fe and Cr, respectively and (g) the corresponding lines profiles. [1]R.Nechache,C.Nauenheim,U.Lanke,A.Pignolet,F.Rosei,A.RuedigerLocalelectronicand magneticinvestigationsofepitaxialBi2FeCrO6nanostructures,submitted
UNEXPECTEDLY LARGE ELECTRONIC CONTRIBUTION TO MAGNETOELECTRICITY

Eric Bousquet1,2 and Nicola Spaldin1 Materials Theory, ETH Zurich, Switzerland 2 Physique Thorique des Matriaux, Universit de Lige, Belgium email: eric.bousquet@mat.ethz.ch
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ISIF 2011, Multiferroics and Magnetoelectrics: Theory and Experiments
Magnetoelectrics are materials that respond with a change in electric polarization to a magnetic field, and conversely with a change in magnetization to an electric field. The research challenges in identifying materials with useful magnetoelectric (ME) responses are threefold: (i) Symmetry requirements that both space-inversion and time-reversal symmetries be broken are satisfied by few materials, (ii) materials satisfying these criteria tend to do so only in phases that develop at relatively low temperatures, and (iii) most of the MEs discovered to date have weak responses. Recently, a number of developments have led to a significant revival of activity in the search for novel magnetoelectric materials, including the observation that multiferroics can have strong ME responses [1]. First-principles methods are emerging as a valuable tool for computing the strength of ME response in real materials without any empirical input. The methods are becoming sufficiently reliable to be used in a predictive capacity in searching for new ME materials. While many approaches have been explored or can be envisaged, by far the most successful and widely used approach to date has been a linear-response approach based on the latticedynamical quantities [2]. However, this approach computes only the so-called latticemediated part of the ME response and ignores purely electronic contributions. The common justification is that such contributions are expected to be weak, just as in strong dielectrics the electronic response is negligible compared to the ionic contribution. Here we show, using an alternative numerical approach involving a self-consistently applied magnetic field, that the purely electronic ME response can in fact be large [3], even in materials with relatively strong ME response in which one might expect the response to be dominated by lattice mechanisms. We will illustrate this effect in three cases: (I) The beststudied ME crystal, Cr2O3, (ii) the lithium orthophosphate LiNiPO4 and (iii) strained multiferroic perovskites ABO3. While the two first cases will allow us to highlight the non negligible electronic contribution in regular ME, we will focus on the later case to show that even around a ferroelectric phase transition, where we would expect a large and dominant lattice contribution to the ME response, the electronic contribution can still be strong. Furthermore this last example will be used as a key case to demonstrate the possibility to tune giant linear and non-linear ME responses in multiferroic ABO3 by playing with epitaxial strain. [1] M. Fiebig, J. Phys. D 38, R123 (2005). [2] J. Iniguez, Phys. Rev. Lett. 101, 117201 (2008). [3] E. Bousquet, N. A. Spaldin and K. T. Delaney, Phys. Rev. Lett. 106, 107202 (2011).
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CALORIMETRIC STUDY OF GIANT ELECTROCALORIC EFFECTS IN BaTiO3 SINGLE CRYSTALS X. Moya1, E. Stern-Taulats2, D. Gonzlez-Alonso2, Ll. Maosa2, A. Planes2 and N. D. Mathur1
1 2
Department of Materials Science, University of Cambridge, Cambridge, CB2 3QZ, UK Departament dEstructura i Constituents de la Matria, Facultat de Fsica, Universitat de Barcelona, Diagonal 647, E-08028 Barcelona, Catalonia, Spain
Session: Electrocalorics, Thermoelectrics, and Energy Harvesting E-mail: xm212@cam.ac.uk Preferred presentation type: Oral The electrocaloric (EC) effect is the isothermal entropy change S or adiabatic temperature change T in a material driven by a change in applied electric field. EC effects are normally evaluated via electrical polarization measurements using indirect methods based on a Maxwell relation. This approach is valuable for rapid testing, but is no substitute for direct measurements. Here, we report direct measurements of electrically driven heat and entropy changes in single crystals of the prototypical ferroelectric BaTiO3 by means of a purpose-built differential scanning calorimeter with electrical access. Large heat and entropy changes of ~900 J kg-1 and ~2.2 J K-1 kg-1, respectively, have been obtained in electric fields of 4 kV cm-1. Results are compared with those obtained from electrical polarization data.
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Bottom electrode materials for BST thin film varactors

Karsten Rachut, Shunyi Li, Robert Schafranek, Andreas Klein Technische Universitt Darmstadt, Department of Materials and Earth Sciences, Surface Science Division, Petersenstrasse 32, D-64287 Darmstadt, Germany Yuliang Zheng, Rolf Jakoby Technische Universitt Darmstadt, Institute for Microwave Engineering and Photonics, Merckstrasse 25, D-64283 Darmstadt, Germany Abstract: Bottom electrode materials are of particular interest for the performance of barium strontium titanate (BST) thin film varactors. (Ba,Sr)TiO3 serves as a tunable dielectric material in typically used metal-insulator-metal structures. High quality factors (Q-factors) as well as high tunability are of great importance for the application. The preparation of bottom electrodes is particularly challenging because it requires good interface properties to BST, chemical stability at elevated temperatures and oxidizing atmospheres during the BST deposition process. In addition, a high conductivity and a good adhesion to the substrate is demanded. Whereas dielectric losses at MHz frequency are dominated by the BST properties, the metallization loss is dominant in the GHz range. The resistance of the bottom electrode can either be reduced by increasing film thicknesses or using low resistivity materials. Pt is mostly used for this application. Yet there are morphological difficulties like hillocking or delamination besides the high price making thick bottom electrodes commercially impractical. We have studied the growth of Pt by DC magnetron sputtering on different substrates like TiO2/SiO2/Si-wafers and Al2O3 (0001) single crystals. AFM examinations demonstrate morphological influences of the substrate materials. Hillock formation is significantly reduced on sapphire substrates providing homogeneous defined surfaces for subsequent BST deposition. This allows a systematic study of the dependence of the (di-)electric properties (permittivity, tunability, Q-factor, leakage current) of Pt/BST/Pt varactors on Pt film thickness. Further understanding of Pt bottom electrode may allow total device optimation including BST improvement for microwave applications. We also address the difficulties with alternative, less expensive, bottom electrode structures like base-metals combined with diffusion barrier layers or passivation layers. Interdiffusion of metallic multilayers and electric contact formation with BST are examined using photoemission (XPS, UPS) and (di)electric measurements. Different material combinations are tested with respect to their interaction with RF magnetron sputtered BST films and the resulting varactor properties.
The topic under which your abstract should be considered for presentation Tunable Dielectrics for RF Applications and Devices Presenting author's affiliation and email address Darmstadt University of Technology, Germany krachut@surface.tu-darmstadt.de Preference to oral or poster presentation Oral presentation
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GIANT AND REVERSIBLE STRAIN-MEDIATED MAGNETOCALORIC EFFECTS IN FERROMAGNETIC-FERROELECTRIC HETEROSTRUCTURES
X. Moya1, L. E. Hueso2,3, F. Maccherozzi4, A. I. Tovstolytkin5, D. I. Podyalovskii5, C. Ducati1, L. Phillips1, M. Ghidini1, O. Hovorka2, A. Berger2, M. E. Vickers1, S. S. Dhesi4 and N. D. Mathur1 Department of Materials Science, University of Cambridge, Cambridge, CB2 3QZ, United Kingdom. 2 CIC nanoGUNE Consolider, Tolosa Hiribidea 76, E-20018 Donostia - San Sebastian 3 IKERBASQUE, Basque Foundation for Science, E-48011 Bilbao, Spain. 4 Diamond Light Source Ltd., Harwell Science and Innovation Campus, Chilton, Didcot, Oxfordhire, OX11 0DE, United Kingdom. 5 Institute of Magnetism, 36b Vernadsky Blvd., Kyiv 03142, Ukraine. Session: BiFeO3 and other Multiferroics E-mail: xm212@cam.ac.uk Preferred presentation type: Oral Concomitant magnetic and structural phase transitions are important in many applications, e.g. magnetostriction, magnetoresistance and magnetocalorics. However, structural phase transitions arise in only a few classes of magnetic materials. Here, we report the existence of extrinsic magnetostructural transitions in ferromagnetic La1-xAxMnO3 (A = Sr, Ca) manganite films due to strain from ferroelastic-ferroelectric BaTiO3 substrates. Using macroscopic magnetometry and calorimetry data, we will show that giant magnetically driven entropy changes arise in our films near these transitions, with magnitudes that are comparable with the best magnetocaloric materials. Microscopic insight into these extrinsic magnetocaloric effects is provided by photoemission electron microscopy (PEEM) with x-ray magnetic circular dichroism (XMCD) contrast, and also ferromagnetic resonance (FMR).
1
16
PATTERN TRANSFER AND ELECTRIC-FIELD INDUCED MAGNETIC DOMAIN FORMATION IN MULTIFERROIC HETEROSTRUCTURES
Tuomas H.E. Lahtinen, Jussi O. Tuomi, and Sebastiaan van Dijken* NanoSpin, Department of Applied Physics, Aalto University School of Science, P.O. Box 15100, FI00076 Aalto, Finland The ability to tailor magnetic properties via coupling to ferroelectric domains is of great interest for the design of electric-field tunable magnetic devices. Imprinting of ferroelectric domains into continuous magnetic films would enable local control over magnetization dynamics, but requires interfacial coupling to overcome exchange and magnetostatic interactions within the ferromagnet. Here, we demonstrate full pattern transfer and electric-field induced magnetic domain formation in multiferroic heterostructures consisting of a ferroelectric substrate (BaTiO3) and a thin magnetic film (CoFe). Simultaneous imaging of ferroelectric and ferromagnetic domains and local magnetization reversal analysis using polarization microscopy reveals strong lateral modulations of magnetic hysteresis due to strain coupling to the underlying ferroelectric substrate. While the magnetic configuration is an exact copy of the ferroelectric domain structure in the as-deposited state, new magnetic domains form when an external electric field is applied. In fact, the electric-field response of the magnetic film is characterized by a superposition of two patterns, one that mirrors the current ferroelectric domain configuration (electric-field induced pattern) and another that reflects the ferroelectric domain structure during deposition (growth-induced pattern). This ability to electrically write magnetic domains in continuous magnetic films opens up new avenues for electric-field control of magnetic functionalities and provides a framework for the exploration of ferroelectric, ferroelastic, and ferromagnetic domain interactions in multiferroic heterostructures.
Magnetic hysteresis curve and polarization microscopy images of the ferroelectric (FE) and magnetic domain structure during several stages of the magnetization reversal process (R1, S1, R2, S2). The images clearly demonstrate full imprinting of the ferroelectric stripe pattern into the continuous magnetic film in the as-deposited state. The arrows in the images indicate the orientation of ferroelectric polarization (FE) and film magnetization in the remnant state (R1 and R2) and during abrupt magnetic switching (S1 and S2). The imaged areas are 30 40 m.
* E-mail: sebastiaan.van.dijken@aalto.fi
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The application of bismuth-based oxides in hybrid photovoltaic devices

Feng Yan and Zhike Liu Department of Applied Physics and Materials Research Center, The Hong Kong Polytechnic University, Hong Kong, Peoples Republic of China. Email: apafyan@polyu.edu.hk Bi-based ferroelectric oxides, a large family that includes BiFeO3, Bi2WO6, BiVO4, etc. have drawn much interest recently due to their interesting physical properties, such as multiferroic, photocatalytic and photovoltaic properties. Recently, people have paid much attention on hybrid solar cells based on the combination of n-type inorganic and p-type organic semiconductors that form a p-n junction. Such hybrid solar cells based on TiO2 or ZnO have been extensively studied for many years. In this paper we will report the application of bismuth-based ferroelectric oxide films in hybrid photovoltaic devices since the bismuth oxides show higher light absorbance than TiO2, ZnO in the visible region, which is critical to the photovoltaic devices. The photovoltaic effect of the heterojunction based on BiFeO3 and organic semiconductor poly(3-hexylthiophene) (P3HT) has been carefully studied. Figure 1a shows a typical rectifying J-V characteristic of the heterojunction with a rectifying ratio of ~103. The power conversion efficiency of the device is comparable to those of hybrid solar cells based on P3HT and other oxide semiconductors, such as TiO2 or ZnO, indicating that BiFeO3 is a promising material for photovoltaic devices. We find that the photovoltaic property of the heterojunction can be improved by optimizing the fabrication conditions and the device structure ( Figure 1b ). Bi2WO6 and BiVO4 films are prepared by pulsed laser deposition method and used as n-type semiconductors to form p-n junctions with P3HT. We find that both devices show excellent photovoltaic performance ( Figure 1c ). In the three types of Bi-based ferroelectric oxides, BVO combined with P3HT exhibits the highest open circuit voltage (0.68V) and short circuit current (0.332 mA/cm2) and thus the highest power conversion efficiency (0.082%), which can be attributed to the suitable band structure of BVO.
Figure 1. (a) Rectifying current-voltage characteristics of a BFO/P3HT heterojunction. The annealing temperature of BFO is 450 C. (b) Current-voltage (J-V) curves of BFO/P3HT photovoltaic devices with different thermal annealing temperatures of BFO. Inset: energy band diagram for the ITO/ BFO/P3HT/Au device; (c) The photovoltaic performance of Bi-based oxide/P3HT, TiO2/P3HT and ZnO/P3HT heterojunctions fabricated at the same condition.
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TETRAGONAL BiFeO3 PHASE WITH GIANT C/A RATIO ON SrTiO3 SUBSTRATES Huajun Liu1, 3,*, Ping Yang2, Kui Yao3 and John Wang1
1
Department of Materials Science and Engineering, National University of Singapore, Singapore 117574, Singapore
2
Singapore Synchrotron Light Source (SSLS), National University of Singapore, 5 Research Link, Singapore 117603, Singapore
Institute of Materials Research and Engineering, A*STAR (Agency for Science, Technology and Research), Singapore 117602, Singapore * Presenting author, email: g0800350@nus.edu.sg
Fig.1. (002) and (-103) HL plane reciprocal space mappings of the BiFeO3 films grown by sputtering at the power of 180 W, showing a tetragonal phase with giant c/a ratio of ~1.23.
Fig.2. Lattice parameters and c/a ratio of the BiFeO3 films grown by sputtering at the powers from 30 to 180 W.
Tetragonal and monoclinic BiFeO3 (BFO) phases with giant c/a ratio have attracted great attention recently, owing to their giant polarization values and outstanding piezoelectric behavior. First principles calculation claimed that it was highly unlikely to form the tetragonal phase with giant c/a on SrTiO3 (STO) substrate. However, by using high resolution synchrotron X-ray diffraction reciprocal space mappings, we demonstrated the existence of tetragonal BFO phase with giant c/a ratio of ~1.23 on SrRuO3 (SRO) buffered STO substrates when grown at a high rate of 180W by radio frequency sputtering (Fig. 1). We further identified the phase transitions from widely reported monoclinic phase to a mixture phase of tetragonal lattice T1 with c/a ~ 1.05 and tetragonal lattice T2 with c/a ~ 1.23, finally to a single tetragonal phase T2 when the growth rate increases (Fig. 2). The origin for forming this tetragonal phase T2 of giant c/a ratio is attributed to self-assembly of a kinetically favored meta-stable phase and the in-situ strain state at high growth rate. The growth rate induced phase transitions promise as an alternative pathway to control new phases in ferroelectric epitaxial thin films.
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Dependence of the Structural, Dielectric, and Ferroelectric properties with Periodicity and Composition in artificial BaTiO3/ (Ba,Sr)TiO3 superlattices
N. Ortega1, A. Kumar1, O.A. Maslova2, Yu. I. Yuzyuk2, J. F. Scott1,3 and R. S. Katiyar1.
1
Department of Physics and Institute for Functional Nanomaterials, University of Puerto Rico, San Juan, PR 00931-3343 USA 2 Faculty of Physics, Southern Federal University, Zorge 5, Rostov-on-Don, 344090, Russia 3 Department of Physics, University of Cambridge, Cambridge CB2 3EQ, UK
ABSTRACT Artificially fabricated superlattices (SLs) constructed by alternate layers of different polar and non-polar perovskite oxides BaTiO3 (BT), SrTiO3 (ST), LaAlO3 and PbTiO3 have been the subject of investigations over the past few years. In addition to novel physics, SLs exhibit superior properties, such as low-loss, high dielectric constant, high polarization, and high Curie temperature that make them attractive for thinfilm device applications. Interesting physical properties, different from parent materials, can be achieved in the SL structure by modifying the lattice, i.e. change in the unit cell, strain, and the lattice mismatches across the interface between the layers and/or at the film-substrate interface. Local stress in the epitaxial films can be controlled by several ways: varying the deposition conditions, the substrate, varying the film thickness, varying the thickness, or altering the lattice parameters by doping. Superlattices of BT/ST and BT/Ba(1-x)SrxTiO3 (BT/BST) with x = (0, 0.3, 0.4, 0.5, 0.6, 0.7, 1) were grown on (001) MgO substrate by pulsed laser deposition techniques. Thin-film stacks were deposited by alternately focusing the beam on stoichiometric BT, ST, and BST targets. The films modulation period () in BT/2/ST/2 SL was varied between ~16 < < 136 , while a constant period of = 136 was kept in BT/2/BST/2 SLs. Irrespective of stacking geometry, the total thickness of each SL film was ~10000 = 1 m. The XRD
patterns of SLs contain so-called satellite peaks typical of modulated structures. X-ray results can be interpreted as diffraction from entire superlattice structure (BT/2 /BST/2) where the unit cell of the SL has a period . This effect was clearly seen in both sets of SLs, while the central peak was at the same position in BT/ST SLs, in case of BT/BST SLs, the central peak moved toward ST position peak when decreasing Ba concentration in BST sublayer. Additionally X-ray diffraction (XRD) patterns and surface topography of the modulated period revealed a StranskiKrastanov growth mechanism. Polarized Raman spectra obtained for BT/ST SLs with 64 and BT/BST are very close to those of the single-domain BT crystal. The most significant difference with respect to pure BT and ST thin films was observed in crossed polarized spectra where the E(TO) component of the soft mode is markedly altered from the bulk value of the BT crystal. The frequency of the E(1TO) soft mode increases with decreasing the modulated
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period from 115 cm-1 ( = 136 ) to 124 cm-1 ( = 64 ) (Figure 1(a)). The compositional changes in BT/BST SLs give large spectral changes at x = 40% where the lowest E(1TO) soft mode became underdamped, the frequency of the E(1TO) mode increased from 35 cm-1 to 115 cm-1 when Ba concentration in the BST sublayers was changed from 100 to 0. The upward frequency shift of the E(1TO) in SLs with decrease in or Ba-concentration in the BST layer was attributed to the in-plane compressive stress induced by the lattice mismatch of the constituent layers. Due to the new artificial periodicity imposed by the superlattice structure, folded acoustic phonon doublets was observed in the low-frequency region of Raman spectra for both sets of SLs. The frequency dependence of the dielectric constant and loss tangent of BT/BST SLs showed almost constant high values of dielectric constant ranging between 1000-2000 below 10 kHz and relatively low loss tangent (~ 0.1) at frequencies below 10 kHz. All BT/BST SLs showed ferroelectric properties, nevertheless strong polarization switching with well saturated hysteresis was observed in BT/Ba0.3Sr0.7TiO3 (BT/BST3070) and BT/Ba0.7Sr0.3TiO3 (BT/BST7030) (Figure 1(b)) at different frequencies. I-V characteristic show a asymmetric behavior due to effect of the dissimilar top and bottom electrodes (Pt and La0.67Sr0.33MnO3), however the superlattices show very low leakage current density far above its coercive field. The temperature dependence of dielectric and ferroelectric properties of the SLs will be discussed.
200 180 160
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20 10 0 -10 -20 -30 -40 -20 0 20 40
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Fig. 1. (a) Frequency () and FWHM of the E(1TO) soft mode as a function of Ba/Sr (%) content in BST layer of BT/BST SLs. (b) Ferroelectric hysteresis loop of BT/Ba0.3Sr0.7TiO3 (BT/BST3070) and BT/Ba0.7Sr0.3TiO3 (BT/BST7030) SLs with a constant modulation period ( = 136 ). Total thickness of the films was ~1000 nm.
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Topic: Ferroelectric Materials: Theory & Experiments Presenting author: Pintilie Lucian, pintilie@infim.ro Preference: oral presentation COMPARISON BETWEEN THE ELECTRICAL PROPERTIES OF TETRAGONAL Pb(Zr,Ti)O3 AND BaTiO3 EPITAXIAL THIN FILMS Pintilie Lucian National Institute of Materials Physics, Atomistilor 105bis, Bucharest-Magurele, 077125 Romania Lead zirconate-titanate (PZT) and barium titanate (BaTiO3-BTO) are prototype ferroelectrics. The two materials are very much studied due to their appealing properties and potential for applications. Both PZT with high Ti content and BTO posses the same tetragonal structure, and the origin of ferroelectricity is similar. Based on these facts, the two materials are treated in the same way when it is about the ferroelectric behavior and the theoretical simulation of the electric properties. This fact is not entirely correct. The present study is dedicated to the detailed analysis of the electrical properties of two sets of epitaxial films: one set is of PZT with tetragonal structure (Ti-rich composition), and with different thicknesses in the 50-300 nm range; one set is of BTO with different thicknesses in the 20-200 nm range. It is worth to mention that the test samples were grown on SrRuO3/SrTiO3 (SRO/STO) substrates and that the top electrodes were of SRO/Pt. Therefore, the test ferroelectric capacitors were SRO/PZT/SRO and SRO/BTO/SRO. The electric characterization comprises hysteresis, current-voltage (I-V) and capacitance-voltage (C-V) measurements. The results of the electrical measurements allowed us to draw some very interesting conclusions: - The hysteresis loops have different shapes, with different values for the coercive field and saturation polarization. In the case of PZT, the hysteresis loop is rectangular, with large and frequency dependent coercive field. The polarization magnitude is also high and is frequency independent. For the BTO films the hysteresis loops have round corners, and the coercive field is low and frequency independent. The saturation polarization is lower than in PZT and is frequency independent. All these results suggest that the polarization switching has some differences between PZT and BTO. These results correlate well with the fact that the leakage current is higher in PZT than in BTO. It can be assumed that the concentration of the free carriers is large in PZT. They can screen the applied voltage, leading to larger coercive fields, on one hand, and can contribute to a more efficient compensation, leading to the rectangular hysteresis, on the other hand. - The behavior of the C-V characteristics is also very different. For both PZT and BTO capacitors the butterfly shape is obtained, only that for PZT the capacitance peaks associated to polarization switching are sharp and followed by an abrupt change in the capacitance value, while for BTO the peaks are round, with no discontinuity in the capacitance value. The frequency dependence of the C-V characteristics is also different. The results suggest that the PZT films are partly depleted for the voltage range used in the measurements, while the BTO films are fully depleted for most of the voltage range. This finding is coherent with the assumption that the concentration of the free carriers is larger in PZT films than in BTO ones. - The most intriguing difference is in the case of the I-V results. As expected, the leakage is with about three orders of magnitude larger in PZT than in BTO. However, the thickness dependence of the leakage current is different. While in the case of PZT this dependence is very weak, in the case of BTO films a clear increase of the current density with increasing the thickness is observed. The detailed analysis of the results suggests that: in PZT the conduction mechanisms is a combination of interface limited injection and bulk limited drift-diffusion, governed by the Schottky-Simmons equation for the current density; in BTO the most probable conduction mechanism is the small polaron hopping. It can be that in both cases the oxygen vacancies play a role: in case of PZT as shallow donor leading to a large concentration of free carriers, and in case of BTO as a deep defect level allowing the hopping of the injected electrons under the applied electric field. A possible explanation for these differences can be based on the fact that the nature of the Pb-O and Ba-O bonds is different (see Cohen, Nature 358, pp. 136-138, 1992). As a consequence, PZT is a wide gap semiconductor, and BTO is a dielectric. Therefore, the two materials, although both ferroelectrics, are very different and should be treated correspondingly. The author acknowledges the help of MPI-Halle, Germany (for PZT) and FZ Juelich, Germany (for BTO) in
providing the samples for measurements. Work in the frame of FP7 IFOX project (GA number 246102).
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SWITCHING BEHAVIOR AND ELECTRONIC PROPERTIES OF ULTRATHIN FERROELECTRIC HETEROSTRUCTURES
A. Gruverman Department of Physics and Astronomy, University of Nebraska, Lincoln, NE 68588, USA Maintaining and controlling a stable electrical polarization at room temperature in ferroelectric perovskite oxide thin films is essential for exploiting the functionality of these materials for nanoscale applications. We report investigation of the switching behavior and polarization relaxation in single-crystalline ultrathin (in the range from 2 to 20 nm) BaTiO3 capacitors by means of piezoresponse force microscopy (PFM) and pulsed switching current measurements (PUND). It is shown that although polarization is stable in ultrathin BaTiO3 films with no top electrodes, deposition of top metal oxide electrodes (SrRuO3 or La0.7Sr0.3MnO3) results in severe polarization relaxation. This effect is a consequence of strong effective depolarizing fields due to unfavorable interface terminations with the deposited electrodes, as opposed to more complete screening in the films by adsorbed charges on the free surface. These interface effects can smear out the ferroelectric transition and can even make the ferroelectricity unstable at room temperature. Several approaches to enhance polarization retention in the case of a deposited electrode, including strain engineering and control of electrically boundary conditions, were explored. In particular, first-principle calculations based on density functional theory show that engineering of the atomic termination at the electrode interface with BaTiO3 by insertion of ultrathin dielectric layers of SrTiO3 can alleviate stability issues in the case of SrRuO3 electrodes. This approach is confirmed by PFM observations showing spatially resolved dynamics of relaxation, local PFM spectroscopy and determination of the characteristic relaxation times by PUND. Topic: Nanoscale Ferroelectrics and 3-D Geometries for High Density Memories Presenting author: A. Gruverman Department of Physics and Astronomy, University of Nebraska, Lincoln, NE 68588, USA agruverman2@unl.edu Type: Invited
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A CASE STUDY OF LiNbO3 PVDF COMPOSITE THIN FILM Ahmad Mukifza Harun, Tim Comyn, and Andrew J. Bell
Institute for Materials Research, The University of Leeds, Leeds, LS2 9JT, UK e-mail: pmamh@leeds.ac.uk
Many research publications have been produced on lithium niobate (LiNbO3) because of its excellence ferroelectric, piezoelectric and pyroelectric properties, and also its non-linear properties for electro-optical applications. Our previous preparation of LiNbO3, characterized by X-ray diffraction and TEM, showed that a good nanocrystal, with an average size of 80nm, can be prepared via the molten salt synthesis method. With the right choice of surfactant and coupling agents, a well dispersed lithium niobate and polyvinylidene fluoride (PVDF), thin film can be prepared using a spin coating process. A few drops of composite spun on the gold coated silicon substrate were used to prepare a uniform thin film with an average thickness of 3m. Microscopic investigation through SEM later found that the surfactant and coupling agent used helped to minimize the porosity problems. Measurements of polarization hysteresis and permittivity, as a function of applied field, were studied and compared to existing models of ferroelectric polymer composite properties.
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MAGNETIC PROPERTIES OF BiFeO3 CERAMICS OBTAINED BY HOT-PRESSING OF NANOPOWERS
B. Andrzejewskia, E. Markiewicz, B. Hilczer Institute of Molecular Physics, Polish Academy of Sciences, Smoluchowskiego 17, PL-60179, Poland a) presenting author, e-mail: andrzejewski@ifmpan.poznan.pl
We report here on the magnetometric studies and on correlations between magnetic and dielectric properties of hot-pressed ceramics obtained by hot-pressing of BiFeO3 nanopowders. The nanopowders were synthesized by means of a mechanochemical reaction in solid state forced by milling in high-energy ball mills. It was found that the milling parameters like; duration time, shock frequency and kinetic energy influence the properties of the ceramics investigated. Among others the ceramics exhibit three various dielectric processes and a high dielectric permittivity caused by inhomogeneous composition of semiconducting grains separated by insulating grain boundaries. This enhanced permittivity corresponds well to the mixed valences of Fe2+ and Fe3+ ions, and can be explained by analogy to other perovskites containing polyvalent cations which are known to exhibit high permittivity due to electron transfer between various valence states.
Acknowledgements: The financial support from the Ministry of Science and Higher Education of Poland under grant No. N N507 229040 is gratefully acknowledged.
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EFFECT OF ERBIUM DOPANT ON THE BAND GAP ENERGIES OF RF SPUTTERED Ba0.8Sr0.2TiO3 THIN FILMS
M. Nath, N. Roy & A. Roy* Department of Physics, National Institute of Technology Silchar, India, 788010 * Corresponding author email: ashim@nits.ac.in & 28.asim@gmail.com
The effect of Erbium dopant on the structural properties and band-gap energies of Ba0.8Sr0.2TiO3 thin films grown on fused quartz substrates has been investigated by grazing incidence X-ray, atomic force microscopy, UV-VIS spectroscopy and Raman spectroscopy. Er doped Ba0.8Sr0.2TiO3 thin films have been prepared by rf magnetron sputtering system (EDWARDS ESM 100). The content of Er in the deposited films was controlled by the coverage area of Er piece on Ba0.8Sr0.2TiO3 target. The Grazing incidence X-ray diffraction patterns of pure and doped BST thin films were shown in Fig1. Both pure and doped BST thin films show crystallized cubic perovskite polycrystalline structures without preferred orientation which indicates that Er has entered the unit cell maintaining a single-phase perovskite structure. The peak intensities of Er-doped BST thin films decreased and the full widths at half maximum increased with increasing Er content. The peak broadening effects mentioned in our experiments may be connected with the decrease in grain size with increasing Er content1. Using Tauc,s law2 the band gap energies of the undoped and Er doped samples have been calculated and it was found that the energy gap of Ba0.8Sr0.2TiO3 films increased linearly with the increase of Er concentration. From Raman spectra it was revealed that the peak at wave number around 525 cm-1 which is identified3 as A1 (TO) has shown blue shift nature in the sample with Er doping concentration. Based on the analyses and calculation, the variation of the band-gap energies can be attributed to the combined effects of stress, grain size, and phase transformation in Er doped BST thin films.
100
110
200
211
BST 3
intensity (a.u.)
BST 2
BST 1
BST0
10
20
30
40 50 2 (degrees)
60
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Fig. 1: Grazing incidence X-ray-diffraction patterns of undoped and Er-doped Ba0.8Sr0.2TiO3 thin films deposited on quartz substrates References: 1. S. B. Desu, Phys. Stat. Solidi (a) 141 119 (1994). 2. J. C. Tauc, Amorphous and Liquid Semiconductor, Plenum Press, New York, 1974, p. 3. J. D Freire and R.S Katiyar Phys. Rev. B 37, 2074 (1998).
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STUDY OF LOCAL DOMAIN STRUCTURE IN LiTaxNb1-xO3 AND VTE-TREATED LiTaO3 CRYSTALS BY BIREFINGENCE IMAGING, RAMAN SPECTROSCOPY AND PIEZO FORCE MICROSCOPY I. Gregora1, F. Borodavka1, A. Bartasyte2, J. Hlinka1, S. Margueron3, A.M. Glazer4, N. Zhang4, P.A. Thomas5, D. Keeble5 and S. Huband5
1 2
Institute of Physics AS CR, Na Slovance 2, 18221 Prague 8, Czech Republic
Institut Jean Lamour, CNRS (UMR 7198 )-Nancy University, Boulevard des Aiguillettes, 54506 Vandoeuvre-lsNancy Cedex, France
3
Laboratoire Matriaux Optiques, Photonique et Systmes, EA 4423, University of Metz and Suplec, 2 rue E. Belin, 57070 Metz, France
4
Department of Physics, Oxford University, Parks Road, Oxford OX1 3PU, UK

5
Department of Physics, University of Warwick, Coventry, UK e-mail: gregora@fzu.cz
The presence of unusual periodic self-organized stripes has been observed in LiTaxNb1-xO3 crystals by Birefringence Imaging Microscopy (BIM) [1]. Orientation of the stripes correlates with the cleavage and twin planes in this material. To understand the origin and nature of these stripes, the domain structure has been studied by Raman spectroscopy mapping and Piezo Force Microscopy (PFM). Neither of these techniques reveals any periodic stripes. The stripes in birefringence images often appear near mechanical twin walls (Fig. 1). Fig. 1: |sin| images ( is the phase shift), measured by BIM (a) and PFM image (b) of an X-cut section of the LiTa0.67Nb0.33O3 crystal. This indicates that the stripes are not structural twins or ferroelectric domains, but are rather due to optical interference. The effect is even more striking in LiTaO3 crystals that have been treated by vapour transport equilibration (VTE). In this case they are only seen for compositions that possess near-zero birefringence and are not seen in congruent and stoichiometric crystals. Careful analysis shows that they arise from wedge-shaped domain walls, often repeating across the crystal and of a smaller length than the crystal thickness. [1] A.M. Glazer, N. Zhang, A. Bartasyte, D.S. Keeble, S. Huband and P. A. Thomas, J. Appl. Cryst. 43 (2010) 1305.

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IMPEDANCE SPECTROSCOPY AND DIELECTRIC MODELLING OF (KxNa1-x)1/2Bi1/2TiO3 Andrew J Bell, Adam Royles and Timothy P Comyn Institute for Materials Research, University of Leeds, Leeds, LS2 9JT, UK
(KxNa1-x)1/2Bi1/2TiO3 (KNBT) is a candidate lead-free piezoelectric, with a phase boundary between the Na-rich rhombohedral and K-rich tetragonal forms at around x = 0.2, where te piezoelectric properties peak with a piezoelectric d33 coefficient of approximately 200 pC N-1. In common with other Na1/2Bi1/2TiO3 based materials, the dielectric properties are characterised by a frequency independent high temperature maximum in the weak-field permittivity often referred to as the Curie temperature, TC, and a lower temperature frequency dependent peak which appears to be coincident with depolarization temperature, TD. Here we report the results of complex impedance measurements from 100 Hz to 10 MHz from room temperature through both the TD and TC regions for virgin, poled and de-poled samples. The results are interpreted in terms of the relaxation of polar nano-regions which form at TC and establish long range order at TD. Attempts are made to fit the high temperature peak to a size dependent Landau-Ginzburg-Devonshire model. The implications of the model for the mechanism of the unusual time dependent poling behaviour, reported for the x = 0.2 composition, are discussed.
Topics: 9 & 10 Presenting author: Andrew Bell University of Leeds a.j.bell@leeds.ac.uk
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A MECHANISM FOR
H YBRID IMPROPER FERROELECTRICITY: CONTROLLABLE POLARIZATION - MAGNETIZATION COUPLING
Nicole A. Benedek School of Applied & Engineering Physics, Cornell University, Ithaca, NY 14853 USA
The utility of multiferroics for low-power electronic devices stems from the possibility for electric-eld control of magnetism at room temperature. A challenge that has so far not been overcome is to identify a stable, single-phase multiferroic material in which the magnetization can be deterministically switched 180 . A large electrical polarization strongly coupled to the magnetization is generally thought to be a key requirement. The structural and chemical complexity of many oxide and uoride materials leads naturally to the presence of multiple competing interactions, which makes the systematic experimental exploration of multiferroic materials a challenge. However, advances in theoretical methods (particularly those based on rst-principles density functional theory) mean it is now possible to not only explore the properties of existing materials, but also to predict the properties of as yet unsynthesized materials with unprecedented accuracy. Theoretical methods have been used to reveal the origin and mechanism of multiferroic behavior in complex materials and to elucidate design rules for the synthesis of new materials. In addition, improvements in experimental synthesis and characterization techniques have allowed researchers to start testing the predictions made by theorists. Using rst-principles density functional theory, we have identied a general mechanism (one that is applicable to a large class of materials) by which ferroelectricity and ferromagnetism are induced by the same lattice instability.[1] The results of our calculations on the layered perovskite Ca3 Mn2 O7 reveal a rich set of coupled structural, magnetic and polar domains in which oxygen octahedron rotations ubiquitous in perovskites and related materials induce ferroelectricity, magnetoelectricity and weak ferromagnetism. The key point is that the polarization arises from a rotation distortion that is a combination of two non-polar modes with different symmetries.[2] We use the term hybrid improper ferroelectricty to describe this phenomenon and demonstrate how the mechanism can be exploited to allow the electric-eld switching of the magnetization. We also discuss general results concerning the interaction between ferroelectricity and octahedral rotations in perovskite oxides and uorides and show that, contrary to the common assumption, the two different distortions do not always compete. References [1] N. A. Benedek and C. J. Fennie, Phys. Rev. Lett. 106, 107204 (2011); G. Lawes, Physics 4, 18 (2011). [2] E. Bousquet, M. Dawber, et al, Nature 452, 732 (2008).
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MODELLING SCREENING MECHANISMS IN POLAR OXIDE THIN FILMS N. C. Bristowe*,1,2 Massimiliano Stengel,3 J. M. Pruneda,4 P. B. Littlewood,1 and Emilio Artacho2
*Presenting author (ncb30@cam.ac.uk) Cavendish Laboratory, University of Cambridge, JJ Thomson A ve, Cambridge CB3 0HE, UK 2 Department of Earth Sciences, University of Cambridge, Downing Street, Cambridge CB2 3EQ, UK 3 Institut de Cincia de Materials de Barcelona (ICMA B-CSIC), Campus UA B, 08193 Bellaterra, Spain 4 Centre dInvestigacin en Nanocincia I Nanotecnologia (CSIC-ICN), Campus UA B, 08193 Bellaterra, Spain
1
Selected Topic: Ferroelectric and Piezoelectric Materials - Theory (Invited talk) The interface between LaAlO3 (LAO) and SrTiO3 (STO) has received worldwide attention since the discovery of the interface quasi two-dimensional electron gas (2DEG) in 2004 [1]. It has since been shown that the 2DEG, which can be spin-polarised, superconducting or charge ordered, is reversibly switched on or off with an external electric field, promising potential applications in field-effect transistors with reduced feature sizes, and added functionality over conventional semiconductor systems. Despite this progress the origin of the 2DEG is still debated, which is not only important for basic scientific understanding, but also for the design and engineering of improved and novel devices. One of the debated mechanisms, called the polar-catastrophe [2], is based on the result that LAO has a fixed spontaneous, but non-switchable, polarisation of precisely 0.5 electrons per unit cell [3,4], which requires screening charges at its surfaces via an electronic transfer from the LAO surface to the interface STO Ti 3d conduction band. However several experimental findings have raised doubts to the validity of this explanation: missing interface electrons, lack of surface holes, no internal field in thin insulating films and an inconsistent LAO critical thickness for metallicity. We present a paradigm that plausibly explains several pieces to this puzzle. It is based on a surface redox reaction (e.g. surface oxygen vacancies) and a subsequent electronic transfer across the film that screens the LAO polarization charge [5]. The process is studied with a simple model describing the formation energy of such redox screening processes, supported by first principles calculations. The model predicts the growth of the density of related surface defects and hence STO Ti 3d population with LAO thickness, showing a minimum critical thickness, in agreement with spectroscopic data. We also show that the surface defects generate trapping potentials that will affect the mobility of the interface 2DEG. We build upon these models to include thin films of a ferroelectric material whose polarization can be switched, unlike LAO. The redox process in these systems may now not only be responsible for the interface carriers, but also the facilitation of ferroelectricity itself, which is again thickness dependent. Results from first principles calculations and phenomenological models will be presented.
1. 2. 3. 4. 5. A. Ohotmo and H. Hwang, Nature 427, 423 (2004) N. Nakagawa, H. Hwang and D. Muller, Nat. Mater. 5, 204 (2006) M. Stengel and D. Vanderbilt, Phys. Rev. B 80, 241103 (2009) N.C. Bristowe, P.B. Littlewood and E. Artacho, J. Phys.: Condens. Matter 23, 081001 (2011) N.C. Bristowe, P.B. Littlewood and E. Artacho, arXiv:1008.1951 (2010)
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IN-SITU REAL TIME STRUCTURAL RESPONSE OF A FERROELECTRIC TO AN APPLIED EXTERNAL ELECTRIC FIELD OF VARYING FREQUENCY M G Cain1, S H M Ryding2, R Cernik2, P Thompson3, T L Burnett1, M Stewart1 1 National Physical Laboratory, Hampton Road, Teddington UK 2 The University of Manchester, Grosvenor Street, Manchester, UK and 3 The XMaS CRG BM28, European Synchrotron Radiation Facility, France e-mail: markys.cain@npl.co.uk Relaxor ferroelectrics are well known to exhibit frequency dependent behaviour. Single crystal relaxors have been shown to exhibit electric field induced, as well as temperature induced, crystallographic phase transitions. There are very few x-ray scattering stations anywhere in the world that provide the ability to switch an external electric field whilst simultaneously observing the changes in crystal structure. In a series of recent experiments, at the XMaS BM28 beam line at the European Synchrotron Radiation Facility (ESRF), a single crystal of Pb[Mn1/3Nb1/3]O3 0.32PbTiO3 (PMN-0.32PT) was mounted on an insulating substrate of sapphire with electrical contacts were placed on the electroded (110) faces. The beam penetrated the (100) face of the crystal. An oscillating electric field was applied to the crystal and the crystal response was measured simultaneously at several key points in reciprocal space. Reflected intensity data was collected simultaneously at each applied ac voltage driven at a frequency of 0.01Hz, 0.1Hz, 1 Hz and 10Hz, and also at temperatures from room temperature to 90C. The single crystal was found to contain two phases, tetragonal P4mm and monoclinic Cm. It was observed that the phase transition with applied electric field was rate dependent and that a hysteretic behaviour of the phase change was exhibited at all four frequencies. This rate dependence is shown to have practical implications for applications of these materials in for this class of material. Piezoresponse force microscopy (PFM) measurements have been made on the same PMN-0.32PT single crystal mapping the ferroelectric domain structure at the local scale. A direct comparison of the diffraction peak shape is made with respect to the orientation, morphology and size of the domains imaged with PFM.
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BiFeO3-PbTiO3 THIN FILMS AROUND THE MPB: A STRUCTURAL STUDY Faye Bygrave1, Tim P Comyn1, Andrew J Bell1
1
Institute for Materials Research, School of Process, Environmental and Materials Engineering, University of Leeds e-mail: pre4fb@leeds.ac.uk
Bismuth ferrite (BiFeO3) is both ferroelectric and antiferromagnetic at room temperature, with high Curie and Nel temperatures. The solid solution with lead titanate (PbTiO3) is known as bismuth ferrite lead titanate (xBiFeO3 ((1-x)PbTiO3) which exhibits a morphotropic phase boundary between the rhombohedral R3c and tetragonal P4mm phase that forms at x = 0.7. Switching across this morphotropic phase boundary (MPB) is of relevant interest as it offers the opportunity to exploit three different ferroic order parameters at room temperature, with the rhombohedral form being antiferromagnetic, the tetragonal form being paramagnetic and both forms ferroelectric. At this phase boundary there is potential to electrically switch between the paramagnetic and antiferromagnetic forms via a field enforced transition between the tetragonal and rhombohedral phases. The exploitation of this transition requires a greater understanding of xBiFeO3 (1-x)PbTiO3 film orientation and structure, since the electrical and magnetic properties of thin films are directly linked to the degree of film orientation and overall structural properties. This work reports on xBiFeO3 (1-x)PbTiO3 x = 0.7 and 0.6 thin films either side of the reported MPB deposited by pulsed laser deposition on polycrystalline Pt/TiOx/SiO2/Si. XRD alongside peak profile fitting describes the presence of extra crystallographic phases within the films that are present to accommodate the strain imparted by the substrate. As the film thickness is increased, the crystallography tends towards that seen in the bulk therefore eliminating the need for the secondary phases. The link between electrical properties and grain size distribution is investigated using AFM, SEM and PFM. STEM-EDX elemental mapping has been used to explore the interactions at the film substrate interface and is used to investigate the thickness dependence of the films on electrical properties.
Topic: 1. Ferroelectric Materials: Theory & Experiments (ORAL)
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FLEXOELECTRICITY IN THIN FILMS AND SINGLE CRYSTALS Gustau Catalan1, Jiawang Hong2, Emilio Artacho3, Jim Scott4, Axel Lubk5, Etienne Snoeck5, Beatriz Noheda6.
1 2
Institucio Catalana de Recerca i Estudis Avanats (ICREA), CIN2, Barcelona, Spain. Department of Physics, Rutgers University, New Jersey, USA. 3 Department of Earth Sciences, University of Cambridge, UK. 4 Cavendish Laboratory, Department of Physics, University of Cambridge, UK. 5 Group NanoMaterials, CEMES-CNRS, Tolouse, France. 6 Zernike Institute for Advanced Materials, University of Groningen, The Netherlands. The coupling between strain and polarization is inherent in ferroelectrics, as they are of course piezoelectric. The coupling between strain gradients and polarization, known as flexoelectricity, is more general, as it affects all dielectrics. Though this effect has been known since the sixties, it has only begun to attract serious attention in this last decade, with the measurement of large flexoelectric polarizations in high-permittivity materials. The interest in this effect has been further reinforced by the realisation that strain gradients are very big at the nanoscale, so that flexoelectricity can have considerable impacts, both negative and possitive, on device performance. This talk will begin with a brief overview of flexoelectricity to then focus on our most recent findings. These concern the theoretical and experimental investigation of the true value of intrinsic flexoelectricity in several materials of interest, on one hand, and the discovery of new ways to engineer flexoelectric effects into nanostructured ferroelectric thin films.
36
INCREASE OF GENERATING POWER OF CANTILEVER TYPE PIEZOELECTRIC GENERATORS BY INTERCONNECTING THE GENERATORS
Choong Hyo Park, Jong Wook Kim, Jung Hoon Lim, Seong Su Jeong, Myong Ho Kim, Tae Gone Park Changwon National University, Korea A cantilever-type piezoelectric generator has merits of simple structure, easy fabrication and large displacement by transverse vibration of a beam. It is easy to control the natural frequency, and also possible to increase output power by changing length, width, and thickness of the generator. In this paper, generators were designed and fabricated to resonate at frequency of 120Hz, which was a mechanical vibrating frequency of vibrating source (electric transformer). For increasing output power, eight generators were arrayed on parallel lines to form an interdigital shape and the output terminals of each generator were electrically interconnected by combination of series and parallel circuits. To increase generating voltage, series connection of generators was effective and for increasing current, parallel connection was effective.
<Design of a cantilever type piezoelectric generator>
<Generators application>
38
Soft Modes and Structural Phase Transitions R. A. Cowley Oxford Physics, Clarendon Laboratory, Parks Road, Oxford OX1 3PU, UK Soft modes were put forward as an explanation of structural phase transitions by Cochran and Anderson in the late 1950s. Comparing with Landaus theory of phase transition led to the suggestion that the square of the frequency of a soft mode was proportional to |T-Tc| where Tc is the phase transition temperature. Experimental measurements on a variety of materials then showed that this was a reasonable approximation to many experimental results. However, in the early 1970s, experiments were performed that showed there were two characteristic frequencies that differed in frequency by at least an order of magnitude. The theory of pure materials failed to produce an explanation and still the only explanation is that of Halperin and Varma who suggested that the two time scales arose from impurities, but the nature of the impurities has not been identified. In the late 1980s x-ray measurements showed that there were also two length scales. After considerable experimental effort, the second long length scale was identified as coming from the surface, but unexpectedly penetrated into the sample about 10,000 for a wide variety of different materials. This is surprising and there is not a satisfactory explanation for this long length scale other than impurities or dislocations. All these results were obtained mostly for antiferrodistortive phase transitions but more recently attention has changed to ferroelectric phase transitions. The uniaxial ferroelectric phase transition of lead germanate has below the phase transition elastic scattering that is broad and intense perpendicular to the ferroelectric direction. Similar results have been found for KH2PO4. This scattering arises from the domain wall structure that is inevitably present in ferroelectrics in the absence of an applied electric field and enables a measurement to be made of the domain wall thickness. The situation becomes more complex for relaxor ferroelectrics particularly those that have a cubic crystal structure. Relaxors such as PMN, PbMg1/2Nb2/3O3, have a disordered structure with the Mg and Nb atoms arranged randomly over the B site of the perovskite structure. These materials have a phase transition at about 400K similar to that of lead germanate but below the transition they remain cubic and do not have a ferroelectric structure but the scattering is very similar to that from the domain walls of uniaxial systems. However, an applied electric field only produces a ferroelectric phase below 220K. We do not have an explanation for this behaviour although it may arise because the domain structure is not frozen, as suggested by Imry and Ma for systems with continuous symmetry. Then since the symmetry is cubic and not isotropic the domain structure could freeze at the ferroelectric transition temperature of 220K if the cubic anisotropy is then large enough. This brief report shows that soft modes, although a beautifully simple concept, have left a trail of not understood experimental results, which will continue to require considerable effort if we are to understand soft modes at structural phase transitions.
Topic 11, Oral presentation, R. A. Cowley Oxford Physics, r.cowley@physics.ox.ac.uk
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STUDIES ON FIELD DEPENDENT DOMAIN STRUCTURES IN MULTI- GRAINED 0.85PbMg1/3Nb2/3O3-0.15PbTiO3 THIN FILMS BY DYNAMIC CONTACT FORCE MICROSCOPY D.Saranya*, Neena S. John, Jayanta Parui, S.B.Krupanidhi Materials Research Centre, Indian Institute of Science, Bangalore, India- 560012
0.85PbMg1/3Nb2/3O3-0.15PbTiO3 ferroelectric relaxor thin films have been deposited on La0.5Sr0.5CoO3 (LSCO)/ (111) Pt/TiO2/SiO2/Si by pulsed laser ablation at various oxygen partial pressures ranging between 0.05 to 0.4 Torr. All the films showed a rhombohedral perovskite structure. The grain morphology and orientation are drastically affected by the oxygen pressure, studied by X-ray diffraction and scanning electron microscopy. The domain structure investigations by dynamic contact electrostatic force microscopy have revealed that the distribution of polar nanoregions and their dynamics are influenced by the grain morphology, orientation and more importantly oxygen vacancies. The correlation length extracted from autocorrelation function images has showed an increasing trend or decreasing polarization disorder from 0.01 to 0.3 Torr films. The presence of polarized domains and their electric field induced switching are discussed in terms of internal bias field and domain wall pinning. Films deposited at 0.4 Torr deposited film presents a curious case with unique tetrahedral grain morphology and large polarization disorder.
*presenting author *email id: saranstar@gmail.com, saranya@mrc.iisc.ernet.in Preference of presentation: POSTER Topic: Ferroelectrics Materials: Theory and Experiments *Affiliation: Materials Research Centre, Indian Institute of Science, Bangalore, India- 560012
40
NOVEL ELECTRODE GEOMETRY TO INDUCE EXOTIC DOMAIN STATES

Donald M. Evans, R. G. P. Mc Quaid, L. J. McGilly, J. M. Gregg and A. Schilling
School of Mathematics and Physics, Queens University of Belfast, Belfast, BT7 1NN, United Kingdom Corresponding author: devans92@qub.ac.uk
For extremely small scale ferroelectric geometries in non-charge-compensating environments, vortex states, which exhibit a flux-closing continuous rotation of polarisation, are predicted to occur. In recent atomic simulations by Prosandeev et al [1], the response of ferroelectric vortices to inhomogeneous applied electric fields is investigated. Motivated by this study, we have developed a novel four-electrode geometry, in which each electrode is individually addressable, enabling study of local domain switching in single crystal BaTiO3 {100}pseudocubic lamellae under inhomogeneous applied electric fields. We combine functional testing (via measuring capacitance-voltage characteristics) with Piezoresponse Force Microscopy (PFM) enabling explicit mapping of resulting domain states. This work represents an extension on previous switching studies performed using a simpler coplanar geometry and a Focused Ion Beam (FIB) based methodology for preparing single crystal BaTiO3, see [2,3]. PFM images show that such contact electrodes can create domain configurations with symmetry related to that of the fourelectrode structure, figure 1 (c). Additionally, recent measurements suggest that the electron-beam deposited electrodes, whilst able to supply a switching field, are insufficiently conducting for effective surface charge compensation[4]; this may allow idealised switching experiments in uncompensated environments such as those proposed in reference [1] to be realised.
(a)
(b)
(c)
10m
Figure 1. (a) Schematic of four-electrode test geometry. Electron-beam deposited strips extend from each isolated electrode and over the edge of the BaTiO3 lamella providing electrical contact. (b) A scanning electron microscope image of the real structure schematically illustrated in (a). The BaTiO3 lamella is located in the centre of the image. (c) Lateral PFM data. Red is applied voltage (10V) and blue electrode is earthed, grey electrodes are floating. The top image is the amplitude, the bottom phase.
[1] [2] [3] [4] Prosandeev, S. et al. Phys. Rev. Lett. 96, 237601 (2006). Chang, L. W. et al. Appl. Phys. Lett. 93, 13290 (2008). McQuaid, R. G. P. et al. Nano Lett. 10, 3566 (2010). Botman, A. et al. Nanotech. 17 37793785 (2006).
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TETRAGONAL BaTiO3 EPITAXIAL FILMS WITH OUT-OF-PLANE C-AXIS ORIENTATION ON SrTiO3 BUFFERED-Si(001): STRUCTURE AND ELECTRICAL PROPERTIES
C. Dubourdieu1, A. Posadas2, J. Jordan-Sweet1, J. Bruley1, E Cartier1, D. Frank1, T. Arruda3, S. Kalinin3, A. Demkov2, M.M. Frank1, V. Narayanan1 1. IBM T.J. Watson Research Center, Yorktown Heights, NY 10598, USA 2. Dept of Physics, The University of Texas at Austin, Austin TX 78712, USA 3. Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA
The integration of epitaxial ferroelectric oxides on silicon would enable the realization of new devices for logic and memory applications. It has been proposed that introducing a ferroelectric as a gate oxide could decrease the subthreshold slope below 60 mV/dec in field-effect transistors (FET)1, thereby enabling low voltage operation. The perovskite BaTiO3 (BTO) compound is ferroelectric with a Curie temperature of 120C. In the ferroelectric state, BTO is tetragonal with a = 3.994 and c = 4.0335 . A ferroelectric FET requires that the polarization is perpendicular to the Si channel. However, the misfit between BaTiO3 and Si in-plane parameters is of the order of 4.0%, which leads to a rapid relaxation of BTO by misfit dislocations. Due to the large mismatch in the thermal expansion coefficients, the BTO film is subjected to a large tensile in-plane strain, resulting in the polar c-axis lying in-plane. The use of a relatively thick 30 nm Ba1-xSrxTiO3 buffer layer has been proposed to overcome this problem2. In this work, we show that a relaxed ~8 nm SrTiO3 film can be employed as a buffer and allows reduction of both the in-plane lattice and thermal mismatches, thus promoting the growth of tetragonal out-of-plane c-axis BTO. The epitaxial stacks are grown by molecular beam epitaxy on Si(001) substrates. A STO film (20 ML) is first deposited at 590C. BaTiO3 film is then grown at 750C, with thicknesses in the range 2 to 50 nm. The crystalline structure of the stack was studied by X-ray diffraction at the NSLS. The STO buffer film has an in-plane lattice parameter (3.918) larger than that of the bulk (3.905). BTO films of typically 2-20 nm are found to be tetragonal with the c-axis out of plane. This result is also confirmed by electron diffraction. The c/a tetragonal distortion decreases with increasing thickness, reaching the cubic ratio of 1 for 50 nm thickness. An interfacial layer with Si is formed as shown in Fig. 1(a). The elemental distribution within the stack was studied by EDX and EELS and will be discussed. Stacks with ~ 15 nm BTO exhibit a capacitance density of 1.07 F/cm2 (see Fig. 1(c)), independent of frequency. The flatband voltage (~ -0.60 V) is shifted towards negative values, which is typical for alkali-based dielectrics. In contrast to many high-K dielectrics, the CVs show little hysteresis, suggesting limited charge trapping in these films. The CVs response at different frequencies and under different stress conditions will be discussed. A ferroelectric hysteresis is not observed in the CVs and the possible reasons will be presented. Ferroelectricity is, however, evidenced locally by piezo force microscopy (PFM). Domains are written and switched under a typical DC voltage of 10V. The piezoresponse shows a hysteresis loop whose amplitude depends on the location probed on the surface. These results will be discussed with respect to the few experiments reported for epitaxial BTO films on Si. (a)
10 10 10 10 10
5
(b)
001
(c)
C/A (F/cm2)
1.0
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0.5
1.0
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qL ( )
-4
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Figure 1: (a) and (b): TEM image and X-ray /2 scan for a BTO/STO/Si stack (the TEM shows the presence of an amorphous interfacial layer between Si and STO) - (c): Capacitance density as a function of gate voltage for the same stack.
1. S. Salahuddin and S. Datta, Nano Letters 8, 405 (2008) 2. V. Vaithyanathan et al., J. Appl. Phys. 100, 024108 (2006)
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PFM IMAGING AND FAR-INFRARED SPECTROSCOPIC STUDY OF POLYDOMAIN PbTiO3 THIN FILM ON LaAlO3
E. Simon1, A. Bartasyte2, S. Margueron3, F. Borodavka1, D. Nuznhyy1, S. Kamba1, V. elezn1 and J. Hlinka1

1 2
Institute of Physics AS CR, Na Slovance 2, 182 21 Prague 8, Czech Republic
Institut Jean Lamour, UMR 7198 CNRS-Nancy University, Boulevard des Aiguillettes, 54506 Vandoeuvre-les-Nancy, France Laboratoire Matriaux Optiques, Photonique et Systmes, University of Metz and Suplec, 2 Rue E. Belin, 57070 Metz, France
Domain structure formed on epitaxial PbTiO3 thin films grown on LaAlO3 by MOCVD was studied using PFM imaging and far-IR spectroscopy. Comparative study of IR reflectivity spectra (Fig 1) of polar phonon modes in polydomain lead titanate thin films of different thicknesses allows us to discuss process of domain formation and stress relaxation in these films. PFM images give an additional confirmation for our conclusions based on the spectroscopic studies. Resulting dielectric function in farinfrared spectral range is discussed in terms of effective dielectric medium approach.
1.0 0.8
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0.6 0.4 0.2 0.0

LAO PTO/LAO 55 nm PTO/LAO 110 nm PTO/LAO 250 nm
300K
100 200 300
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Fig 1: IR spectra of LaAlO3 substrate and PbTiO3 films with thicknesses of 55 nm, 110 nm and 250 nm. Arrows mark frequencies of polar phonons in the thin films.
Acknowledgement: This work is supported by the Czech Science Foundation (Project GACR P204/10/0616).
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STRUCTURE AND NANOSECOND DYNAMICS OF FERROELECTRIC-DIELECTRIC SUPERLATTICES IN APPLIED ELECTRIC FIELDS

Paul G. Evans, Pice Chen, Ji Young Jo, and Rebecca J. Sichel University of Wisconsin, Madison, WI 53706, USA Ho Nyung Lee Oak Ridge National Laboratory, Oak Ridge, TN 3783, USA Matthew Dawber Stony Brook University, Stony Brook, NY 11794, USA Serge M. Nakhmanson and Eric M. Dufresne Argonne National Laboratory, Argonne, IL 60439, USA
Ferroelectric/dielectric superlattices exhibit a range of fascinating phenomena, including the introduction large steady-state electrical polarizations into layers with nominally dielectric compositions and the formation of domain patterns with nanoscale periodicity. It has been a challenge in the past to probe and to understand the properties of these superlattices under applied fields, and in particular to determine the relationship between their overall functional properties and the atomic-to-mesoscale evolution of their structure. Time-resolved synchrotron x-ray microdiffraction provides insight into the non-equilibrium properties of superlattices at the length-scale of the structure of individual layers and allows the ns-scale dynamics of domains to be probed. We describe two experimental studies of ferroelectric/dielectric superlattices using this approach. The piezoelectric expansion of a CaTiO3/BaTiO3 superlattice results in a shift in the x-ray reflections arising from the superlattice periodicity, as shown in Fig. 1. The evolution of the intensities of these reflections depends on the distribution of the piezoelectric strain between the BaTiO3 and CaTiO3 component layers. In the CaTiO3/BaTiO3 system, the strain is shared equally between components, consistent with the theoretically expected zero-field polarization of the superlattice. The time-evolution of satellite reflections associated with the periodic domain structure of a SrTiO3/PbTiO3 superlattice (Fig. 2) shows that the domains evolve with a characteristic timescale of tens of ns. The timescale of the overall electromechanical properties of the superlattice are determined by the dynamics of this domain evolution.
Figure 1 Piezoelectric expansion of the superlattice reflections (indexed with l=-3..+1) of a CaTiO3/BaTiO3 superlattice, measured during the applied field shown in the leftmost panel. The SrTiO3 substrate (right panel) is unchanged by the field.
Figure 2 Dynamics of the satellite reflection associated with stripe polarization domains in a SrTiO3/PbTiO3 superlattice in response to an applied field of 0.84 MV/cm, applied after at t=0.
46
OPTIMIZATION OF BOTTOM ELECTRODE STRUCTURE FOR THIN FILM FERROELECTRIC RF DEVICES
C. Fragkiadakis, R. V. Wright, P. B. Kirby Department of Materials, Nanotechnology Centre, Cranfield University, Bedfordshire, United Kingdom There is currently great interest in thin film ferroelectrics for tunable RF devices in applications such as re-configurable radio front ends [1]. In these devices, which are generally metalferroelectric-metal layer structures, the choice of materials for the bottom electrode is severely limited by the need for this electrode to withstand the high temperature (up to ~800 C) and oxidising atmosphere used for the growth of the ferroelectric layer. As a result it is difficult to optimize the electrical resistance of the bottom electrode and this often limits device performance particularly where a high device Q is required. Pt is the most widely used electrode material for ferroelectric growth as it promotes crystallization at a relatively low temperature, has good stability in high temperature oxidising atmospheres and gives low leakage current device structures [2], but it does have the disadvantage of a low electrical conductivity. Highly conductive metals like Cu [3] have been used for ferroelectric growth but these require additional oxidation barrier layers and precision controlled fabrication process environments. Recently, a bottom electrode combining Pt and Au layers on TiO2 [4] has been implemented for high Q BST varactors, resulting in substantial decrease in electrode resistance compared to Pt by itself, however, due to Pt-Au inter-diffusion [5] the final electrode resistance can degrade significantly compared to its as deposited value, depending on the process temperature and annealing time. Although ferroelectrics and specifically BST, have also been deposited on single layer Au electrodes [6], the properties of the whole bottom electrode stack including SiO2 and TiO2 barrier and adhesion layers, have not been fully investigated in terms of adhesion, sheet resistance, surface morphology and crystal structure after being subjected to the ferroelectric annealing temperatures. In the present work we have investigated the thermal stability of a range of bottom electrode structures with the aim of improving the performance of our lead strontium titanate (PST) ferroelectric varactors for which a sol-gel process with a growth temperature of 700C is used to deposit the PST [7]. Using thermally oxidised Si wafers, with an additional 120nm thick TiO2 barrier layer on top for some of the trials, a range of Pt, Au and combined Pt/Au bottom electrode structures, with individual layers thicknesses in the range 50-5000nm, were deposited, both with and without an underlying thin (10nm) Ti adhesion layer, by RF magnetron sputtering at room temperature. The films were characterized for their crystallinity, surface morphology, adhesion and electrical properties by x-ray diffraction (XRD), scanning electron microscopy (SEM), tape test and 4 point probe measurements, respectively, before and after annealing at 700oC for 10 min. in air. The results of the sheet resistance and tape test measurements at room temperature (R.T.) and after annealing (700C) are shown in table I. The main finding is that although the combination of Au and Pt can offer a significant reduction in sheet resistance compared to Pt alone, it is still more resistive than Au alone. Also, the TiO2/Ti/Au with 400nm thick Au layer presents the lowest resistance, while still retaining good surface morphology and adhesion. The improvement in surface quality when a TiO2 interlayer is used, points to its effectiveness as a thermal and diffusion barrier. Following the above trials PST ferroelectric varactors have been fabricated using the optimised TiO2/Ti/Au bottom electrode structure and as shown in figure 1 the performance is significantly enhanced compared to devices with Pt bottom electrodes although in both cases dielectric loss is still the main factor limiting Q. Table I. Sheet resistance and tape test measurements On Si/SiO2 Sheet Res. (/sq) Tape test R.T. 700C R.T. 700C x x Au(100nm) 0.35 0.3 x x Au(400nm) 0.096 0.091 Ti/Au(100nm) 0.4 0.49 x x Ti/Au(400nm) 0.1 0.092 x TiO2/Au(100nm) 0.4 0.35 x x TiO2/Au(400nm) 0.1 0.099 TiO2/Ti/Au(100nm) 0.48 0.42 TiO2/Ti/Au(400nm) 0.12 0.12 Pt(100nm) 2.56 1.47 Ti/Pt(100nm) 2.55 2 x x Ti/Pt(500nm) 0.37 0.37 Ti/Pt*/Au(200nm)/Pt* 0.14 0.74 Ti/Pt*/Au(400nm)/Pt* 0.065 0.295 TiO2/Ti/Pt*/Au(200nm)/Pt* 0.166 0.851 * Ptlayer thickness: 50 nm, otherwise shown in brackets
Figure 1. Measured Q for 20x20um2 PST varactors with TiO2/Ti/Au and Ti/Pt bottom electrode structures up to 3 GHz REFERENCES [1] H. J. De Los Santos et al, IEEE Microwave Mag., 5(4), 5065(2004) [2] H. J. Nam, D.K. Choi and W. J. Lee, Thin Solid Films, 371, 264-270 (2000) [3] W. Fan, S. Saha, J. A. Carlisle, O. Auciello, R. P. H. Chang and R. Ramesh, Appl. Physics Lett., vol. 82, 1452-1454 (2003) [4] A. Vorobiev, P. Rundqvist, K. Khamchane and S. Gevorgian, Appl. Physics Lett., 83, 3144-3146 (2003) [5] A. K. Sinha, T. E. Smith and T. T. Sheng, Thin Solid Films, 22, 1-10 (1974) [6] I. Yoshihiko, S. Takeshi and J. D. Baniecki, FUJITSU Scientific Tech. J., 38, 22-30 (2002) [7] C. Fragkiadakis, A. Luker, R. V. Wright, L. Floyd and P. B. Kirby, J. Appl. Physics, 105, 061635-7(2009)
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HIGH TEMPERATURE DIELECTRIC PROPERTIES OF C-AXIS ORIENTED EPITAXIAL BISMUTH LAYER-STRUCTURED DIELECTRIC THIN FILMS
HIROSHI FUNAKUBO1), ITARU TAKUWA1), JUNICHI KIMURA1), YUKI MIZUTANI2) TOMOAKI YAMADA1, 3, 4) AND HIROSHI UCHIDA2) 1) TOKYO INSTITUTE OF TECHNOLOGY, 2) SOPHIA UNIVERSITY, 3) NAGOYA UNIVERSITY, 4) PRESTO, JST
Contact e-mail address: funakubo@iem.titech.ac.jp Capacitor materials applicable up to high temperature become an important due to the commercialization of so called power devices using SiC, GaN and so on as well as the automobile application, such as inside the engine room. Conventional dielectric materials such as (Ba, Sr)TiO3 has fundamental problems for this applications, such as degradation of dielectric constant and insulating characteristics. We proposed the c-axis oriented bismuth layer- structured dielectrics (BLSDs) with the octahedron number of 2 and 4. Psudo-perovskite block was sandwiched by the (Bi2O2)2+ layer with high insulating characteristics. In this presentation, we demonstrate the dielectric property comparison between (100)-oriented (Ba0.3Sr0.7)TiO3 and (001)-oriented CaBi4Ti4O15 films prepared by sputtering method. These two kinds of films were epitaxially grown on same (100)cSrRuO3//(100)SrTiO3 substrates. As results, it was found that CaBi4Ti4O15 had stable dielectric and insulating characteristics against the temperature (up to 500 oC) and an electric field. These results indicate that c-axis oriented BLSDs are the candidate for the capacitor materials applicable to high temperature.
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MAGNETO-ELASTIC EFFECT IN CuCrSe2 ANTIFERROMAGNET

Anna Ggor1, Adam Pietraszko1, L. Gulay2
U U
Institute of Low Temperature and Structure Research Polish Academy of Sciences, Oklna 2, 50-422 Wroclaw, Poland 2 Department of Ecology and Protection of Environment, Volyn National University, Voli Ave 13, Lutsk, Ukraine
The consequences of antiferromagnetic phase transition on the crystal structure in CuCrSe2 are discussed. Ternary triangular lattice dioxides and chalcogenides crystallize in a layered structures with a strong crystalline anisotropy perpendicular to the layers forming quasi two-dimensional structures. The magnetic ions are arranged on triangular lattice within the layers. Materials with this specific geometry are a subject of ongoing interest due to the strong correlations of magnetic and electric properties. Triangular arrangement of magnetic ions leads to magnetic frustration states that may lead to complex three dimensional spin structures and multiferroic properties. This, so called spin driven ferroelectricity has been reveald in ternary chromium based dioxides as e.g. CuCrO2, AgCrO2 [1,2]. Recently it was postulated for AgCrS2 [3] although the question on origin of spin driven multiferroicity in this compound has been left open. In the ACrX2 (A: Cu, Ag; X=S, Se) the microscopic investigations of magnetic and crystal structure properties has been reported so far only for CuCrS2 system where magnetic ground state is obtained due to relief of geometric frustration and where the spiral magnetic structure sets as a result of strong interlayer exchange via CrS-Cu-S-Cr path [4]. Magnetic susceptibility and specific heat measurements of CuCrSe2 reveal antiferromagnetic anomaly at TN=55 K. Basing on the single-crystal x-ray diffraction measured down to 15 K we show that the magnetic phase transition is accompanied by a lattice distortion. The CuCrSe2 crystals at room temperature adopt R3m rhombohedral symmetry with lattice parameters a=3.6768(2) , c=19.380(2) and =120. Below TN=55 K the symmetry of the crystal system decreases to the monoclinic. Reconstructions of reciprocal space unambiguously reveal additional diffraction peaks that appear below TN pointing to formation of domains in the crystal structure. The best fit to the experiment at 15 K was obtained for reduced monoclinic cell with lattice parameters a=6.380(1) , b=3.6809(7) , c=6.769(1) and =108.4420o and Cm space group, that differs from the results obtained for CuCrS2 [4]. However, as in the sulfur analog magnetic ordering in CuCrSe2 appears simultaneously with the distortion of the crystal structure.
Acknowledgments: This work was supported by Ministry of Science and Higher Education in the frame of grant No. NN202 260939 References. [1] Seki, S.; Onose, Y.;Tokura, Y. Phys Rev Lett. 2008,101,067204 [2] Kimura, K.; Nakamura, H.; Ohgushi, K.; Kimura T. Phys Rev B 2008,78,140401 [3] Singh, K.; Maignan, A.; Martin. C.; Simon. Ch. Chem. Mater. 2009, 21 5007-5009 [4] Rasch, J.; Boehm. M.; Ritter. C.; Mutka. H.; Schefer. J.; Keller. L.; Abramova G.; Cervellino, A.; Loffler J.F. Phys Rev B 2009, 80, 104431
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REVERSIBLE CONTROL OF PERPENDICULAR MAGNETIC ANISOTROPY IN FERROMAGNETIC FILMS VIA THERMAL AND ELECTRICAL TREATMENTS OF THE FERROELECTRIC SUBSTRATE
M. Ghidini , X. Moya , L. Phillips , W. Yan , N.-J. Steinke , R. Mansell , C. H. W. Barnes , F. Maccherozzi , S. S. Dhesi , N. D. Mathur
1 1
1,2
Department of Materials Science, University of Cambridge, Pembroke Street, Cambridge, CB2 3QZ, UK.
2 3
Department of Physics, University of Parma, v.le G.P. Usberti 7/A, 43100 Parma, Italy.
Cavendish Laboratory, University of Cambridge, J. J. Thomson Avenue, Cambridge CB3 0HE, UK
Diamond Light source Ltd, Harwell Science and Innovation Campus, Chilton, Didcot, Oxfordshire, OX11 0DE, United Kingdom.
Polycrystalline nickel films evaporated on single-crystal ferroelectric BaTiO3 (BTO) substrates show strain-mediated magnetoelectric coupling [1] but the microscopic details are unknown. Here we employ photoemission electron microscopy with magnetic contrast from x-ray magnetic circular dichroism (XMCD-PEEM), and magnetic force microscopy (MFM), to study the effects of thermally and electrically driven changes in the BTO substrate on the magnetic domain structure of the nickel films. By recording XMCD-PEEM images at different in-plane orientations of the grazing-incidence beam, we show that the room-temperature magnetic domain structure of the nickel films comprises a combination of large domains with in-plane magnetization and regular stripe domains with perpendicular magnetization. The perpendicular component of the magnetization can be erased and reset by thermally cycling through the structural transitions of the substrate. We also show MFM images which reveal that the perpendicular component of the magnetization can be electrically controlled at room temperature, and reset by an excursion above the BTO Curie temperature and subsequent cooling in a perpendicular magnetic field. [1] S. Geprags, A. Brandlmaier, M. Opel, R. Gross and S. T. B. Goennenwein, Appl. Phys. Lett. 96 (2010) 142509.
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ORIENTATION DEPENDANT ELASTIC PROPERTIES OF FERROELECTRIC THIN FILMS

Glenn J T Leightoni, Robert A Dorey, and Zhaorong Huang Department of Materials, Cranfield University, MK43 0AL, United Kingdom.
ig.j.t.leighton@cranfield.ac.uk
Abstract for consideration in topic 1. Ferroelectric Materials: Theory and Experiments Preferred for consideration as oral presentation Piezoelectric lead zirconate titanate (PbZrxTi1-xO3, PZT) thin films have received considerable interest for their use as a functional material within micro-electro-mechanical systems (MEMS). Accurate knowledge of the electrical and mechanical properties of these materials is essential for the effective modelling and design of novel MEMS devices. With macro-scale devices this can be accomplished, as all properties can be determined for a given bulk material. In MEMS devices this is not true due to the difficulties involved in measuring properties such as the elastic modulus of thin films, which is why most modelling results are considered acceptable if they are within 10% of experimental values. The main difficulties in measuring the elastic modulus of piezoelectric ceramic films are the influence of the substrate and any additional layers required to grow them e.g. electrodes and seeding layers. We report here the preparation of self-supported PZT cantilevers 3 to 10 m in thickness and the determination of their elastic coefficients using vibrometry measurements of vibrating beams both in and out of the plane of the wafer, the technique has been verified using a known bulk sample manufactured into a cantilever structure. Using this method we have determined the elastic modulus of a composite PZT film cantilever, made from a bulk powder slurry and pure Sol to be 51.7 GPa in plane and 51.4 GPa out of plane (as defined in figure 1 b). The effect of poling induced stiffness on the elastic coefficients measured on the composite cantilever reduces the in plane property by 10% while the out of plane property increases by 1% giving 46.7 GPa and 52 GPa respectively. These figures after poling are also commensurate with results from a 3 m thick film made using a Sol-gel process shown in figure 1 a, which has elastic moduli after poling of 60.7 GPa and 65.6 GPa for in and out of plane respectively. Figure 1 b shows the geometry of the device which allows the in and out of plane measurements while figure 1 c shows a typical frequency measurement of a composite beam. It is important to note that these values of elastic modulus determined here are much lower than previously reported values in literature.
Out of-plane Cantilever beam In-plane
Figure 1 a, a 700 x 100 x 3 m freestanding PZT cantilever beam. b, die design to allow in and out of plane measurements using vibrometry. c, typical frequency response of PZT beam from which elastic coefficients can be calculated.
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TRANSPORT THROUGH BIOGENIC SILICA NANOPORE MEMBRANES ON SILICON SUBSTRATES K.-C. Lin2, X. Wang1, S. Ramakrishnan1, S. K. Dey2, B. L. Ramakrishna2, and M. Goryll1
1 2
School of Electrical, Computer and Energy Engineering School for Engineering of Matter, Transport and Energy Arizona State University, Tempe, AZ 85287, USA
Nanopore membranes exhibit tremendous potential for applications such as molecular filtration, nanoparticle counting, and sizing studies. However, fabrication of of nanopore membranes using top-down silicon microfabrication technology requires slow serial electron or ion-beam patterning, making it unsuitable for large-scale manufacturing. Marine diatoms on the other hand feature biomineralized silica shells with the smallest pore diameters on the order of 40 nm. Their hierarchical pore architecture makes these nanomembranes exceptionally mechanically stable. Moreover, the nanopores are homogeneous in size and have a low aspect ratio, enabling fast diffusion-driven transport. The challenge of using biomineralized structures is that they have to be combined with preexisting micromachined structures to be used in microsystems. Our approach to this problem consists of immobilizing the biogenic structures on micromachined silicon substrates. These substrates feature micron-sized, through-wafer vias, enabling free fluidic access to the nanopore membrane. The diatom shells are positioned and mounted on top of the silicon via using either poly-L-lysine or UV-polymerizable low-stress epoxy. This presentation will discuss the fabrication of biogenic silica nanopore membranes on silicon substrates and their nanoparticle transport properties. Studies using fluorescent nanoparticles showed that particles with a diameter larger than that of the nanopores were completely retained, while smaller particles, such as polystyrene beads or gold nanoparticles did permeate through the membrane. Upon translocation of these particles through the nanopore membrane, we were able to observe a reduction in ionic current corresponding to the ratio of the bead and pore size. The characteristic electrophoretic mobility of the beads allows for a distinction between nanoparticles of different origin. During the experiments, no evidence for leakage around the diatom was found. Thus, the devices can be used not only for particle monitoring, but also as size-selective filters with a low probability of complete clogging, due to the large (>200) number of nanopores available. The feasibility of combining biomineralized and microfabricated structures shows a pathway for integrating low-cost nanostructures with BioMEMS devices. In addition, the biomineralized nanopore membranes can be coated with materials such as alumina using atomic layer deposition to change the size of the nanopores and their surface charge, allowing a precise modification of the molecular transport properties. 1. Topic: Inorganic Materials for Medical Applications 2. Affiliation: Arizona State University (Michael.Goryll@asu.edu) 3. Oral presentation preferred
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GREEN NANO-ENABLED SOLUTIONS FOR LOCAL ENERGY NETWORKS R.A. Dorey1, Q. Zhang1, M. Zhu1, C. Sansom2, M. Pozzi1, P.M. Jones1, S.A Rocks3 1) Microsystems and Nanotechnology Centre; 2) Precision Engineering Centre; 3) Risk Centre, Cranfield University, Cranfield, MK43 0AL, UK Local energy networks are an alternative approach to managing energy production and supply whereby energy is generated locally and shared across a local area network to satisfy neighbourhood energy needs. The advantages of such systems include reduced transmission losses, enhanced network robustness and flexibility in power generation technologies. The concept is especially useful for small scale energy requirements such as individual households through to remote environments. At the scale of such networks the harvesting of energy from ambient energy sources such as heat, vibration and light is an attractive and green proposition. Microscale energy generation devices, based on piezoelectric, pyroelectric, magnetic and thermoelectric materials, have been produced using green nanomaterial synthesis and processing. In addition to small scale energy harvesting devices, the same fabrication technologies have been used to realise energy storage devices such as batteries, fuel cells and capacitors. By structuring individual parts of these devices at the nanoscale improvements in capability can be achieved including enhanced sensitivity, greater storage and enhanced performance. Together, these micro energy harvesting and storage devices offer an intriguing future for personal energy networks.
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ELECTRIC MODULATION OF MAGNETIZATION IN FERROELECTRICFERROMAGNETIC HETEROJUNCTIONS

H. Lu1, T. George1, J. D. Burton1, A. Stamm1, I. Ketsman1, A. Sokolov1, C. W. Bark2, C. B. Eom2, P. A. Dowben1, E. Y. Tsymbal1, A. Gruverman1 1. Department of Physics and Astronomy, University of Nebraska-Lincoln, Lincoln, NE, United States, 2. Department of Materials Science and Engineering, University of Wisconsin-Madison, Madison, WI, United States. We report observation of the magnetoelectric coupling in ferroelectric/ferromagnetic heterostructures, namely the electrical modulation of magnetization realized via ferroelectric polarization reversal. Single-crystalline epitaxial BaTiO3 ferroelectric films have been fabricated by atomic layer controlled growth on atomically smooth TiO2terminated (001) SrTiO3 substrates with ferromagnetic La0.67Sr0.33MnO3 bottom electrodes (BTO/LSMO/STO). The global ferroelectric poling of the BTO layer was performed by an electrically-biased micro-probe through a vacuum gap and was subsequently examined using piezoresponse force microscopy. The magnetization of the LSMO layer was measured using a SQUID magnetometer as a function of temperature. It is found that upon polarization reversal the saturation magnetization value of the 25-nm thick LSMO films changes by more than 10% at room temperature. This change is significantly larger than that predicted by our first-principle calculations showing that the change in magnetization is limited to a screening length of a few unit cells of LSMO. The measured magnetization change is approximately scaled as 1/d, where d is the LSMO film thickness, indicating the interfacial nature of the effect. A further insight into the observed behavior is obtained from temperature-dependent measurements of the electrical resistivity of the LSMO films of various thicknesses.
Topic: Multiferroics and Magnetoelectrics: Theory & Experiments Presenting author's affiliation and email address: Haidong Lu Department of Physics and Astronomy, University of Nebraska-Lincoln, Lincoln, NE 68588, United States lvhaidong@gmail.com Preference: Oral presentation
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THE SOFT MODE OF PbMg1/3Nb2/3O3 INVESTIGATED BY HYPER-RAMAN SCATTERING B. Hehlen1, A. Al-Zein2, J. Rouquette3, and J. Hlinka4 Laboratoire Charles Coulomb (LCC), UMR CNRS 5221, University of Montpellier II, F-34095 Montpellier, France 2 Laboratoire Structures, Proprits, et Modlisation des Solides (SPMS) Ecole Centrale Paris, F-92295 Chatenay-Malabry, France 3 Institut Charles Gerhardt (ICG), UMR CNRS 5253, Equipe C2M, University of Montpellier II, F -34095 Montpellier, France 4 Institute of Physics, Academy of Sciences of the Czech Republic, Na Slovance 2, 18221 Praha 8, Czech Republic
1
High resolution hyper-Raman spectroscopy (HRS) of single crystals of the relaxor PbMg1/3Nb2/3O3 has been performed. The temperature dependence of the three F1u-symmetry polar modes is investigated between 20 K and 800 K. The soft mode is clearly observed above 520 K (Fig. 1) [1]. It is splitted into a doublet up to the highest temperature investigated. The high frequency component (A1) appears to be underdamped even hundred of degrees below the Burns temperature Td 620 K in PMN. Its frequency nicely matches with previous high resolution neutron scattering experiments (Fig. 2) but is too high to explain the behaviour of the dielectric constant of PMN. This is the reason why the search of a lowerfrequency vibration was subject to numerous experimental studies, but still, a clear understanding of the soft mode dynamics of relaxors was lacking. This vibration, labelled E1 in Figure 1, is clearly observed in HRS. It is underdamped at high temperature and becomes overdamped near Td and below. Its frequency 0 as well as its relaxational frequency rel = 02/, (, full width at half maximum) extrapolate to zero at the Curie-Weiss temperature T0 400 K (Fig. 2). Moreover, the static dielectric constant calculated from the Lyddane-Sachs-Teller relation nicely mimics the behaviour of that obtains from dielectric measurements. These observations strongly suggest that this vibration corresponds to the primary soft mode of PMN. Similar observations have been made in others relaxor-type compounds, thus suggesting a universal behaviour of the low-frequency dynamics of cubic relaxors.
Figure 1: (a) Unpolarized HRS spectra of the soft TO- mode of a PMN single crystal at 748 K showing a doublet structure. (b) Temperature evolution of the TO-doublet emphasizing the softening of the E1component on cooling. [1]
Figure 2: Temperature dependence of the E1 and A1 frequencies (full and open circles) measured by HRS as compared to literature INS and IR data. The lower line (E1) corresponds to a fit with a Cochran law.
A. Al-Zein, B. Hehlen, J. Rouquette, and J. Hlinka, Phys. Rev. B 78, 134113 (2008).
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MODIFICATION OF THE STRAIN AND MAGNETORESISTANCE OF La0.7(Ca1-xSrx)0.3MnO3 THIN FLIMS USING FERROELECTRIC POLING AND MAGNETOSTRICTION
Z.K. Zheng1, Y. Wang1, H.S. Luo2 and H.L.W. Chan1

1
Department of Applied Physics and Materials Research Centre, The Hong Kong Polytechnic University, Hunghom, Kowloon, Hong Kong, China.
Shanghai Institute of Ceramics, Chinese Academy of Sciences. Email: apahlcha@inet.polyu.edu.hk
La0.7(Ca1-xSrx)0.3MnO3 (LCSMO) thin films were epitaxially grown on ferroelectric 0.67Pb(Mg1/3Nb2/3)O3-0.33PbTiO3 (PMN-PT) single crystal substrates. The strain, magnetization, Curie temperature TC, and magnetoresistance of the films were dynamically modified using ferroelectric-poling-induced strain. The poling of the substrate reduces the in-plane tensile strain in the LCSMO film, giving rise to a decrease in the resistance and an increase in the magnetization and TC. However, the induced strain leads to opposite effect on the magnetoresistance below and above TC, which can be explained based on a phase separation model. After the LCSMO/PMN-PT structure was bonded to a Terfenol-D alloy to form a LCSMO/PMN-PT/Terfenol-D laminate structure, it was found that, when a dc magnetic field is applied perpendicular to the film plane, the magnetoresistance of the LCSMO film in the paramagnetic (ferromagnetic) state for the LCSMO/PMN-PT/Terfenol-D structure is larger (smaller) than that for the LCSMO/PMN-PT structure without Terfenol-D. These effects are caused by the magnetostriction-induced in-plane compressive strain in the Terfenol-D, which is transferred to the PMN-PT substrate, leading to a reduction in the in-plane tensile strain of the epitaxial LCSMO film and thereby modifying the magnetoresistance of the LCSMO film. These results demonstrate that the ferroelectric poling and magnetostriction of Terfenol-D are effective ways to in-situ modify the strain of complex oxide thin films. Financial support from the NSFC/RGC Joint Research Scheme (Project No. N_PolyU501/08) is acknowledged. Topic: 2. Multiferroics and Magnetoelectrics: Theory & Experiments Presenting author: H.L.W. Chan, Department of Applied Physics, The Hong Kong Polytechnic University, email: apahlcha@inet.polyu.edu.hk Prefer Oral presentation
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HEISENBERG-LIKE SWITCHING IN FERROELECTRICS
J. Hlinka Institute of Physics, Academy of Sciences of the Czech Republic, Na Slovance 2, 18221 Praha 8, Czech Republic Macroscopic polarization switching in ferroelectric materials usually occurs through various combinations of domain nucleation and growth processes. At the nanometric scale, the local polarization is typically pinned to one of few crystallographically preferred directions and the switching itself consists in a more or less abrupt transition between them. Recently, however, several research groups reported experiments suggesting that some materials may show very low effective crystalline anisotropies. The aim of this contribution is to overview some of these recent experiments and to discuss possible consequences, such as formation of exotic domain structures and switching via motion of chiral ferroelectric walls analogous to Bloch walls known from ferromagnetism.
This work has been funded by the Czech Science Foundation (Project GACR P204/10/0616). References: [1] P. Marton, I. Rychetsky and J. Hlinka, Domain walls of ferroelectric BaTiO3 within the GinzburgLandauDevonshire phenomenological model, Phys. Rev. B 81, 144125 (2010). [2] J. Hlinka, V. Stepkova, P. Marton, I. Rychetsky, V. Janovec and P. Ondrejkovic, Phasefield modelling of 180 degree Bloch walls in rhombohedral BaTiO3, Phase Transitions (2011).
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Nanostructured ZnO and ZnTe for Energy Harvesting Applications

Hongbin Yu , Ebraheem Ali Azhar, Jhih-Hong Peng, James Mertens and Sandwip Dey Arizona State University, Tempe, AZ; * email: yuhb@asu.edu Topic category: 5. Electrocalorics, Thermoelectrics, and Energy Harvesting Presentation preference: oral Semiconductor solar cells have been explored extensively for energy harvesting applications. Among the key components of the semiconductor solar cell are the active photon absorption materials and transparent conducting electrodes. In this presentation, we discuss our recent results in synthesis and characterization of nanostructured materials, including ZnO and ZnTe, that can be tailored to enhance the solar cell performance at reduced cost. Transparent conducting oxide is an essential component of a solar cell which is typically deposited in the flat film geometry. Nanostructured ZnO electrodes, particularly vertically-aligned nanostructures like nanowires (NW), nanorods (NR), have the advantages of enhanced photon absorption, more effective and larger pn junction area due to their Fig. 1. Top view, left, and tilted view, right, of vertically aligned 3D geometry, n-type property for ZnO nano rods synthesized on silicon substrate using chemical as-grown material that can be vapor deposition technique. used for part of the pn junction, as well as transparent conducting electrode. We have explored the growth of such vertically grown ZnO nano rods using both high temperature chemical vapor deposition technique, as shown in Figure 1, as well as low temperature solution grown strategy including the important role of the seeding layer and their physical properties. Zinc telluride (ZnTe) is one of the attractive and important II-VI compound semiconductor for solar cell applications in the high energy range, as it has a direct bandgap of 2.3 eV. The as-grown ZnTe typically has p-type conductivity, and this character can be further combined with other n-type semiconductors allowing the formation of p-n junction. The control of ZnTe morphology and properties are critical in its applications. ZnTe thin lms can be prepared by several techniques, such as molecular beam epitaxy (MBE), electrodeposition, metal-organic chemical vapor deposition (MOCVD), thermal evaporation, etc. We present the study of ZnTe thin films and nano-structures, for example nanowires (NWs), that are synthesized through a simple vaporliquidsolid (VLS) method. The growth of ZnTe was performed on Si substrate with or without Au catalysts deposited by sputtering technique. By controlling the presence or the absence of Au catalysts and controlling the growth parameters such as growth temperature, we can obtain different morphologies of ZnTe, such as thin films and NWs or nanosheets in the same run. The morphology of ZnTe through SEM analysis is shown in Figure 2, which shows ZnTe NWs are grown with the aid of Au catalysts, while without Au catalysts, ZnTe polycrystalline thin films are prevalent. The Fig. 2 Left: ZnTe nanowires grown on Au seeds coated Si characterization of the ZnTe NWs was substrate. Right: with Au as catalyst, ZnTe polycrystalline performed using scanning electron films are formed. microscope (SEM), X-ray diffraction (XRD), Photoluminescence (PL), as well as Energy-dispersive X-ray spectroscopy (EDX).
*
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PREDICTED COEFFICIENT OF PERFORMANCE FOR ELECTROCALORIC MATERIALS IN AN IDEAL REFRIGERATION CYCLE Emmanuel Defay1,2,*, Sam Crossley2, Sohini Kar-Narayan2, Neil Mathur2 1 CEA LETI Minatec Campus, Grenoble, France 2 Department of Materials Science, Cambridge University, UK * edefay@cea.fr
The giant electrocaloric (EC) effect, i.e. a large temperature change due to a change in the electric field across EC thin films, was first reported in 2006 in lead zirconate titanate films (PZT) [1]. It has generated a new area of research mainly focused on two kinds of thin-film materials: perovskite ceramics such as PZT, and polymers from the Polyvinylidene Fluoride (PVDF) family. The EC temperature changes for both are similar even though these materials come from families that are very different in terms of density, dielectric constant and breakdown electric field. Therefore it is difficult to make meaningful comparisons in terms of just one parameter such as entropy change or temperature change. We will compare perovskite and PVDF materials by using literature data to compare the cooling efficiency and the Coefficient Of Performance (COP). Refrigeration devices are often compared with respect to the ideal Carnot cycle, involving two isothermal and two isentropic steps, and this analysis can be performed for EC materials as well. The simplest analysis for EC cooling is therefore to consider the ratio between the heat exchanged during the low-temperature isothermal step, and the electrical work required to charge the EC capacitor. Moreover, by using the Landau-Ginzburg-Devonshire approach, we will show which materials properties should be improved in order to increase EC efficiency.
5. Electrocalorics, Thermoelectrics, and Energy Harvesting Preference: Oral presentation [1] A. S. Mischenko, Q. Zhang, J. F. Scott, R. W. Whatmore, and N. D. Mathur, Science 311, 1270 (2006)
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FERROELECTRIC THIN FLMS FOR MOBILE COMMUNICATION APPLICATIONS
H.W. Gundel, D. Averty, C. Borderon, R. Renoud, R. Sveno IREENA, EA 1770, University of Nantes, Nantes Atlantic Universities 2 rue de la Houssinire, Nantes, F-44322, France e-mail: hartmut.gundel@univ-nantes.fr The development of mobile communication applications is an important subject matter in the today information society, longing for an ever growing number of services integrated in one single terminal. Miniaturisation and functionalizing of such embarked systems, where volume, weight and energy are limited, hence remains a main research topic on these devices. The traditional microelectronics approach is based on line width reduction by improved photolithographic techniques. In the case of mobile telecommunication applications, where the need of different services imposes multi-standard antennas or the possibility of reconfiguration, miniaturisation due to the employ of new materials properties is more striking. Tunability, allowing a number reduction of components, thus is an important research issue. Miniaturisation as well as reconfiguration may be obtained using functional dielectrics, like ferroelectric perovskites, owing to the high-k character and the electrically tuneable permittivity of those materials. The present work reports on the use of BaSrTiO3 thin films, elaborated by chemical solution deposition techniques, for the conception of antennas designed for the UHF television frequency band. The materials synthesis route is presented, the dielectric properties are discussed, and different telecommunication applications are shown.
63
TUNNELJUNCTIONSFORMEMORYAPPLICATIONS
H.Kohlstedt1,A.Petraru1,DooSeokJeong2,R.Soni1,M.Hambe1,andN.A.Pertsev3
Nanoelektronik,TechnischeFakultt, ChristianAlbrechtsUniversittzuKiel,24143Kiel,Germany 2 ElectronicMaterialsCenter,KoreaInstituteofScienceandTechnology, 391Hawolgokdong,Seongbukku,Seoul136791,RepublicofKorea 3 A.F.IoffePhysicoTechnicalInstitute,Polytekhnicheskaya26, StPetersburg,Russia It is expected that, with the trend of aggressive downscaling of commercial electronic devicesintothenanoscaleregime,quantummechanicaleffectswillbecomesteadilymore important. This will lead to a change of paradigm, i.e., future nanoelectronic devices exploiting electron tunneling and/or spin transport will rely on the fundamental laws of quantummechanicsratherthanonclassicalelectrodynamics.Inthiscontext,newmaterials and material combinations are urgently required in orderto develop tunnel junctions and noveltransistorswithenhancedfunctionalitiesandperformance. Inparticular,tunneljunctionsofferinterestingandnovelapproachestowardsnonvolatile data storage. We will discuss a variety of phenomena and devices in which electron tunnellingisemployedasthebasisforbinarycomputationaswellasamemristortypeof storage. Formultiferroichybridscomprisingferromagneticlayersgrownonaferroelectricsubstrate, it will be shown theoretically that the spontaneous magnetization may be reoriented by about90byamoderateelectricfieldappliedtothesubstrate.Inmagnetictunneljunctions with a high tunnelling magnetoresistance (TMR) ratio and ferromagnetic multilayers and spinvalvesdisplayingagiantmagnetoresistance(GMR)effect,thedifferencebetweenthe high and lowresistance states, which results from such reorientation, becomes large enoughtobedetectedexperimentally.Hencethedescribedhybridmultiferroicdevicesmay be employed as electricwrite nonvolatile magnetic memory cells with nondestructive readout. Furthermore, the talk will focus on tunneling device structures in which the unique and extremely interfacesensitive properties of the quantum mechanical electron tunneling processareapplied.Inparticular,theconsiderableprogressintheoreticalandexperimental studies of complex oxide multiferroic and ferroelectric tunnel junctions is discussed. In addition, results on IV characteristics of tunnel junctions comprising amorphous barriers (Aloxide)andanadjacentultrathinelectrolyte(Tioxide)arepresented.IVcharacteristics and XPS data indicated an electro formingfree process which could be explained by a homogenous interfacial effect rather than by a curiositydriven filamentary mechanism. Solidstate electrolyte tunnel junctions are useful for binary data storage or a memristor typeofbehaviour.
65
METAL-INSULATOR TRANSITION IN TUNABLE 2D/3DEG SrTiO3/(Sr1-x,Lax)TiO3 SUPERLATTICES

Euiyoung Choi and Jaichan Lee School of Advanced Materials Science and Engineering, Sungkyunkwan University, Suwon, 440-746, Korea. Yayoi Takamura Department of Chemical Engineering and Materials Science, University of California, Davis, CA 95616, USA Warren Pickett Department of Physics, University of California, Davis, CA 95616, USA
We report low dimensional oxide structures made by La doping on SrTiO3, represented by SrTiO3/(Sr1-x,Lax)TiO3 superlattices. The low dimensional transition metal oxide structures provide electronic confinement through orbital reconstruction of d orbital of the transition metal ion and correspondingly exhibit metal to insulator transition with the thickness of SrTiO3 layers. This is contrast to the behavior of bulk SrTiO3 doped with La. The carrier density of the low dimensional structures also had a non-linear relationship with the stacking period while the carrier density of bulk SrTiO3 had a linear relation with La doping content. Through the orbital reconstruction, degenerate narrow 3d bands are lifted and dxy band is shifted lower than dxz, dyz bands, making dxz band the first available state upon the La doping. Moreover, doped electrons occupying dxz band are strongly localized next the doped layer. As a result, the low dimensional oxide structure has two types of carriers, one localized at the interface (La doped layer) and the other extended into SrTiO3 layer, which exhibit quite different transport characteristics from bulk doped case. Transport behavior of such a low dimensional structure can be tuned by varying dimensionality and the corresponding metal-insulator transition is induced.
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FERROELECTRICALLY ACTIVE ACOUSTIC WAVE PROPAGATION
Wontae Chang US Naval Research Laboratory, Electronics Sci. &Tech. Division, Washington DC 20375, USA
The nonlinear variation of strain, polarization, and dielectric constant with applied electric field in ferroelectrics is taken into account in the constitutive equations of stress and electric displacement, in addition to the linear elastic, electric, and piezoelectric effects. Electricallycontrollable acoustic wave propagation in ferroelectrics is formulated from Newtons mechanical equation and Maxwells electromagnetic equation combined with the ferroelectric constitutive equations. The elastic, piezoelectric, ferroelectric acoustic waves, and consequently the electromechanical coupling factors in BaTiO3 (BTO) are computed as a function of the wave propagation direction in the [100]-[010] plane, and the excitation electric field direction (e.g., TE and LFE). Film bulk acoustic resonator (FBAR) using ferroelectrically active acoustic wave propagation in BTO film is simulated. In this study, the analysis of the electrically-controllable acoustic waves needed to effectively apply the ferroelectric material to make useful devices is provided.
1. This presentation is related to (i) Ferroelectric Materials: Theory & Experiments, and (ii) Tunable Dielectrics for RF applications and Devices 2. Dr. Wontae Chang, Code 6851, Electronics Sci. & Tech. Division, US Naval Research Laboratory, Washington, DC, USA, 202-404-4607 (office), 202-767-0455 (fax),
wontae.chang@nrl.navy.mil
3. Oral presentation
ISIF 2011, July 31 August 4, 2011, Cambridge, England
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Ferroelectric and Piezoelectric Materials - Theory
STRAIN-INDUCED FERROELASTIC DOMAINS AT METAL-INSULATOR PHASE TRANSITIONS IN VO2

A. Tselev , I. A. Lukyanchuk , I. N. Ivanov , J. D. Budai , J. Z. Tischler , (c) (c) (a) E. Strelcov , A. Kolmakov , and S. V. Kalinin
(a) (b) (a) (b),1 (a) (a) (a)
Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA LPMC, University of Picardy, Amiens, 80170, FRANCE (c) Physics Department, Southern Illinois University Carbondale, Carbondale, Illinois 6290, USA
Vanadium dioxide VO2 is a strongly correlated electron oxide, which exhibits an abrupt firstorder metal-insulator transition (MIT) at 68 C in with a few orders of magnitude change of electrical conductivity. The drop in conductivity is accompanied by a ferroelastic tetragonalto-monoclinic lattice structure transformation that evidences the significant lattice contribution in the formation of the electronic band gap. This multifunctionality makes VO2 an excellent candidate for numerous applications in optical, electronic, and optoelectronic devices. The ability to synthesize VO2 in the form of nanocrystals uncovered a number of previously unknown aspects of MIT in this oxide. In particular, the transition MIT can proceed through competition between two monoclinic (insulating) phases M1 and M2 and the tetragonal (metallic) R phase under influence of the strain. Here we show that the competition between M-phases is purely lattice-symmetry-driven. Within the symmetry approach, both M phases correspond to different directions of the same 4-component structural order parameter. We analyze the strain-controlled phase diagram of VO2 in the vicinity of the R-M2-M1 triple point (that is isomorphic to cubic-tetragonal-orthorhombic morphotropic point in ferroelectric PZT compounds) using the Ginzburg-Landau formalism, identify the pathways for strain-control of the transition and theoretically predict phases that have not been previously observed. Existence of various degenerate low-temperature phases in VO2 leads to formation of ferroelastic twin domains in strained single-crystalline nanobeams that are coupled to the strain-controlled metal-insulator transition. We report and theoretically explain the emergence of several possible families of ferroelastic domains in VO2 thus allowing systematic studies of strain-controlled transitions in the presence of geometrical frustration. We calculate also the phase diagram of the strain-induced domain state and compare it with experiment. These insights open the door toward more systematic approaches to synthesis of VO2 nanostructures in desired phase states and to use of external fields in the control the domains of different phases of VO2.
[1] A. Tselev, E. Strelcov, I. A. Luk'yanchuk, J. D. Budai, J. Z. Tischler, I. N. Ivanov, K. Jones, R. Proksch, S. V. Kalinin, and A. Kolmakov, Nano Letters 10, 2734-2734 (2010) [2] A. Tselev, V. Meunier, E. Strelcov, W.A. Shelton , I.A. Lukyanchuk, K. Jones, R. Proksch, A. Kolmakov, and S.V. Kalinin ACS NANO 4 4412 (2010) [3] A. Tselev, I. A. Lukyanchuk, I. N. Ivanov, J. D. Budai, J. Z. Tischler, E. Strelcov, A. Kolmakov, and S. V. Kalinin: Nano Lett 10, 4409 (2010).
lukyanc@ferroix.net
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Role of Ru nano-dots embedded in TiO2 thin films for improving the resistive switching behavior Jung Ho Yoon, Kyung Min Kim, Min Hwan Lee, Seong Keun Kim, Gun Hwan Kim, Seul Ji Song, Jun Yeong Seok, and Cheol Seong Hwang* Department of Materials Science and Engineering and Inter-university Semiconductor Research Center, Seoul National University, Seoul 151-744, Korea Thermochemical type resistive switching resistive switching (RS) phenomena,[1] where the formation and rupture of local and metallic conducting filaments (CFs) induces RS, has attracted considerable interest owing to its high data retention and stability, which are crucial factors for the next generation nonvolatile memory. TiO2 is a typical example of this type of RS having both unipolar and bipolar RS behaviors,[2-4] where the formation and rupture of a Magnli TinO2n1(n is typically 4 or 5) phase CF in the TiO2 matrix play a key role in RS.[5-7] Although TiO2 has several promising aspects as a RS material, the large scattering of the resistance values is a critical problem possibly due to the relatively ill controlled motion of the CFs. The repeated rupture and rejuvenation do not necessarily occur at a given location, and the status of the given connected or ruptured CFs may not be identical.[5] On the other hand, the Magnli phase CF is a derived structure of rutile TiO2. An excessive amount of oxygen vacancies in rutile TiO2 is gathered on the (121) crystallographic planes of rutile TiO2 to form the Ti4O7 or Ti5O9 material.[8] Therefore, the back and forth transition between the rutile TiO2 and Magnli CF is more fluent than that between other insulating TiO2 structures, such as anatase and Magnli CF. These considerations suggest that the optimal structure for achieving the uniform and fluent RS in TiO2 could be narrow columnar shaped rutile TiO2 structure embedded in anatase (or even amorphous) TiO2. An even more optimal structure must correspond to the case where rutile TiO2 is formed on a locally protruded region, which may concentrate the electric field to rutile (also Magnli phase CF) TiO2. In this study, the optimal RS cell structure was achieved using atomic layer deposition (ALD) techniques for the TiO2 film containing embedded Ru nano-dots grown by another ALD technique. For this purpose, Ru nano-dots were grown on thin (~5 nm) ALD TiO2 coated Pt substrates, and the main layer (50nm-thick) TiO2 was deposited subsequently on the Ru nano-dot/TiO2/Pt structure. Because of the growth of rutile and anatase TiO2 on the Ru and Pt portions, respectively, the desired improvement in RS was expected to be realized by the localized formation and rupture of the Magnli phase CF in the rutile TiO2 region. The Ru nano-dots were embedded in the lower part of the ~55-nm-thick TiO2 RS film sandwiched between the two Pt electrodes. The local TiO2 region over the Ru nano-dots has a rutile structure, which is a favorable structure for inducing the Magnli phase CF. Repeated I-V switching showed that the sample with the Ru nano-dots has a much higher uniformity in HRS resistance at the reading voltage than the sample without them. This was attributed to the better controlled rupture of the CF as well as the increased background leakage current of that sample in the low voltage region over the leakage current via the residual CF, which must be highly nonuniform according to the results from the sample without the Ru nano-dots.
[1] R. Waser, R. Dittmann, G. Staikov, and K. Szot, Adv. Mater. 21, 2632 (2009). [2] D. S. Jeong, H. Schroeder, and R. Waser, Electrochem. Solid-State Lett.10, G51 (2007). [3] K. M. Kim, G. H. Kim, S. J. Song, J. Y. Seok, M. H. Lee, J. H. Yoon, and C. S. Hwang, Nanotechnology 21, 305203 ( 2010). [4] M. H. Lee, K. M. Kim, G. H. Kim, J. Y. Seok, S. J. Song, J. H. Yoon, and C. S. Hwang, Appl. Phys. Lett. 96, 152909 (2010). [5] D.-H. Kwon, K. M. Kim, J. H. Jang, J. M. Jeon, M. H. Lee, G. H. Kim, X.-S. Li, G.-S. Park, B. Lee, S. Han, M. Kim, and C. S. Hwang, Nat.Nanotechnol. 5, 148 (2010). [6] B. J. Choi, D. S. Jeong, S. K. Kim, S. Choi, J. H. Oh, C. Rohde, H. J. Kim, C. S. Hwang, K. Szot, R. Waser, B. Reichenberg, and S. Tiedke, J. Appl. Phys. 98, 033715 (2005). [7]K. M. Kim, B. J. Choi, Y. C. Shin, S. Choi, and C. S. Hwang, Appl. Phys. Lett. 91, 012907 (2007). [8] L. A. Bursill and B. G. Hyde, Prog. Solid State Chem. 7, 177 (1972).
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Kinetic study on the formation and rupture of conducting nano-filaments in RRAM
Seul Ji Song, Jun Yeong Seok, Kyung Min Kim, Gun Hwan Kim, Min Hwan Lee, Jung Ho Yoon and Cheol Seong Hwang* Department of Materials Science and Engineering, WCU Hybrid Materials Program, Inter-university Semiconductor Research Center, Seoul National University, Seoul 151-744, Korea
Abstract
In this study, the formation process of conducting filaments in TiO2 film was interpreted by using equivalent circuit analysis in a pulse switching system. When a set switching occurs, the transition current was interpreted to be comprised of a leakage part that depends on the resistance of the memory and supplied current, and a discharging part that comes from the dissipation of the capacitive charge of the memory. The change in the volume fraction of filamentary regions can be calculated from the absolute value of resistance. In TiO2 film, it was shown that filaments revealed a recurring 1dimensional and 2-dimensional growth in terms of the Johnson-Mehl-Avrami kinetic model. From these results it is expected that the filaments are initially generated at high field concentrated-local regions with 1 dimensional shape, and then the volume of these initial filaments expand two dimensionally after connecting the top and bottom electrodes. Therefore, this physical model provides a practical method to identify the shape of filaments using the Johnson-Mehl-Avrami theory. The modeling approach was applied to the atomic layer deposited and sputtered TiO2 films which show different switching kinetics.
* E-mail: cheolsh@snu.ac.kr
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Topic: Electrocalorics, Thermoelectrics, and Energy Harvesting Preference: Oral Presentation
Effect of top electrode on the Photo-voltaic properties of PLZT thin film capacitors
Harshan V Nampoori and Sushma Kotru

Department of Electrical & Computer Engineering, The University of Alabama, Tuscaloosa, AL 35487, USA
Presenting author e-mail: skotru@eng.ua.edu
A recent report suggesting the possibility of above band gap voltages from ferroelectric materials has attracted the interest of research community to study these materials for the applications towards non-conventional solar cells devices. Although these ferroelectric (FE) solar cells materials do not exhibit very high conversion efficiency compared to the conventional solar devices, but the control of the PV characteristics with controlled polarization in these FE materials, gives it an edge over the semi-conducting counterparts. It is now, widely agreed that the PV effect in a ferroelectric material is induced by internal polarization of the material which in turn separates the photo generated electron-hole pairs. However apart from controlling the polarization of the material, there are various other factors which could contribute to the PV output, choice of electrodes, is one among them.
In this work, PV response of ferroelectric PLZT thin films using various top-electrodes was investigated. The films were prepared using sol gel deposition process. The ferroelectric/metal barrier as well as the bulk depolarizing field was shown to influence IV characteristics of the films. Use of a metal top electrode with lower work function was found to increase the open circuit voltage (Voc) from 0.17 V to 0.36 V for 210 nm thin films. It was seen that use of a transparent conducting electrode could increase the Voc further to ~ 1.3V. Such increase is attributed from the contribution of ferroelectric/metal barrier rather than from the bulk ferroelectric. These results indicate that choosing an appropriate top electrode can result in significant increase in the efficiency of the ferroelectric photovoltaic devices. Results on preparation and characterization of PLZT films along with their PV properties will be presented.
77
AN AUTONOMOUS NON-VOLATILE MEMORY LATCH Joe T. Evans, Jr. Radiant Technologies, Inc. The author will describe a novel method for implementing autonomous memory using ferroelectric capacitors. An autonomous memory is one that operates without need of a regulated power supply or a microprocessor to write or read data. A single bit of autonomous memory is a latch using a single ferroelectric capacitor as the storage medium. The state of the capacitor forces the state of the latch during the rise in power. The latch in turn re-writes the original state of the non-volatile storage capacitor once the supply voltage has been reached. The ferroelectric capacitor retains the stored state when power is removed. No internal or external clock or timing signals are necessary. The autonomous latch will be especially useful in wireless sensor systems that work from scavenged power sources where the cycle time and reliability of the power source are questionable.
Figure 607.4: Plot of the supply and output voltages during power up from the opposing retained states. The plot resembles the bit line operation of an FeRAM but the traces move in opposite directions from their counterparts in the FeRAM.
78
Improvement and evaluation on sorting algorithm with functional memory based on FeRAM
Hiroaki Watanabe1, Naoki Fujita2, and Hiroshi Nozawa1 1: Graduate School of Energy Science, Kyoto University, Kyoto, Japan 2: Department of Electric and Electronics, Kyoto University, Kyoto, Japan Abstract In this paper, improvement and evaluation on sorting algorithm with functional memory based on FeRAM has been described. The aim of this study is an application of FeRAM for information technology. Recently, information technology is rapidly developed. Therefore, high performance in data processing is strongly required. Sorting, which is one of the most important data processing, has a problem of explosive increment in calculation time as the number of data increases. Therefore, sorting is focused on. Functional memory provided with local ALU(Arithmetic and Logic Unit) can execute bit-serial and word-parallel operation. As a result, both high performance and low consumed power are expected to be achieved. On comparison of the number of operation times, in the case of bubble sorting, it is known to be n2. On the other hand, in the case of functional memory, it is reported to be n[1]. In this study, it is proposed that it is improved to reduce to log n. For improved algorithm described above evaluation with SPICE(Simulation Program with Integrated Circuit Emphasis) simulator is executed to compare to conventional ones. Firstly, a simulation limited to local ALU is executed and resulted in significant improvement in delay time and consumed power for bubble sort. Furthermore, delay time of improved algorithm with functional memory is revealed to be shorter than that of conventional one with functional memory. Secondarily, a simulation including bus line transmission is executed because it is inevitable to transmit data between CPU(Central Processing Unit) and main memory. As a result, significant improvement in delay time and consumed power for bubble sort is shown. On the other hand, delay time of improved algorithm with functional memory is similar to that of conventional one with functional memory. It implies that data transmission is a dominant factor. Solution for the problem will be presented at the symposium. [1] H. Nozawa, to be published in international journal of integrated ferroelectrics, 2011
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The influence of different types of La-incorporated TiN metal gate stacks on HfO2 ; TiN/La/TiN and TiLaN
Hyo Kyeom Kim1,2, Hyung-Suk Jung1, Jae Hyuck Jang1, Sang Young Lee1, Cheol Seong Hwang1* WCU Hybrid Materials Program, Department of Materials Science and Engineering and Inter-university Semiconductor Research Center, Seoul National University, Seoul 151-744, Korea 2 Department of Nano Science and Technology, Graduate School of Convergence Science and Technology, Seoul National University, Seoul 151-744, Korea
1
Tel +82-2-880-7988, Fax: +82-2-874-6414, E-mail; khk1014@snu.ac.kr
Hf-based gate dielectrics are currently implemented in highly scaled Complementary Metal Oxide Semiconductor Field Effect Transistors (CMOSFET) in the 45nm logic technology node [2]. With the high-k gate dielectric, polycrystalline silicon (poly-Si), used in conventional CMOSFET devices, is no more appropriate gate material because several issues such as poly-Si gate depletion, boron penetration and high gate resistance were aggravated in highly scaled transistors [3]. Therefore, as an attempt to overcome these issues, TiN-based gate materials have been widely studied. However, the work function of the TiN single metal is not low enough for n-channel metal oxide semiconductor (NMOS) transistors to achieve a low enough threshold voltage (Vth). To overcome this obstacle, thin La2O3 capping layers have been implemented to lower the Vth [4]. However, using a capping layer raises several issues such as difficulty in further scaling of equivalent oxide thickness (EOT) and the unintended degradation of high-k dielectric reliability due to the physical thickness increase and La ion diffusion. Recently, two basic approaches to integrate gate stacks with high-k gate dielectrics and a metal gate electrode were introduced; a gate-first approach and gate-last approach. In the gate-last approach, the gate stack is formed after the source and drain formation in a conventional CMOS process. This means that the extreme heat-budget is not imposed to the gate metal in gate-last integration scheme, so that various gate materials can be used to this integration scheme. Therefore, in this work, the influence of different types of La-incorporated gate stacks on high-k dielectric films for NMOS was investigated. A detailed comparison on the electrical properties and physical characteristics of TiN/La/TiN and TiLaN metal gates stacked on HfO2 are given. Single layer TiN and Pt films were used as reference metal gates. HfO2 films with various thicknesses ranging from 3nm to 6nm were deposited on a HF cleaned p-type Si substrate by atomic layer deposition (ALD) at a wafer temperature of 270 using Tetrakis[EthylMethylAmino]Hafnium (Hf[N(CH3)(C2H5)]4) and O3 as Hf- precursor and oxygen source, respectively. TiN and La were deposited on the as-deposited HfO2 by a reactive- sputtering method. A number of metal gate stacks were prepared by controlling the thickness of TiN and La. In the case of the TiN/La/TiN (TLT) structure, each of the thicknesses of the bottom TiN and the inserted La layer was changed from 2nm to 15nm. For comparison, a co-sputtered TiLaN film with 15nm thickness was also prepared. Finally, a Pt electrode was deposited in-situ after the deposition of the La-doped TiN films. By plotting the physical thickness as a function of CET, the interfacial layer thickness was extracted from the intersection with zero physical thickness. Compared to simple TiN and Pt, a substantial reduction of IL thickness was observed in TLT and TiLaN. La incorporation into the TiN metal gate accelerated the scavenging effect, in which the La ions take out the oxygen from the interfacial layer and decrease its thickness. Moreover, rapid thermal annealing (500~600oC, 30sec) on the TLT and TiLaN films showed a further reduction of IL thickness compared to as-deposited films. The reduction of IL thickness was also confirmed by transmission electron microscopy images. In addition, by measuring the density of interface states (Dit) from the conductance method and Vfb values from the capacitance-voltage curves, it was confirmed that the incorporated La affects the Dit values and causes a flat band modulation by changing the effective work function (EWF). The chemical bonding status of TLT and TiLaN were examined by ex-situ X-ray photoelectron spectroscopy (XPS). Here, the intensity difference between the shake-up feature and the La-3d core peaks indicated that La-O bonding exists in both the TLT and TiLaN films. This suggests that the La layer was not only oxidized in air after the deposition of the films, but also received oxygen from the interface and bulk oxide dielectrics. Acknowledgement : This work was support by the System IC 2010 project (2009-0081961) and the WCU program (R31-2008-00010075-0) 1. S. Thompson, et al., IEDM Technical Digest, p.61 (2002) 2. http://www.intel.com/technology/index.htm 3. Q. Lu et al., Symposium on VLSI Tech., Digest of Technical Papers, p.72 (2000) 4. L. Lin and J. Robertson, Appl. Phys. Lett. 95, 012906 (2009)
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TRAVELING WAVE-INDUCED AERODYNAMIC PROPULSIVE FORCE USING ACTIVE CONTROL OF THE DYNAMIC SHAPE OF PIEZOELECTRICALLY-DEFORMED PLASTIC SUBSTRATES. Noah T. Jafferis1,3, Howard A. Stone2,3, and James C. Sturm1,3 1 Department of Electrical Engineering, Princeton University, Princeton, NJ 08544 USA 2 Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, NJ 3 Princeton Institute for the Science and Technology of Materials (PRISM) In this work we use integrated piezoelectric actuators and sensors to demonstrate the aerodynamic propulsive force produced by traveling mechanical waves in a thin plastic substrate in air above a flat surface. These traveling waves have been predicted to produce a force in the direction opposite that of the wave propagation [1, 2] (Fig. 1), and the resulting forward motion of the sheet near the ground should cause it to lift up as it moves, leading to a so-called flying carpet [2]. Experiments are conducted to determine the dependence of this force on the height above the ground and the amplitude of the traveling wave, qualitatively confirming previous theoretical predictions. Two sheets of PVDF (28m) are glued together with a thin epoxy layer (~ 30m). The metal coating on each PVDF sheet is patterned into eight regions four of which are used as actuators (25mm by 35mm), and four as sensors (25mm by 3mm). The sensors are used to measure the actual time-varying shape of the sheet, which FIG. 1: Traveling wave pump. This allows the actuator control signals to be adjusted to optimize the traveling wave. In time-varying shape pulls air in from order to measure the force produced by the traveling wave, the sheet is suspended the left, and pushes it out to the from three elastic threads (1m long), which act as a simple pendulum, allowing the right, resulting in a propulsive force, Fp, to the left. force to be determined from the equilibrium displacement. With low frequency (<10Hz) traveling waves of voltages applied to the actuators, the actual deformations were close to the desired traveling waves. However, these frequencies are too low to give an observable propulsive force. At higher frequencies, dynamic effects and nonlinearities caused the deformation shape to be far from a traveling wave. At these higher frequencies, measuring a linear control matrix for the system, which relates the four applied voltages to the four measured curvatures, is always required. To correct for nonlinearities, feedback is very useful, especially in situations when higher frequency modes are also present in the output. By applying feedback separately for each harmonic with a significant undesired component present, all but the desired fundamental frequency can be cancelled out (Fig. 2). With this approach, traveling waves have been produced with amplitudes up to ~500um, and at 100Hz, we have measured forces exceeding 100uN when the sheet is suspended ~1mm above the ground. We observe FIG 2: Demonstration of a traveling wave, showing significance of qualitatively good agreement with theory [2]: the propulsive sensors and feedback to achieve ideal traveling wave shape. Data shown is at 600Hz. The upper axis shows the applied voltages, and force reverses direction when the traveling wave direction is the lower axis shows the shape of the sheet at various times, as reversed, drops rapidly as the sheet is raised, and increases reconstructed from the sensor measurements. (A) Without using with larger amplitude waves, as expected. Theory also sensors, the shape is close to a standing wave. (B) Applied predicts that such forces should be able to accelerate a freely voltages determined by the linear control matrix, and feedback on higher order modes up to 5 times the fundamental, needed to moving sheet up to a velocity of ~10cm/s (currently, the sheet is not free, so the observed velocity is ~1cm/s). achieve a traveling wave shape. In summary, we have successfully produced controllable traveling waves in a thin sheet of material, and measured the aerodynamic propulsive force created by these waves, thus confirming the physical basis for a flying carpet near a horizontal surface. This work also demonstrates the advantages of using integrated sensors to control the dynamic shape of thin plastic sheets deformed by piezoelectric elements.
[1] A. J. Reynolds, The Swimming of Minute Organisms. J. Fluid Mech. 23 (2), 241-360 (1965). [2] M. Argentina et al., Settling and Swimming of Flexible Fluid Lubricated Foils. Phys. Rev. Lett. 99, 224503 (2007).
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TSDC (Thermally Stimulated Depolarization Current) study of the rare earth and magnesium co-doped BaTiO3
Noriyuki Inoue1,2, Russell A. Maier1, Hiroshi Takagi2 and Clive A. Randall1 1 The Pennsylvania State University, USA 2 Murata Manufacturing Co., Ltd., Japan
The multilayer ceramic capacitors (MLCCs) are widely used in advanced electronic devices because of their high volumetric efficiency and superior performance at high frequencies. BaTiO3 has generally been used as a dielectric for MLCCs owing to its low dielectric loss and high permittivity. To suppress the resistance degradation and improve thermal characteristics of dielectric constant, rare earth elements (RE) and Mg are frequently co-doped into BaTiO3. The reason of the degradation is generally considered to be caused by the oxygen vacancy migration. Therefore RE and Mg co-doping is considered to have the effect of suppressing oxygen vacancies and/or redistribution. Recently, the TSDC measurements have been shown as a tool to analyze oxygen vacancies in dielectric materials in terms of defect dipoles and space charge distributions. Here we extend TSDC to investigate the RE and Mg co-doping compositions with oxygen vacancies behavior and determine differences associated with RE by TSDC measurements. (Ba0.94RE0.06)(Ti0.97Mg0.03)O3 (RE = Dy, Y, Ho) monolithic ceramics were prepared by conventional solid state synthesis with silver electrodes to form parallel plate capacitors. The capacitors were held at a polarization temperature Tp, and polarized by a dc electric field Ep, and then cooled to 100C, after being short circuited, the depolarization current was recorded
J (pA/mm2)
800 700 600 500

400 300 200 100 Ho Dy 200 Temp. (C) 300 Y
as function of temperature under a constant heating rate. As shown in Fig. 1, the magnitude of TSDC peaks over temperatures 200C increases and the peak temperature becomes higher by the high temperature polarization. These changes are caused by the oxygen vacancy migration, and the peak of Dy specimen is much smaller than those of Y and Ho. This means the oxygen vacancy in Dy specimen is more difficult to migrate by the electric field and temperature. Another peak caused by the defect dipole exists under 200C. We also evaluate the dissociation energy of oxygen vacancy from the defect dipole and compare the trap strength quantitatively for each composition.
0 100
Figure 1 Relative Variation of TSDC spectra of (Ba0.94RE0.06)(Ti0.97Mg0.03)O3 ceramics with different de-polarization temperatures and current densities. (closed circle: Tp = 200C, Ep = 100V/mm, open circle: Tp = 250C, Ep = 100V/mm)
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The impact of ALD grown SiOxNy and AlOxNy passivation layers on the electrical properties of metal gate/high-k Ge MOS capacitors
Hyung-Suk Jung1,2,*, Joohwi Lee1, Hyo Kyeom Kim1, Sang Young Lee1, Nae-In Lee2, and Cheol Seong Hwang1
1
WCU Hybrid Materials Program, Department of Materials Science and Engineering and Inter-university Semiconductor Research Center, Seoul National University, Seoul 151-744, Korea 2 TD3 Team, System LSI Division, Samsung Electronics Co. Ltd., Gyeonggi-do 446-711, Korea
Tel +82-2-874-6414, Fax: +82-2-874-6414, E-mail; johnjung@snu.ac.kr*
Hf-based gate dielectrics have been recently implemented as gate dielectrics in the 45nm complementary metal oxide semiconductor (CMOS) devices1. To increase transistor performance for the future technology node, it was proposed that high-k gate dielectrics should be combined with the high mobility channel materials such as Ge and III-V compound semiconductors2. Ge is one of the promising candidates for the future CMOS devices due to its higher carrier mobility (especially hole) compared to Si. However, several challenges have to be overcome to implement Ge into a fully CMOS-compatible process. One of the key issues for Ge integration is achieving a high quality passivation layer at the Ge/oxide interface to reduce the interfacial trap density. Several passivation techniques such as nitridation in NH3 ambient3, thin epitaxial Si layer4, and AlN layer5 have been proposed to achieve high quality interfaces. In this study, ALD grown SiOxNy and AlOxNy were used as the passivation layer for HfO2 or ZrO2 gate dielectrics, and the influence of these layers have on the electrical characteristics of the MOS capacitors such as C-V hysteresis and Dit were systematically investigated. Various high-k gate dielectrics (6nm) were deposited directly onto HF cleaned Ge wafers by atomic layer deposition (ALD) at a wafer temperature of 280oC. Hf[N(C2H5)(CH3)]4, Zr[N(C2H5)(CH3)]4, Al(CH3)3 and SiH[N(CH3)2]3 were used as the metal precursors for HfO2, ZrO2, Al2O3 and SiO2, respectively. Ozone was used as the oxygen source. In order to investigate the effect of passivation layers on the electrical characteristics, Al2O3 or SiO2 with various thicknesses ranging from 0.5nm to 2nm were deposited prior to the deposition of HfO2 (or ZrO2). After depositing the passivation interfacial layer, annealing at 600oC were performed in an NH3 or N2 ambient to incorporate nitrogen and densification of the films. After the deposition of HfO2 (or ZrO2), post deposition annealing at 600oC were performed in a N2 ambient. Then, platinum was deposited through a shadow mask to define the gate electrode. When HfO2 and ZrO2 were deposited directly onto the HF cleaned Ge substrate, a significantly large C-V hysteresis > 1500mV was observed, which can be understood from the diffusion of Ge into HfO2 and ZrO2.6 However, a relatively smaller C-V hysteresis, approximately 250mV, were observed when Al2O3 was deposited directly onto the HF cleaned Ge substrate. In order to overcome the lower dielectric constant of Al2O3 and the poor interface quality of HfO2 or ZrO2, Al2O3 was used as the passivation layer for the HfO2 and ZrO2 gate dielectrics. In addition, an ALD grown SiO2 layer was also used for the passivation layers. To achieve an electrically benign passivation layer, nitrogen was incorporated into the SiO2 and Al2O3 passivation layer. In both ZrO2 and HfO2 gate dielectrics, SiOxNy and AlOxNy passivation layers can effectively decrease the C-V hysteresis. When the thicknesses of the SiOxNy and AlOxNy passivation layers increase, the C-V hysteresis was found to substantially decrease. The SiOxNy passivation layer was found to decrease the C-V hysteresis to less than 40mV when increasing the layer thickness, while the C-V hysteresis of AlOxNy passivation layer was saturated at 350mV. The effect of passivation layers on the interface quality was also evaluated from the Dit values which were measured by the conductance method. The existence and thickness of passivation layers had no significant effect on the Dit values.
Acknowledgement : This work was support by the System IC 2010 project (2009-0081961) and the WCU program (R31-2008000-10075-0)
1 2
http://www.intel.com/technology/index.htm. D. K. Sadana, III-V Sub. Eng., 2005 3 N. Wu et al., Appl. Phys Lett., 84, 3741 (2004) 4 P. Zimmerman et al., IEDM Tech. Dig., 2006, 655 5 F. Gao et al., Appl. Phys Lett., 86, 113501 (2006) 6 S. V. Elshocht et al., Appl. Phys Lett., 85, 3824 (2004)
86
The intrinsic coercive field for P(VDF-TrFE) thin-films with different thickness
X.B. Liu , A.Q. Jiang , T.A. Tang State Key Lab of ASIC and System, Fudan University, Shanghai, 200433, China e-mail: 09110720030@fudan.edu.cn
Generally, the organic ferroelectric P(VDF-TrFE) thin film is partially crystallized and a mixture of crystalline and noncrystalline molecules, besides the presence of additional nonferroelectric impurity phase, e.g., Trifluoroethylene, in the copolymers. Therefore, it is almost impossible for the domains to switch under a normal field without incurring of charge injection across these nonferroelectric phases. Once the injection field is high enough across the nonferroelectric phases, the domain switching within the ferroelectric is possible when the switching current equals the injection current. Once the domain switching speed is increased, much higher switching field is required to achieve a large enough injection current across these nonferroelectric phases even if the intrinsic ferroelectric domain switching field is the same. Therefore, the huge coercive field of the total poly(vinylidene fluoride-trifluoroethylene) copolymer thin film with a nanosecond-range domain switching time composes of the fields across the ferroelectric and nonferroelectric phases, respectively, which is far higher than the intrinsic coercive field across the ferroelectric only. From an equivalent-circuit description of the film consisting of a nonferroelectric capacitor Ci in series with a ferroelectric capacitor Cf, we can extract the intrinsic coercive field for the ferroelectric only, and the derived value is far smaller than the total coercive field of the film, which is comparable between the films with different thicknesses.
Preference to poster presentation
87
New Soft Magnetoelectrics: Mixtures of the Ferroelectric Liquid Crystal and Magnetic Nanoparticles
Brigita Roi1, Marko Jagodi2,4, Sao Gyergyek1, Mihael Drofenik1, Samo Kralj3,Gojmir Lahajnar1, Zvonko Jaglii2, George Cordoyiannis4, and Zdravko Kutnjak1 Jozef Stefan Institute, Jamova 39, 1001 Ljubljana, Slovenia Institute of Mathematics, Physics and Mechanics, Jadranska 19, 1000 Ljubljana, Slovenia 3 Faculty of Natural Science and Mathematics, University of Maribor, 2000 Maribor, Slovenia 4 EN-FIST Centre of Excellence, Dunajska 156, 1000 Ljubljana, Slovenia
2 1
e-mail: brigita.rozic@ijs.si Magnetoelectrics are recently very attractive topic for researchers due to their properties, i.e., in such materials it would be possible to control the magnetic properties via electrical ones, and vice versa and also due to their potential for different applications, for example in information storage industry [1]. It is known that mixtures of nanoparticles (NPs) and other conventional materials could exhibit special behaviour not found in the individual components [2]. Such conventional material which we are interesting in are liquid crystals (LCs). It has been shown that the spontaneous onset of liquid crystal ordering could be a way to obtain very well aligned NPs [3]. We experimentally analysed mixture of maghemite magnetic NPs and ferroelectric liquid crystal (LC) SCE9 in the vicinity of the ferroelectric smectic C* phase. The impact of the magnetic NPs on the Goldstone and soft mode dielectric response has been determined by the dielectric spectroscopy measurements, and the disordering effects on the ferroelectric phase transition have been studied by the high resolution calorimetry. Similar disordering effects were found as in case of the aerosil particles [4-5]. Measurements of the impact of the electric field on the magnetic susceptibility via SQUID susceptometer verified the indirect coupling between the NP's magnetic moments and LC's electric polarization. This demonstrates that magnetoelectricity can be found in soft composite materials such as mixtures of magnetic NPs and ferroelectric LCs. [1] W. Erenstein, N. D. Mathur and J. F. Scott, Nature 442, 05023 (2006). [2] A. C. Balazs, T. Emrick, and T. P. Russell, Science 314, 1107 (2006). [3] P. G. de Gennes and J. Prost (The Physics of Liquid Crystals, Oxford University Press, Oxford 1993). [4] G. Cordoyiannis, G. Nounesis, V. Bobnar, S. Kralj, and Z. Kutnjak, Phys. Rev. Lett. 94, 027801 (2005). [5] G. Cordoyiannis, S. Kralj, G. Nounesis, S. umer, and Z. Kutnjak, Phys. Rev. Lett. 75, 021702 (2007).
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SUB-MICRON FERROELECTRIC-GATE THIN FILM TRANSISTOR USING SOL-GEL ITO CHANNEL AND STACKED (BLT/PZT) INSULATOR Bui Nguyen Quoc Trinh,1,a) Takaaki Miyasako,1 Toshihiko Kaneda,1 Phan Trong Tue,2 Pham Van Thanh,2 Eisuke Tokumitsu,1,3 and Tatsuya Shimoda 1,2
1
Japan Science and Technology Agency, ERATO, Shimoda Nano-Liquid Process Project, 2-5-3 Asahidai, Nomi, Ishikawa 923-1211, Japan 2 Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi, Ishikawa 923-1292, Japan 3 Precision and Intelligence Laboratory, Tokyo Institute of Technology, 4259-R2-19 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan a) Electronic mail: tnq-bui@jaist.ac.jp
Ferroelectric-gate thin film transistor (FGT), which uses an active oxide-semiconductor channel and a ferroelectric-gate insulator as drawn in Fig.1 (a), has attracted wide attention for the application of a new nonvolatile memory because of its prominent features such as simple device structure, high-speed operation and low power consumption. In recent, several groups have demonstrated excellent operation of FGTs with various active channels and gate-insulators.1-3) However, all FGTs developed have channel lengths (LDS) more than 1m, which should be reduced for high-density storage in integration circuits. Therefore, we tried to develop the FGTs with sub-micron LDS. For FGT fabrication, at first, we deposited a 100-nm-thick Pt film by sputtering technique as a gate on SiO2/Si substrate. Second, a new stacked gate-insulator, whose 160-nm-thick PZT film and 20-nm-thick BLT film were prepared by sol-gel technique and crystallized at 600oC and 650oC, respectively. Here, the BLT film layer prevents diffusion of Pb from the PZT film and creates a well-formed interface with the channel. Third, a 50-nm-thick Pt film was deposited by sputtering technique, then patterned by e-beam lithography and dry-etched to obtain a sub-micron gap between the source and the drain. Finally, a 20-nm-thick ITO film was coated by sol-gel technique and isolated by photo-lithography and dry-etching to form the channel width (W) of 2000 nm. Figure 1(b) shows the top view of the fabricated sub-micron FGT, and Fig. 1 (c) shows 3D-AFM image of the clear 200nm gap between the source and the drain. Transfer characteristics of the FGTs with LDS=1000, 300, and 200 nm are shown in Figure 2 (a), where wide memory-functioned hysteresis loops are observed for all cases with memory windows of 4 V and on/off current ratios of 104-5. Figure 2 (b) and (c) shows a comparison of the output characteristics of the FGTs between LDS=1000 and 200nm, in which both cases show a saturation behavior. These results imply that the memory properties are not so degraded with the size downing to 200 nm. In this symposium, further investigation on electrical properties of the submicron FGTs will be presented and discussed in details. [1]. T. Fukushima, T. Yoshimura, K. Masuko, K. Maeda, A. Ashida, and N. Fujimura, Jpn. J. Appl. Phys. 47, 8874 (2008). [2]. Y. Kaneko, H. Tanaka, and Y. Kato, Jpn. J. Appl. Phys. 48, 09KA19 (2009). [3]. T. Miyasako, B.N.Q. Trinh, M. Onoue, T. Kaneda, P.T. Tue, E. Tokumitsu, and T. Shimoda, Appl. Phys. Lett. 97, 173509 (2010).
Fig. 1 (a) FGT structure, (b) the top view of the fabricated FGT, and (c) 3D-AFM image of the fabricated LDS=200nm.
Fig. 2 (a) Transfer characteristics of the FGTs, (b) and (c) output chacteristics of LDS=1000nm and LDS=200nm, repectively.
91
Pt/Ti/Al2O3/Al tunnel junctions showing electroforming-free bipolar resistive switching behavior
Doo Seok Jeong, Byung-ki Cheong , and Hermann Kohlstedt

1
Electronic Materials Center, Korea Institute of Science and Technology, 39-1 Hawolgok-dong, Seongbuk-ku, Seoul 136-791, Republic of Korea
Nanoelektronik, Technische Fakultt, Christian-Albrechts-Universitt zu Kiel, D-24143 Kiel, Germany e-mail: dsjeong@kist.re.kr
Recently, crossbar arrays are considered as an interesting approach for ultra-large-scaled Gbit resistive random access memories (RRAMs) circuits as well as neuromorphic logic circuits based on synapse-mimic analog switches comprising TiO2 memristor. Switching elements applicable to these devices need a pre-treatment process termed electroforming, which leads to the formation of nm-sized conduction filaments. In subsequent resistance-programming cycles, large parameter spread between individual cells could be a critical obstacle for the application of resistive switching phenomena to electronic devices. The objective of the present investigation is to seek the answer to the question How can we achieve an electroforming-free resistive switch on the basis of metal-insulator-metal (MIM) structure?. We investigated electroforming-free bipolar resistive switching behavior in Pt/Ti/Al2O3/Al tunnel junctions where the Al2O3 tunnel barrier was naturally formed on Al in air. The fabricated resistive tunnel junctions (RTJs) showed reproducible bipolar resistive switching behavior without electroforming. The resistance of an as-fabricated RTJ was found to be identical to that of the high resistance state, implying no filament forming during switching operation. Various compliance current values for the junctions set switching successfully lead to various resistance values in its low resistance state, suggesting the possibility for multi-level-operation. A mechanism for the bipolar switching is qualitatively discussed in terms of the modulation of the tunnel barrier by the reactive Ti layer on top of the barrier.
Figure 1. Typical current-voltage switching curve of an Ti/Al2O3/Al RTJ.
Figure 2 I-V switching curves measured with various compliance current values. HRS and LRS resistances and maximum set voltage as a function of the cc values are plotted in the inset.
92
CAN OXYGEN VACANCIES SWITCH POLARISATION AXIS IN FERROELECTRICS? EXAMPLES OF BaTiO3 AND KNbO3 A. V. Kimmel1, 2, P. V. Sushko1, P. Weaver2, M. Cain2
1
Department of Physics and Astronomy, University College London, Gower Street, London, WC1E 6BT, UK 2 National Physical Laboratory, Hampton Road, Teddington, TW11 0LW, UK
Oxygen vacancy is a common defect in perovskite materials. In ferroelectrics, it is believed to be responsible for pinning the domain walls and appearance of non-polarisable areas, leading to degradation of materials ferroelectric properties and, ultimately, failure of ferroelectric devices. Understanding the impact of the neutral and charged oxygen vacancies on the materials properties is important for the development of robust nanoscale ferroelectric devices. In this work we study the effect of a neutral vacancy defect on the lattice structure of the bulk BaTiO3 (BTO) and a promising for health-care applications KNbO3 (KNO). We have described two types of the oxygen vacancies in the tetragonal lattices of these materials. The axial vacancy has been found to be more stable than the equatorial one by as much as 0.22 and 0.42 eV, respectively. The equatorial vacancies can become stabilised via two mechanisms: diffusion to the axial vacancy site and reorientation of the polarisation axis locally. The vacancy diffusion is always temperature-activated. For example, the calculated barrier for the equatorial-to-axial vacancy diffusion is 1.2 eV in BTO and 0.74 eV in KNO. On the contrary, the local reorientation of the polarization axis can take place spontaneously if the local vacancy concentration increases to 210-3 -3. We have found that in BTO such reorientation takes place at lower vacancy concentrations than in KNO. These results suggest that equatorial oxygen vacancies can facilitate the formation of domains switched at 90 to the local polar axis.
93
INFRARED SPECTROSCOPY OF NANOSCOPIC EPITAXIAL BaTiO 3 /SrTiO 3 SUPERLATTICES V. elezn1, A. Soukiassian2, X.X. Xi3, D.G. Schlom2, J. Hlinka1, C. Kadlec1, S.M. Nakhmanson4
2
Institute of Physics, ASCR, Na Slovance 2, 182 21 Praha 8, Czech Republic Department of Materials Science and Engineering, Cornell University, Ithaca, New York, 14853-1501, USA 3 Department of Physics, Temple University, Philadelphia, Pennsylvania 19122, USA 4 Argonne National Laboratory, 9700 S. Cass. Ave., Argonne, Illinois 60439, USA
Artificially layered ferroelectric superlattices have enormous appeal from both a technological and a fundamental standpoint. However, it is difficult to measure and monitor their properties on nanoscale level. Infrared spectroscopy is a very effective tool for studying and understanding their behavior. It also represents a complement to Raman spectroscopy having different selection rules. The incident infrared radiation couples directly to the order parameter (polarization) and this can be used for determination of the parameters important for lattice dynamics including the absolute value of the dielectric function. Here we report farinfrared reflectivity measurements on epitaxial ferroelectric BaTiO 3 /SrTiO 3 superlattices grown on rare-earth scandate substrates by molecular-beam epitaxy. Varying temperature enables us to study the sample behavior in the vicinity of the expected phase transition in nanoscale ferroelectric heterostructures. The experimental spectra were measured in two polarizations along the c (long) axis and perpendicular to it on the (110) cut of substrates. The spectra are very complicated because of the large number of infrared active phonons (25 in substrate and at least 3 in superlattice) and a fitting procedure is needed in order to extract phonon parameters for both the substrates and superlattices. We used a dielectric function in factorized form (four-parameter model) for both substrate and superlattice. First we fit the spectrum of the bare substrate then we fixed all of its parameters and added a top layer to the model corresponding to the superlattice on the substrate. Fitting our model to the total reflectance (substrate + superlattice), we were able to determine the effective parameters of the superlattice and obtain its spectrum. In this way, we calculated the spectrum of a typical perovskite shape, which is very close to the BaTiO 3 spectrum polarized perpendicular to the c axis. It is worth noting that no spectral shift with respect to bulk crystalline BaTiO 3 was discerned experimentally. The lowest phonon (soft mode) is quite smeared and it is very difficult to determine its parameters even using a fitting procedure. The total thickness of our superlattices was (~ 240 nm) and their behavior was quite different from the very thin film (~10-20 nm), where the shift was found. The results of infrared measurements were compared and good areement was found with a theoretical ab initio study of polar phonons, which provides the ionic Born effective charges, eigenvalues and eigenvectors. A W-shaped spectral feature with minima at 33 and 54 cm-1 was observed. Their positions are quite close to the frequencies where folded acoustic longitudinal phonons were found by Raman scattering. The previous observation was confirmed by terahertz time-domain spectroscopy whose measurement was in good agreement with the infrared data. This work was partially supported by the Grant Agency of the Czech Republic under Contract No. P204/11/1011 and by the Ministry of Education of the Czech Republic under Contract ME08109.
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Lateral Size Dependence of Crystal Structure in The Pb(Zr,Ti)O3 Thick Film at The Morphotropic Phase Boundary
Masamichi Nishide1, Takashi Katoda2, Shintaro Yokoyama3, Hiroshi Funakubo3, Ken Nishida1, Takashi Yamamoto1
Department of Communications Engineering, National Defense Academy, Yokosuka 239-8686, Japan Department of Electronic and Photonic Systems Engineering, Kochi University of Technology, kami-shi, 782-8502 Japan 3 Department of Innovative and Engineered Materials, Tokyo Institute of Technology, Yokohama 226-8502, Japan
1
Pb(ZrxTi1-x)O3 (PZT) films have been applied to various ferroelectric and piezoelectric devices because of their excellent polarization and piezoelectric properties. It is known that tetragonal and rhombohedral phases are coexistent near morphotropic phase boundary (MPB). Especially, the MPB has a band width to the Zr content in film form because of the strain introduced to the films. Recently, several researchers have reported that the electrical properties and the crystal structure of the PZT films varied with a reduction of the lateral size of the films (island form) due to release of the strain imposed by the substrates [1, 2]. However, a structural change in microscopic region to the lateral size has not been clear. In this paper, a change of cross-sectional distribution of tetragonal and rhombohedral phases against the lateral size in MPB-PZT film is reveled using Raman spectroscopy. The epitaxial PZT film with Zr/(Zr+Ti) = 0.58 was grown on (100)SrRuO3/SrTiO3 substrate using metal organic chemical vapor deposition (MOCVD) method. The film thickness was 3 m. The PZT film was oriented to (001)/(100). The crystal structure of the PZT film was characterized by micro-Raman spectroscopy (Renishaw inVia Raman microscope). An Ar+ laser with 514.5 nm in wavelength was used for excitation source and spot size of incident light was about ~1 m in diameter. The PZT film was fabricated to island form using focused ion beam (FIB) and annealed at 600 C for 1h to remove the milling damage. Figure 1 shows changes of the Raman spectra along film thickness for the PZT film and the PZT island with 0.5 0.5 m2 in lateral size. It was found that the Raman spectra were changed from the film-substrate interface to the film surface, and the spectrum shape at the film surface indicates that the crystal symmetry was rhombohedral in both the film and the island. At the film-substrate interface the intense peaks (denoted by arrow) were observed in the Surface Surface 3 m film (Fig. 1 (a)). These peaks indicate existence of the 3 m tetragonal phase. On the other hand, the peak intensities of the tetragonal phase were decreased at the interface in the island (Fig. 1 (b)), indicating that the crystal structure changed from tetragonal phase to rhombohedral phase. It is considered that these changes are caused by release of the cramping strain imposed by the substrate. It was cleared that the change of the crystal structure in microscopic region to the lateral size of the film. References [1]. V. Nagarajan et al.: Nat. Mater., 2 (2003) 43. [2]. K. Lee et al.: Appl. Phys. Lett., 86 (2005) 202901.
Intensity (arb. unit) 2.4 m
2.4 m
1.5 m
1.5 m
PZT
0.9 m Interface 0 m 200 400 600 -1 Raman shift (cm )
0.9 m Interface 0 m 200 400 600 -1 Raman shift (cm )

SRO STO
(a)
(b)
Fig. 1 Change of Raman spectra along film thickness direction for (a) PZT film and (b) island (0.50.5 m2). The inset numbers and arrows indicate a distance from film-substrate interface and the peak of the tetragonal phase.
95
STUDY OF DEFECTS AND DOMAIN STRUCTURE FOR CONTROLLING PIEZOELECTRIC RESPONSE IN (Na,K)NbO3
Keisuke Kobayashi1 2, Keiichi Hatano2, Youichi Mizuno2 and Clive A. Randall1 The Pennsylvania State University1, Taiyo Yuden Co., Ltd.2 The perovskite (Na,K)NbO3 system (hereafter NKN) is one of the promising candidates for non-lead piezoelectric materials. It has merit, as it has a relatively high Curie temperature above 400oC, a high d33 and electromechanical coupling factor (Kp). The defects and ferroelectric domain structures are believed to play an important role for piezoelectric properties and 220 reliability of NKN. Especially extrinsic contribution 115 200 that is mainly caused by motion of non-180o domain 110 wall in NKN grains is a key factor for improving 105 180 properties. We studied the effect of the domain and 100 160 defects structure upon piezoelectric properties in Li 95 modified NKN materials to achieve high quality 90 140 piezoelectric materials. 85 120 The Lix(Na0.5K0.5)1-xNbO3 ceramics with x=0.0, 0.03, 0.00 0.02 0.04 0.06 0.08 0.05, 0.06, 0.08 were fabricated by solid state Amount of Li (x) Fig. 1 Mechanical quality factor synthesis route from reagent-grade Li2CO3, Na2CO3, and piezoelectric coefficient with K2CO3 and Nb2O5. various amounts of Li. Fig. 1 shows the d33 and Qm value measured by x10-13 2.5 resonance-antiresonance method. The d33 and Qm value has a maximum and minimum, respectively, at 2.0 x=0.06, which are consistent with previous studies. 1.5 We evaluated the extrinsic contributions to the piezoelectric response via a Rayleigh analysis to 1.0 access the nature and relative magnitude of the 0.5 extrinsic contribution. Fig. 2 shows the estimated 0.00 0.02 0.04 0.06 0.08 Rayleigh coefficient d value. We also observed the Amount of Li (x) domain structure in our Lix(Na0.5K0.5)1-xNbO3 samples Fig. 2 Rayleigh coefficient d with by transmission electron microscope (TEM) and found various amounts of Li. 1 um fine 60o, 90o, 180o domain wall structures in x=0.06 sample as shown in Fig. 3, which implies this sample has orthorhombic or lower crystallographic symmetry. 60o domain We have also investigated the defect structure caused by Li substitution using thermally stimulated depolarization currents (TSDC) to determine defect dipoles in NKN systems. In this presentation, the effects of domains and defects on piezoelectric 180o domain 90o domain properties will be discussed in detail based on these electrical and microstructural results.
Rayleigh Coefficient (d)
Piezoelectric coefficient d33 (pC/N)
Mechanical quality factor (Qm)
Li0.06(Na0.5K0.5)NbO3
Fig. 3 Dark field TEM image of Li0.06(Na0.5K0.5)0.94NbO3.
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Submitted to ISIF2011
Weak ferromagnetism of HfO2 film on compressively strained Si83Ge17/Si substrate

Y.T. Tu1), X.F. Chen1) ,G . D. Zhou1) , J.Y. Dai2) , X. Y. Qiu1)* School of Physic Science and Technology, Southwest University, Chongqing 400715, Peoples Republic of China 2) Department of Applied Physics, The Hong Kong Polytechnic University, Hung Hom, Kow loon, Hong Kong, Peoples Republic of China (Prefer oral presentation under topic 6) Abstract The effects of working power and thermal annealing on weak ferromagnetic properties of HfO2 films on strained Si83Ge17 deposited by RF Magnetron Sputtering were investigated. Ferromagnetic properties of HfO2 films were characterized by using vibrating-sample-magnetometer (VSM). It was found that HfO2 films deposited at room temperature (RT) with working power of 70 W resulted in the largest magnetic moments (see figure 1). After annealed at 350 in high vacuum (~3 -4 Pa) for 30min , magnetic moments 10 of as-deposited HfO2 films slightly increased. However, it subsequently decreased when the annealing temperature was higher than 500, as shown as figure 2. These results suggest that, the optimized deposition conditions for HfO2 films with large magnetic moment are room temperature growth with working power of 70 W and high vacuum thermal annealing at 350for 30min. The compressive strain of the Si83Ge17 layer and existence of oxygen vacancies in the HfO2 films may be responsible for the observed weak ferromagnetism. Key words: weak ferromagnetism; HfO2 films; RF Magnetron Sputtering
6 4 2 0 -2 -4 -6 -1.0
40w 50w 60w 70w 80w 100w 120w 1.8 1.5 1.2 0.9 0.6
1)
Magnetic Moment(emu/cm )
Magnetic Moment(abr.unit)
Annealed in HV, H // film surface

RT
100 W
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RT, H // film surface
70 W 50 W 40 W 0 100 200 300 400 500 600 0 Annealing Temperature ( C ) 700
-0.5
0H(Tesla)
0.0
0.5
1.0
Fig.1 M-H curves for HfO2 films deposited at RT with working power of 70 W after subtracting the paramagnetic background from the Si83Ge17 substrate. Inset shows magnetic moments of HfO2 films deposited at RT with working power of 40, 50, 60, 70, 80,100 and 120 W
Fig.2 Magnetic moments of HfO2 films deposited at RT on Si83Ge17 substrate with working power of 40, 50, 70 and 100 W. All as-deposited films were subsequently annealed at 350, 500, 600 in high vacuum for 30min.
*Corresponding & presenting author; email address qxy2001@swu.edu.cn
97
FABRICATION OF PbTiO3 AND Pt SELF-ORGANIZED NANOCRYSTAL ARRAY STRUCTURE FOR HIGH DENSITY FERROELECTRIC MEMORIES Takashi Nishida1,2, Masahiro Echizen1, Lu Li1, Kenshiro Asahi1, Yasuhiro Yoneda3, Hideo Kimura4, Yasuaki Ishikawa1,2, Yukiharu Uraoka1,2
1. Graduate School of Materials Science, Nara Institute of Science and Technology (NAIST) 8916-5 TAKAYAMA-CHO, IKOMA, NARA 630-0101, JAPAN, e-mail: tnishida@ms.naist.jp 2. Competitive Funding for Team-based Basic Researches, Japan Science and Technology Agency 3. Japan Atomic Energy Agency, 1-1-1 KOUTO, SAYO-CHO, SAYO-GUN, HYOGO 679-5148, JAPAN 4. National Institute for Materials Science, 1-2-1 SENGEN, TSUKUBA, IBARAKI, 305-0047, JAPAN
The fabrication of Pb(Zr, Ti)O3 (PZT) nanocrystal has been widely interesting because of high density FeRAM and ferroelectric domain physics in nanosize-region. We have investigated fabrication of PbTiO3 nanocrystals by a bottom-up approach, such as sputtering deposition. From this investigation, we successfully obtained the PbTiO3 nanocrystal array that is, position control of nanocrystal growth using our newly developed sputtering methods (low angle incidence sputtering) and atomically flat sapphire substrates. (Fig.1) The electric properties of PbTiO3 nanocrystals cannot be measured because the crystals were deposited on electrical insulation materials, such as sapphire substrates. Thus, Pt was also deposited using our sputtering methods, and the atomically flat Pt layers can be obtained on the sapphire substrates. In order to investigate the crystal structure, the nanocrystal specimens were evaluated by the synchrotron radiation XRD (Spring-8), revealing that the highly oriented Pt(111) and PbTiO3(111) crystals were obtained on sapphire (001) substrates. The FWHM of rocking curve measurements was under 0.1o. The growth rate dependences of PbTiO3 were also evaluated using a combinatorial approach of specimens that had the growth rate gradation in the surface (position: Y), and it was found that high quality films can be obtained at optimum growth rate. (Fig.2)
FFT
20
8 Inten. (kcps) 6 4 2 0 -3
10
-20
-10
10
20
-20
1 m
Low Growth rate High Transition zone Continuous Nanocrystal Film
-10
-2
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0 Y (mm)
Fig. 1 PbTiO3 nanocrystal array
Fig.2 XRD intensity vs. growth rate
98
Ferroelectric polarization modulation of bipolar diode current in a ferroresistive memory with a high integration density
A.Q. Jiang,1 a) C.S. Hwang2, J.F. Scott3, H.H. Yu1, and T.A. Tang1
1
State Key Lab of ASIC & System, Department of Microelectronics, Fudan University, Shanghai 200433, China Department of Materials Science and Engineering, WCU Hybrid Materials Program, Interuniversity Semiconductor Research Center, Seoul National University, Seoul 151-744, Korea Department of Physics, University of Cambridge, Cambridge CB3 0HE (the United Kingdom)
Binary data in 1T1C/2T2C non-volatile ferroelectric random access memories are readable through the polarization charge difference between switching and non-switching events of the cells, which is proportional to the capacitor area, and the data are no longer detected reliably in a high-density memory. The nondestructive readout of the binary information is possible from the high- and low-conductance bipolar switching of a ferroelectric tunnel junction with a very thin film barrier upon polarization reversal. However, the homogeneity requirement of the atomic layer smoothness is a big challenge for the manufacturer as the atomic-layer thick film is homogeneously deposited on a large 8 Si wafer with a high production yield. To resolve this fabrication problem in the factory, we observed the same electroresistance effect in some semiconducting ferroelectric films with the thicknesses of 100-500 nm. The ferroelectric semiconductors have a unipolar diode current in a p-n junction, and the junction direction can be switched upon polarization reversal. The on/off current ratio is over 100 as the diode current density is below 20 mA/cm2. However, the ratio drops down quickly as the current density increases up to 1 A/cm2 for the guarantee of a sufficient readable signal in a nanometer-sized memory cell. After the separation of the displacement current charge and leaky current charge in the diode from pulse measurements, we confirmed the modulated diode current under different writing voltages proportional to the switched polarization. With the microscopic detection of the local diode current via the AFM tip over the film area, the p-n junction formation is found to be homogeneous, which is different from the random formation of conduction paths in other RRAM. The working mechanism and application future of the ferroresistive memory is briefly discussed. .
a)
Email: aqjiang@fudan.edu.cn.
100
Topic: Tunable Dielectrics for RF Applications and Devices Preference to oral presentation (invited talk if possible)
CHARACTERISTICS OF FERROELECTRIC TITANATE/III-V SEMICONDUCTOR HETEROSTRUCTURE
Jianhua Hao*, Wen Huang, Xianhua Wei, Zhibin Yang Department of Applied Physics and Materials Research Center, The Hong Kong Polytechnic University, Hong Kong, China apjhhao@inet.polyu.edu.hk Abstract Transistors based on GaAs could function at much higher frequencies, and have therefore been widely used in microwave integrated circuits. The integration of ferroelectric titanates with GaAs is highly desirable to take advantage of the tunable dielectrics with GaAs-based integrated circuits for microwave device applications. In this work, we have grown epitaxial SrTiO3 (STO) films on GaAs substrates without any buffer layers using laser molecular beam epitaxy technique. Ferroelectric BaTiO3 (BTO) thin films were also epitaxially grown on GaAs substrate using SrTiO3 as a buffer layer. The P-E loop with a small leakage current can be considered that the interface between BTO and GaAs is improved by inserting STO as buffer layer. A good epitaxy of BTO layer exhibits enhanced electrical properties. Furthermore, the epitaxial growth of the ZnO thin film on GaAs has been achieved using STO as a buffer layer. The behavior of temperature-dependent reversible resistance switching was observed in the heterostructure. This work is supported by a GRF grant (PolyU500910) from the Research Grants Council of Hong Kong and Hong Kong Polytechnic University grant (A-PH89).
101
EXPLORING TOPOLOGICAL DEFECTS IN EPITAXIAL BIFEO3 THIN FILMS R.K. Vasudevan1, Y.-C. Chen2, H.-H.Tai2, N. Balke3, P.P. Wu4, S. Bhattacharya4, L.Q. Chen4, Y.-H. Chu5, I.-N. Lin6, S.V. Kalinin3 and V. Nagarajan*,1
1 2
School of Materials Science and Engineering, University of New South Wales, Sydney 2052, Australia
Department of Physics, National Cheng Kung University, No.1, University Road, Tainan City 701, Taiwan R.O.C.
The Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA Department of Materials Science and Engineering, Penn State University, University Park, PA 16802 USA
4 5
Department of Materials Science and Engineering, National Chiao Tung University, Hsinchu 30010, Taiwan
6
Department of Physics, Tamkang University, Tamsui 251, Taiwan *E-mail, Presenting Author: nagarajan@unsw.edu.au
Using a combination of piezoresponse force microscopy (PFM) and phase-field modeling, we demonstrate ubiquitous formation of center-type and possible ferroelectric closure domain arrangements during polarization switching near the ferroelastic domain walls in (100) oriented rhombohedral BiFeO3. The formation of these topological defects is determined from the vertical and lateral PFM data and confirmed from the reversible changes in surface topography. These observations provide insight into the mechanisms of tip-induced ferroelastic domain control and suggest that formation of topological defect states under the action of local defect- and tip- induced fields is much more common than previously believed. (a) (b)
Figure 1: (a) Phase-field simulation of a center-type domain forming from a high-voltage negative pulse applied through the tip to the surface of the film. (b) Experimental In-plane PFM image of a domain pattern formed by application of a -30V pulse, confirming the formation of such defects within the film.
Vasudevan, R. K.; Chen, Y.-C.; Tai, H.-H.; Balke, N.; Wu, P.; Bhattacharya, S.; Chen, L. Q.; Chu, Y.-H.; Lin, I. N.; Kalinin, S. V.; Nagarajan, V., Exploring Topological Defects in Epitaxial BiFeO3 Thin Films. ACS Nano 2011, 5, 879-887.
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ISIF 2011
Topic 2: Multiferroics and Magnetoelectrics: Theory & Experiments( Oral Presenation)
Strain-induced Low Symmetry Ferroelectric Phases in Epitaxial BiFeO3 Zuhuang Chen,1 Ping Yang,2 Zhenlin Luo,3 Yajun Qi,1 Chuanwei Huang,1 Junling Wang,1 Chen Gao,3 and Thirumany Sritharan,1 Lang Chen1.*
1
School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798, Singapore
Singapore Synchrotron Light Source (SSLS), National University of Singapore, 5 Research Link, Singapore 117603, Singapore
National Synchrotron Radiation Laboratory & Department of Materials Science and Engineering, University of Science and Technology of China, Hefei, Anhui 230029, People's Republic of China
Epitaxial BiFeO3 films grown by pulsed laser deposition on (001) substrates inducing different misfit strains (LaSrAlO4, LaAlO3, NdGaO3, LSAT, SrTiO3, DyScO3 and KTaO3) have been studied by piezoelectric force microscopy and synchrotron x-ray diffractometry. Our experimental results reveal that the T-like phase of ultrathin BFO films is monoclinic MC, which is different from MA type monoclinic phase reported in films grown on low misfit substrates, and further suggest that the proposed strain-induced iso-symmetrical phase transition in previous studies is oversimplified. The presence of the lowest symmetry ferroelectric phases such as triclinic ones, to the best of our knowledge is first reported experimentally by us, will be explained too. The above low symmetry phase coexistence could be one major reason behind the reported huge piezoelectric response in highly strained BiFeO3 films and introduce novel magnetic phases as well. Presenter, Email address: langchen@ntu.edu.sg
104
ISIF2011
Submitted to Topic 2: Multiferroics and Magnetoelectrics: Theory & Experiments
Nanoscale Phase Separation in Quasi-uniaxial Strained Multiferroic Epitaxial Thin Films Yajun Qi1, Chuanwei Huang1, Zuhuang Chen1, Zhenlin Luo2, Chen Gao2, Junling Wang1, Thirumany Sritharan1, and Lang Chen1 a)
1
2
School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798, Singapore National Synchrotron Radiation Laboratory & Department of Materials, Science and Engineering University of Science and Technology of China, Hefei, 230029, P.R. China
We present the nanoscale phase separation in strained BiFeO3 (BFO) films under uniaxial and biaxial constraint. In highly biaxial strained BFO thin films on substrate, the rhombohedrallike (R) phase was believed to appear as the relaxation of stresses due to the formation of tetragonal-like (T) phase with a film critical thickness around 35 nm [2-3]. Surprisingly, the coexistence of the R-like and T-like phases was observed in the quasi-unaxial TEM foil specimens of BFO films with thickness range from 12 nm to 30 nm; although these biaxial clamping films are pure T-like phase revealed by both synchrotron X-ray reciprocal space maps and the atomic force microscopy studies. The phenomenological Landau-Devonshire theory calculation confirmed that the phase separation appears in a much smaller thickness in unaxial clamping films than that in biaxial ones. The interesting nanoscale phase separation between Tlike and R-like phases suggests a nanoscale adaptive film structure, which can mimic an adaptive polydomain c/a structure and gives rise to high elastic susceptibilities and ultra large piezoelectric responses.
References: 1. 2. R. J. Zeches et al., Science 326, 977 (2009). Z. H. Chen et al. Adv. Funct. Mater. 21, 133 (2011); Appl. Phys. Lett. 96, 252903 (2010).
Preference: Oral Presentation
a) Presenting author, Email: langchen@ntu.edu.sg
105
MECHANISMS FOR FERROELECTRIC DISPLACEMENTS FROM FIRST PRINCIPLES
Claude Ederer
School of Physics, Trinity College, Dublin 2, Ireland
The study of multiferroic materials, has prompted new interest on the question of what can drive a ferroelectric distortion, and how the underlying mechanism is affected by the presence of magnetic cations. It was generally assumed that the standard charge transfer mechanism for ferroelectricity in perovskites such as BaTiO3 requires a completely empty d shell on the perovskite B-site [1]. Nevertheless, it was recently shown by density functional theory calculations that CaMnO3 exhibits a polar instability that even dominates over the octahedral tilting for slightly enlarged unit cell volume [2]. Here, we present equivalent calculations for LaCrO3 , which has the same d3 B-site electron conguration as CaMnO3 . We nd that LaCrO3 exhibits a polar instability very similar, albeit much weaker, to that of CaMnO3 . In addition, while the Born eective charge (BEC) of the Mn4+ cation in CaMnO3 is highly anomalous, the BEC of Cr3+ in LaCrO3 is only slightly enhanced. By decomposing the BECs into contributions of individual maximally localized Wannier functions [3], and comparing to the case of the prototypical d0 ferroelectric BaTiO3 , we show that the polar instabilities in both magnetic perovskites can be understood in terms of charge transfer between transition metal (TM) d and O p states, analogously to the standard d0 perovskite ferroelectrics [4]. We will also give a brief discussion of so-called geometric or topological ferroelectricity, where charge transfer between anions and cations is not the driving force for the ferroelectric displacments.
References
[1] N. A. Hill, J. Phys. Chem. B 104, 6694 (2000). [2] S. Bhattacharjee, E. Bousquet, and P. Ghosez, Phys. Rev. Lett. 102, 117602 (2009). [3] M. Marzari and D. Vanderbilt, in First principles calculations for ferroelectrics: Fifth Williamsburg workshop, edited by R. E. Cohen (AIP, Woodbury, New York, 1998). [4] C. Ederer, T. Harris, and R. Kovik, arXiv:1011.4486 (2010). ac
106
DOMAIN PATTERNS IN NANOSCALE FERROELECTRICS L. J. McGilly, R. G. P. McQuaid1, A. Schilling1, S. Prosandeev2, L. Bellaiche2, J. F. Scott3, A. Gruverman4 and J. M. Gregg1
1
Center for Nanostructured Media, School of Maths and Physics, Queens University, Belfast, BT7 1NN, N. Ireland, U. K. 2 Department of Physics, University of Arkansas, Fayetteville, Arkansas 72701, USA. 3 Department of Physics, Cavendish Laboratory, University of Cambridge, J. J. Thompson Avenue, Cambridge, CB3 0HE, England, U. K. 4 Department of Physics and Astronomy, University of Nebraska-Lincoln, 202 Ferguson Hall, Lincoln, NE 68588-0111, USA
Exotic domain configurations, such as vortex and antivortex states, have been seen in ferromagnetic materials for over 10 years [1]; the more basic groups of 90o domains, in flux closure arrangements, have been recognized for considerably longer (over 50 years) [2]. By contrast, in ferroelectric systems, arrangements of dipoles in novel topological patterns are not well established at all. It seems that ferroelectrics are more reticent than ferromagnets to depart from their conventional stripe domain configurations a tendency which is presumably related to their relatively large anisotropy energy. Nevertheless, in very small ferroelectric objects (in nanodots and nanowires with dimensions of the order of 10nm or less) atomistic simulations modeling has predicted that the depolarising fields associated with free surfaces should force the creation of both closure domain sets and genuine dipole vortex states [3]. The race is therefore on to find such states experimentally and explore their properties. In this talk we will present some recent work on mapping and analyzing exotic dipole patterns that spontaneously form in single crystal BaTiO3 objects that have been cut to meso and nano scale dimensions using a Focused Ion Beam microscope. Four key results will be discussed: (i) (ii) that chains composed of pairs of dipole closure domain sets and quadrupoles can form at boundaries between bundles of 90o stripe domains [4], in a similar fashion to those previously seen in BiFeO3 [5]; that groups of 90o stripe domains often form into quadrant arrangements which result in both flux closure and quadrupole formation at the mesoscopic scale; flux closure groupings appear to be particularly stable, but in our experiments only form upon relaxation from an electrically poled state; that the positioning of quadrupole structures in rectangular platelets changes from being centred to being off-centred as the shape of the platelet is changed; such behaviour has been successfully rationalized as a shape-induced phase transition in the domain pattern; in air, superdomain packets of 90o ferroelastic-ferroelectric subdomains form into stripe patterns which themselves obey Landau-Kittel scaling laws.
(iii) (iv)
References: [1] Shinjo, T.; Okuno, T.; Hassdorf, R.; Shigeto, K.; Ono, T. Magnetic Vortex Core Observation in Circular Dots of Permalloy. Science 2000, 289, 930. [2] Kittel, C. Theory of the Structure of Ferromagnetic Domains in Films and Small Particles. Phys. Rev. 1946, 70, 965. [3] Naumov, I.; Bellaiche L.; Fu, H. Unusual phase transitions in ferroelectric nanodisks and nanorods, Nature 2004, 432, 737. [4] McGilly, L. J.; Schilling, A.; Gregg, J. M. Domain Bundle Boundaries in Single Crystal BaTiO3 Lamellae: Searching for Naturally Forming Dipole Flux-Closure/Quadrupole Chains, Nano Letters, 2010, 10, 4200. [5] Balke, N.; Choudhury, S.; Jesse, S.; Huijben, M.; Chu, Y. H.; Baddorf, A. P.; Chen, L. Q.; Ramesh, R.; Kalinin, S. V. Deterministic control of ferroelastic switching in multiferroic materials, Nature Nanotechnology 2009, 4, 86.
107
FABRICATION OF EPITAXIAL BISMUTH FERRITE NANOSTRUCTURES BY CHEMICAL ETCHING
Florian Johann, Alessio Morelli, and Ionela Vrejoiu Max Planck Institute of Microstructure Physics, Weinberg 2, 06120, Halle, Germany
Multiferroic bismuth ferrite (BiFeO3) has been studied intensively in the last years, given its ferroelectric and antiferromagnetic properties at room temperature, which is interesting for both fundamental research and applications. In nanostructures the effect of the constrains and clamping by the surrounding material can be removed, which has been shown to increase the piezoelectric response in ferroelectrics and to improve the retention properties of the ferroelectric switching.[1, 2] Ferroelectric nanostructures can be obtained by a bottom-up approach and a topdown approach. Given the complex phase diagram of BiFeO3, the bottom-up approach is difficult to realize due to many impurity phases which are stabilized easily. On the other hand, in a top-down approach, one can start with a high quality epitaxial film and structure the film afterwards. One possibility for a top-down approach is focused ion beam milling, which despite being easy and straightforward induces extensive damage to the fabricated area.[3] A recovery method can be applied to reduce most of the damage, however it can not be excluded that some of the generated defects remain. Therefore we fabricated BiFeO3 nanostructures by means of a top-down chemical wet etching method, which can lead to less defective nanostructures. Lateral sizes smaller than 1x1 m were achieved and piezoresponse force microscopy measurements reveal the preservation of good piezoelectric properties after structuring (Fig.1). This study is useful for future size effect studies and ferroelectric retention studies in bismuth ferrite nanostructures.
a) b)
2 m
FIG. 1: Topography (a) and corresponding LPFM phase image (b) of a 2x2 m structure fabricated from an (001) oriented BiFeO3 film. The film has not been etched completely to the bottom electrode, therefore showing a piezoresponse next to the structure as well. Topography color scale is 150 nm.
[1] J. H. Li, L. Chen, V. Nagarajan, R. Ramesh, A. L. Roytburd, Appl. Phys. Lett, 2004, 84, 2626-2628 [2] S. H. Baek, H. W. Jang, C. M. Folkman, Y. L. Li, B. Winchester, J. X. Zhang, Q. He, Y. H. Chu, C. T. Nelson, M. S. Rzchowski, X. Q. Pan, R. Ramesh, L. Q. Chen, C. B. Eom, Nat. Mater., 2010, 9, 309-314 [3] A. Morelli, F. Johann, N. Schammelt, I. Vrejoiu, submitted to Nano Tech.
108
TUNGSTEN BRONZE STRUCTURED RELAXOR FERROELECTRICS FOR THERMOELECTRIC APPLICATIONS

Jonathan Bock, Soonil Lee, Susan Trolier-McKinstry, and Clive A. Randall
Center for Dielectric Studies, Materials Research Institute, The Pennsylvania State University, University Park, PA 16802, USA
As the need for environmentally-friendly energy production increases, there is a strong drive to develop improved thermoelectric power generation systems to increase efficiencies in many applications. Disordered crystal structures such as Skutterudites and Zintl phases have shown promise due to their low thermal conductivities. Likewise, based on our previous studies, the tungsten bronze-structured ferroelectric Sr1-xBaxNb2O6- (SBN) has been shown to be an interesting new n-type thermoelectric material. SBN single crystals annealed under a reducing condition have power factors of ~20 W/cmK2 at 516 K along the c-axis, extrapolating to ~40 W/cmK2 at 550K. This is comparable to bismuth telluride at room temperature. The conduction mechanism varied as a function of the degree of reduction and the measurement temperature. A strong anisotropy was seen in both thermopower and electrical conductivity, with superior thermoelectric properties observed along the ferroelectric c-axis. In this paper, high temperature measurements of Seebeck coefficient and electrical conductivity are reported and discussed for polycrystalline SBN samples and two other tungsten bronze structured ferroelectrics: K3Li2Nb5O15 and Ba2NaNb5O15. The thermoelectric properties were dependent on the nonstoichiometry and phase equilibria at the reduction conditions. Correlations between the ferroelectric transition and the thermoelectric properties will also be discussed.
109
INVESTIGATION OF 0.4Na1/2Bi1/2TiO3- (0.6-x)SrTiO3-xPbTiO3 SOLID SOLUTIONS
. Svirskas1, M. Ivanov1, .Bagdzeviius1, J. Banys1, M. Dunce2, M. Antonova2, E. Birks2, A. Sternberg2

2
Vilnius University, Faculty of physics, Saultekio av. 9, III b., LT-10222 Vilnius, Lithuania Institute of Solid State Physics, University of Latvia, Kengaraga street 8, LV-1063 Riga, Latvia
Na1/2Bi1/2TiO3 and its modified solid solutions are of great interest for scientists. Mainly because its environmental friendly content and promising characteristic that might enable to use NBT for practical use in various applications. Also peculiarities of phase transitions makes NBT systems even more interesting from fundamental point of view. So far there are only one report can be found on such solid solutions as NBT-ST-PT in [1]. Dielectric measurements were made for x = 0, 0.1, 0.15 in 110-500K temperature range and 20 Hz 40 GHz frequency range on cooling with 1 K/min rate, except near phase transitions where it was lowered to 0.4 K/min. Silver paste was used for contacts. Investigations from 20 Hz to 1 MHz were made by measuring capacity and loss tangent with LCR meter HP-4284A. Measurements in 1 MHz 3 GHz range were made with vector network analyzer Agilent 8714ET forming a capacitor in a coaxial line. In frequency range 8 - 40 GHz measurements have been performed by scalar network -6 10 analyzers R2400 produced by Elmika company. Complex dielectric permittivity was -7 calculated from absolute values of reflection 10 and transmission coefficients. Fig. 1 shows temperature dependency of mean relaxation time for 0.4NBT-0.5ST-0.1PT. Experimental points agree with Vogel-Fulcher law: =
( )
[s]
10
-8
10
-9
10
-10
280 300 320 340 360 380 400 420 440 460 Temperature [K]
The purpose of the report is to discuss dynamic dielectric properties of NBT-ST-PT solid solutions.
Fig. 1 Temperature dependence of mean relaxation time

for x = 0.1. Solid line represents fits with Vogel-Fulcher formula
References
[1] Birks, E., Dunce, M., Antonova, M. and Sternberg, A., Phase transitions in modified Na1/2Bi1/2TiO3-SrTiO3 solid solutions, Physica Status Solidi C, vol.6, No.12 (2009)
111
SCANNING THERMAL MICROSCOPY STUDIES OF ELECTROCALORIC FILMS AND DEVICES Sohini Kar-Narayan, Sam Crossley and Neil Mathur Department of Materials Science, University of Cambridge, UK. Electrocaloric (EC) refrigeration is a candidate for solid-state cooling that exploits electric field-driven temperature/entropy changes near phase transitions in ferroelectric materials. Large EC effects of 12 K were predicted using thermodynamic analysis of ferroelectric hysteresis loops in thin ceramic films of PbZr0.95Ti0.05O3 [1] as well as organic PVDF-TrFE films [2]. Direct measurements have been elusive so far as films are difficult to measure by standard thermometry/calorimetry, and have only recently been carried out in the polymer films confirming the large EC effect [3]. We present a new method to measure these large effects directly using scanning thermal microscopy (SThM), where a scanning-probe tip containing a resistive thermometer is deployed in contact mode. The scanning-probe tip contains a platinum resistance thermometer and is very sensitive to temperature such that it can record 0.1 K changes. The small thermal mass of the thermometer-tip in comparison to EC thin films allows quick and accurate direct measurements of EC temperature changes. We will demonstrate the versatility of this method in EC studies of organic and ceramic thin-film samples as well as devices. We will compare these results with other direct measurement methods, including topelectrode thermometry where the top driving electrode is patterned to form a thin-film metal thermometer whose resistance can be monitored when EC effects in the film are driven by a change in electric field. It should be noted that SThM has the added advantage that it can produce a map of temperature change which represents a significant advance in the field given that all previous studies simply report a temperature change with no spatial resolution. This is particularly attractive for the study of epitaxial films of SrBi2Ta2O9 in which an in-plane polarization is addressed via a lateral electric field from interdigitated electrodes. Appropriate thermal models will also be discussed for a complete understanding of the experimental results. References
1. A. S. Mischenko, Q. Zhang, J. F. Scott, R. W. Whatmore and N. D. Mathur, Science 311 (2006) 1270. 2. B. Neese, B. Chu, S-G. Lu, Y. Wang, E. Furman and Q. M. Zhang, Science 321 (2008) 821. 3. S. G. Lu, B. Roi, Q. M. Zhang, Z. Kutnjak, R. Pirc, Minren Lin, Xinyu Li and Lee Gorny, Appl. Phys. Lett. 97 (2010) 202901.
112
Formation of ferroelectric inclusions in the matrix (Sb2S3)100-x(AsSI)x and (As2S3)100-y(SbSI)y glasses

Rubish V.M.1, Stefanovich V.O.2, Kaynts D.I.2, Mykaylo O.A.2, Gorina O.V.1, Guranich O.G.1, Solomon A.M.3, Shtets P.P.1, Rigan M.Yu.1, Gomonnaj A.V.3 Uzhgorod Scientific-Technological Center of the Institute for Information Recording, NASU, 4 Zamkovi Skhody Str., 88000, Uzhgorod Ukraine 2 Uzhgorod National University, 46 Pidhirna Str., 88000, Uzhgorod, Ukraine 3 Institute of Electron Physics, NASU, Universytetska Str.,21, 88000, Uzhgorod, Ukraine The possibility of practical applications attracts the interest to the non-crystalline materials whose crystalline analogues possess pronounced ferroelectric properties. The glasses on the basis of SbSI (antimony sulphoiodide), which in crystalline state is distinctly defined as ferroelectric-semiconductor, are very promising in this aspect. In the present paper the results of investigation of structure and dielectric properties of (Sb2S3)100-x(AsSI)x (30x100) and (As2S3)100-y(SbSI)y (50y95) glasses depending on heat treatment regimes are given. Glassy alloys were prepared by vacuum (0,01 Pa) melting method in quartz ampoules. Investigations of X-ray diffraction patterns for glassy, crystallized and crystalline materials were carried out on DRON-3 X-ray apparatus (=1.5418 ). Raman spectra were investigated with help of DFS-24 spectrometer on the =630 nm). Dielectric parameters ' and '' of glasses and glassceramics were measured at the frequency of 1.0 MHz and the measuring fields of 1.0 and 0.1 V/cm in the temperature range 80-600 K. The dielectric permittivity was measured within the accuracy of 3%, '' within 10%. Nanoheterogeneous structure of (Sb2S3)100-x(AsSI)x and (As2S3)100-y(SbSI)y glasses established on the basis of Raman spectra investigations. It is shown that the glass matrix is formed by binary structural groupings with heteropolar bonds (SbS3, AsS3, SbI3, AsI3) and contains molecular fragments with homopolar bonds. Chain molecular associates (SbI3)m and (AsI3)n of different length can be formed in their matrix in case of considerable content of iodide in the composition of glasses. It was established that in the studied glasses in the conditions of continuous heating, prevailing mechanism crystallization with stable phase separation of antimony sulphoiodide and is taking place in the temperature range Tg-Tc (Tg, Tc the temperature of glassforming and crystallization). Reflexes coinciding with diffraction lines for polycrystalline antimony sulphoiodide appear on X-ray diffraction patterns of crystallized glasses (Sb2S3)100-x(AsSI)x and (As2S3)100-y(SbSI)y and their Raman spectra contain sharp bands at 107-110, 138-140 and 316320 cm-1. A mechanism of forming nanocrystals SbSI in glass matrix was suggested. Formations in the glass matrix at heating nanosized crystals SbSI and their growth are accompanied by anomalies on the temperature dependences of dielectric parameters (' and ). Glass crystallization is accompanied by a sharp increase of '. Maxima confirming the presence of smeared ferroelectric phase transition in crystallized glasses, the parameters of which depend on chemical composition and heat treatment conditions, were found on dependences ' (T) and '' (T). The effect of annealing regimes on structure and dielectric properties of ferroelectrics glassceramic are discussed.
1
114
A MODEL FOR TRANSIENT POLARIZATION SWITCHING IN FERROELECTRICS
M. Khn1, H. Kliem1 and V. M. Fridkin2

1
Saarland University, Institute of Electrical Engineering Physics, Saarbrcken, Germany 2 Russian Academy of Sciences, Institute of Crystallography, Moscow, Russia
In recent papers the Weiss model originally developed for ferromagnetics was applied to ferroelectrics [1, 2, 3] and typical ferroelectric properties could be simulated. The model assumes dipoles in the material which interact by their electric fields. The assumption is that all these dipolar fields lead to the same molecular field P at the dipole sites which is proportional to the polarization of the system. The superposition of the external field and the current molecular field yields the locally prevailing field, which is time-dependent during switching, at the sites of the permanent dipoles with dipole moment p:
Eloc ( t ) = Ea + P ( t )
25
current density [A/m]
The time constant of the polarization transient is obtained by the dipole transition rates in a double well potential model with barrier height W0 and thermally activated dipole flips. It depends on the current local field (0: phonon frequency):
Ea [GV/m]:
20
15
10
0.2 0.4 0.6 0.8 1.0
W exp 0 kT {Eloc ( t )} = p 2 0 cosh Eloc ( t ) kT

The transient polarization is described by a first-order differential equation:
5 0 0.00 0.02 0.04
time [s]
{Eloc ( t )}
dP p + P ( t ) = P {Eloc ( t )} = n p tanh Eloc ( t ) dt kT
The destination value P and are time-dependent since they are related to the time-dependent local field. From the numerical solution of this differential equation starting at the negative remanent state we obtain the polarization transients where the steady-state values are given by the static Weiss model. The time derivative of the polarization yields the current densities. For fields higher than the coercive field switching occurs and we find a maximum in the current transient. In [4] Merz reports of a current maximum during the switching. With increasing field we find that the peak current increases and moves towards shorter times to peak (see figure) which is in accordance to the measurements of Merz. REFERENCES [1] P. Weiss, Sur la nature du champ molculaire., Archives des sciences physiques et naturelles. 37 (1914): 105116, 201213. [2] J. Burfoot, G. Taylor, Polar Dielectrics and their Applications, Macmillan Press, London, 1979. [3] H. Kliem, M. Khn, B. Martin, "The Weiss field revisited", Ferroelectrics 400, pp. 41-51 (2010). [4] W. J. Merz, "Domain Formation and Domain Wall Motions in Ferroelectric BaTiO3 Single Crystals", Phys. Rev., 95:3, pp. 690-698 (1954).
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ISIF2011 VINYLIDENE FLUORIDE-BASED POLYMER AND OLIGOMER THIN FILMS ON SUBSTRATES Kui Yao1*, Shuting Chen1,2, Xue Li,1,2 Mojtaba Rahimabady1,2, Francis Eng Hock Tay2, and Li Lu2
1
Institute of Materials Research and Engineering, A*STAR (Agency for Science, Technology and Research), 3 Research Link, 117602, Singapore
Department of Mechanical Engineering, National University of Singapore, 21 Lower Kent Ridge Road, 119260, Singapore *e-mail: k-yao@imre.a-star.edu.sg
Vinylidene fluoride (VDF)-based ferroelectric polymers have been well accepted for applications in many functional devices as piezoelectric sensors, transducers and capacitors. With the strong requests from industry today and in the future for structure monitoring, mechanical energy harvesting, and high power energy storage, low-cost and large-area ferroelectric VDF coatings are highly demanded. PVDF homopolymer has a much lower cost in comparison with its copolymers such as P(VDF/TrFE), but the non-ferroelectric -phase is most thermodynamically stable in PVDF homopolymer. Thus post-treatments, mainly including mechanical stretching, are often required to achieve the most polar -phase PVDF to obtain the desired piezoelectric properties. However, as for applications of PVDF-based piezoelectric coatings or ferroelectric thin films on substrates, the conventional mechanical stretching process is not applicable due to the existence of the substrates. A preparation method has been developed in our lab for achieving dense ferroelectric -phase PVDF homopolymer thin films on substrates with performance properties comparable with the much more expensive copolymers by introducing hydrogen bonds during the thin film processing. The solution fabrication approach, mechanism for promoting the polar crystalline phase, and the performance properties of the obtained PVDF thin films will be introduced. It should be noted that VDF oligomer, with the similar molecular configuration to PVDF but significantly shorter molecular chains, has not been well explored for its values as a ferroelectric material. The short chains of VDF oligomer should be more mobile than the long chains of polymers during crystallization process, and the high crystallinity and improved polarization can be expected. Although some efforts are reported to investigate VDF oligomer films with relatively large polarization, these films are mainly prepared with evaporation techniques under very special and inconvenient conditions such as cooling to liquid nitrogen temperature or with specific substrates. These preparation methods are difficult to scale up for commercial applications. Through our recent efforts, we prepared dense and highly crystallized VDF oligomer-based films on silicon substrates by an innovative solution coating approach. The crystalline structure of the VDF oligomer-based films could be conveniently tuned to either highly crystallized nonpolar phase or ferroelectric phase. With highly crystallized phase, the VDF oligomer film exhibited a remnant polarization (Pr) of 91 mC/m2, which is higher than that of -phase PVDF and P(VDF/TrFE) thin films; with highly crystallized phase, the VDF oligomer-based films exhibited a high electric energy density above 27 J/cm3, which is among the highest value reported in PVDF family. The low-cost and scalable solution process and the excellent performance properties show that VDF-based oligomer is a promising material in many ferroelectric devices and energy storage applications.
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COMPLEX DOMAIN STRUCTURES INDUCED-BY CLAMPING EFFECT IN RELAXOR FERROELECTRIC 88%Pb(Zn1/3Nb2/3)O3-12%PbTiO3 (001) SINGLE CRYSTAL THIN FILMS
L. W. Chang* and J. M. Gregg Centre for Nanostructured Media, School of Math & Physics, Queens University Belfast, U.K., BT7 1NN Relaxor ferroelectric 88%Pb(Zn1/3Nb2/3)O3-12%PbTiO3 (PZN-PT) single crystal sheets, with composition close to the morphotropic phase boundary (MPB),[1] have been cut in the forms of terraced and flat thin films by the focused ion beam microscope (FIB) and domain structures have been investigated by transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), and piezoresponse force microscopy (PFM). Prior to making observations of the domain patterns present, all the thin sheets were annealed above their Curie Temperature and allowed to cool to room temperature in air. Two different sets of sample geometries were used in the annealing process: one set of lamellae were set on their edges onto MgO single crystals and after annealing were then transferred to mesoporous carbon grids for further microscopy (these lamellae were not clamped to any substrates during processing); the other set were placed flat onto thin windowed SiN TEM grids before annealing and, after cooling, were then imaged directly without further preparation steps (these samples were clamped in some form onto the SiN). Domain structures in the two sets of PZN-PT single crystal sheets were dramatically different. In the unclamped sheets some domain contrast was observable, but domain walls were somewhat meandering and, overall, the domain patterns were relatively disordered (showing tendencies to relaxor domain features). In the clamped PZN-PT a complicated banded structure in which bands were composed of 90o stripe domains was observed: in alternate bands the orientation of the 90o stripe domains changed from having c-axes entirely inplane (a-a domain sets) to having alternate stripe domains with c-axes out-of-plane (a-c domain sets). Such domain patterns very closely resemble 2nd order polysynthetic sets (as defined by Roytburd [2]) in an orthorhombic system. Prior crystallographic mapping of the phase diagram suggests that 12%PT should stabilize a tetragonal form of PZN-PT (although still displaying some polar nanocluster properties). We suggest that the clamping to the SiN thin windows has been sufficient to induce a stabilisation of the orthorhombic state found close to the MPB even in nominally tetragonal compositions. The elastic stiffness constants of BaTiO3 [3] and PZN-12%PT as those of polycrystalline PbZr0.52Ti0.48O3
[5] [4]
single crystals were compared as well
thin films. PZN-12%PT single crystal possesses the lowest elastic
stiffness constants among these materials. The softness of the PZN-12%PT is thought to be the reason why the microstructure changes so radically even when clamped by a thin layer of SiN (some 100nm thick). [1] J. J. Lima-Silva et al., Solid State Commun. 131, 111 (2004) [2] A. L. Roitburd, Physica Status Solidi A-Applied Research 37, 329 (1976) [3] Z. Li, S. K. Chan, M. H. Grimsditch and E. S. Zouboulis, J. Appl. Phys. 70, 7327 (1991) [4] T. Delaunay et al., IEEE Transactions on Ultrasonics Ferroelectrics and Frequency Control 55, 476 (2008) [5] X. J. Zheng et al., Journal of Central South University of Technology 14, 130 (2007) * Presenting author's email address: lchang01@qub.ac.uk
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INVESTIGATIONS OF ELECTROCALORIC COOLING EFFICIENCIES IN FERROELECTRIC THIN-FILMS BY SOLID STATE MODEL Rami N Chukka1, Santirajan Sannigrahi2 and Lang Chen1
1
School of Materials Science & Engineering, Nanyang Technological University Singapore 639798, Singapore
Institute of Materials Research and Engineering, Singapore 117602, Singapore
Abstract: Electrocaloric (EC) refrigeration in ferroelectric materials has commended increasing interest due to its intriguing applications in electronics cooling. We developed a theoretical model to investigate cooling efficiencies of ferroelectric thin-films in EC devices using cascade systems. To evaluate the thermodynamic efficiencies of EC cooling line in terms of Carnot and Stirling cycles were compared. Experimentally derived PbZr0.52Ti0.48O3 thin-film cooling profiles were considered as EC cooling elements in our solid state model. The thin-film capacitors were estimated to demonstrate temperature swings over a wide working temperature ranges near its Tc. At an operating temperature of 660 K, the efficiency is 0.67 Carnot, which is considerably exceeds the efficiencies of any other cycle. To address the practical considerations in device operation, time steps of thermal and electrical pulse fronts were carefully incorporated in cooling cycles. The numerical simulations were also used to predict effects of various design parameters on EC device performance. We also describe a method of controlling a cooling device with multiple working elements in transferring heat from a heat source to sink.
E-mail: rami0002@ntu.edu.sg; LangChen@ntu.edu.sg
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FORMATION AND EVOLUTION OF EXOTIC POLARIZATION TEXTURES IN NANOFERROELECTRICS

Laurent Baudry1 , Igor A. Lukyanchuk 2 , and Ana Sen2 s e Institut dlectronique, de Microlectronique et de Nanotechnologie, , Cit e e e Scientique,Villeneuve d Ascq, 59652, France 2 Laboratory of Condensed Matter Physics,, University of Picardie Jules Verne, Amiens, 80039, France
Self-organization and evolution of phase-transition-induced topological defects: vortices, solitons and domain walls is the fascinating problem of condensed matter physics, including bose-condensation, magnetism and superconductivity. In ferroelectricity, such defects are usually presented by domain structures where polarization peridically alternates between several degenerate steady states to minimize the global electrostatic or/and elastic energy of the sample. However the recent ab-initio study of polarization distribution in nite-size nano-scale ferroelectrics clearly demonstrated the existence of unconventional buckling textures1 , known as polarization vortex rings, toroidal vortices . . . Formation of such patterns can be qualitatively understood on the purely electrostatic basis. Polarization is always trying to nd the optimal conguration with divP = 0 to avoid the bounded-charge-provided energetically unfavorable depolarizing electric eld. Topological classication and description of vector elds satised the zero-divergence constraint is the challenging mathematical problem. In current communication we explore the solution of this problem for the experimentally realized 2D geometry of electrode-deposited ferroelectric nanodot of arbitrary boundary shape. As the working material we consider the multi-axial cubic perovskite-like displacive ferroelectric with weak polarization anisotropy, like, e.g. the Lead Zirconate Titanate (PZT) close to the morphotropic phase boundary. Thus, the order parameter is presented by three-component almost-constant-amplitude polarization vector, living in 2D xy space of the nanodot. Although the description of the nonuniform polarization texture in such system is somehow close to the analytically-solved skyrmion problem in magnetism, the requirement of absence of bounded charges and depolarizing eld substantially changes the situation. In fact only the chiral skyrmions satisfying the condition divP = 0 should be considered . Our analytical modeling was based on the Ginzburg-Laudau theory, coupled with Maxwell equations in a nite ferroelectric media. The dynamics of non-uniform polarization structures is accounted for by Lifshitz-Khalatnikov dissipation formalism. Special attention was given to buckling instability and further chiral skyrmion evolution under the applied electric eld. The formation of this topological defect is discontinuous via the rst order transition, induced by the electric eld. Moreover we found that the critical eld required for chiral skyrmion formation is lower than thermodynamical coercive elds2 . In reality, however the nite viscosity of polarization rotation leads to progressive and continuous dynamical evolution of such defect. Next, we studied the instability towards the multiskyrmion formation in case of arbitrary shape of the nanodot and demonstrated that the situation is similar to elastic Euler instability of the at membrane buckling. We conclude that the skyrmion-like topological defects, having the relatively small buckling eld, can be considered as a possible source of the switching mechanism in ferroelectrics. One can expect that the formation of such defects could explain, at least partially, the dierence between the experimental and the thermodynamical coercive elds, known as Landauer paradox 3 .
Naumov I. and Fu H. , Phys. Rev. Lett.98, 077603, (2007) Iwata M. and Ishibashi Y. Jpn. J. Appl. Phys. 38, 5670, (1999) 3 Landauer R. J. Appl. Phys. 28, 227, (1957)
2 1
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GRAPHENE SPINTRONIC DEVICES WITH HIGHLY SPIN-POLARIZED OXIDE ELECTRODES Lee C. Phillips* Department of Materials Science, University of Cambridge, UK Antonio Lombardo and Andrea C. Ferrari Department of Engineering, University of Cambridge, UK Neil D. Mathur Department of Materials Science, University of Cambridge, UK
Session: Spintronics Preference: Oral presentation
Abstract The ferromagnetic manganite La2/3Sr1/3MnO3 (LSMO) is widely used as an electrode material in spintronic devices [1-3] because of its experimentally confirmed high spin polarization [4]. Recently large magnetoresistance effects were observed in lateral spin-valve devices where the channel is a multi-walled carbon nanotube [1]. Here we discuss similar results in devices with channels made from single- and multilayer graphene [5], which combine low spin-orbit coupling and long spin lifetimes with a large surface area suitable for gating in an alternative spin-transistor design. The magnetoresistance effects are the largest yet measured in local (two-point) resistance measurements of single-layer graphene spin valves.
[1] Hueso et al., Nature (2007) 445, 410 [2] Bowen et al., Appl. Phys. Lett. (2003) 82, 233 [3] Garcia et al., Science (2010) 327, 1106 [4] Park et al., Nature (1998) 392, 794 [5] Geim and Novoselov, Nature Materials (2007) 6, 183 * Presenting author, email: lcp29@cam.ac.uk
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DOMAIN CONFIGURATIONS IN MORPHOTROPIC PHASE BOUNDARY PbZr(1-x)Ti(x)O3

L. J. McGilly, A. Schilling, and J. M. Gregg Centre for Nanostructured Media, School of Maths and Physics, Queens University Belfast, University Road, BELFAST, BT7 1NN. U.K. Recent studies on single crystal BaTiO3 nanodots, created by use of a Focused Ion Beam (FIB) microscope, have [1] shown complex domain configurations that form into quadrant packets of 90 domains . As the size of such BaTiO3 nanostructures decreases to small enough dimensions, modelling predicts a transition to a vortex domain [2] state . However, the required dimensions for genuine vortex formation are thought to be extremely small; as anisotropy energy is usually high in ferroelectrics, depolarising fields, which increase as structure size decreases, must be sufficient to merit the energy cost incurred through the continuous dipole rotation characteristic of vortices. Therefore morphotropic phase boundary (MPB) PbZr(1-x)Ti(x)O3 (PZT) perhaps presents a more suitable candidate material for the observation of vortices in larger objects, as the orientation of dipoles is more flexible. Indeed experimental studies already exist purporting to show evidence of ferroelectric vortices in PZT [3,4] structures . In this work, lamellae with thicknesses < 200 nm have been milled directly from ceramic MPB PZT(52/48) by use of a FIB microscope. Large grains, with lateral sizes up to 15 m, allow selection of lamellae from single grains for study in Transmission Electron Microscopy (TEM). Lamellae are removed from the bulk ceramic and placed on Si3N4 thin membranes that allow annealing above the Curie Temperature in order that equilibrium domain states have an opportunity to form. Further ion beam milling allows for patterning of the lamellae into well defined, free-standing structures that can then be imaged by TEM and characterised through analysis of selected area diffraction patterns as seen in Fig. 1.
(a)
(a)
(b)
(c)
600 nm
400 nm
200 nm
Figure 1: Transmission Electron Microscopy (TEM) shows complex arrangements of domains in lamellar thin films, (a) wires (b) and dots (c) of PZT(52/48). In (b) the change in wire diameter leads to a decrease in the domain period. Stripe domains are still present in the smallest dots fabricated thus far (c) and can be characterised from analysis of the associated selected area diffraction pattern (inset).
References: [1] A. Schilling, D. Byrne, G. Catalan, K. Weber, Y. Genenko, G. Wu, J. F. Scott and J. M. Gregg, Nano Lett., 9, 3359 (2009) [2] I. I. Naumov, L. Bellaiche and H. Fu. Nature, 432, 737 (2004) [3] A. Gruverman, D. Wu, H-J. Fan, I. Vrejoiu, M. Alexe, R. J. Harrison and J. F. Scott. J. Phys.: Condens. Matter., 20, 342201 (2008) [4] B. J. Rodriguez, X. S. Gao, L. F. Liu, W. Lee, I. I. Naumov, A. M. Bratkovsky, D. Hesse, and M. Alexe, Nano Lett., 9, 1127 (2009)
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POLARIZATION RELAXATION AND CHARGE INJECTION IN THIN FILMS OF P(VDF-TrFE) COPOLYMERS

M. F. Mai, B. Martin, M. Kuehn and H. Kliem Institute of Electrical Engineering Physics, Saarland University, D-66123 Saarbruecken, Germany Email:manfangmai@mx.uni-saarland.de
Ferroelectric thin films of P(VDF-TrFE) copolymers are prepared by Langmuir-Blodgett deposition and spin coating with thicknesses ranging from 60 to 400nm as metal-ferroelectric-metal structures. Polarization relaxation effects and charge injection in P(VDF-TrFE) thin films are studied. In time domain measurements of polarization reversal, the switching transients show two stages: a rapid increase of polarization followed by a continuous slow increase lasting for several decades. This continuous increase of the polarization corresponds to a t- (Kohlrausch law) behaviour of the current density in the long time range. For a constant electric field, these currents in the long time range are independent of the sample thickness as expected for a relaxational volume polarization effect. Furthermore, the polarization and depolarization currents saturate at high fields. We described the experiments using an asymmetric double well potential model with a distribution of relaxation times in which dipoles are fluctuating thermally activated between the two minima. As temperature increases, a charge injection process sets in. The charging currents deviate from the t- behaviour and become constant. The discharging currents are found to be a superposition of dipole relaxational currents and space charge relaxational currents. For the short time range only the dipole relaxational currents are found. These Kohlrausch currents are nearly temperature independent. At longer times sc of several seconds a space charge depolarization sets in. The time sc is shifted to shorter values with increasing temperature and it is also shifted to shorter values with increasing fields applied before.
Topic: Ferroelectric Materials: Theory&Experiments Preference: Oral presentation
131
SWITCHING PROPERTIES OF NANOSTRUCTURES OF EPITAXIAL BISMUTH FERRITE
Alessio Morelli, Florian Johann, Norbert Schammelt and Ionela Vrejoiu Max Planck Institute of Microstructure Physics, Weinberg 2, 06120, Halle, Germany Multiferroic BiFeO3 (BFO) has been the subject of wide investigations, given its antiferromagnetic and ferroelectric ordering with large polarization at room temperature. The interest in such material lies particularly in the possibility of electric field controlled antiferromagnetic ordering, given the fact that the antiferromagnetic planes lie orthogonal to the polarization axis [1]. Removal of constraints from the surrounding material is beneficial for retention properties [2] and has supposedly influence on the domain configuration and switching properties [3]. Focused ion beam milling (FIB) fabricated nanostructures have been successfully employed to study size effects in different ferroelectric materials [4]. Therefore we fabricated by FIB nanostructures (down to 250 nm in lateral size) in BFO epitaxial thin films. However, it is well known that FIB milling by gallium ion beam sputtering gives rise to contamination by gallium implantation and crystal damage in the form of partial amorphization of the sample under patterning [5]. Therefore we developed a post-FIB annealing strategy, leading to a successful recovery of the ferroelectric properties in structures down to 500 nm in lateral size [6]. Here we present switching properties and retention characteristics studies of the FIB fabricated nanostructures, in dependence on size and shape, investigated by piezoresponse force microscopy. Preliminary measurements by piezoresponse hysteresis loops show increased imprint inside the structures with respect to the film away from the structured area. In particular, it further increases with decreasing area and with approaching the structures sides. This study is of interest for understanding the influence of defects and size effects in FIB fabricated bismuth ferrite nanostructures. [1] T. Zhao, A. Scholl, F. Zavaliche, K. Lee, M. Barry, A. Doran, M. P. Cruz, Y. H. Chu, C. Ederer, N. A. Spaldin, R. R. Das, D. M. Kim, S. H. Baek, C. B. Eom, and R. Ramesh, Nat. Mater. 5, 823 (2006) [2] S. H. Baek, H. W. Jang, C. M. Folkman, Y. L. Li, B. Winchester, J. X. Zhang, Q. He, Y. H. Chu, C. T. Nelson, M. S. Rzchowski, X. Q. Pan, R. Ramesh, L. Q. Chen, and C. B. Eom, Nat. Mater. 9, 309 (2010) [3] S. Hong, J. A. Klug, M. Park, A. Imre, M. J. Bedzyk, K. No, A. Petford-Long, and O. Auciello, J. Appl. Phys. 105, 061619 (2009) [4] V. Nagarajan, A. Roytburd, A. Stanishevsky, S. Prasertchoung, T. Zhao, L. Chen, J. Melngailis, O. Auciello, and R. Ramesh, Nat. Mater. 2, 43 (2003) [5] A. Stanishevsky, B. Nagaraj, J. Melngailis, R. Ramesh, L. Khriachtchev and E. McDaniel J. Appl. Phys 92 063275-8 (2002) [6] A. Morelli, F. Johann, N. Schammelt, I. Vrejoiu, submitted to Nanotech.
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Resistive switching characteristics of ALD-HfO2 films annealed in oxygen and UV-irradiated oxygen ambient
M. S. Lee, C.-H. An, Y.-C. Byun, K. Park, and H. Kim* School of Advanced Materials Science and Engineering, Sungkyunkwan University, Suwon 440-746, Korea
Resistive switching characteristics observed in many metal-oxide systems have attracted a lot of attention because of their potential application in the future high-density memory technology. Along with developing highly reliable new materials, extensive studies have focused on understanding the transport and switching mechanism in the resistive switching materials. Although many theories have been introduced, recently, the resistive switching is believed to be closely related to the oxygenrelated defects in the filamentary region [1]. In this presentation, we will report the effects of postdeposition anneal (PDA) with different oxygen species on the resistive switching characteristics of the HfO2 films grown by an atomic layer deposition (ALD) technique. After the ALD of HfO2 films on Pt/Ti/SiO2/Si substrates, PDA was performed on some samples using a rapid thermal processer (RTP) at 400C for 30 min. During PDA, either pure oxygen or oxygen irradiated with UV light was introduced into the RTP chamber. For the measurement of the resistive switching characteristics of the HfO2 films, metal-insulator-metal capacitor structures were fabricated by a sputter-deposition of Al (capping electrode)/TaN electrodes and a subsequent lift-off patterning process. According to the electrical characterization, RHRS/RLRS ratio was increased by an additional PDA, however, the reliability characteristics were significantly deteriorated by the UVirradiated oxygen gas anneal. The different annealing effect on the resistive switching characteristics will be discussed based on several physical/chemical characterization results of the annealed HfO2 films. Reference [1] N. Xu, L. F. Liu, X. Sun, X. Y. Liu, D. D. Han, Y. Wang, R. Q. Han, J. F. Kang, and B. Yu, Appl. Phys. Lett. 92, 232112 (2008).
*Corresponding author: hsubkim@skku.edu
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NON-SILICON PIEZOELECTRIC MICROSYSTEMS R.A. Dorey, A. Pickwell, S.P. Shaw, H.J. Almond, D. Underhill Microsystems and Nanotechnology Centre, Cranfield University, Cranfield, UK, MK43 0AL. Silicon has long been considered the material of choice for creating piezoelectric microsystems for a variety of reasons including cost, processing knowhow and extensive use in microelectronics. The challenges associated with integrating piezoelectric ceramics with silicon have received considerable attention and there now exist a number of ways in which this can be successfully achieved. Where non-silicon microsystems have been considered these have typically been based on ceramic materials such as alumina and low temperature co-fired ceramic materials. This still leaves a vast array of materials that could potentially be used in piezoelectric microsystems. One of the primary reasons why such materials have not been used previously is due to the harsh thermal processing conditions that are required to create piezoelectric ceramic materials. This issue can be overcome by applying new processing methods. This work explores some of these routes that can be used to successfully integrate piezoelectric ceramics with materials such as nickel, copper, steel, glass and glassy carbon. Two fundamental approached have been adopted to achieve this level of integration. In the first, more conventional, approach appropriate interface control has been achieved through managing the processing temperatures and selection of effective diffusion barriers that prevent unwanted interdiffusion of species while at the same time ensuring effective adhesion across the interface. When inappropriate materials are selected complete destruction of the micro devices can be achieved during processing. The second approach is to adopt an additive process whereby the piezoelectric ceramic material is used as the base onto which the device is then constructed using additive processes such as electroforming and micromoulding. The challenge in this instance is that the deposited ceramic material is often less than 10m thick requiring careful support to prevent failure during processing while at the same time requiring a way to release the device at the end of processing. Details of the various strategies adopted and challenges faced will be discussed through this presentation. Using these materials it has been possible to create a number of piezoelectric actuator and sensor devices including acoustic emission structural health monitors, micromanipulators and heavy metal sensors. Examples of these devices will be showcased to demonstrate the operation of these non-silicon microsystems.
135
INFLUENCE OF SECONDARY PHASE ON MULTIFERROIEC PROPERTIES OF Bi5Co0.5Fe0.5Ti3O15 CERAMICS MADE FROM MOLTEN SALT METHOD
Meghdad Palizdar1, Tim P Comyn1, Mike Ward1 , John Harington1,Andrew Brown 1 , Andrew J Bell1 , Santosh Kulkarni2, Lynette Keeney2 , Saibal Roy2, Martyn Pemble2, Roger W Whatmore2, Sue Kilcoyne3and Christopher Quinne3
1
Institute for Materials Research, University of Leeds, LS2 9JT, Leeds, UK
Tyndall National Institute, University College Cork, Lee Maltings, Dyke Parade, Cork, Ireland Maxwell Building, University of Salford, M5 4WT, Salford, UK e-mail: ml07m2p@leeds.ac.uk
The Aurivillius layer structure of modified bismuth titanate, (BiFeO3)n Bi4Ti3O12 , potentially shows multiferroic properties. It has recently been claimed recently that Bi5Co0.5Fe0.5Ti3O15, in which n = 1, exhibits both ferroelectric and ferromagnetic order parameters simultaneously at room temperature.i We have used a molten salt method to produce plate-like particles of the same nominal composition, which are then processed into highly oriented ceramics using uniaxial die-pressing and sintering. X-ray diffraction pole figures and rocking curve data, show strong orientation of the c axis parallel to the pressing direction. Electron back-scattered images highlight the existence an iron and cobalt rich secondary phase which is homogeneously distributed within the microstructure, with a concentration is less than 2.5% by volume. Although this phase is not detected by X-ray diffraction, electron diffraction reveals that the secondary phase is cobalt ferrite. The samples have been characterized by polarization-field measuremenst, vibrating sample and SQUID magnetometry as a function of temperature and orientation. . Magnetic force microscope (MFM) around the secondary phase surface, has been used to identify the amount of secondary phase contribution on the main phase magnetic result. It is concluded that the magnetic characteristics are dominated by the magnetic properties secondary phase.
X. Mao, W. Wang, X. Chen, Y. Lu, Multiferroic properties of layer-structured Bi5Fe0.5Co0.5Ti3O15 ceramics, Appl. Phys Let., vol. 95, pp. 082901, 2009
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Investigation of Local Switching Behavior in Nanostructured Ultrathin Ferroelectric Polymers
Pankaj Sharma, Timothy J. Reece, Shashi Poddar, Stephen Ducharme, and Alexei Gruverman Department of Physics and Astronomy and the Nebraska Center for Materials and Nanoscience, University of Nebraska, Lincoln, NE 68588-0299
Piezoresponse Force Microscopy (PFM) has been used to investigate the 3D spatial arrangement of polarization and switching behavior of ultrathin films of polyvinylidene fluoride trifluoroethylene (PVDF-TrFE). Orientational imaging with sub-10 nm spatial resolution of static domain patterns in PVDF-TrFE grains using a combination of vertical and lateral modes of PFM is reported. Detection of azimuthal variations in the lateral PFM signal is attributed to the alignment of the molecular chains along different directions. The surface plots of the piezoelectric response are constructed based on the piezoelectric tensor of PVDF-TrFE and are shown to be consistent with the observed vertical and lateral PFM maps. Local switching studies in individual PVDF-TrFE nanomesas have been performed as a function of voltage pulse amplitude and duration. It is shown that, depending upon the strength of the applied electric field, polarization reversal can occur via 120 or 180 rotation of dipoles around the molecular chain. Furthermore, it has been found that local polarization reversal proceeds via formation of profoundly irregular domains and remote domain nucleation as far as 100 nm away from the tip-sample contact point suggesting strong variations in the local built-in potential. Nanoscale local spectroscopy and time-voltage dependence of the switched polarization provide a basis for consistent interpretation of the observed switching behavior, which is related to a random-bond type disorder associated with defects in conformation and molecular packing. Fractal analysis of the developing domain patterns yielded the fractal dimension lower than that reported for solid-state crystalline ferroelectrics, which is explained by a shorter polarization correlation length in PVDF-TrFE.
139
ELECTRORESISTANCE AND TUNNEL MAGNETORESISTANCE IN FERROELECTRIC Pb(Zr0.2Ti0.8)O3 BARRIERS Daniel Pantel, Silvana Goetze, Dietrich Hesse, and Marin Alexe Max Planck Institute of Microstructure Physics, Weinberg 2, 06120, Halle, Germany Nondestructive resistive readout of the ferroelectric polarization direction based on tunneling in a metalferroelectric-metal device would be advantageous for prospective non-volatile data storage applications. Furthermore, in multiferroic heterostructures where the metal electrodes are ferromagnetic, four-state memory devices can be envisaged relying on both the tunnel electroresistance and the tunnel magnetoresistance [1]. The latter devices may also give insight into the magnetoelectric coupling at the ferroelectric / ferromagnet interface. Lately, the influence of polarization direction on resistivity in metalferroelectric-metal heterostructures was theoretically investigated [2] and experimentally by atomic force microscopy methods [3,4]. But results on real capacitor-like devices are still scarce. Here, we investigated Pb(Zr0.2Ti0.8)O3/La0.7Sr0.3MnO3 (PZT/LSMO) heterostructures grown by pulsed laser deposition on SrTiO3 (001) substrates. X-ray diffraction, transmission electron microscopy, and piezoresponse force microscopy proved the good structural and electrical properties of all layers within the heterostructures. For electrical characterization well-ordered capacitor arrays were fabricated. Gold-capped copper top electrodes with typical sizes below 0.1 m2 were produced on the PZT surface by self assembly nanosphere lithography. A large electroresistance with a switched current density as high as 10 A/cm2 is found on a 9 nm thick PZT barrier. The large ON/OFF ratio of about 1000, obtained at voltages below the coercive voltage, is in agreement with simulations which reveal that the electroresistance increases for increasing ferroelectric barrier thickness [5]. A combined PFM and conductive-AFM approach used on these nanoscale electrodes reveals that indeed the polarization direction is responsible for the resistive switching in these nanoscale ferroelectric capacitors. For PZT/LSMO heterostructures with thinner PZT barriers, appropriate for direct tunneling, macroscopic cobalt electrodes were deposited. Here, low temperature measurements reveal electroresistance and tunnel magnetoresistance on the same Co/PZT/LSMO device, equivalent to a four-state multiferroic memory device. [1] V. Garcia et al. Science 327, 1106 (2010) [2] H. Kohlstedt, N. A. Pertsev, J. Rodrguez Contreas, and R. Waser, Phys. Rev. B 72, 125341 (2005) [3] P. Maksymovych, S. Jesse, P. Yu, R. Ramesh, A. P. Baddorf and S. V. Kalinin, Science 234, 1421 (2009) [4] A. Gruverman, D. Wu, H. Lu, Y. Wang, C. M. Folkman, M Ye. Zhuravlev, D. Felker, M. Rzchowski, C.-B. Eom and E. Y. Tsymbal, Nano Lett. 9, 3539 (2009) [5] D. Pantel and M. Alexe, Phys. Rev. B 82, 134105 (2010)
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INTERLAYER COUPLING AND UNIT-CELL SCALE SPECTROSCOPIC MAPPING OF LOCAL DISTORTIONS IN FERROELECTRIC SUPERLATTICES
P. Zubko, N. Jecklin, C. Lichtensteiger, N. Stucki and J.-M. Triscone DPMC, 24, University of Geneva, Quai Ernest-Ansermet, CH-1211, Geneva, Switzerland A. Torres-Pardo , A. Gloter, K. March and O. Stephan Laboratoire de Physique des Solides, UMR 8502, Universit Paris Sud, 91405, Orsay cedex, France The study of domains in ultrathin ferroelectric films is of both fundamental and technological importance. The formation of 180 ferroelectric domains provides an efficient mechanism for screening the depolarising field, allowing ferroelectricity to survive in films as thin as a few unit cells[1]. At the same time, the response of domains to applied fields plays a crucial role in determining the electrical and mechanical properties of the material. Superlattices composed of ferroelectric components separated by paraelectric layers are an ideal system for studying the static and dynamic properties of such ferroelectric domains. X-ray diffraction studies reveal that superlattices composed of ultrathin layers of PbTiO3 and SrTiO3 exhibit a regular periodic arrangement of 180 ferroelectric domains, only a few nanometres in size. Large uniform fields can be applied and the domain wall response can be investigated using X-ray diffraction as well as dielectric measurements[2]. It is found that under applied bias, the domain periodicity remains unchanged, but the relative sizes of domains with polarisation parallel and antiparallel to the applied field are modified, in qualitative agreement with calculations[3]. The existence of the dense domain structure directly impacts the ferroelectric and dielectric properties of these artificial materials. The stability of the polydomain state at zero field leads to the suppression of the remnant polarisation and a large enhancement of the dielectric response over a wide range of temperatures. To gain microscopic insight into the structure of the superlattices and possible interactions between the ferroelectric layers, high resolution transmission electron microscopy in combination with electron energy loss spectroscopy (EELS) and detailed X-ray diffraction measurements were used to study the local distortion with unit-cell resolution. When individual layer thicknesses exceed just a few unit cells, the ferroelectric layers appear to be electrostatically decoupled. No significant (polar) distortions were found in the paraelectric SrTiO3, yet nevertheless, the domain structures in the different PbTiO3 layers were found to be highly coherent. The EELS mapping also reveals an interfacial region, several unit cells thick, of reduced tetragonality confined to the PbTiO3 layers. [1] D. D. Fong, G. B. Stephenson, S. K. Streiffer, J. A. Eastman, O. Auciello, P. H. Fuoss, C. Thompson, Science 304, 1650 (2004). [2] P. Zubko, N. Stucki, C. Lichtensteiger, J.-M. Triscone, Phys. Rev. Lett. 104, 187601 (2010). [3] B.-K. Lai, I. Ponomareva. I. I. Naumov, I. Kornev, H. Fu, L. Bellaiche, G. J. Salamo, Phys. Rev. Lett. 96, 137602 (2006).
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Moving Towards Electrocaloric Refrigeration T.M.Correia and Q. Zhang* Cranfield University, Department of Materials, Cranfield, Bedfordshire MK43 OAL, United Kingdom *q.zhang@cranfield.ac.uk Abstract The recent progress made towards achieving electrocaloric refrigeration based on the development of electrocaloric materials is reviewed. Herein, the parameters that should be taken into account when selecting an electrocaloric material as a working body in a cyclic refrigerator are discussed. Within this context, the reported electrocaloric thin films are assessed in terms of electrocaloric effect and efficiency. This paper attempts to rank electrocaloric thin films investigated over the last five years, and to present the challenges that are evident as we move towards to a new era of electrocaloric refrigeration.
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IMAGING DOMAIN SWITCHING AND FLUX-CLOSURE QUADRANT FORMATION IN SINGLE CRYSTAL BaTiO3 LAMELLAE.
1 School of Mathematics and Physics, Queens University of Belfast, Belfast, BT7 1NN, United Kingdom 2 Department of Physics and Astronomy, University of Nebraska, Ferguson Hall, Lincoln, Nebraska, 68588-0111, Corresponding author: rmcquaid04@qub.ac.uk
R. G. P. McQuaid1, L. J. McGilly1, P. Sharma2, A. Gruverman2, J. M. Gregg1
In a first step towards mapping domain dynamics in morphologically complex ferroelectric geometries we employ Piezoresponse Force Microscopy (PFM) to explicitly visualise domain switching in 300nm thick single crystal BaTiO3 lamellae, freely suspended across a co-planar interelectrode gap [fig.1a] (a similar methodology is used in [1]). Whilst textbook 180o domain switching by growth/reduction of two antialigned in-plane domain variants is anticipated, the surprising scenario of a global ac stripe domain structure is instead consistently observed; we highlight that such ordering is not observed in virgin states and is field generated. Polarisation reversal occurs within this very stable parent ac configuration where a domains align in-plane with the field and c domains remain out-of-plane. In partially switched states we see bundles of 90o domains each characterised by the a domain orientation [fig.1b]. Most exciting is that PFM imaging indicates switching to be mediated by movement of the boundaries separating these domain bundles. Bundle boundary motion reverses neighbouring regions with opposing a domain orientation towards field alignment whilst preserving the parent stripe structure. Importantly, we see that a different picture of domain dynamics than the simple 180o switching model is applicable here; nonetheless, analogies between motion of a bundle boundary and a conventional 180o wall exist. We have also observed a case where four bundles of 90o domains successfully form into a mesoscopic flux-closure quadrant structure inferred by careful interpretation of vector PFM data [fig.1c]; other examples of when this structure has partially formed are commonplace. Remarkably this quadrant structure seems relatively thermodynamically stable and preferentially reforms in the remnant domain configuration even after being annihilated through switching.
(a)
(b)
(c)
Fig.1 (a) Schematic of co-planar test geometry showing SPM tip in position over BaTiO3 lamella. (b) Top: Lateral-PFM reveals orientation of a domains within bundles. Electrode positions illustrated. Bottom: Vertical-PFM reveals parent ac stripe structure. (c) Reconstruction of the closure object with labeled in-plane polarization components enabled by in-plane 2D vector PFM analysis.
[1] Balke, N.; Gajek, M.; Tagantsev, A. K. et al. Adv. Func. Mat. 20, 20, 3466-3475 (2010).
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ADVANCED CHEMICAL SOLUTION DEPOSITION METHODS FOR THE LOW TEMPERATURE PROCESSING OF FERROELECTRIC THIN FILMS.
R. Jimnez, I. Bretos and M. L.Calzada Instituto de Ciencia de Materiales de Madrid (ICMM-CSIC). Sor Juana Ins de la Cruz 3, Cantoblanco, 28049-Madrid (Spain)
Abstract: There is a strong interest in the peparation of complex oxides (ferroelectrics) thin films at temperatures compatible with Si-technology and flextronics (<450C) [1]. Are many the advantages of reducing the energy budgets in the fabrication of films such as the possibility of using metal foil substrates of nonnoble metals, a real integration into CMOS processes or the extension of the range of applications of ferroelectrics onto polymeric substrates. In addition, the use of low-fabrication temperatures avoids the emission of some components from the film, such as Pb, which produces cross-contamination and environmental pollution. Chemical Solution Deposition (CSD) is a low-cost fabrication technique that can be used for a wide range of compositions and that is available for the preparation of large area deposits. In the recent years, the novel technique of PhotoChemical Solution Deposition (PCSD) that combines CSD and UV-irradiation has shown to be highly efficient for the fabrication of ferroelectric thin films at low temperatures [2]. The keypoint of this processing technology lies on the design of photosensitive precursor solutions containing UV-absorbing species. It presents the strong advantage that is only based on the tailoring of the chemistry of the precursor solution, nor substrate modifications neither additional fabrication/integration steps are needed. Therefore, it is a method easily transferred to any type of substrate (metalfoils, low-melting point substrates as glass or plastics, etc) and to any of the functional oxide compositions. The understanding of the key parameters of this processing technology has allowed us the successful preparation of ferroelectric PbTiO3 based films, derived from nominally stoichiometric solutions (without PbO excess) at temperatures as low as 400C. The flexibility in the solution tailoring of this process makes also possible the synergetic combination with other low-temperature solution methods, this approach has proved to be efficient for the fabrication of Pb-perovskite ferroelectric thin films at temperatures even below 400C. Here, a review on the recent results of the group on the low-temperature fabrication of ferroelectric thin films using PCSD will be presented and the possibility of application of these low temperature fabricated ferroelectric thin films in NVFeRAM discussed. References:
1: K.H.Xue, J.Celinska and C.A.Paz de Araujo. Appl.Phys.Letts., 95, 05908 (2009). J. Li, H. Kameda, B. Nguyen, Q. Trinh, T. Miyasako,P.T. Trong, E. Tokumitsu, T. Mitani, T. Shimoda. APL 97, 102905 (2010). 2: I. Bretos et al., Chem. Mater. 20, 5731 (2008); I. Bretos et al., Chem. Mater. 20, 1443 (2008); M.L. Calzada et al., J. Mater. Res. 22, 1824 (2007); M.L. Calzada et al., Adv. Mater. 16, 1620 (2004). N.Marbella et al. J.Am.Ceram.Soc. 94(2), 396 (2011)
This work has been financed by the Spanish Project MAT2010-15365 Topic: Non-Volatile Memories (RRAMs, MRAMs, FeRAMs, PCMs). Preferred oral presentation
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THERMAL AND INTRINSIC NONLINEARITIES OF FERROELECTRIC-BASED MICROWAVE DEVICES
Eduard Rocas1,2, Carlos Collado2, Jordi Mateu2, James C. Booth1

1
National Institute of Standards and Technology (NIST), Boulder, CO
Universitat Politecnica de Catalunya (UPC), Barcelona, Spain
Tunability makes ferroelectric materials attractive for applications where an electronically-controlled material property change is desired. However, nonlinear effects are inherent to tunable devices and, in communication systems, they can produce a performance degradation or interference. Stringent specifications of communication systems set limits for the nonlinear behavior of passive devices. Understanding, modelling and minimizing the harmonics and intermodulation generation is a key process for current communications. To address this issue, we perform measurements and modeling of different types on nonlinearities occurring in ferroelectricbased microwave devices.
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COULOMB DRAG IN GRAPHENE / BORON NITRIDE HETEROSTRUCTURES

R.V. Gorbachev1, L.A. Ponomarenko1, A.S. Mayorov1, S.V. Morozov1,2, L. Britnell1, R. Jalil1, K.S. Novoselov1, A.K. Geim1, K. Watanabe3, T. Taniguchi3 School of Physics and Astronomy, University of Manchester, Oxford Road, Manchester M13 9PL, United Kingdom 2 Institute for Microelectronics Technology, 142432 Chernogolovka, Russia 3 National Institute for Materials Science, 1-1 Namiki, Tsukuba, 305-0044 Japan
1
The presented work describes fabrication and transport properties of multilayer boron nitride/graphene heterostructures. We developed a new fabrication technique, which allows transferring of graphene (or boron nitride) crystals from one substrate to another with positioning accuracy of few microns. Using this technique, we have fabricated sandwich structures where a graphene sheet is encapsulated between two BN monocrystals. AFM studies show that large areas of such heterostructures are atomically flat and contain little or no contamination trapped between the layers. Placed on an oxidized silicon wafer with metal contacts, such encapsulated graphene has the carrier mobility as high as 10 m2/Vs [1] and exhibit ballistic transport on micron scale even at room temperature. Later is directly confirmed our transport experiments in cross-shaped graphene samples [2], where electrons travel from one metallic contact to another ballistically. Taking into account that the boron nitride layers can be only a few atomic layers thick, this technique offers the highest on substrate device quality, as well as chemically inert thin dielectric top layer, ready for further processing. Taking further lead, we deposit another graphene sheet on top of the existing sandwich structure. Both graphene layers are conveniently shaped using electron beam lithography and oxygen plasma etch. This allows us to do electric transport measurements in two independently contacted graphene layers without a direct resistive link between them. However, if the separating BN layer is thin enough (less than ~ 50 nm), the charge carriers in two 2DEGs are able to interact with each other, leading to interesting transport phenomena. One of interaction effects, the Coulomb drag, was studied earlier in GaAs/AlGaAs double quantum well heterostructures and attracted significant interest in scientific society. However, those studies were limited due to a technological problem: 2DEGs positioned closer than ~20 nm were resistively coupled due to spacer imperfections [3]. Because of the high quality BN spacer now we are able to reach significantly smaller interlayer separation (~4 nm) without noticeable leakage currents. Coulomb drag in such conditions exhibits unusual behaviour beyond the scope of previously studied weakly interacting regime. Indeed, in that regime the size of electron density fluctuations (1/) in 2DEGs is much smaller than interlayer distance (d), which is no longer the case in our structures, where d~1. We present our report on drug effect at different temperatures, carrier densities and layer separation and compare our results with existing theoretical understanding of the problem.
[1] C.R. Dean, A.F. Young, I. Meric, C. Lee, L. Wang, S. Sorgenfrei, K. Watanabe, T. Taniguchi, P. Kim, K.L. Shepard, J. Hone. Nature Nanotechnology 5, 722-726 (2010) [2]. A.S. Mayorov, R.V. Gorbachev, S.V. Morozov, L. Britnell, R. Jalil, L.A. Ponomarenko, K.S. Novoselov, A.K. Geim, K. Watanabe, T. Taniguchi. Unpublished. [3] R. Pillarisetty, Hwayong Noh, E. Tutuc, E. P. De Poortere, K. Lai, D. C. Tsui, and M. Shayegan Phys. Rev. B 71, 115307 (2005)
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Bioinspired Peptide Supramolecular Structures: Ferroelectricity at Nanoscale

Gil Rosenman School of Electrical Engineering - Department of Physical Electronics, Tel Aviv University, 69978 Tel Aviv, Israel, gilr@eng.tau.ac.il Elementary biological units such as proteins and peptides self-assemble into natural biological nanostructures such as protein fibers and neurodegenerative diseases (Alzheimer, Parkinson, etc) related amyloid fibrils (AF). Another class of bionanomaterials is man-made bioinspired materials, which are composed from chemically synthesized biomolecules and can self assemble into nanotubes (PNT), nanospheres, hydrogels, etc. AF and PNT are supramolecular ensembles which are built from subunitshighly ordered crystallized structures at the nanoscale possessing unique intrinsic physical properties: a. Quantum confined phenomena in AF and PNT We found electron-hole quantum confinement phenomena in AF and PNT indicating on formation of nanocrystalline regions in these supramolecular structures which behave as quantum dots and quantum wells. This effect is well known for semiconductor materials but was never observed in bio-organic structures. Studies of this electron-optical phenomena allows direct dynamic observation of the self assembly process of low dimensional ~1-2 nm size crystalline subunits and nanotubes (nanofibers) in biological and bioinspired structures b. Asymmetric space structure and polar dielectric properties in AF and PNT Space asymmetry of elementary crystalline subunits of AF and PNT makes available exploration of unique polar dielectric properties such as piezoelectric effect, second harmonic generation, ferroelectric spontaneous polarization PNT quantum structures. We observed ferroelectric phase transition when initial quantum dots structure is transformed to quantum wells structure followed by space symmetry transformation from asymmetric to symmetric. Understanding of these fundamental intrinsic physical effects have tremendous potential to develop a new generation of nano-bio-nonlinear materials and their applications.
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Mn Doping Effect on Electrical and Magnetic Properties of BiFeO3-BaTiO3 Thin Films Prepared by Chemical Solution Deposition Wataru Sakamoto1, Yuya Ito1, Makoto Moriya1, Toshinobu Yogo1 1 EcoTopia Science Institute, Nagoya University, Japan Increased demand for thin film processing for integrated device development and the development of new functional materials is expected to produce a wide variety of thin-film devices. In such a situation, BiFeO3-based thin films have been receiving great attention because of their multiferroicity and large ferroelectric polarizations [1-5]. In our group, BiFeO3-BaTiO3 solid solution thin films have been studied to enhance the structural stability of perovskite BiFeO3. Also, as a fabrication method of thin film, chemical solution deposition (CSD) was selected to control the chemical composition precisely. Perovskite single-phase BiFeO3-BaTiO3 thin films were successfully fabricated on Pt/TiOx/SiO2/Si substrates by optimizing the processing conditions and the BaTiO3 content. By controlling the BaTiO3 concentration more than 20 mol%, perovskite structure of BiFeO3-BaTiO3 was stabilized and the process window of perovskite BiFeO3-BaTiO3 thin films was enlarged to wide temperature range. Furthermore, with an increase of the BaTiO3 content, the shape of ferroelectric P-E hysteresis loops was improved, whereas the values of magnetization of the films under the magnetic field decreased due to the decrease of Fe concentration of BiFeO3-BaTiO3. Since P-E hysteresis curves contained leakage current components because of the relatively low insulating resistance around room temperature, Mn doping to the 80 P (C/cm ) BiFeO3-0BaTiO3 thin films with a relatively high 60 BiFeO3 concentration was also conducted, and found to 40 be effective in improving the leakage current and 20 E (kV/cm) ferroelectric properties. The leakage current density 0 -800 -400 400 800 lowered more than two digits in comparison with the -20 film without Mn doping in the high electric field range. -40 (a) The P-E and M-H hysteresis curves of the 5 mol% Mn-60 -80 doped 0.7BiFeO3-0.3BaTiO3 thin film prepared at 700oC are shown in Fig. 1. The 0.8BiFeO3-0.2BaTiO3 20 M (emu/cm3) thin films with 5 mol% Mn doping also exhibited 15 10 typical ferroelectric P-E and ferromagnetic M-H 5 H (kOe) hysteresis loops simultaneously at room temperature. -30 -20 -10 10 30 0 20 -5 Detailed Mn doping effect on the improvement of -10 electrical and magnetic properties of the resultant -15 (b) BiFeO3-BaTiO3 thin films will be discussed. -20
2
[1] Wang et al., Science 299, 1719 (2003). [2] Singh et al., Appl. Phys. Lett. 88, 262908 (2006). [3] Yun et al., Appl. Phys. Lett. 89, 192902 (2006). [4] Sakamoto et al., J. Appl. Phys. 104, 104106 (2008). [5] Sakamoto et al., Mater. Chem. Phys. 116, 536 (2009).
Fig. 1 (a) P-E and (b) M-H hysteresis curves of 5 mol% Mn-doped 0.7BiFeO3-0.3BaTiO3 thin film fabricated at 700oC [Measured at 300 K].
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A CASE IN DEFENCE OF PEROVSKITE SnTiO3 AS A STRONG, LEAD-FREE FERROELECTRIC MATERIAL; A FIRST-PRINCIPLES INVESTIGATION
William Parker, James Rondinelli and Serge Nakhmanson Argonne National Laboratory, Argonne, Illinois 60439, USA Perovskite-structured SnTiO3 has been recently identified in a number of computational studies as an attractive, environmentally-friendly material with potential to replace ferroelectric PbTiO3 [1-3]. However, additional computational evidence suggests that bulk perovskite SnTiO3 may be metastable, with the hexagonal ilmenite structure being energetically more favorable [4]. Furthermore, the high-temperature synthetic routes to all bulk SnTiO3 polymorphs are inhibited by the ease of disproportionation of Sn2+ into Sn4+ and Sn metal [3]. In this investigation, we use density-functional theory and phonon-band instability analysis to investigate avenues for epitaxial stabilization of ferroelectric perovskite SnTiO3 thin films with applied strains of up to 2% with respect to a non-polar cubic case. Consistent with previous studies [1-3], we calculate a dynamically stable polar structure with space group P4mm (Px=Py=0, Pz0) for all compressive bi-axial strain states investigated. We find that tensile strain stabilizes a polar structure, space group Cm (Px=Py0, Pz0), with an in-plane polarization component. For vanishing stresses, both perovskite phases have total polarizations in excess of 1.2 C/m2, however, the very high tetragonality (c/a=1.123) of the P4mm phase indicates that it could be difficult to switch its polarization with an electric field of a reasonable magnitude [5]. We argue that these polarization switching complications in the supertetragonal regime could be circumvented by the appropriate choice of growth substrate: here, tetragonal (P4mm) phases with modest c/a ratios and large spontaneous polarizations, similar to those of PbTiO3, would be accessible. Comparing the energies of the strain stabilized perovskite phases with those of other SnTiO3 polymorphs, we find that the tetragonal P4mm ones have the lowest energies of all the considered structures. The perovskite Cm and polar (total polarization of ~0.9 C/m2) R3c Lithium-Niobate-type phases are approximately 40 meV per structural unit (s.u.) higher in energy than the P4mm ones, while ilmenite, and hexagonal P63mc and P63/mmc phases are at least 0.4 eV/s.u. higher than the Cm and R3c phases. Although we do not specify the growth conditions necessary to stabilize perovskite SnTiO3, our investigation shows that it should be possible to achieve a ferroelectric (i.e., both highly polar and switchable) structure through modern layer-by-layer synthesis techniques. It also suggests that, by virtue of its strong lone-pair activity, Sn2+ is a good candidate for replacing lead in the Goldstone ferroelectric PbSr2Ti2O7 [6]. The resulting Pb-free compound should exhibit the elusive isotropic in-plane polarization effect that is rarely observed in conventional ferroelectrics. This project is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under contract No. DE-AC02-06CH11357.
References: 1. Y. Konishi, M. Ohasawa, Y. Yonezawa, Y. Tanimura, T. Chikyow, T. Wakisaka, H. Koinuma, A. Miyamoto, M. Kubo, and K. Sasata, Mater. Res. Soc. Symp. Proc. 748, U3.13.1 (2003). 2. Y. Uratani, T. Shishidou, and T. Oguchi, Jpn. J. Appl. Phys. 47, 7735 (2008). 3. S. F. Matar, I. Baraille, M. A. Subramanian, Chem. Phys. 355, 43 (2009). 4. G. Hautier, C. C. Fischer, A. Jain, T. Mueller, and G. Ceder, Chem. Mater. 22, 3762 (2010). 5. M. R. Suchomel, A. M. Fogg, M. Allix, H. Niu, J. B. Claridge, and M. J. Rosseinsky, Chem. Mater. 18, 4987 (2006). 6. S. M. Nakhmanson and I. Naumov, Phys. Rev. Lett. 104, 097601 (2010).
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BREAKDOWN ANALYSIS OF Cu DOPED Ge0.3Se0.7 BASED RRAM DEVICES TO UNDERSTAND THE STOCHASTIC NATURE OF THE RESISTIVE SWITCHING PROCESS R. Soni,1,+,* P. Meuffels,1 G. Staikov,1 R. Weng,1 C. Kgeler,2 A. Petraru,3 M. Hambe,3 R. Waser,1 and H. Kohlstedt3 Institut fr Festkrperforschung, Forschungszentrum Jlich GmbH, Jlich, 52425, Germany 2 Fraunhofer-IFAM, 26129, Oldenburg, Germany 3 Nanoelektronik, Technische Fakultt Kiel, Christian-Albrechts-Universitt Kiel, Kiel, 24143, Germany
1
Despite recent progress in solid electrolyte based resistive switching memory devices, our understanding of the microscopic origin of the switching process and its stochastic nature is still limited. In order to understand this behavior, we present a breakdown analysis performed on Cu doped Ge0.3Se0.7 based memory devices under elevated temperature and constant voltage stress conditions. Within the framework of classical nucleation theory, the observed statistical distribution of the time-to-breakdown is found to be consistent with the stochastic nature of critical nucleus formation. For the voltage stress range used in this study, the calculated critical Gibbs nucleation energy, Gcrit, is found between 0.71 and 0.22 eV, while the corresponding number of atoms forming the critical nucleus, Ncrit, values varies between 12 and 2.3.
E-mail: soro@tf.uni-kiel.de Present Address: Nanoelektronik, Technische Fakultt Kiel, Christian-Albrechts-Universitt Kiel,
159
MEDICAL APPLICATIONS OF PIEZOELECTRIC MICROELECTROMECHANICAL SYSTEMS

F. Griggio, H. Kim, I.S. Kim, T.N. Jackson, K. Choi, R.L. Tutwiler, and S. Trolier-McKinstry Pennsylvania State University, University Park, PA, USA STMcKinstry@psu.edu
Piezoelectric microelectromechanical systems (MEMS) offer the opportunity to create miniaturized electromechanical transducers and energy harvesting systems. Advances over the last two decades have enabled films with high piezoelectric e31,f coefficients to be fabricated on large-area substrates and micromachined into useful devices. This paper will describe some examples of the medical applications of this technology. Particular emphasis will be placed on the development of miniaturized medical imaging systems, as well as the possibility of flexible, reconfigurable transducer arrays. Lead zirconate titanate piezoelectric films have been integrated into prototype one-dimensional array transducers. The resonance frequency is adjusted through the use of flexural structures. Two principal geometries have been investigated: xylophone-bar transducer with a length:width aspect ratio greater than 5:1 in order to isolate the desired resonance modes and diaphragm arrays. In both cases, the PZT and remaining films in the stack were patterned using either ionbeam etching or reactive ion etch. The structures were then released from the underlying silicon substrate by XeF2 etching. Impedance measurements on the fabricated structures showed resonance frequencies between 3 and 70 MHz for fully and partially released structures depending on the transducer dimensions and vibration modes. In-water transmit and receive functionalities have been demonstrated. A bandwidth on receive of 66 % has been determined for partially released structures.
Flexible, reconfigurable MEMS transducer arrays would also address a crucial need for accurately detecting a patient pulse by first-responders. In situations of cardiac arrest, the presence or absence of a pulse should be ascertained within 10 seconds in order to make a decision on external defibrillation. Unfortunately, in many cases, assessment takes much longer, and the error rate even among trained personnel is high (22% error for pediatric patients even among doctors and nurses), significantly degrading patient outcomes. Thus, a Doppler ultrasound bandaid for detecting pulse would be of considerable value. In order to achieve this goal, it is necessary to be able to prepare piezoelectric films on conformable substrates such as metal foils or polymers. Several approaches to achieving this will be discussed.
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EFFECT OF THE CATION INTERMIXING AND SURFACE DEFECTS ON THE ELECTRONIC STRUCTURE OF THE LaAlO3/SrTiO3 (001) HETEROJUNCTION 1, Scott A. Chambers2 Peter V. Sushko 1 Department of Physics and Astronomy and the London Centre for Nanotechnology, University College London, Gower Street, London WC1E 6BT, UK. 2 Fundamental and Computational Science Directorate, Pacific Northwest National Laboratory, Richland, WA, USA. Advances in the film growth and deposition techniques [1] have stimulated extensive work on oxide superlattices, in which thin films and interfaces between different oxides are used as functional elements. Such interfaces can exhibit properties, which are not characteristic to either of the constituents. For example, electric conductivity at the interface of two dielectrics non-polar SrTiO3 (STO) and polar LaAlO3 (LAO) has been attributed to the formation of two-dimensional electron gas at this interface [2]. Consequent theoretical studies (see, for example, a recent review [3]) have explained this phenomenon in terms of electronic reconstruction to alleviate so-called polar catastrophe, which results in the electron transfer from the LAO to the STO and makes it conductive. However, most of the electronic structure calculations of the STO/LAO interfaces conducted so far have assumed that this interface is atomically abrupt. Here we investigate the thermodynamic stability of the STO/LAO interfaces with respect to intermixing of Al, Ti, Sr, and La atoms using the density functional theory. Our results suggest that the abrupt interfaces are thermodynamically unstable. For example, intermixing of Al and Ti atoms across the TiO2/LaO interface can stabilise it by as much as 0.31.0 eV depending on the concentration of the defect pairs and thickness of the LAO film deposited on the STO substrate. Extensive analysis of the intermixed configurations suggests that the most thermodynamically stable interface structures are obtained by intermixing of all four metal species. The calculated profiles of the band bending in the vicinity of the interface suggest that the cation intermixing compensates for the electrical dipole induced by the ideal LAO film and significantly reduces the magnitude of the band bending in comparison to that found for the atomically abrupt STO/LAO interface. Hence, we suggest that the experimentally observed properties of the STO/LAO interfaces ought to be associated with complex quaternary La-Al-Sr-Ti oxide structures [4,5]. We then discuss the effect of n-type dopants, surface defects, and contaminants on the electronic properties of this system. [1] S.A. Chambers, Adv. Mater. 22, 219 (2010). [2] A. Ohtomo and H. Y. Hwang, Nature 427, 423 (2004). [3] H. Chen, A.M. Kolpak, S. Ismail-Beigi, Adv. Mater. 22, 2881 (2010). [4] L. Qiao, T.C. Droubay, V. Shutthanandan, Z. Zhu, P.V. Sushko and S.A. Chambers, J. Phys.: Consens. Matter 22, 312201 (2010). [5] S.A. Chambers, M.H. Engelhard, V. Shutthanandan, Z. Zhu, T.C. Droubay, L. Qiao, P.V. Sushko, T. Feng, H.D. Lee, T. Gustafsson, E. Garfunkel, A.B. Shah, J.-M. Zuo and Q.M. Ramasse, Surf. Sci. Reports 65, 317 (2010).
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LEAD-FREE FERROELECTRIC HETEROSTRUCTURES FOR ENERGY STORAGE TECHNOLOGIES
T. M. Correia1, P.M. Weaver1, M. McMillen2, J. M. Gregg2, M. G. Cain1

1
National Physical Laboratory, Hampton Road, Teddington TW11 0LW, United Kingdom
2
Department of Pure and Applied Physics, Centre for Nanostructured Media, School of Maths and Physics, Queens University Belfast, Belfast BT7 1NN, United Kingdom Email: tatiana.correia@npl.co.uk
Ferroelectrics have been envisaged as a potential material solution for energy storage in pulsed power applications. Although some progress has been reported in the literature in achieving high-energy density materials, most work has been carried out with lead-based ferroelectric materials. In the current political and economic background supporting the safe and sustainable use of lead-free materials, alternative materials compositions are being developed, worldwide. There is evidence that interface effects in heterostructures can significantly modify ferroelectric properties, offering the possibility of achieving enhanced energy storage through the engineering of interfacial properties. This paper sets out an alternative approach to achieving high-energy density electrical storage, based on the interfacial coupling of ferroelectric (Pb-free) multilayers. Investigations carried out on BaTiO3/SrTiO3 multilayer thin films are presented and the role of the interfacial coupling on the dielectric, piezoelectric and stored energy is discussed.
163
INITIAL RESULTS FROM ON-ORBIT TESTING OF THE FRAM MEMORY TEST EXPERIMENT ON THE FASTSAT MICRO-SATELLITE
Todd C. MacLeod NASA Marshall Space Flight Center W. Herb Sims NASA Marshall Space Flight Center Kosta A. Varnavas NASA Marshall Space Flight Center Fat D. Ho University of Alabama Huntsville Abstract: The Memory Test Experiment is a space test of a ferroelectric memory device on a low Earth orbit satellite that launched in November 2010. The memory device being tested is a commercial Ramtron Inc. 512K memory device. The circuit was designed into the satellite avionics and is not used to control the satellite. The test consists of writing and reading data with the ferroelectric based memory device. Any errors are detected and are stored on board the satellite. The data is sent to the ground through telemetry once a day. Analysis of the data can determine the kind of error that was found and will lead to a better understanding of the effects of space radiation on memory systems. The test is one of the first flight demonstrations of ferroelectric memory in a near polar orbit which allows testing in a varied radiation environment. The initial data from the test is presented. This paper details the goals and purpose of this experiment as well as the development process. The process for analyzing the data to gain the maximum understanding of the performance of the ferroelectric memory device is detailed.
Topic: Presenting Author Email: Type:
Non-Volatile Memories Todd C. MacLeod NASA Marshall Space Flight Center todd.macleod@nasa.gov Oral
167
EPITAXIAL SUBMICRON-SIZED HETEROSTRUCTURES OF FERROELECTRIC AND FERROMAGNETIC/FERRIMAGNETIC OXIDES
Ionela Vrejoiu, Alessio Morelli, Daniel C. Biggemann Tejero Max Planck Institute of Microstructure Physics, Weinberg 2, 06120 Halle, Germany Email: vrejoiu@mpi-halle.de Epitaxial heterostructures combining ferromagnetic and ferroelectric perovskite oxides are a possible route to explore coupling mechanisms between the two independent order parameters, magnetization and polarization. We report on the fabrication and investigation of the properties of hybrid epitaxial structures of ferromagnetic La0.7Sr0.3MnO3 and ferroelectric PbTiO3, and of ferrimagnetic CoFe2O4 or NiFe2O4 and ferroelectric PbZr0.52Ti0.48O3, with lateral dimensions from 200 nm to 1000 nm. The structures were grown in situ by pulsedlaser deposition, employing suitable stencil masks attached to SrTiO3(100) substrates. Room temperature ferroelectric and the ferromagnetic domain structures were imaged by piezoresponse force microscopy (PFM) and magnetic force microscopy (MFM). For example, Fig. 1(a) and Fig.1(b) show the atomic force microscopy (AFM) of the topography of bare La0.7Sr0.3MnO3 dots, and after they were embedded in an epitaxial PbTiO3 film. The topography of an embedded dot is given in Fig. 1(c). In Fig.1(d) the piezoresponse phase acquired in the imaged area is displayed. Domains of polarization oriented up (bright) and down (dark) can be seen in Fig.1(d). The piezoresponse hysteresis loops measured in the middle of the dot (up polarization) and in the middle of the area with down polarization are shown in Fig. 1(e) and Fig. 1(f), respectively. The dzz piezoelectric coefficient was about 50 pm/V, similar to what we measure on simple epitaxial PbTiO3.
Figure 1. AFM (on 3 m x 3 m areas) and PFM (on a 2 m x 2 m area) investigations of ferromagnetic La0.7Sr0.3MnO3 dots embedded in an epitaxial ferroelectric PbTiO3 film.
168
ENERGY LOSS IN PIEZOELECTRIC ENERGY HARVESTING CANTILEVERS

Weaver P.M., Stewart M., Cain M.G. National Physical Laboratory Hampton Road Teddington Middlesex TW11 0LW UK Phone: +44 (0) 20 8943 6228 Email: paul.weaver@npl.co.uk
Energy harvesting technology aims to use largely untapped sources of ambient energy resulting from human activity and environmental energy flows to provide power for applications including wireless communications for remote sensing, communications and control. Reducing dependency on powerline and batteries will enable widely distributed deployment in structures or in mobile, remote or inaccessible locations. Piezoelectric materials are one of the most promising methods for harvesting energy from movement and vibration, particularly for micro- and nanoscale devices. Power output from piezoelectric harvesters is typically quite low so that efficiency in the harvester as well as the energy collection, storage and use is a crucial consideration. This paper presents new results on a significant source of energy loss in piezoelectric cantilevers that results from redistribution of the generated charge. It is shown that losses of 25% can occur by this mechanism. The loss mechanism is quantified and it is demonstrated that surprisingly, the overall energy output as well as efficiency can be boosted by reducing the amount of piezoelectric material used.
Topic: 10.Ferroelectric and Piezoelectric Materials Experiment Preference: Oral presentation
169
PHOTOELASTIC, FERROELECTRIC, AND FERROMAGNETIC PROPERTIES OF PEROVSKITE SUPERLATTICES STUDIED BY FEMTOSECOND X-RAY DIFFRACTION Michael Woerner1
1
Max-Born-Institut f r Nichtlineare Optik und Kurzzeitspektroskopie, 12489 Berlin, Germany u E-mail: woerner@mbi-berlin.de
Polar solids crystallizing in a perovskite structure have received much interest because of their particular structural and electronic properties. Electronic and/or spin correlations in such materials give rise to charge ordering, ferroelectricity, superconductivity, ferromagnetism and other phenomena. The macroscopic electric and/or magnetic behavior depends sensitively on the atomic arrangement in the crystal lattice and, thus, can be changed by inducing structural rearrangements, e.g., via built-in or external mechanical stress. This concept has been used to generate materials and/or devices with tailored properties. So far, perovskite materials have mainly been studied under (quasi)static conditions. Complex phase diagrams and the changes of electronic properties upon changing parameters such as temperature or pressure have been determined by a variety of experimental techniques. Lattice coordinates relevant for ionic ferroelectricity and structure related magnetic properties have been identied for both bulk and nanolayered materials. The latter allow for strain engineering in epitaxial growth and, thus, for tailoring the electronic properties. Femtosecond x-ray diffraction provides direct insight into the ultrafast reversible lattice dynamics of materials with a perovskite structure [1-8]. Superlattice (SL) structures consisting of a sequence of nanometer-thick layer pairs allow for optically inducing a tailored stress prole that drives the lattice motions and for limiting the inuence of strain propagation on the observed dynamics. We demonstrate this concept in a series of diffraction experiments with femtosecond time resolution, giving detailed information on the ultrafast lattice dynamics of ferroelectric and ferromagnetic superlattices. Anharmonically coupled lattice motions in a SrRuO3 /PbZr0 .2Ti0 .8O3 (SRO/PZT) SL lead to a switch-off of the electric polarizations on a time scale of the order of 1 ps. Ultrafast magnetostriction of photoexcited SRO layers is demonstrated in a SRO/SrTiO3 (STO) SL. [1] C. von Korff Schmising et al., Phys. Rev. Lett. 98, 257601 (2007). [2] C. von Korff Schmising et al., Appl. Phys. B 88, 1 (2007). [3] C. von Korff Schmising et al., Z. Kristallogr. bf 223, 283 (2008). [4] C. von Korff Schmising et al., Phys. Rev. B 78, 060404(R) (2008). [5] M. Woerner et al., Appl. Phys. A 96 83 (2009). [6] F. Zamponi et al., Appl. Phys. A 96 51 (2009). [7] T. Elsaesser et al., in: Ultrafast Phenomena XVI, 101, (2009). [8] C. von Korff Schmising et al., Phys. Procedia 3, 333 (2010).
171
ENHANCEMENT OF THE ELECTROCALORIC AND ELECTROMECHANICAL EFFECTS NEAR THE CRITICAL POINT IN FERROELECTRIC RELAXOR MATERIALS
Zdravko Kutnjak1, Brigita Roi1, Barbara Mali1, Hana Uri1, Janez Holc1, Marija Kosec1, R. Pirc1, Sheng-Guo Lu2 and Q. M. Zhang2
2
Jozef Stefan Institute, Jamova 39, 1001 Ljubljana, Slovenia Materials Research Institute, The Pennsylvania State University, University Park, PA 16802, USA e-mail: zdravko.kutnjak@ijs.si
Electromechanical and electrocaloric effects have attracted considerable attention in recent years due to their potential application in a new generation of actuators and heating/cooling devices, respectively. The electrocaloric effect (ECE) in a given material is related to the conversion of the electrical energy into heat and vice versa. Until recently the effect itself did not attract extreme attention due to its relatively modest magnitude observed in typical ferroelectric materials. Very recently, however, this situation changed dramatically with the prediction based on the indirect measurements of the existence of a giant electrocaloric effect in both inorganic PZT thin films and P(VDF-TrFE)-type polymeric ferroelectric systems [1,2]. A review of recent direct measurements of the giant ECE in solid and soft ferroelectric materials including thick and thin films of PMN, PMN-PT, PLZT, and P(VDF-TrFE)-based terpolymers, copolymers, and various blends will be given. It was found that the giant ECE is common in these systems. The effective ECE responsiveness T/E exhibits a maximum in the vicinity of the liquid-vapour type critical point in bulk relaxor ferroelectrics [3,4]. The relevance of the critical point proximity for the enhancement of the giant electrocaloric effect and the enhancement of the giant electromechanical response [5] will be discussed. [1] A. S. Mischenko, Q. Zhang, J. F. Scott, R. W. Whatmore, N. D. Mathur, Science 311, 1270 (2006). [2] B. Neese, B. Chu, S.-G. Lu, Y. Wang, E. Furman, Q. M. Zhang, Science 321, 821 (2008). [3] R. Pirc, Z. Kutnjak, R. Blinc, Q.M. Zhang, Appl. Phys. Lett. 98, 021909 (2011). [4] S.-G. Lu, B. Rozic, Q. M. Zhang, Z. Kutnjak, X. Li, E. Furman, L. J. Gorny, M. Lin, B. Malic, M. Kosec, R. Blinc, R. Pirc, Appl. Phys. Lett. 97, 162904 (2010). [5] Z. Kutnjak, J. Petzelt, R. Blinc, Nature 441, 956 (2006).
172
BiScO3 DOPED (Na0.5K0.5)NbO3 LiTaO3 PIEZOELECTRIC CERAMICS

F Y Zhu*, T A Skidmore, M B Ward, T P Comyn, A J Bell, S J Milne Institute for Materials Research, SPEME, University of Leeds, Leeds, LS2 9JT, UK *pmfyz@leeds.ac.uk The structure property relationships of the (Na0.5K0.5)NbO3 LiTaO3 BiScO3 ternary system has been investigated for (Na0.5K0.5)NbO3 - rich compositions by using temperature variable X-ray diffraction along with, dielectric and piezoelectric measurements. The modified phase diagram of the [NKN1-x - LTx]1-y [BS]y system will be presented. Results are reported for measurements of strain-field, piezoelectric charge and coupling coefficients (d33, d31, k31), polarisation-electric field, relative permittivity and loss. The value of d33 piezoelectric charge coefficient is dependent on variations in the temperature of a polymorphic phase transition. The piezoelectric charge coefficient, d33, is ~220 pC/N for x = 0.02 LT: [(Na0.5K0.5NbO3)0.98 (LiTaO3)0.02]0.98 [BiScO3]0.02 with a Curie point, Tc, of ~ 370 oC.
The relative permittivity vs. temperature plots
exhibit varying degrees of peak broadening for x 0.03 LT. Chemical inhomogeneities were detected in the latter compositions by using transmission electron scanning (TEM).
Fig. (a) Lattice parameter as a function of temperature for NKN- 2% BS, showing the transitions from monoclinic (M) to tetragonal (T) and cubic (C) phase. Insert shows variation in angle. The shaded area is the mixed phase in the phase transitions. Fig. (b) Transmission electron micrographs of [NKN0.95 LT0.05]0.98 BS0.02 ceramics. Fig. (c) Relative permittivity as a function of temperature measured at a frequency of 100 Hz for [NKN0.95 LT0.05]0.98 BS0.02 ceramics.
Topics: 1. Ferroelectric Materials: Theory & Experiments.

Preference to oral presentation.
173
FERROELECTRIC DOMAINS IN LEAD TITANATE/STRONTIUM TITANATE SUPERLATTICES
P. Zubko, N. Jecklin, C. Lichtensteiger, N. Stucki and J.-M. Triscone DPMC, 24, University of Geneva, Quai Ernest-Ansermet, CH-1211, Geneva, Switzerland A. Torres-Pardo , A. Gloter, K. March and O. Stephan Laboratoire de Physique des Solides, UMR 8502, Universit Paris Sud, 91405, Orsay cedex, France The performance of ferroelectric devices such as ferroelectric random access memories is intimately linked with the static and dynamic properties of ferroelectric domains. As the dimensions of the ferroelectric are reduced, the domains that form spontaneously in response to depolarising fields or stress, get progressively smaller in accordance with Kittels law[1]. In ultrathin films, such domains can be as small as a few nanometres[2] and have a profound impact on the structural and electrical properties of the material. We have investigated in detail the static and dynamic properties of ferroelectric domains in superlattices, composed of thin layers of ferroelectric PbTiO3 and paraelectric SrTiO3, using X-ray diffraction, transmission electron microscopy, electron energy loss spectroscopy and electrical measurements. Here we will focus on the large permittivity enhancement due to nanoscale domain wall motion and its evolution with temperature, as well as the extent of the electrostatic interactions between the ferroelectric layers and their effect on the functional properties of the superlattices. Such superlattices give unique access to the physics of ultrathin ferroelectrics, bypassing the usual complications associated with the finite conductivity and small material volume of ultrathin films, and allowing the simultaneous application of large uniform electric fields and X-ray diffraction imaging of the domain structure[3]. In addition they provide additional degrees of freedom for tuning materials properties though artificial chemical ordering and fascinating interface effects[4-6].
[1] L. Landau and E. Lifshitz, Phys. Z. Sowjetunion 8, 153 (1935); C. Kittel, Phys. Rev. 70, 965 (1946);T. Mitsui and J. Furuichi, Phys. Rev. 90, 193 (1953). [2] S. K. Streiffer et al., Phys. Rev. Lett. 89, 067601 (2002). [3] P. Zubko, N. Stucki, C. Lichtensteiger, J.-M. Triscone, Phys. Rev. Lett. 104, 187601 (2010). [4] M. Dawber et al., Phys. Rev. B 95, 177601 (2005). [5] M. Dawber et al., Adv. Mater. 19, 4153 (2007). [6] E. Bousquet et al., Nature 452, 732 (2008).
174
VARIATION OF FERMI LEVEL POSITION IN FERROELECTRIC MATERIALS: BARRIER HEIGHTS AT ELECTRODE INTERFACES AND ELECTRICAL CONDUCTIVITY A. Klein, R. Schafranek, F. Chen, S. Li, C. Ghinea, T.J.M. Bayer, K. Rachut Technische Universitt Darmstadt, Department of Materials and Earth Sciences, Surface Science Division, Petersenstrasse 32, 64287 Darmstadt, Germany The Fermi level position at surfaces of Pb(Zr,Ti)O3 (PZT) and (Ba,Sr)TiO3 (BST) thin films is determined quantitatively by X-ray und ultraviolet photoelectron spectroscopy (XPS/UPS). Contaminations from the surfaces are avoided either by in-situ deposition or surface cleaning in the same vacuum system. The Fermi level varies considerably depending on the used substrate material. In addition, contact formation with different electrode materials leads to Schottky barrier height variation of more than 1 eV. The variation of the barrier height is almost identical for PZT and BST. A quantitative comparison indicates that the energy bands of PZT are approximately 1.1 eV higher in energy than those of BST. A similar difference is obtained in the ionization potential and electron affinity, which is determined using UPS. In addition, the energy band alignment between PbTiO3 and SrTiO3 is obtained from an interface experiment, which is studied by stepwise deposition of SrTiO3 onto PbTiO3. The derived valence band offset amounts to 1.1 eV, in excellent agreement with the different Schottky barrier heights and the different ionization potentials. The higher valence and conduction band energies of PbTiO3 compared to SrTiO3 can be rationalized in terms of the contribution of Pb 6s states to the valence band. For BST the Fermi level position at different interfaces varies between EF-EVB = 2.2 3.2 eV, which corresponds to Schottky barrier heights for electron injection of 0 1.2 eV. The barrier heights are in good agreement with the current-voltage behaviour of thin films. Barrier-free electron injection and spacecharge-limited-current behaviour are observed with Sn-doped In2O3 (ITO) electrodes, while only little charge injection and capacitive behaviour is found with Pt electrodes. Due to the higher energy bands of PZT, the barrier heights for electrons and holes are always larger than 1 eV. No strong charge injection is therefore expected at the interface. The variation of Fermi levels at the surfaces and interfaces corresponds well with the different electrical conductivities of the two materials. While donor doped SrTiO3, BaTiO3 and BST exhibit high electron concentration and electrical conductivity at room temperature, both donor and acceptor doped PbTiO3 and PZT essentially remain insulating. This indicates that a close correspondence between the Variation of Fermi level in BST and PZT determined possible range of Fermi level positions in the by XPS/UPS from a large number of thin film interior and at surfaces/interfaces of the materials samples on different substrates and with different exists. The allowed range of Fermi levels, which is electrode materials during contact formation. The restricted by the defect properties of the materials, difference in valence band energy VB corresponds can therefore be accessed by surface/interface well with the experimental band offset. studies using XPS/UPS. Topic: Ferroelectric and Piezoelectric Materials Experiment Presenting author: Andreas Klein, Technische Universitt Darmstadt, Germany, aklein@surface.tudarmstadt.de Preference: Oral presentation
175
ORGANIC FERROELECTRICS FOR MEMORY AND DISPLAY APPLICATIONS

Kamal Asadi1, Martijn Kemerink2, Dago M. de Leeuw1,3, and Paul W. M. Blom1,4
Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, NL-9747 AG, Groningen, The Netherlands 2 Department of Applied Physics, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands 3 Philips Research Laboratories, High Tech Campus 4, NL-5656 AE, Eindhoven, The Netherlands 4 TNO/Holst Centre, High Tech Campus 31, 5605 KN Eindhoven, The Netherlands
New non-volatile memories are being investigated in order to keep up with the organic electronics road map. Ferroelectric polarisation is an attractive physical property as the mechanism for non-volatile switching, since the two polarisations can be used as two binary levels. The challenge is to develop a storage medium in which the favourable properties of ferroelectrics such as bistability and non-volatility can be combined with the beneficial properties provided by semiconductors such as conductivity and rectification. We present an integrated solution by blending semiconducting and ferroelectric polymers into phase separated networks. The polarisation field of the ferroelectric modulates the injection barrier at the semiconductormetal contact. The underlying switching mechanism originates from the fact that in the On-state the stray field of the ferroelectric causes a substantial injection barrier lowering in the semiconductor. As a result, charge transport through the semiconductor is switched from injection limited in the Off-state to space charge limited in the On-state. The combination of ferroelectric bistability with (semi)conductivity and rectification allows for solution-processed non-volatile memory arrays with a simple cross-bar architecture that can be read-out nondestructively. Light-emitting polymers have great potential for large area applications like signage, because they can be processed from solution. The bottleneck that prevents realization of large lightemitting billboards is the driving scheme; a single transistor per pixel for signage applications is cost prohibitive. As a solution we here present a new device, the MEMOLED, an organic lightemitting diode with a built-in ferroelectric switch. The bistable diode can be programmed into a non-emissive off-state and a non-volatile emissive on-state. Static images are generated with a passive matrix driving scheme that can be scaled to large area.
176
EFECTS OF STRAIN ON THE MAGNETOELECTRIC BEHAVIOUR OF ORTHORHOMBIC YMnO3 THIN FILMS I. Fina1, X. Mart2, L. Fbrega1, F. Snchez1 and J. Fontcuberta1 Institut de Cincia de Materials de Barcelona (ICMAB-CSIC), Campus UAB s/n, 08193 Bellaterra, Spain 2 Department of Condensed Matter Physics, Faculty of Mathematics and Physics, Charles University, Ke Karlovu 5, 121 16 Praha 2, The Czech Republic.
Multiferroic orthorhombic (o-) manganites display unproper ferroelectricity related to the antiferromagnetic spin arrangement. Since the magnetic phase diagram of these materials, arising from competing magnetic interactions, is quite complex and strongly dependent on their detailed crystal structure, it can be expected small modifications of the latter to unbalance the interactions, leading to sensitive changes of the magnetic and dielectric properties. The aim of this work is to overview the effects of substrate-induced epitaxial strain on magnetic and electric properties in o-YMnO3 thin films. The strain is modified by changing the thickness in a- and c-axis textured films. Among orthorhombic manganites, these films are especially interesting because recent data [1] have suggested that they display a bc-cycloidal ordering, in contrast to the observed collinear arrangement in the bulk material. We will show that the modification of interatomic bonds in these films, due to substrate strain, induces the appearance of ferromagnetism, which can be modulated (Fig. 1a). In parallel, the peak in the dielectric permittivity at the lock-in transition a signature of the magnetoelectric coupling-, reduces its height as strain increases (Fig. 1b); this points to a weakening of the magnetoelectric coupling accompanying the enhancement of ferromagnetic interactions. Finally, hysteresis loops reveal that ferroelectric polarization gradually vanishes with increasing strain. We will argue that all these data are compatible with the strain induced destabilization of the bccycloidal antiferromagnetic structure (observed in the relaxed thin films) in benefit of a canted magnetic structure.
60 50
YMnO3 thin films a-oriented (mr) a-oriented (mFC) c-oriented (mr) c-oriented (mFC) c-oriented (mFC) TbMnO3 thin films c-oriented (mFC[5]) bulk material YMnO3 HoMnO3 TbMnO3 LaMnO3
YMnO3 thin filma 30 c-textured a-textured
M (emu/cm )
40 30 20 10 0
a,c (%)
20
10
(a)
0.90 0.92 0.94 0.96
(b)
0.90 0.92 0.94 0.96
a/b
a/b
Figure 1. (a) Remanent magnetization measured at 5K for several o-manganites (films and bulk) versus a/b ratio (built from ref. [2] plus data for TbMnO3 thin films from ref. [5]). (b) Height of the dielectric peak as a funtion of the a/b ratio, for several a- and c-textured o-YMnO3 films; the solid line is a guide to the eye.
References
[1] I. Fina et al., Appl. Phys. Lett. 97, 232905 (2010) [2] J. Fontcuberta et al., Phase Trans. doi:10.1080/01411594.2010.548023. (Online) [3] X. Marti et al, Appl. Phys. Lett. 95, 142903 (2009) [4] X. Marti et al, J. Appl. Phys. 108, 123917 (2010) [5] X. Marti et al., Appl. Phys. Lett. 96, p222505 (2010)
178
GIANT ELECTROCALORIC EFFECT IN FERROELECTRIC POLYMERS AND THEIR DEVICE DEMONSTRATIONS

1
Q. M. Zhang, 1S. G. Lu, 1Xinyu Li, 1Haiming Gu, 1Minren Lin, 1Eugene Furman, 2 Z. Kutnjak, 2B. Rozic, and 2R. Prac 1 Electrical Engineering Department and Materials Research Institute The Pennsylvania State University, University Park, PA 16802, USA 2 Jozef Stefan Institute, 1000 Ljubljana, Slovenia
The electrocaloric effect is the induced change in the entropy and temperature in a dielectric material by an applied voltage. Although ECE has been studied for many decades, the relatively small ECE observed, i.e., adiabatic temperature change T<2.5 oC, made it unsuitable for practical applications. Recently, it was discovered that in a class of ferroelectric polymers, a giant electrocaloric effect can be achieved. That is, these polymers can exhibit an adiabatic temperature change T ~ 20 K and isothermal entropy change S > 90 J/kgK at room temperature. This talk will present the basic materials considerations and experimental results of ECE in both normal ferroelectric and the relaxor ferroelectric polymers. It will be shown that although ECE exhibits a sharp peak around the ferroelectric-paraelectric phase transition in normal ferroelectrics, the relaxor ferroelectric polymer displays a nearly flat ECE response over a broad temperature range about the broad dielectric constant peak, which is very attractive for practical cooling device applications. Besides the materials works, we will also present recent advances in developing practical cooling devices based on these ferroelectric polymers. Especially, simulation results reveal that the cooling devices based on the concept of the active electrocaloric regenerative refrigeration cycle exhibit a high cooling power, wider temperature lift, and high efficiency. Moreover, the materials with giant ECE create totally new cooling device design paradigms which features very compact size and high cooling power.
Topic: 5. Electrocalorics, Thermoelectrics, and Energy Harvesting; Presenting author: Distinguished Prof. Q. M. Zhang, Electrical Engineering Department and Materials Research Institute The Pennsylvania State University University Park, PA 16802 USA Email: qxz1@psu.edu
179
LOCAL STRUCTURE AND DYNAMICS OF A SINGLE FERROELECTRIC DOMAIN WALL Venkatraman Gopalan1, Vasudeva Rao Aravind1, A. N. Morozovska2, S. Jesse4, S. Bhattacharyya1, D. Lee3, E. A. Eliseev2, S. R. Phillpot3, L. Q. Chen1 and S. V. Kalinin4
1
Materials Science and Engineering, Pennsylvania State University, University Park, PA 16802
2 3
National Academy of Science of Ukraine, Kiev, Ukraine 03028
Materials Science and Engineering, University of Florida, Gainesville, Florida 32611
Center for Nanophase Materials Science, Oak Ridge national Laboratory, Oak Ridge, Tennessee 37831 e-mail: vgopalan@psu.edu
Two insights into the structure and dynamics of a single ferroelectric wall will be presented. First, Using localized electric field of a scanning probe microscopy tip, we experimentally demonstrate a surprisingly rich range of polarization reversal behaviors in the vicinity of the initially flat 180 ferroelectric domain wall in lithium niobate. The nucleation bias is found to increase by an order of magnitude from a two-dimensional 2D-nucleus at the wall to threedimensional nucleus in the bulk. The wall is thus significantly ferroelectrically softer than the bulk. The wall profoundly affects switching on length scales on the order of micrometers (Phys. Rev. B 82, 024111 (2010)). Second: A classic antiparallel ferroelectric wall is shown to have mixed Ising-Nel and Ising-Bloch-like character even in classic ferroelectrics such as lithium niobate, barium titanate, and lead titanate. This character is significantly enhanced in strain-engineered multilayers (Phys. Rev. B 80, 060102(R) (2009)). Figure 1. Switching phase diagram showing polarization dynamics as a function of bias window and tip-wall separation. Shown are the regions of no switching, wall-mediated switching with asymmetric loops and symmetric loops region near x=0 (wall position), and bulk nucleation. The threshold bias for polarization reversal at the wall is Vi and in the bulk is Vb. Shown below are experimental PFM hysteresis loops or a bias window of 14 V at x=220,140, 0, +80, and +120 nm. Reference: V. Aravind et al.
Correlated polarization switching in the proximity of a 180 domain wall, Phys. Rev. B 82, 024111 (2010).
180
SCALING AND INTERFACE CONTROL OF HIGH-K/III-V INTERFACES Susanne Stemmer, Yoontae Hwang, Varistha Chobpattana and Roman Engel-Herbert Materials Department, University of California, Santa Barbara, CA 93106-5050, USA This presentation will discuss two topics: (i) quantification of interface trap state densities (Dit) at high-k/III-V interfaces, and (ii) development of deposition methods capable of scaled high-k/III-V interfaces with an equivalent oxide thickness (EOT) of ~ 1 nm, low Dit and an unpinned Fermi level. Methods for quantifying Dit and the degree of Fermi level (un)pinning are critical in the development of high-quality high-k/III-V interfaces. Interpreting the admittance response of high-k/III-V metal-oxide-semiconductor capacitors (MOSCAPs) in terms of Dit is less straightforward than for Si, because of the low conductance band density of states, different band gaps that result in a wide range of trap response times and the typically very high Dit, with an energy distribution that is different from that of SiO2/Si interfaces. In the first part of the talk, we will discuss the application of conductance and capacitance-based methods to determine Dit at highk/III-V interfaces. We compare the results from the different methods. Commonly observed features in the CV characteristics are interpreted and guidelines are developed to obtain reliable estimates of Dit and the degree of Fermi level (un)pinning. In the second part of the talk we discuss the development of deposition methods for scaled HfO2/InGaAs interfaces. We show that the judicious use of trimethylaluminum (TMA) during chemical beam deposition using hafnium tert butoxide as the source of hafnium and oxygen, allows for HfO2 films with less than 5 nm physical thickness, with EOTs of ~ 1 nm and a Fermi level that is not pinned at midgap. We will discuss systematic experiments that reveal the role of TMA in the quality of these interfaces and in EOT scaling.
184
DIELECTRICS BY DESIGN: CHEMICAL CONTROL OF DIPOLE BEHAVIOUR IN TETRAGONAL TUNGSTEN BRONZES AND BISMUTH FERRITE Andrei Rotaru1, Donna C. Arnold1,2, Andrew J. Miller1, Christopher M. Kavanagh1, Philip Lightfoot1 and Finlay D. Morrison1,*1
1
EaStCHEM School of Chemistry, University of St Andrews, St Andrews KY16 9ST, UK

2
School of Physical Sciences, University of Kent, Canterbury, Kent, CT2 7NH, UK

*
email: finlay.morrison@st-andrews.ac.uk
There is considerable drive to develop novel ferroelectric (piezoelectric) materials for both high permittivity applications (e.g. capacitors) and lead free alternatives to PZT. My talk will outline two of our current areas of activity in this broad area of materials development and characterisation. The first will describe our recent work on oxides with the tetragonal tungsten bronze structure where we have related the local and average chemical structure to the dynamics and stability of dipoles. We have identified two broad types of behaviour in the materials studied: firstly that the macroscopic tetragonal crystal strain determined by the B-site cation size determines the dipole stability in the active c-axis; secondly that local strain gradients induced by judicious choice of A-cation can also be employed to control the dipolar behaviour. By careful and selective doping it is possible to develop materials with dipolar behaviour ranging from disordered (relaxor dielectric) to fully ordered (ferroelectric). The second topic will describe our work on rare earth-modified bismuth ferrite. We present phase field maps as a function of composition and temperature for the various polymorphs of La- and Nd-doped bismuth ferrite, including the appearance of intermediate crystal structures not present in the component ferrites. We also outline how the defect chemistry can be exploited during synthesis to vary the electrical conductivity by over 5 orders of magnitude.
Topic 1, Ferroelectric Materials: Experiment Invited talk
188
GROWTH AND CHARACTERISATION OF BIFEO3-LAFEO3 SUPERLATTICES Gijsbert Rispens, Benedikt Ziegler, Patrycja Paruch DPMC, University of Geneva, Switzerland
The growth of high quality oxide superlattices opens an almost endless playground for modifying the properties of these materials in a controlled manner. Beautiful examples include the appearance of a ferromagnetic ordering at the interface between two antiferromagnetic materials[1] and the stabilization of an improper ferroelectric phase in PbTiO3-SrTiO3 superlattices[2]. We present results on superlattices of the room temperature multiferroic BiFeO3 and the antiferromagnetic insulator LaFeO3. This system is chosen such that only the A-cation is varied between the layers. Moreover, rotation of the oxygen octahedra plays an important role in both materials, making this an interesting system to study the propagation of such rotations across the interfaces. BiFeO3-LaFeO3 superlattices of various periods have been grown on both SrTiO3 and DyScO3 substrates using RF-sputtering. We have characterized these superlattices using X-ray diffraction, atomic force microscopy and macroscopic electrical measurements. We find that the phase diagram shows at least two different ferroelectric phases and some interesting behavior at the boundary between them.
[1] [2]
T. Ueda, K. Tabata, K. Kawai, Science 280, 1064-1066 (1998). Eric Bousquet, Matthew Dawber, Nicolas Stucki, Cline Lichtensteiger, Patrick Hermet, Stefano Gariglio, Jean-Marc Triscone, and Philippe Ghosez, Nature 452, 732-6 (2008).
189
FERROELECTRIC TUNNEL JUNCTIONS FOR LOW-POWER NON-VOLATILE CHARGE- AND SPIN-BASED DATA STORAGE
A. Chanthbouala1, S. Valencia2, A. Crassous1, V. Garcia1, X. Moya3, L. Bocher4, S. Fusil1, K. Bouzehouane1, C. Deranlot1, A. Gloter4, N.D. Mathur3, A. Barthlmy1 and M. Bibes1*
1
Unit Mixte de Physique CNRS/Thales, Campus de Polytechnique, 1 avenue Fresnel, 91767 Palaiseau, France 2 Helmholtz-Zentrum-Berlin fr Materialen und Energie, Albert-Einstein-Strasse 15, 12489 Berlin, Germany 3 Department of Materials Science, University of Cambridge, Cambridge, CB2 3QZ, UK 4 Laboratoire de Physique des Solides, Universit Paris-Sud, CNRS UMR-8502, 91405 Orsay, France
Because it is spontaneous, stable and electrically switchable the polarization of ferroelectrics is an excellent state variable for non-volatile data storage. In addition, polarization reversal can be as fast as tens of ps [1] and only dissipates the modest power associated with polarization charge switching (with current densities typically lower than 104 A/cm). When ferroelectrics are made as thin as a few nm, they can be used as tunnel barriers and the tunneling current is influenced by the polarization direction [2] enabling a simple non-destructive readout of the polarization state. In this talk, I will show how the tunnel resistance can vary by more than two orders of magnitude upon polarization switching in highly-strained ultrathin BaTiO3 tunnel barriers. This strong electroresistance effect can be probed using a conductive AFM tip as the top electrode [3], or using solid-state submicron pads. Such ferroelectric tunnel junctions show large, stable, reproducible and reliable tunnel electroresistance, with abrupt resistance switching related to ferroelectric polarisation reversal [4]. They emerge as an alternative to other resistive memories, with the additional advantage of not being based on voltage-induced migration of matter at the nanoscale, but on a purely electronic mechanism. The low-power, electric-field-driven control of information in ferroelectric tunnel barriers can also be interesting for spintronics if ferromagnetic electrodes here La2/3Sr1/3MnO3 and Fe are used (thereby defining artificial multiferroic tunnel junctions). We have found that such devices not only show tunnel magnetoresistance (TMR) and tunnel electroresistance (as expected from their ferromagnetic electrodes, and their ferroelectric barrier, respectively) but also a tunnel electromagnetoresistance effect, i.e. a dependence of the TMR on the ferroelectric polarization direction [5]. This signals a magnetoelectric coupling at the interface between BaTiO3 and Fe, in line with first-principles calculations [6]. A predicted corollary of this coupling is the induction of a magnetic moment by Fe in BaTiO3. I will present soft X-ray resonant magnetic scattering data revealing that, in addition to being ferroelectric, such ultrathin BaTiO3 fims possess a spontaneous and hysteretic magnetization at room temperature, qualifying them as novel interface-induced multiferroics [7].
[1] [2] [3] [4] [5] [6] [7] D.S. Rana et al. Adv. Mater. 21, 2881 (2009) E.Y. Tsymbal and H. Kohlstedt, Science 313 (2006) V. Garcia et al, Nature 460, 81 (2009) A. Chanthbouala et al, submitted V. Garcia et al, Science 327, 1106 (2010) C.G. Duan et al, Phys. Rev. Lett. 97, 047201 (2006) ; M. Fechner et al, Phys. Rev. B 78 212406 (2008) S. Valencia et al, submitted
* manuel.bibes@thalesgroup.com
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BARIUM-STRONTIUM-TITANATE THIN FILM BASED VARACTORS FOR MICROWAVE APPLICATIONS Hailing Yue, Chenhao Zhang, Mark Patterson, Guru Subramanyam Department of Electrical and Computer Engineering University of Dayton 300 College Park, Dayton, Ohio 45469, USA Kevin Leedy and Charles Cerny Air Force Research Laboratory Sensors Directorate, WPAFB, Dayton, OH 45432
Abstract - Barium-Strontium-Titanate(BST) thin film based varactors were designed for specific zero-voltage capacitance values. The BST varactor device operation is based on the nonlinear dielectric tunability of BST thin film sandwiched between two metal layers in a coplanar waveguide(CPW) transmission line configuration. The varactor capacitance at zero volt dc bias is determined by the overlap area between the center signal line in the top metal electrode and the shunt line in the bottom electrode. Series of devices with capacitances ranging from 0.8pf to 4.8pf were designed and fabricated based on changing their corresponding overlap areas according to the basic parallel plate capacitance calculation as shown in Table 1. A schematic model is also created to extract the designed and measured capacitance. The relationship between the sizes of overlap areas and the extracted capacitances from the electromagnetic and schematic models is demonstrated by a reasonable agreement with the experimental measurements from fabricated devices as shown in Figure 1.
Device Number Capacitance Area (pF)

(um*um)
1 0.8 112.9
2 1.2 169.4
3 1.6 225.9
4 2.0 282.4
5 2.4 338.8
6 3.2 451.8
7 4.0 564.7
8 4.8 677.7
Table 1: Relationship between varactor capacitance and overlap area 6 5 4 Capacitance 3 (pF) 2 1 0 Measured Capacitance Designed Capacitance
Device Number
Figure 1: Designed capacitance versus measured capacitance extracted from schematic model
192
DOMAIN AND DOMAIN WALL ROLE IN PHOTOVOLTAIC EFFFECT IN BiFeO3

Marin Alexe Max Planck Institute of Microstructure Physics, 06120 Halle, Germany
Bismuth ferrite, known as the only oxide perovskite having multiferroic properties at room temperature, has shown recently another interesting face as a wide bandgap semiconductor. Its bandgap of only 2.7 eV, which is lying in the visible spectrum, is one of the lowest among other well known ferroelectrics such as LiNbO3, BaTiO3, or Pb(Zr,Ti)O3. Intriguing photoelectric effects, such as switching of the photocurrent sign or photo-induced expansion, have been already shown to exist in bulk BiFeO3 (BFO) single crystals. 1,2 Moreover, BFO thin films with periodically ordered ferroelectric domains have shown to generate open circuit photovoltages as large as 15V by illumination with light having the photon energy above the band gap.3 The ferroelectric domain walls were paying a major role in a model developed to explain this anomalous photovoltaic effect. The strong local electrical field existing at the domain walls was assumed to split the electron-hole pairs (ehp) photo-generated within the domain wall, whereas within the domains was (a-priori) assumed that ehp will strongly recombine. Thus the photogenerated electrons and holes will accumulate only at the domain walls, building in such way a small voltage across each domain wall. At the macroscopic level the voltages will sum up and generate the open circuit voltage. In order to closely investigate this nanoscale photovoltaic mechanism, we have developed an AFM-based local measurement of photoelectric and photovoltaic effects. We have shown using photoelectric AFM that, besides a significant tip-enhancement, the photovoltaic currents BFO single crystals are rather uniformly distributed at the crystals surface, suggesting that there is no strong electron-hole recombination within the ferroelectric domains.4 The present work takes a step forward and addresses the largely unknown generationrecombination mechanism of photoinduced carriers in BFO using light-modulated (ac) photoelectric AFM. In order to unveil the role of the domain walls we have developed a measurement method, i.e. photo-induced transient spectroscopy (PITS) scanning probe microscopy (PITS-SPM), to evaluate and locally map the generation and recombination rates. We have in this way quantified the local (nanoscale) generation and recombination rates showing the role of the domain walls in photovoltaic mechanism.
1
T. Choi, S. Lee, Y. J. Choi, V. Kiryukhin, and S.-W. Cheong, Switchable Ferroelectric Diode and Photovoltaic Effect in BiFeO3, Science 324, 63-66 (2009). B.Kundys , M Viret , D. Colson D and D.O. Kundys , Light- induced size changes in BiFeO3 crystals, Nature Materials 9, 803 (2010) S.Y. Yang, et al., Photovoltaic effects in BiFeO3, Appl. Phys. Lett. 95, 062909 (2009). M. Alexe and D. Hesse , Nature Communications 2:256, DOI: 10.1038/ncomms1261.
3 4
Session: 3. Nanodomains and nanocrystals (Chairs: J. M. Gregg and A. Gruverman) Invited talk Presenter email: malexe@mpi-halle.de
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FUNCTIONAL CARBON NANOTUBE ARRAYS FOR 3D FERROELECTRICS
S. G. Shivareddy1, A. Kumar2, Y. Choi, G. Lee2,4,S. Hong2,4, R. S. Katiyar2, J. F. Scott2,3 and G. A.J. Amaratunga1.
1
Electrical Engineering Div, Department of Engineering, University of Cambridge, Cambridge, CB3 0FA, U.K 1 Department of Physics and Institute for Functional Nanomaterials, University of Puerto Rico, San Juan, PR 2 Department of Physics, Cavendish Laboratory, University of Cambridge, Cambridge CB3 OHE, U.K 3 Argonne National Laboratory, Material Science Division, Argonne, IL 60439
Abstract: Ferroelectric films have been deposited on vertically aligned multi-walled carbon nanotube
(MWNT) arrays by pulsed laser deposition. By this technique, we have deposited materials like BaTiO3, BaxSr1-xTiO3, PZT. The as deposited films on MWNTs are conformal with high aspect ratios, nano crystalline and retain their respective 2-D material properties. We find that the MWNTs are robust and endure the high temperature range ~ 450-800C that is a prerequisite for high quality film growth. Ferroelectric properties of BaTiO3 coated vertical MWNT will be discussed. These functionalized nanotubes could be used in a range of nanoscale devices from 3D ferroelectric memory elements to piezoelectric energy generators and high energy density storage devices.
Fig.1 (above left) MWNT array coated with BST (scale 1m). (above right) PFM images of a BaTiO3-MWNT. a) 3-D Topography. b) phase information c) amplitude of the Piezoelectric signal. d) P-E hysteresis from the position marked X in c) indicating ferroelectric switching.
Fig. 2. TEM images of BaTiO3 coated CNT. a) Bright field image with selected area for ED. b) Dark field image with [011] oriented grains highlighted. c) SAED of a). d) High resolution image of BaTiO3-MWNT
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ISIF 2011
University of Cambridge, Cambridge, UK July 31-Aug 4, 2011
Invited talk Oxide and Ultrananocrystalline Diamond Films as Platform Materials for a New Generation of Multifunctional Biomedical Devices and Biosensors O. Auciello (Argonne Distinguished Fellow, AAAS and MRS Fellow) Materials Science Division and Center for Nanoscale Materials, Argonne National Laboratory, Argonne, IL 60439, USA
The submitted manuscript has been created by UChicago Argonne, LLC, Operator of Argonne National Laboratory ("Argonne"). Argonne, a U.S. Department of Energy Office of Science Laboratory, is operated under Contract No. DE-AC02-06CH11357. The U.S. Government retains for itself, and others acting on its behalf, a paid-up nonexclusive, irrevocable worldwide license in said article to reproduce, prepare derivative works, distribute copies to thepublic, and perform publicly and display publicly, by or on behalf of the Government.
This work was supported by US Department of Energy, Office of Science, Office of Basic Energy Sciences-Materials Science, under contract DE-AC02-06CH11357 and DARPA under contracts MIPR 06-W238. Use of the Center for Nanoscale Materials was supported by the U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.
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ISIF 2011
Abstract
This talk will focus on discussing recent research performed at Argonne National Laboratory, and in collaboration with researchers from academia and industries, showing that oxide and diamond thin films exhibit multifunctionalities that can be used to develop a new generation of multifunctional biomedical devices, biosensors, and more. The first part of the talk will focus on discussing research on multifunctional oxide thin films for biodevices: 1) R&D to integrate transparent Pb(ZrxTi1-xO3) (PZT)films with glass substrates for development of a bio-nanofluidic device. This type of application requires the integration of dissimilar materials such as biomolecules (proteins, DNA, antibodies) and inorganic materials (electrodes, semiconductors, ferroelectrics) to create next-generation functional devices such as biosensors, micro/nanofluidic devices, and biochips. Among the materials issues to be addressed are control and tailoring of the properties of interfaces (particularly to improve adhesion and to promote compatibility between the inorganic and biological components), the precise positioning or patterning of the functional components, and the development of inexpensive, high-throughput fabrication strategies. The talk will include a discussion of research on surface polarization-mediated control of electrostatic forces as a means to control tethered adsorbate conformational states or alternatively as an approach towards promoting or guiding the self-assembly of appropriately designed biomolecules. We have demonstrated the utility of the phage display technique as a means to identify heptapeptide sequences that preferentially bind to PZT, and characterized the binding strength and specificity of the peptide to the PZT substrate, Fig.1. R&D focused on developing a fully integrated prototype nanofluidic device, using charged biomolecules actuated by polarization fields on the surface of PZT films to control flow for analysis of biofluids via a chemical lab-on-a chip will be discussed(Fig.2). 2) Work will be reviewed also on R&D to develop high-dielectric constant supercapacitors based on biocompatible TiO2/Al2O3 superlattices that exhibit giant dielectric constant (up to ~ 1000) to produce supercapacitors for energy storage embedded in the microchip implantable in the eye to restore sight to people blinded by genetically-induced degeneration of photoreceptors.
The second part of the talk will focus on discussing the fundamental science and application of a novel ultrananocrystalline diamond (UNCD) material developed and patented in thin film form at Argonne National Laboratory, which represents a new paradigm in multifunctional materials. UNCD thin films are grown by microwave plasma chemical vapor deposition or hot filament chemical vapor deposition using novel patented Ar-rich/CH4 or H2/CH4 chemistries. All these processes produce films with 2-5 nm grain sizes (thus the trade name UNCD). The UNCD films exhibit exceptional mechanical, tribological, chemical, electrical, electron emission, and biocompatible properties, which enable a new generation of macro, micro and nanoscale multifunctional devices, namely: 1) Mechanical pump seals coated with UNCD for every mechanical pump in many industries (e.g., petrochemical, chemical, cars); 2) RF MEMS/NEMS resonators and switches for wireless communications and radar systems and for biosensors (this part of the talk will include a brief discussion of research performed to integrate piezoelectric PZT films with the UNCD MEMS cantilevers to develop piezoactuated biosensors), 3) New NEMS logic devices; 4) UNCD nanowires for sensors; 5) Nitrogen and Boron-doped UNCD films for field emission cold cathodes for a new generation of devices (e.g., field emission displays, portable X-ray sources) or a new generation of biocompatible electrodes for nerve stimulation; 6) UNCD coatings for Biomedical devices (e.g., bioinert coating for encapsulation of a microchip implantable in the retina to restore sight to people blinded by retina degeneration, UNCD coating for MEMS drug delivery or eye saline solution drain devices, tribological coating with low friction and negligible wear for prosthesis knees, hips, heart valves). An overview of the multiple applications of the UNCD film technology can be seen in Fig.3.
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ISIF 2011
Figure 1. Selective bio-functionalization of PZT substrate. PZT surface was masked with a patterned e-beam resist. Fluorescence from a dye tagged phage.
Rodamine B (in)
nanochannel
mixture (out)
DI water (in)
Figure 2. (left) Photo of micro/nano fluidic device. (right) Zoom into nanomixer. PZT is the top coating of the ITO/glass substrate.
Figure 3. Application of multifunctional UNCD, oxides, and metals to A new generation of multifunctional device
200
SHEAR STRAIN EFFECT ON THE PHASE TRANSITIONS AND ANOMALOUS DIELECTRIC/PIEZOELECTRIC PROPERTIES FOR BiFeO3 THIN FILMS
C. W. Huang,a Z. H. Chen, Junling Wang, S. Thirumany, and Lang Chenb School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore
The recent strain-induced structural phase transitions and coexistence of different phases in epitaxial BiFeO3 (BFO) thin films have rejuvenated the interest comparing to compositioninduced lead-based ferroelectrics. This coexistence of phases leads to a large piezoelectric coefficients and points to diversified promising applications in actuators, sonar, ultrasonic transducers, and micro-electromechanical systems. Strain-driven phase transitions and related properties were studied for BFO thin films based on modified Landau-Devonshire theory. Due to the higher Curie temperature compared to that of deposition, the effect of shear strain from BFO film itself is considered in our calculation and induces a new Mc phase formation at a compressive normal misfit strain um=-0.04. In contrast with the experimental results quantitatively, the extrinsic contributions to the piezoelectric response is dominate for compressive misfit strains. On the other hand, we proposed another morphotropic phase boundary-like characteristic for the sharply peaks on dielectric and piezoelectric responses near the monoclinic and orthorhombic phase boundary for tensile misfit strain um=0.0272.
______________________________________________ Electronic mail: a) M080100@e.ntu.edu.sg b)langchen@ntu.edu.sg

1
200
Figure 1: The free energies plotted as a function of misfit strain for different phases at room temperature with a shear strain u 6 = 0.01. The inset is the enlarged section of shaded area.
Figure 2: Misfit strain dependent intrinsic dielectric constant 33 /0 and piezoelectric coefficient d33 for single domain BiFeO3 thin films.
201
FERROELECTRIC CYLINDRICAL NANO-SHELLS: MATERIALS, PROPERTIES AND DEVICES

JONATHAN E SPANIER DEPT. OF MATERIALS SCIENCE & ENGINEERING, DREXEL UNIVERSITY, PHILADELPHIA PA, USA
The study of ferroic nanostructures is motivated in part by opportunities for manipulating functional phase stability and properties via nite size, shape, and surface chemical environment[1]. I shall present our recent work investigating the functional properties and their device functionalities in electrically-interfaced co-axial core-shell nanowires (NWs) consisting of a ferroelectric (FE) oxide shell surrounding a core composed of a normal[1] or ferromagnetic metal, or a semiconductor. I shall discuss how polarization P oriented along the nite thickness direction in lms possessing extreme curvature can be locally and controllably switched[2]. P is enhanced by extreme curvature, thereby suppressing the nite-size-driven evolution of the FE phase transition temperature Tc . Measured responses within individual nanoshells possess magnitudes 3x their planar counterparts while exhibiting nite curvature-dependent osets in FE hystereses. Landau-Ginzburg model calculations indicate geometric curvature-driven polarization gradients in ultrathin lms result in signicant increases in Tc [3]. I shall also highlight experimental characterizations of the electroresistive properties in, and gating by these nanoshells. In metal-FE core-shell NWs reversibility in conduction state following dierent stages of a redox anneal cycle provides evidence of an oxygen vacancy concentration-based conduction mechanism[4], during which FE switching is also observed. In semiconductor-FE core-shell NWs, eld-eect modulation of carrier transport is demonstrated[5]. The co-axial NW geometry also permits an unexpectedly large magnetoelectric coupling within individual NWs each consisting of a ferromagnetic metal core and a FE oxide shell. NWs exhibit a magnetic eld-tunable piezoelectric response and FE switching owing to magneto-elastic coupling through the interfacial boundary[6]. These results provide insight into the design of integrated functional devices and magnetoelectric sensors. They are also relevant to magnetoelectric composites, where the potential benet of maximizing interfacial area using nanostructured constituent ferroic components is typically oset by a suppression of functional properties at small scale. [1]. J. E. Spanier, A. Kolpak, I. Grinberg, J. J. Urban, L. Ouyang, W. S. Yun, A. M. Rappe and H. Park, Nano Lett. 6, 735-739 (2006). [2]. S. S. Nonnenmann, E. M. Gallo, M. T. Coster, G. R. Soja, C. L. Johnson, R. S. Joseph, and J. E. Spanier, Appl. Phys. Lett. 95, 232903 (2009). [3]. S. S. Nonnenmann, O. D. Leaer, E. M. Gallo, M. T. Coster and J. E. Spanier, Nano Lett. 10, 542-546 (2010). [4. S. S. Nonnenmann, E. M. Gallo and J. E. Spanier, Appl. Phys. Lett. 97, 102904 (2010). [5]. S. S. Nonnenmann, B. R. Beatty and J. E. Spanier, submitted, (2011). [6]. S. H. Johnson, O. D. Leaer, P. Finkel, G. Chen, S. S. Nonnenmann, K. Bussman, and J. E. Spanier, submitted, (2011). *Work supported by ARO (W911NF-08-1-0067) and ONR (N00014-1-11-0370).
1
202
LaNiO3/LaMnO3 SUPERLATTICES: TRANSPORT AND MAGNETIC PROPERTIES
M. Gibert,1 R. Scherwitzl,1 P. Zubko,1 J. Iiguez2 and J.-M. Triscone1

1
Dpartement de Physique de la Matire Condense, University of Geneva, 24 Quai Ernest-Ansermet, 1211 Geneva 4, Switzerland Institut de Cincia de Materials de Barcleona, ICMAB-CSIC, Campus de la UAB, 08193 Bellaterra, Spain
In transition-metal oxides, the interplay between the spin, charge, orbital and lattice degrees of freedom is responsible for the large variety of electronic properties displayed by these materials. The generation of artificial layered structures enables the enhancement of these properties or even the emergence of completely new physical phenomena. Following our recent research on the transport properties of LaNiO3 thin films,1, 2 we now focus on the generation of LaNiO3/ LaMnO3 (LNO/LMO) superlattices, a system which constitutes a rich platform to investigate the role of artificially induced charge ordering on functional properties. High quality LNO/LMO superlattices are prepared by rf magnetron sputtering on perovskite singlecrystal substrates. For superlattices grown on (001) SrTiO3 substrates, the transport properties are mainly controlled by the thickness-dependent behavior of the LNO layers. Accordingly, a metal to insulator transition is observed as the LNO thickness is reduced. However, for thin enough LMO layers, charge delocalization seems to occur enabling further tuning of the metal-insulator transition temperature. The magnetic behavior of these superlattices is instead dominated by the LMO constituent, all the investigated superlattices being ferromagnetic with Curie temperatures of ~200 K. The electric and transport properties of LNO/LMO superlattices grown on other substrates are also explored, giving special attention to superlattices synthesized on (111) STO substrates.
1 2
R. Scherwitzl, P. Zubko, C. Lichtensteiger and J. M. Triscone, APL 95, 222114 (2009). R. Scherwitzl, S. Gariglio, M. Gabay, P. Zubko, M. Gibert and J. M. Triscone, arXiv:1101.5111v1 (2011).
203
BiFeO3 HETEROSTRUCTURES FOR ELECTO-OPTIC MODULATORS D. Sando1, J. Allibe1, E. Jacquet1, S. Fusil1, K.Bouzehouane1, C. Carrtro1, C. Deranlot1, J. Bourderionnet2, D.-G. Crt1, J.-C. Mage1, A. Barthlmy1 and M. Bibes1
1
Unit Mixte de Physique CNRS/Thales, Campus de Polytechnique, 91767 Palaiseau, France 2 Thales Research & Technology, Campus de Polytechnique, 91767 Palaiseau, France
Bismuth ferrite (BFO), in addition to its considerable promise in spintronics, exhibits potentially valuable optical properties [1]. Its visible range bandgap, large birefringence, low absorption in the technologically-relevant infrared range, large value of spontaneous polarization, and high Curie temperature, make it a prime candidate as the active medium in thin-film heterostructure integrated electro-optic modulators (EOMs). The bandwidth of traveling-wave EOMs is primarily limited by the phase velocity mismatch between the lightwave and microwave, thus for high performance devices it is desired to bring the microwave index as close as possible to the optical index. A promising approach to achieve this is to use a ferroelectric film grown on a substrate with a low dielectric constant [2]. Various optical properties of BFO have been described by a number of authors, however in particular the electro-optic (EO) coefficients of this material are not well known. The knowledge of these properties is an important step for the potential integration of BFO into high-bandwidth, compact EOM devices. There are two commonly-used geometries for determining the EO coefficients of thin films. One method relies on injecting a light beam into a waveguide structure (Fig. 1) in which the ferroelectric film forms the core of the waveguide and planar electrodes enable the application of an electric field. The EO coefficients of the medium are determined by observing the effect of the applied electric field on the polarization state of the output optical field. The reflection method [3], on the other hand, involves using an optical field reflected from a thin film structure while an electric field is applied between a transparent top electrode and a reflective bottom electrode. This approach is similar in principle to conventional ellipsometry, whereby the change in polarization of the optical field induced by the electric field is related to the EO coefficients. The reflection method offers the advantage of not requiring the construction of a waveguide structure. In this work we will present the results of our efforts in determining the EO coefficients of BFO using both approaches. We will describe the fabrication of smooth epitaxial BFO films suitable for either waveguide structures [4] or reflection measurement geometries, the preliminary findings of our determination of the EO coefficients, and in a more general sense, the potential of these thin film heterostructures in electro-optical modulation applications.
[1] G. Catalan and J.F. Scott, Adv. Mater. 21, 1 (2009); [2] B.W. Wessels, Annu. Rev. Mater. Res. 37, 659 (2007); [3] C.C. Teng and H.T. Man, Appl. Phys. Lett. 56, 1734 (1990) ; [4] J. Allibe et al., Appl. Phys. Lett. 96, 182902 (2010).
Fig. 1 Sketch and photograph of an optical waveguide constructed of a low-epsilon BFO-based heterostructure.
204
ARTIFICIALLY LAYERED SUPERLATTICES BASED ON PBTIO3 M. Dawber1, S. Callori,1 J. Sinsheimer,1 B. Ziegler,1 Y. Benkara1, J. Daley1, D. Su2, T. Yusufaly3, V.R. Cooper4, K.M. Rabe3, P. Chandra3
1 2
Dept. of Physics and Astronomy, Stony Brook University, Stony Brook 11794-3800 USA Center for Functional Nanomaterials, Brookhaven National Laborator, USA 3 Department of Physics, Rutgers University, Piscataway, NJ, USA 4 Oak Ridge National Laboratory, Oak Ridge, TN, USA Email: Matthew.Dawber@stonybrook.edu, Website: http://mini.physics.sunysb.edu/~mdawber/
In this talk we will present a detailed exploration of three artificially layered superlattice systems that contain PbTiO3. We have fabricated high quality examples of PbTiO3/CaTiO3, PbTiO3/BaTiO3 and PbTiO3/SrRuO3 superlattices using an off-axis RF magnetron sputtering technique, allowing us to perform a range of experiments, including x-diffraction, electrical measurements and atomic force microscopy, which probe the nature of these systems. These three systems represent quite different boundary conditions for the PbTiO3 layers; our artificial materials are built up from either repeated ferroelectric/dielectric (PbTiO3/CaTiO3), ferroelectric/ferroelectric (PbTiO3/BaTiO3) or ferroelectric/metal (PbTiO3/SrRuO3), interfaces and the resulting properties of the fabricated materials depend strongly upon both the type of interface and the thickness of the layers that make up the structure. The unifying concept of our work is that competition between the tendencies of the parent materials in our structures, combined with interfacial interactions, can lead to enhanced properties in our artificial materials. It has been shown that in artificially layered PbTiO3/SrTiO3 superlattices, a form of improper ferroelectricity occurs where the rotations of the oxygen octahedra at the interfaces couple with the polar mode and increase the ferroelectric polarization of the material when the layers are very thin. PbTiO3/CaTiO3 superlattices grown on SrTiO3 substrates are also highly likely to display this kind of behavior, as the CaTiO3 ground state is dominated by rotational distortions. This system should also play host to a competition between in-plane ferroelectricity (as CaTiO3 is subjected to a large tensile strain when grown on SrTiO3) and out-of-plane ferroelectricity (the usual result when in PbTiO3 is grown on SrTiO3). We will highlight an experimentally measured compositional phase transition region in this system. PbTiO3/BaTiO3, on the other hand, is a system in which we do not expect to see improper ferroelectricity, but are instead motivated by theoretical predictions that the piezoelectric properties can be enhanced in this system. Our experimental results confirm the prediction from first principles calculations, and we apply a Landau theory model as a useful bridge between the first principles predictions and experimental results at elevated temperature Finally, the PbTiO3/SrRuO3 superlattice system allows us to study how the polarization of PbTiO3 and metallic states of SrRuO3 overlap at the PbTiO3/SrRuO3 interface and the impact this has on the overall properties of the superlattices as the thickness of the layers is varied. Our work on this systems serves as a demonstration that a new set of materials, metallic oxides, can be considered for inclusion as novel dielectric layers in ferroelectric superlattices.
205
NAND FLASH MEMORY BY FERROELECTRIC-GATE FIELD-EFFECT-TRANSISTOR INTEGRATION Mitsue Takahashi, Xizhen Zhang, Le Van Hai, Kang Yan, Wei Zhang, Kousuke Miyaji*, Ken Takeuchi* and Shigeki Sakai National Institute of Advanced Industrial Science and Technology, Tsukuba, Ibaraki 305-8568, Japan * Univ. of Tokyo, Dept. of Electrical Engineering and Information Systems, Tokyo 113-8656, Japan Ferroelectric-gate field-effect transistors (FeFETs) are nonvolatile memory transistors which have appropriate characteristics of high endurance, low operation voltage, and good scalability. Long retention of the FeFETs has been accomplished in 2002, by using a Pt/SrBi2Ta2O9(SBT)/Hf-Al-O(HAO) gate stack [1]. After the breakthrough, we have presented potentially high performance of ferroelectric-NAND (Fe-NAND) flash memory made of the FeFET memory cells [2]. The Fe-NAND flash memory Table 1. Comparison between Fe-NAND and FG-NAND can be operated with low program voltages around 6V Fe-NAND FG-NAND and high program/erase (P/E) endurance of 108 cycles Memory unit 1 transistor 1 transistor while the conventional floating-gate type (FG-) NAND Memory cell area 4F2 4F2 flash memory needs 20V for program and 105 cycle Program voltage 6V 20 V endurance as shown in Table 1. The most suitable P/E endurance cycles >108 105 application for the Fe-NAND with such a high endurance Data retention 10 years 10 years will be high-end enterprise solid-state drives [3]. F: feature size
(a)
WL selector
1 block
64kb array
WL0~7
64kb array
WL selector
BLi BLi+1 (b) SGD 256 NAND strings
after block-erase 0 by 7.0V after all 1 program by 7.5V
32 blocks
BL selector
BL selector SGS FeFET SL A block includes 8cells/string256BLs. Each WL controls 256FeFETs, or 1 page.
Fig. 1 Photos of (a) whole chip and (b) a part of memory-cell array including WL and BL selectors of 64kb Fe-NAND.
Fig 2. Vth distribution of one block (2 kb cells) in 64kb Fe-NAND.
In this paper, 64kb Fe-NAND flash memory array was fabricated and investigated. The 64kb Fe-NAND consisted of 4F2-scale memory-cell array, word line (WL) and bit line (BL) select-circuits (Figs.1(a,b)). All transistors were FeFETs, including the select-logic-circuits. 64 kb cells could be successfully accessed. Threshold voltage (Vth) distributions of 2kb cells in 1 block were obtained as shown in Fig. 2 by read after block-erase 0 and by read after all 1 program. Measured 2kb-cell data retentions did not show degradations. Our recent progress in downsizing the FeFETs will be also introduced. Well-controlled etching for a sharp stacked-gate profile was a key process to downsizing the FeFETs with keeping good electrical 10 properties. Steep SBT sidewall angles are necessary for good isolation L=10m [1]2002/10 between neighbor cells in 4F2 memory cell array of the Fe-NAND. We optimized the etching processes and achieved large SBT-sidewall angle L=0.9m of 85o. SiO2 hard mask was used for the etching of the stacked gates by L=2m (2005) (Unpublished) an inductively coupled plasma reactive ion etching system. As a result, 1.0 L=0.54m 0.26 m-gate FeFETs were successfully fabricated. Static memory L=0.56m (2010) 0.5 windows of the 0.26 m-gate FeFETs were more than 0.9 V when gate L=0.26m voltage was scanned between 15 V. We demonstrated good endurance 0.2 9 performances of the 0.26m-gate FeFETs up to 10 cycles by applying 0.1 continuous P/E pulses with 5 V amplitude and 20 s period. The 2002 2004 2006 2009 2011 2013 Year FeFETs also showed good retention properties which indicated 10 year Fig. 3 Downsizing history of FeFETs. retention times by extrapolated lines on the measured curves. Ongoing downscaling of the FeFETs was summarized in Fig. 3. This work was partially supported by NEDO and by AIST grants for the focused researches. [1] AIST press release, Oct 24, 2002. S. Sakai et al., IEEE Electron Dev. Lett., 25, pp.369-371, 2004. [2] S. Sakai et al., IEEE NVSMW &ICMTD Proc., pp.103-105, 2008. [3]T. Hatanaka, et al., IEEE Symp. VLSI Circuits Dig. of Tech. Papers, pp. 78-79, 2009.
Gate Length L (m)
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COMPARISON OF THE INTERFACIAL AND ELECTRICAL PROPERTIES OF HfAlO FILMS ON Ge WITH S AND GeO2 PASSIVATION
X. F. Li, X. J. Liu, W. Q. Zhang, Y. Y. Fu, A. D. Li,a) H. Li, and D. Wu

National Laboratory of Solid State Microstructures, Department of Materials Science and Engineering, Nanjing University, Nanjing 210093, Peoples Republic of China
We report the characteristics of HfAlO films deposited on S- and GeO2-passivated Ge substrates at 150 C by atomic layer deposition technique using Hf(NO3)4 and Al(CH3)3 as the precursors. The x-ray photoelectron spectroscopic analyses reveal that GeO2 passivation is more effective to suppress GeOx formation than S passivation. It is demonstrated that the capacitors with GeO2 passivation exhibit better electrical properties with less hysteresis, improved interface quality, and reduced leakage current. These results indicate that using GeO2 as an interfacial layer may be a promising approach for the realization of high quality Ge-based transistor devices.
Fig. 1. The TEM images of the annealed HfAlO films with (a) with S passivation, (b) GeO2 passivation. Presenting author: Ai-Dong Li, E-mail: adli@nju.edu.cn, topic 6: High-K dielectrics and polymers; oral presentation
a)
Author to whom correspondence should be addressed. Electronic mail: adli@nju.edu.cn.
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SPIN-VALVE-LIKE MAGNETORESISTANCE OF AN ANTIFERROMAGNET-BASED TUNNEL JUNCTION B.G. Park1, J. Wunderlich1,2, X. Marti2,3, V. Holy3, Y. Kurosaki4, M. Yamada4, H. Yamamoto4, A. Nishide4, J. Hayakawa4, H. Takahashi1,4, A.B. Shick5, and T. Jungwirth2,6 1. Hitachi Cambridge Laboratory, United Kingdom 2. Institute of Physics ASCR - Cukrovarnicka, Czech Republic 3. Charles University in Prague, Czech Republic 4. Hitachi Ltd., Advanced Research Laboratory, Japan 5. Institute of Physics ASCR - Na Slovance, Czech Republic 6. University of Nottingham, United Kingdom A novel strand towards miniaturization of spintronic devices comprises the use of only antiferromagnets (AF) as active elements and the electric field as the controlling tool [1]. Spin-valve structures used in modern hard drive read-heads and magnetic random access memories comprise two ferromagnetic (FM) electrodes whose relative magnetization orientations can be switched between parallel and antiparallel configurations, yielding the desired giant or tunneling magnetoresistance effect. Here we will show the proof of concept operation of a device with only an antiferromagnet (AFM) on one side and a non-magnetic metal on the other side of the tunnel barrier displaying > 100% spin-valve-like signal (Fig. 1) [2].
FIG. 1: 130% magnetoresistance signal recorded on a tunnelling device fabricated in the depicted multilayer structure with the NiFe/IrMn(1.5 nm)/MgO/Pt tunnel junction. The insets illustrate the rotation of AFM staggered moments in IrMn through the exchange-spring effect of the adjacent NiFe ferromagnet.
The electric control of the devices and the total suppression of any FM elements would allow further miniaturization. Inspired by the results on electrical gating in ferromagnetic semiconductors (below room temperature), we have investigated the new I-II-V semiconductors family with room temperature antiferromagnetic ordering [3,4]. The progress will be presented.
[1] A. B. Shick, S. Khmelevskyi, O. N. Mryasov, et al., Phys. Rev. B 81 212409 (2010) [2] B.G. Park, J. Wunderlich, X. Marti et al., Nature Materials, advanced online publication (http://www.nature.com/nmat/journal/vaop/ncurrent/full/nmat2983.html) [3] T. Jungwirth, V. Novk, X. Mart, et al. Phys. Rev. B 83, 035321 (2011) [4] F. Maca, J. Masek, O. Stelmakhovych, et al., Phys Rev. B, submitted, available online at (http://arxiv.org/PS_cache/arxiv/pdf/1102/1102.5373v1.pdf)
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SKIN LAYER OF BiFeO3 SINGLE CRYSTALS Xavi Mart1, Pilar Ferrer2,3, Julia Herrero-Albillos4, Jackeline Narvaez5, Vaclav Holy1, Nick Barrett6, Marin Alexe7, Gustau Catalan5,8
University in Prague, Faculty of Mathematics and Physics, Czech Republic 2 SpLine (BM25), ESRF, Grenoble, France . 3 Instituto de Ciencia de Materiales de Madrid ICMM-CSIC, Madrid, Spain. 4 Helmholtz-Zentrum Berlin fr Materialien und Energie GmbH, 12489 Berlin, Germany Centre dInvestigacions en Nanociencia i Nanotecnologia (CIN2), CSIC-ICN, 08193 Barcelona, Spain 6 CEA , IRAMIS, SPCSI, LENSIS, F-91191 Gif-sur-Yvette, France. 7 Max Planck Institute of Microstructure Physics, 06120 Halle, Germany 8 Institut Catala de Recerca i Estudis Avanats (ICREA), Catalunya, Spain
1 Charles
BiFeO3, has become the cornerstone of magnetoelectric multiferroic research, thanks to its high ferroelectric and magnetic ordering temperatures, large ferroelectric polarization, and coupling between polar direction and magnetic easy plane, all of which are potentially useful for devices [1-3]. An unaddressed issue concerns the existence or otherwise of a surface layer (a skin) in BiFeO3 analogous to the known ones in SrTiO3, BaTiO3, or relaxor Pb(Mg1/3Nb2/3)O3. Here we report on a surface layer (skin) that is functionally and structurally different from the bulk found in single crystals of BiFeO3[4]. Impedance analysis indicates that a previously reported anomaly at T*= 2755C corresponds to a phase transition confined at the surface of BiFeO3. X-ray photoelectron spectroscopy and X-ray diffraction as a function of both incidence angle and photon wavelength unambiguously confirm the existence of a skin with an estimated skin depth of few nanometres, elongated out-ofplane lattice parameter, and lower electron density. Temperature-dependent x-ray diffraction has revealed that the skins out of plane lattice parameter changes abruptly at T*, while the bulk preserves an unfeatured linear thermal expansion (Fig. 1). Special emphasis will be placed on the description of the unconventional X-ray methodology employed which circumvents the virtually unavoidable refraction effects and could be extended to other materials both in thin film and bulk samples.
FIG. 1: Comparison between the thermal expansion at the skin (open symbols) and inside the crystal (solid symbols) evidencing the local phase transition at T* in the surface of BiFeO3.
References [1] W. Eerenstein, N. D. Mathur, and J.F. Scott, Nature 442, 759 (2006). [2] H. Bea, M. Gajek, M. Bibes, et al., J. of Phys.: Condensed Matter 20, 434221 (2008). [3] G. Catalan and J.F. Scott, Advanced Materials 21, 2463 (2009). [4] X. Marti, P. Ferrer, J. Herrero-Albillos, et al., submitted to Phys. Rev. Lett.,
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Comparison of ZnO films deposited via PLD, PE-CVD, sputtering,and misted CVD M. Echizen(1,2), A. Flewitt,(3) W. Milne,(3) T. Tatsuta (2), T.Tusji (2), and J. F.Scott (1) 1 Dept Physics, Cavendish Lab, Cambridge Univ 2 Samco Corp, Kyoto, Japan 3 Engineering Dept.,CAPE, Cambridge Univ
We present a comparison of zinc oxide films prepared via four different deposition techniques.
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GaV4S8: a material in the race towards RRAM memories.

M.-P. Besland*, J. Tranchant, E. Souchier, V. Guiot, B. Corraze, P. Moreau, E. Janod, L. Cario Institut des Matriaux Jean Rouxel (IMN), Universit de Nantes, UMR CNRS 6502, 2 rue de la Houssinire, BP 32229, 44322 Nantes Cedex 3, France * contact: marie-paule.besland@cnrs-imn.fr Information storage stands as a strategic issue in the field of microelectronics. To date, the flash memory is the most frequently memory used in mobile electronic devices (mobile and smart phones, Flash cards, personal computers) [1]. One promising class of emerging memories stands in resistive RAM (RRAM), which is based on functional material exhibiting two stable resistive states, i.e. a high resistance state (HRS) and a low resistance state (LRS), and a reversible non-volatile resistive switching (RS) under electric pulses. In recent works, we have discovered a new type of reversible and non-volatile resistive switching on single crystals of the Mott Insulator compounds AM4X8 (A = Ga, Ge; M = V, Nb, Ta; X = S, Se) [2-3]. More recently, we reported on the successful deposition of GaV4S8 thin layers in the 300-500 nm thickness range [4]. The novelty of our work stands in the mechanism of the resistive switching which differs from those reported in the literature [5]. Indeed, our recent investigations on the AM4X8 compounds evidenced a switching mechanism driven by the electric field which induces an electronic phase change from the Mott insulating state to a metallic-like state. [6]. We report here on further investigations of the reversible and non-volatile resistive switching achieved in GaV4S8 thin layers. Thin layers of GaV4S8 were deposited by RF magnetron sputtering in pure argon using a home-synthesized GaV4S8 target obtained by Spark Plasma Sintering (SPS) technique [7] starting from a polycrystalline GaV4S8 powder. As reported in previous works [8], transfer to a thin layer of a complex ternary material is favoured by soft deposition conditions. Thin layers of GaV4S8 were thus deposited at low deposition pressure and RF power, respectively 40 mTorr and 60 W (i.e. 3 W.cm-2). A one hour ex-situ annealing at 600C in a sulfur-rich atmosphere restore the targeted stoichiometric composition GaV4S8 and the expected crystalline structure, as revealed by the XRD pattern. Scanning Electron Microscope observations (SEM) and HRTEM analyses of the annealed thin layer show a granular morphology with average crystallites size in the 10 to 30 nm range. Besides, EDS chemical analyses at the nanoscale and nano-diffraction pattern (spot size of 300 nm2) of the bulk are consistent with a GaV4S8 phase without any secondary phase. The electrical properties of GaV4S8 thin layers were investigated within MIM structures Au/GaV4S8/Au/Si. Typically, a series of 2.5 V / 10 s pulses applied to the device at 300K induces a resistive switching between the high and low resistance states, with a R/R values close to 33%. Moreover, the resistive switching observed in our thin layers allows reaching fast writing and erasing times in the range of 50 ns at low temperature and 10 s at room temperature, i.e. characteristics comparable with those achieved in Flash technology, i.e. writing time of 1 s and even much better than the typical erasing times of 10 ms. As last important issue, the required voltage for writing/erasing is reported at 12 V for Flash memories [1] but should be as low as possible. The typical voltage range are in the 30-50 V range and 2-3 V range, for 10-30 m thick single crystals and for 300-400 nm thick thin films respectively. Such voltage range would correspond to values below 1 V for 100 nm thick thin films, which is a typical thickness targeted in future devices. Recent studies on electrical stability versus time allows, while controlling pulses duration and period, achieving at room temperature up to 5000 cycles with a controlled ratio R/R. Our studies therefore demonstrated that the narrow gap Mott Insulator AM4X8 compounds could be good candidates for a new type of non-volatile RRAM memory based on a new mechanism of resistive switching, i.e. an electric-field-driven metal insulator transition. References [1] International Technology Roadmap for Semiconductors, Emerging Research Devices (2007), Update 2010, http://www.itrs.net/ [2] L. Cario, B. Corraze, E. Janod, C. Vaju, M.P. Besland, PCT Int. Appl.PCT/EP2008/052968 (2008). [3] C. Vaju et al., Adv; Mat., 20, 2760 (2008); Microelectronics Engineering 85 (12), 2430 (2008). [4] E. Souchier et al., Physica status solidi-Rapid Research Letters (PSS-RRL) 5, 53 (2011). [5] R. Waser, R. Dittman, G. Staikov, K. Szot, Adv. Mat., 21, 2632 (2009) [6] L. Cario et al., Advanced Materials 22 (45), 5193 (2010). [7] C. Elissalde, M. Maglione, C. Estournes, J. Am. Ceram. Soc. 90, 973 (2007). [8] M.P. Besland et al, Thin Solid Films 495, 86 (2006); J. Int. Ferroelectrics 94, 94-104 (2007).
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APPLICATIONS OF FERROELECTRIC POLYMER THIN FILMS AND NANOSTRUCTURES
Stephen Ducharme Department of Physics and Astronomy Nebraska Center for Materials and Nanoscience University of Nebraska, Lincoln, NE 68588-0299 Ferroelectric polymers based on polyvinylidene fluoride offer unique opportunities for making a variety of electronic devices. The ferroelectrics polymer can maintain a large surface charge at an interface, approximately one tenth of a Coulomb per square, and can be readily switched between opposite polarization states. This level of stable interface charge is not realizable with an ordinary dielectric material because of limited dielectric strength or because of leakage. Furthermore, the ferroelectric polymers can be made on nearly any substrate in the form of thin films as thin as one nanometer and nanostructures a few tens of nanometers in size. By virtue of their chemical inertness, they are compatible with so many other materials important to electronic technology, from metals and inorganic semiconductors, to organic semiconductors, and even exotic materials like graphene and carbon nanotubes. I will review some of the recent developments in the application of ferroelectric polymers to a variety of functional devices. In heterostructures they make field-effect transistors into bistable logic elements, increase the efficiency of organic photovoltaic devices, and form two-way magnetoelectric transducers. In nanocomposites they make electrostrictive transducers, electrocaloric materials, and dielectric materials for high-energy-density capacitors. This research was supported by the National Science Foundation, the Department of Energy, The Office of Naval Research, and the Nebraska Research Initiative.
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THE BULK PHOTOVOLTAIC EFFECT: COMPUTATIONAL MATERIALS DESIGN FOR ENERGY APPLICATIONS
Steve M. Young, Tingting Qi, Joseph W. Bennett, Gaoyang Gou, Hiroyuki Takenaka and Andrew M. Rappe
The Makineni Theoretical Laboratories, Department of Chemistry University of Pennsylvania, Philadelphia, PA 19104-6323 USA
A small group of materials exhibit a photovoltaic eect in a single phase without need of an interface. This bulk photovoltaic eect (BPVE) has been reported in ferroelectric perovskite oxides, and oers a promising route to earth-abundant solar energy conversion devices. By calculating the BPVE using ab initio methods, we are able to determine the eect of material properties on photovoltaic response. Finding materials that exhibit highly ecient BPVE will require strong light absorption by high-response transitions, as well as reduced band gaps within the visible energy range. In this regard, two groups of polar semiconducting perovskite oxides, including Pb(Ti1x Nix )O3x solid solutions and highly tetragonal Bi(Zn1/2 Ti1/2 )O3 oxides are proposed. Using post-DFT methods, we investigate their electronic structure, especially the impact of B-site cation ordering on the energy band gaps. Based on our ndings, we illustrate that these ferroelectric oxides are suitable for photovoltaic applications, due to their good match with the solar spectrum.
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PHOTOVOLTAIC AND ELECTROCHROMIC PROPERTIES OF BiFeO3 Jan Seidel

Lawrence Berkeley National Laboratory, Berkeley, USA e-mail: jseidel@berkeley.edu
Understanding and eventually manipulating electronic states in complex oxides is a major goal of contemporary condensed matter physics. Considerable attention is focused on spincharge-lattice interactions, which provide a platform for control of various degrees of freedom, e.g. by applied currents, strain or electric/magnetic fields. Despite this attention, many aspects of these interactions are not fully understood, particularly at interfaces and topological boundaries, such as domain walls, where the same electronic properties are linked to the inherent order parameters of the material, its structure and symmetry. I will discuss a mechanism for photovoltaic charge separation, which operates over a distance of 12 nm and produces voltages that are significantly higher than the bandgap in photovoltaic devices [1]. The separation happens at previously unobserved nanoscale steps of the electrostatic potential that naturally occur at such domain walls. Electric-field control over domain structure allows the photovoltaic effect to be reversed in polarity or turned off. This new degree of control, and the high voltages produced, may find application in optoelectronic devices. In addition, I will show that calcium-doped bismuth ferrite Bi0.9Ca0.1FeO3- thin films exhibit an electrochromic effect arising from an intrinsic mechanism due to redistribution of carriers, without the need for additional electrolytes that are needed in common electrochromic devices. The absorption change and coloration efficiency at the band edge are 4.8106 m-1 and 190 cm2/C, respectively, which are among the highest reported values for inorganic electrochromes. These experimental findings are supported by optical absorption calculations from first-principles theory, confirming the strong absorption change at the band edge. Finally, I will present an outlook on how new functionality in other complex oxides can be found and I will discuss some of our recent efforts in that direction.
[1] S.-Y. Yang et al., Above-bandgap voltages from ferroelectric photovoltaic devices, Nature Nanotechnology 5, 143 (2010)
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SESSION 12: SUPERLATTICES FIRST-PRINCIPLES SIMULATIONS ON PbTiO3 /SrTiO3 SUPERLATTICES Pablo Aguado-Puente, Pablo Garc a-Fernndez, and Javier Junquera a Departamento de Ciencias de la Tierra y F sica de la Materia Condensada, Universidad de Cantabria, Avda. de los Castros s/n, 39005 Santander, Spain Ferroelectric perovskites are materials of great fundamental and applied interest. This family of materials displays a great range of functionalities, from ferroelectricity to superconductivity. More interestingly, perovskites show a very rich phase diagram allowing for a great tunability playing with doping, epitaxial strain, and the combination of dierent materials in heterostructures. This has led to the discovery of completely new interface-based phenomena in the last years, for instance a fundamentally new type of ferroelectricity has been discovered in PbTiO3 /SrTiO3 superlattices, due to the unexpected coupling of ferroelectric and antiferrodistortive structural distortions in these heterostructures [1]. First in this talk, we will present rst-principles calculations, within the density functional theory, on the coupling between epitaxial strain, polarization, P, and oxygen octahedra rotations in monodomain (PbTiO3 )n /(SrTiO3 )n superlattices. We have studied dierent periodicities, n ranged from 1 to 3, with an improper ferroelectric behaviour. P is found to be extremely sensitive to strain, and rotates continuosly from a c-phase (P oriented along the [001] direction) for compressive strains, to an aa-phase (P along [110]) under tensile strain. The out-of-plane component of P, Pz , is always preserved at the interface to minimize the electrostatic energy, and decreases in the PbTiO3 layer with respect the bulk value, reecting the energy cost of polarizing SrTiO3 . At the origin of these new phases with an in-plane component of P, we have found the preference of the polarization in PbTiO3 to rotate, over an homogeneous decrease of Pz . Around the lattice constant imposed by a SrTiO3 substrate, the system displays a large piezoelectric reponse. Changes in polarization are strongly coupled with the response of the oxygen octahedra, whose rotations and tiltings cannot be explained by the usual steric arguments alone. Instead a covalent model on the polarization-tilting coupling is developed. Second, following the suggestion of a recent experimental work [2], who suggested that that the ground state of this system might be actually polydomain for most periodicities, we will also report on simulations on PbTiO3 /SrTiO3 superlattices including the presence of domains to complement the last experimental results and to better understand the properties of domain structures in these superlattices. This work was supported by the Spanish Ministery of Science and Innovation through the MICINN Grant FIS2009-12721-C04-02; by the Spanish Ministry of Education through the FPU fellowship AP2006-02958; and by the European Union through the project EC-FP7, Grant No. NMP3-SL-2009-228989 OxIDes. The authors thankfully acknowledge the computer resources, technical expertise and assistance provided by the Red Espaola de Supercomputacin. Calculan o tions were also performed at the ATC group of the University of Cantabria.
References
[1] E. Bousquet et al. Nature 452, 732 (2008). [2] P. Zubko et al. Phys. Rev. Lett. 104, 187601 (2010).
javier.junquera@unican.es
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COLLOIDAL INORGANIC NANOCRYSTALS AS FLEXIBLE PLATFORMS FOR IMAGING AND SENSING
Abstract Great progress has been made in the last two decades in designing and controlling the size, shape as well as the physical and chemical properties of a variety of colloidal nanostructures. Inorganic nanocrystals such as luminescent quantum dots (QDs), metallic and magnetic nanoparticles exhibit unique optical and physical properties that are not shared by their bulk parent materials. These materials present large surface-to volume ratios and can provide flexible platforms for arraying various functional molecules ranging from proteins and peptides to redox active small molecules. The emission of colloidal QDs, for example, can be highly sensitive to potential interactions with proximal dyes and metal complexes. We have developed approaches based on covalent coupling and non-covalent self-assembly to conjugate various biomolecules to CdSe-ZnS core-shell QDs and Au nanoparticles (AuNPs). These nanocrystals were rendered water-soluble using polyethylene glycol (PEG)-based modular multidentate and multifunctional ligands. In this presentation, we will start with a description of the latest development in ligand design, characterization and capping strategies as applied to luminescent QDs, AuNPs, and magnetic nanoparticles. We then provide a few specific examples of hybrid bioconjugates, and the use of those conjugates in sensor design based, for example, on fluorescence resonance energy transfer or charge transfer interactions. We will also describe a few examples where these conjugates were applied probe specific biological processes in live cells.
Goutam Palui, Hyon Bin Na, Xin Ji, and Hedi Mattoussi Florida State University Department of Chemistry and Biochemistry Tallahassee, FL 32306 Email: mattoussi@chem.fsu.edu
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COUPLING MAGNETISM TO ELECTRICITY IN MULTIFERROIC HETEROSTRUCTURES R. Ramesh Department of Materials Science and Engineering and Department of Physics University of California, Berkeley, CA 94720. Complex perovskite oxides exhibit a rich spectrum of functional responses, including magnetism, ferroelectricity, highly correlated electron behavior, superconductivity, etc. The basic materials physics of such materials provide the ideal playground for interdisciplinary scientific exploration. Over the past decade we have been exploring the science of such materials (for example, colossal magnetoresistance, ferroelectricity, etc) in thin film form by creating epitaxial heterostructures and nanostructures. Among the large number of materials systems, there exists a small set of materials which exhibit multiple order parameters; these are known as multiferroics. Using our work in the field of ferroelectric(FE) and ferromagnetic oxides as the background, we are now exploring such materials, as epitaxial thin films as well as nanostructures. Specifically, we are studying the role of thin film growth, heteroepitaxy and processing on the basic properties as well as magnitude of the coupling between the order parameters. In our work we are exploring the switchability of the antiferromagnetic order using this coupling. What is the importance of this work ? Antiferromagnets(AFM) are pervasive in the recording industry. They are used as exchange biasing layers in MTJs etc. However, to date there has been no antiferomagnet that is electrically tunable. We believe that the multiferroic BiFeO3 is one compound where this can be observed at room temperature. The next step is to explore the coupling of a ferromagnet to this antiferromagnet through the exchange biasing concept. Ultimately, this will give us the opportunity to switch the magnetic state in a ferromagnet( and therefore the spin polarization direction) by simply applying an electric field to the underlying antiferromagnetic ferroelectric. In this talk, I will describe our progress to date on this exciting possibility.
232
REDOX-BASED MEMRISTIVE SWITCHING - SCALING BEYOND FLASH?

Rainer Waser PGI-7, Forschungszentrum Jlich, 52425 Jlich, and IWE2, RWTH Aachen University, 52056 Aachen, Section Fundamentals of Future Information Technology (JARA-FIT), Germany
After following Moores law for more than four decades, the exponential performance increase of silicon based CMOS technology will run into inherent technological and physical limits by 2020. In particular, the Flash memory, widely spread used in MP3 players, cameras, and smart phones, suffers from limits in voltage scaling and endurance. A potential leap beyond these limits may emerge from redox-based switching effects encountered in oxides and higher chalcogenides. A range of systems exist in which ionic transport and redox reactions on the nanoscale provide the essential mechanisms for memristive switching. One class relies on mobile cations which are easily created by electrochemical oxidation of the corresponding electrode metal, transported in the insulating layer, and reduced at the inert counterelectrode. Another important class operates through the migration of ions constituting the oxides, typically oxygen ions, towards the anode, and the reduction of the cation sublattice in the layer locally providing metallically or semiconducting phases. The electrochemical nature of these memristive effects triggers a bipolar memory operation. In yet another class, the thermochemical effects dominate over the electrochemical effects in transition metal oxides which leads to a unipolar switching as known from the phase-change memory. In all systems, the defect structure turned out to be crucial for the switching process. The memristive characteristics of the memory cells provide opportunities for circuit design and computational concepts which go beyond those in the traditional CMOS technology. Passive memory arrays open up the paths towards ultradense and 3-D stackable memory and logic gate arrays in future energy efficient high-performance computer architectures. These passive arrays are made possible by the concept of complementary resistive switches. Despite exciting results obtained in recent years, huge challenges have to be met before these physical effects can be turned into industrial technology. This presentation will outline the fundamental principles, the prospects and challenges, as well as the open questions.
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MAGNETOELECTRIC COUPLING IN EXCHANGE-BIASED MULTIFERROIC HETEROSTRUCTURES
Josep Fontcuberta1, Vassil Skumryev2, Vladimir Laukhin1, 2, Ignasi Fina1, Xavier Mart1, Florencio Snchez1, Marin Gospodinov3
1
Institut de Cincia de Materials de Barcelona ICMAB-CSIC, Campus UAB, Bellaterra, Catalonia (Spain) 2 Instituci Catalana de Recerca i Estudis Avanats (ICREA), Catalonia (Spain) 3 Institute of Solid State Physics, Bulgarian Academy of Sciences, 1784 Sofia, Bulgaria
Magnetic exchange-bias (EB), occurring at the interface between ferromagnetic (FM) and multiferroic (antiferromagnetic AF and ferroelectric FE) materials allows coupling of the magnetic properties of both materials. Indeed, this approach has been used to modulate the magnetic response of magnetic layers by using electric fields. Here we shall overview recent achievements in a variety of systems including BiFeO3 and hexagonal-AMnO3 multiferroics, to illustrate the distinct phenomenologies involved and the mechanisms behind. We will show that the magnetization of a FM in contact with an AF-FE multiferroic, such as hexagonal-LuMnO3 and YMnO3, can be reversed by an electric field and the EB field can switch and recover without the need of changing the settled temperature. Analysis of the low temperature ferroelectric properties of LuMnO3 indicates that the observed effects steam from the distinct dynamics of antiferromagnetic and ferroelectric domain walls.
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PIEZOELECTRIC THIN FILMS A TECHNOLOGY PLATFORM FOR INNOVATIVE DEVICES M. Klee, R. Maucozk, B. Kumar, C. van Heesch, H. Boots, W. Keur, M. de Wild Philips Research Laboratories Eindhoven G. Schmitz, M. Mleczko Medical Engineering, University of Bochum
Piezoelectric thin film technologies get more and more relevance for miniaturized and integrated actuators and transducers. Piezoelectric thin films have been developed, which show high piezoelectric coupling coefficients. The films are processed on membranes and enable a technology platform which offers for example miniaturized piezoelectric thin film ultrasound transducers. With the technology platform devices such as piezoelectric thin film ultrasound transducers have been realized that operate at 50 KHz up to > 4 MHz. The piezoelectric thin film ultrasound transducers, which are operating at 4 MHz show a large bandwidth (>100%) and have been used to realize ultrasound images.
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SPATIALLY RESOLVED PHOTODETECTION IN BISMUTH FERRITE
(Invited Talk: BiFeO3 and Multiferroics) Won-Mo Lee, 1 Ji Ho Sung, 1 Kanghyun Chu,3 Xavier Moya,4 Young-Jun Cho, 1 Cheol-Joo Kim, 1 Neil D. Mathur,
4
S.-W. Cheong,5,6 C.-H. Yang,3,7 and Moon-Ho Jo1,2,*
Department of Materials Science and Engineering; 2Division of Advanced Materials Science, Pohang
University of Science and Technology (POSTECH), San 31, Hyoja-Dong, Nam Gu, Pohang, Gyungbuk 790784, Korea; 3Department of Physics, KAIST, Daejeon, 305701, Korea; 4Department of Materials Science, University of Cambridge, Cambridge CB2 3QZ, UK; 5Rutgers Center for Emergent Materials, Rutgers University, Piscataway, NJ USA; 6Laboratory for Pohang Emergent Materials, POSTECH, San 31, HyojaDong, Nam Gu, Pohang, Gyungbuk 790-784, Korea; 7KAIST Institute for the NanoCentury, Yuseong-gu, Daejeon 305-701, Korea
*
Presenting Author, E-mail: mhjo@postech.ac.kr
Spontaneous polarization in leaky ferroelectric oxides can serve as an in-built optoelectronic circuit element, equivalently to p-n diodes in semiconductors, since it inherently imprints local potential vectors yielding asymmetric and nonlinear photocarrier dynamics. Ferroelectric domains and domain walls that generically determine spatial extent of such electrical polarization should each influence photocarrier generation, separation and transport differently, but the microscopic mechanisms are unknown. Here, we report scanning photocurrent imaging on epitaxial BiFeO3 thin films, where their temporal, spectral and light-polarization dependent photoresponses are spatially resolved at the dynamic domain/domain wall configurations. We provide direct evidence that locally, photocurrent direction is determined by local domain orientation, whereas magnitude is spectrally centred around charged domain walls that are associated with oxygen vacancy migration. Our observations demonstrate that photodetection can be vectorially configurable with electrically manipulating internal orders, which suggests non-volatile optoelectronic memory applications.
236
DOMAIN WALLS IN MAGNETIC NANOSTRUCTURES
Russell P. Cowburn Cavendish Laboratory, Cambridge, CB3 0HE, UK
Magnetic nanostructures exhibit many of the same phenomena as ferroelectric micro- and nanostructures, except the contributing energy terms are slightly different. In this talk I give an overview of work performed to investigate magnetic reversal in magnetic nanostructures. I will cover the 'vortex to single domain' transition which occurs as the size of the nanostructure is reduced, onfigurational anisotropy in geometrically shaped nanostructures and domain walls in magnetic nanowires. I conclude by describing a variant on the domain wall which can occur in multi-layered magnetic structures and which has the potential to offer a route to ultrahigh density 3-dimensional magnetic memories.
237
Magnetically-driven electric polarization in magneto-electrics and multiferroics

M. KENZELMANN1
1
Laboratory for Developments & Methods, Paul Scherrer Institute, CH-5232 Villigen-PSI, Switzerland michel.kenzelmann@psi.ch
Magneto-electric materials are currently attracting much attention. Currently, a large research effort in multiferroics is directed towards a class of materials in which ferroelectricity is induced by magnetism, as observed in Ni3V2O8 or TbMnO3 [1,2,3]. These oxides are magnetic insulators, displaying a sequence of phase transitions between incommensurate and commensurate magnetic phases, some of which are ferroelectric and can be tuned with magnetic fields. We did a number of experiments in order to investigate why materials develop multiferroic ground states, while very similar materials do not. For Ni3V2O8 we find that the degree of magnetic frustration is suppressed with hydrostatic pressure. Ferroelectricity is reduced and ultimately suppressed as the magnetic ground state adopts a simpler symmetry at high pressure [4]. This underlines the important role that competing magnetic interactions play in magneticallyinduced ferroelectrics. On the other hand, neutron diffraction shows that the magneto-electric interactions in spiral ferroelectrics such as Ni3V2O8 are most probably related to magnetoelastically induced Dzyaloshinskii-Moriya interactions. A magneto-electric hysteresis curve (magnetically-driven ferroelectric hysteresis) shows that multiferroic domains can be controlled by magnetic fields [5]. Because the microscopic interactions in spiral ferroelectrics are mediated by spin-orbit interactions, the observed ferroelectric polarizations are relatively small. However, there have also been theoretical suggestions that exchange-striction can lead to ferroelectricity even in the absence of spin-orbit interactions [6,7]. Studying powder samples of orthorhombic TmMnO3 and LuMnO3, we find the theoretically predicted commensurate magnetic order, and a spontaneous electric polarization that is larger than in all other magnetically-induced ferroelectrics [8]. Our study confirms that exchange-striction mediated magneto-electric interactions can lead to large electric polarization. I will report on our most recent efforts to grow thin films of LuMnO3, and the observation of magnetic Bragg peaks of the so-called E-type magnetic structure using neutron scattering [9]. Finally, we also showed that the magneto-electric effect in LiNiPO4 relies on the magnetic tuning of the magnetic structure that breaks inversion symmetry and generates electric polarization, although the electric polarization is not spontaneous in this case [10]. The electric polarization in this magneto-electric is thus also magnetically-driven and its emergence is thus closely related to the mechanisms that are at play in magnetically-driven multiferroics.
[1] T. Kimura, et al, Nature 426, 55 (2003). [2] M. Kenzelmann, et al, Phys. Rev. Lett. 95, 087206 (2005). [3] G. Lawes, et al, Phys. Rev. Lett. 95, 087205 (2005). [4] B. Padmanabhan, Th. Strssle, M. Kenzelmann et al, unpublished. [5] I. Cabrera, et al, Phys. Rev. Lett. 103, 087201 (2009). [6] I. A. Sergienko, et al, Phys. Rev. Lett. 97 227204 (2006). [7] S. Picozzi, et al, Phys. Rev. Lett. 99, 227201 (2007). [8] V.Yu. Pomjakushin, et al, New Journal of Physics 11, 043019 (2009). [9] M. Bator, Y. Hu, J.S. White, C.W. Schneider, C. Niedermayer, T. Lippert, M. Kenzelmann, unpublished. [10] T.B.S. Jensen, et al, Phys. Rev. B 79, 092412 (2009).
238
Creation of Polar Nanoclusters in Relaxors Robert Blinc Joef Stefan Institute, Ljubljana, Slovenia e-mail: robert.blinc@ijs.si
We report the first observation of a magnetic transition in multiferroic Pb5Cr3F19. The system is ferroelectric below TC = 545 K and exhibits a spin glass like phase between TC and TN = 11.5 K when it becomes antiferromagnetic. We as well report the first observation of the temperature dependence of the internal magnetic fields in K3Fe5F15, K3Cr2Fe3F15 and K3Cu3Fe2F15 via muon spin relaxation below TN = 125 K for K3Fe5F15, TN = 42 K for K3Cr2Fe3F15 and TN = 88 K for K3Cu3Fe2F15. Whereas muon spin relaxation gives the internal fields at the muon sites, we have as well determined the internal magnetic fields at the Fe sites by Mssbauer spectroscopy and EPR. The possibilities for new magnetoelectric applications are discussed.
240
MAGNETOELECTRICITY: HISTORICAL REMARKS Igor Dzyaloshinskii University of California,Irvine
Magnetoelectrics are substances which can be electrically polarised by magnetic fields and magnetically polarised by electric fields. The phenomenon was predicted by Pierre Curie in 1894 but the first magnetoelectric Cr2O3 was discovered only in 1960. I will give a short review of the first decade of the research.
244
CONTRALABLE METAL-INSULATOR TRANSITION AND VERTICAL TRANSPORT IN GRAPHENE BASED HETEROSTRUCTURES

L.A. Ponomarenko1, R.V. Gorbachev1, A. A. Zhukov1, S.V. Morozov1,2, L. Britnell1, R. Jalil1, A.S. Mayorov1, K.S. Novoselov1, K. Watanabe3, T. Taniguchi3, A.K. Geim1, School of Physics and Astronomy, University of Manchester, Oxford Road, Manchester M13 9PL, United Kingdom 2 Institute for Microelectronics Technology, 142432 Chernogolovka, Russia 3 National Institute for Materials Science, 1-1 Namiki, Tsukuba, 305-0044 Japan
1
Graphene is the first example of a truly two-dimensional crystal [1]. It is only one atom thick, optically transparent and chemically inert. The charge carriers in graphene exhibit giant intrinsic mobility, have zero effective mass, can travel for micrometers without scattering at room temperature and can be controlled by application of external electric and magnetic fields. All these properties make graphene a promising material for a plethora of applications from nanoelectronics to composites. The linear excitation spectrum of the charge carriers in graphene explains most of its unusual electronic properties. In particular, it has been shown both theoretically and experimentally, that the charge carriers in graphene cannot localize even at low temperatures. Recently we fabricated a new type of graphene-based heterostuctures consisting of two graphene sheets separated by arbitrarily thin (down to one atom) layer of boron nitride (BN). The latter is used as an insulator with an atomically flat surface to isolate the graphene layers from each other. The devices were fabricated on oxidised silicon substrate, which acts as a back gate. In such structures densities of charge carriers in both graphene layers can be controlled independently by varying back gate voltage and the voltage between the graphene sheets. In contrast to expected metallic behaviour we observed the metalinsulator transition (MIT) at low concentrations in one of the graphene layers. Interestingly, the transition can be controlled and even totally suppressed by varying the charge density in second layer. The insulating state can be also suppressed by weak perpendicular magnetic field. We attribute the MIT to localization due to screening of the electron-hole puddles by the adjacent graphene layer and presence of the short-range potential responsible for inter-valley scattering. Our experiment reconciles the normally observed metallic behaviour in graphene with the generally expected localization at small carrier concentrations in the two-dimensional electron gas. We also found that for very thin (<4 nm) BN barriers the tunnelling current between two graphene layers depends significantly on applied gate voltage. The effect is attributed to the quantum capacitance in graphene and can be utilised for making a new type of field effect device.
[1] A. K. Geim and K. S. Novoselov, Nature Materials 6, 183 (2007)
245
Racetrack Memory: a current controlled domain-wall shift register

Stuart Parkin IBM Research Division, Almaden Research Center, San Jose, California, USA A novel storage-class memory is described in which magnetic domains are used to store information in a magnetic race-track [1]. The magnetic race-track promises a solid state memory with storage capacities and cost rivaling that of magnetic disk drives but with much improved performance and reliability: a hard disk on a chip. The magnetic race track is comprised of tall columns of magnetic material arranged perpendicularly to the surface of a silicon wafer. The domains are shifted up and down the race-track by nanosecond long pulses of spin polarized current using the phenomenon of spin momentum transfer[2]. The role of the momentum of the domain wall in the current and field driven dynamics of domain walls in magnetic nanowires is examined by studying the response of the domain wall to single or trains of carefully timed nanosecond long current pulses in nanowires formed from single permalloy layers and from spin-valve structures [3]. We also compare the current induced motion of domain walls in in-plane and perpendicularly magnetized racetracks. We show that high domain wall velocities (~200 m/sec) can be obtained whether the magnetization is oriented in plane or perpendicular ot the plane of the nanowire and that similar current densities are needed for the same domain wall velocity. However, the threshold current needed to observe domain wall motion is much smaller in the case of perpendicularly magnetized nanowires. Finally, we discuss how the depinning fields of domain walls trapped at an engineered pinning site are influenced by thermal gradients induced by pulsed laser heating of metallic pads positioned on the nanowire close (~10 nm) to the pinning site.
[1] S.S.P. Parkin et al., Science 320, 190 (2008); S.S.P. Parkin, Scientific American (June 2009). [2] M. Hayashi, L. Thomas, R. Moriya, C. Rettner and S.S.P. Parkin, Science 320, 209 (2008). [3] L. Thomas et al., Science 330, 1810 (2010), and X. Jiang et al. Nature Communications (2011).
246
ISIF August 2011 Cambridge United Kingdom NEAR ROOM TEMPERATURE MULTIFERROIC TRANSITIONS IN BIFEO3 FILMS I. C. Infante, P. Gemeiner, P.-E. Janolin, B. Dkhil LSPMS UMR8580 - Ecole Centrale Paris- CNRS, Chtenay-Malabry, France S. Fusil, E. Jacquet, M. Bibes, A. Barthlmy Unit Mixte de Physique UMR137 CNRS - Thales, Campus de Polytechnique, Palaiseau, France S. Jaouen, J. Juraszek Groupe de Physique des Matriaux UMR6634, UFR Sciences et Techniques - CNRS, Saint Etienne du Rouvray, France B. Dup, G. Geneste CEA-DAM DIF, Arpajon, France L. Bellaiche Physics Department, University of Arkansas, Fayetteville, Arkansas, USA O. Diguez, J. Iiguez Institut de Cincia de Materials de Barcelona (ICMAB-CSIC), Campus UAB, Bellaterra, Spain J. Pacaud, F. Pailloux LMP SP2MI, Institut P, Boulevard Marie et Pierre Curie, Futuroscope Chasseneuil, France S. Ravy SOLEIL Synchrotron CRISTAL beamline, LOrme des Merisiers - Saint-Aubin, Gif sur Yvette, France The interplay of multiple orders including dipolar, magnetic and elastic ones coupled to different structural parameters as polar displacements and antiferrodistortive motions within the same phase lead to rich phase diagrams on BiFeO3 (BFO) thin films. We focus in this room temperature multiferroic material with the aim of understanding the variety of ferroic phase transitions and the highly tunable functional properties that can be found in BFO thin films. Our work has been devoted to answer relevant remaining questions concerning the effect of misfit strain in multiferroic transitions and in multiferroic phase stabilization. By combining our calculations and experimental results on X-ray, neutron and synchrotron radiation diffraction, piezoresponse microscopy, high resolution transmission electron microscopy and Raman and Mssbauer spectroscopies, we show that the multiferroic phase transitions and phase equilibrium of BFO film is extremely sensitive to strain, temperature and growth conditions. We will discuss on the strategies to control the coexistence and distribution of these phases within the same film in order to obtain near room temperature enhanced multiferroic couplings which could lead to creating giant piezoelectric, magnetoelectric and piezomagnetic responses with potential value for applications.
247
INFLUENCE OF DEFECT DISTRIBUTION ON PHYSICAL PROPERTIES OF LAYERED FERROELECTRIC - SEMICONDUCTORS WITH AN INCOMMENSURATE PHASE Gadjiev B. R. International University for Nature, Society and Man 19 Universitetskaya street, Dubna, 141980, Russia gadjiev@uni-dubna.ru In the present paper we give a generalization of the phenomenological Landau theory for the layered ferroelectric- semiconductors with an incommensurate phase for the systems with a small-world property induced due to the defect presence in a structure [1, 2]. It is shown that in a general case the equation of motion for the order parameter is of fractional order. The parameters of the system of equations for an order parameter depend on an electron concentration at the impurity levels and a fractional order of differential equation is a function of the entropy index. We discuss the deformation of the phase diagram of those compounds caused by a temperature change and the entropy index of a defect distribution function. The temperature and frequency dependencies of thermodynamic functions in an incommensurate phase have been calculated. Comparison of the experimental data of the ternary layered ferroelectric - semiconducting thallium chalcogenides with an incommensurate phase and their solid solutions with the theoretical results has been performed. In particular, we describe results of dielectric measurements which show that with the change of defect distributions in those compounds take place a deformation of the temperature dependence of a dynamical susceptibility from the characteristic for the proper ferroelectrics with an incommensurate phase to the curve characteristic for improper ferroelectrics with an incommensurate phase. References
1. Gitterman M. and Halpern V. Phase transitions: A Brief Account with Modern Applications (World Scientific) 2006 2. Gadjiev B.R. On the theory of phase transition in muliferroics // Journal of Physics: Conference Series, Volume 200, Issue 1, pp. 012044 (2010).

11
STRUCTURAL, ELECTRICAL BiFeO3 THIN FILMS
AND
MAGNETIC PROPERTIES
OF
(La, Mn) CO-SUBSTITUTED
D. Y. Wang*1, N. Y. Chan2, R. K. Zheng3, C. Kong1, S. Li1 and H. L. W. Chan2

1
School of Materials Science and Engineering, The University of New South Wales, Sydney, NSW 2052, Australia 2 Department of Applied Physics and Materials Research Centre, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong, China 3 Australian Key Center for Microscopy and Microanalysis, University of Sydney, Sydney, Australia
Email: dy.wang@unsw.edu.au The (La, Mn) co-substituting has been proposed as a promising strategy to simultaneously optimize ferroelectric and magnetic properties of BiFeO3, but the co-substitution effects of (La, Mn) on BiFeO3 so far have only been examined in form of polycrystalline thin films with rather scattered physical properties. In order to provide the information for revealing the intrinsic mechanism underlying the co-substitution without influences of extrinsic defects, it is desirable to investigate co-substitution effect in epitaxial thin films. In the present study, (La, Mn) co-substituted BiFeO3 thin films (LMBFO) were grown on CaRuO3 electroded (LaAlO3)0.3(Sr2AlTaO6)0.35 [LSAT] (001) single crystal substrates by pulsed laser deposition with optimized growth thermodynamics. Highly epitaxial growth and sharp interfaces of the LMBFO/CaRuO3/LSAT heterostructure were confirmed by x-ray diffraction and high resolution transmission electron microscopy. The films demonstrated square-like ferroelectric hysteresis loops with a large remnant polarization Pr of 65 C/cm2 and a coercive field Ec of 38.5 V/m at room temperature. Saturation magnetizations of MS = 9.1 12.8 emu/cm3, which presumably induced by the canting of antiferromagnetic spins, have been also observed at room temperature. Dielectric and local piezoelectric characteristics of the LMBFO thin films were also investigated.
100 80
20 15 In-plane Out-of-plane
Magnetization (emu/cm )
Polarization (C/cm )
60 40 20 0 -20 -40 -60 -80 -100 -125 -100 -75 -50 -25 0 25 50 75 100 125
10 5 0 -5 -10 -15 -20
-10000
-5000
5000
10000
Electric Field (V/m)
Magnetic Field (Oe)
Figure 1 P-E hysteresis loops of BFOLM thin film grown on LSAT (001) single crystal substrate at 1 kHz and room temperature.
Figure 2 M-H loops of BFOLM thin film grown on LSAT (001) single crystal substrate at room temperature.
TOPIC: Multiferroics and Magnetoelectrics: Theory & Experiments PRESENTATION: Poster

37
GROWTH AND CHARACTERIZATION OF HIGH QUALITY BiFeO3-PbTiO3 SINGLE CRYSTALS
Clare G. Cambridge, Timothy P. Comyn and Andrew J. Bell

Institute for Materials Research, University of Leeds, Leeds, LS2 9JT, UK
Bismuth ferrite (BiFeO3) has been extensively studied due to its piezoelectric and electromechanical properties. It is ferroelectric below its Curie point (TC) of ~826C and antiferromagnetic below its Nels temperature of ~370C. At room temperature it is a rhombohedrally distorted perovskite with space group R3c. BiFeO3 forms a solid solution with lead titanate (PbTiO3), a tetragonally distorted perovskite with space group P4mm. BiFeO3-PbTiO3 (BFPT) has a morphotropic phase boundary at ~70 mol% BiFeO3, with a TC of ~632C and an exceptionally large tetragonal strain. Single crystals of BFPT grown previously were virtually all cracked due to the large spontaneous strain. In this study, compositions of high BiFeO3 content are grown for the first time. Since these crystals display reduced strain, they do not suffer from cracking and are therefore suitable for conventional dielectric testing. A range of BFPT compositions were produced using both a flux growth technique, and melt growth in a vertical Bridgman furnace. Using a cooling rate of 0.5C/h over the temperature range where crystal growth is expected, highly pure, crack free single crystals of 4mm diameter were produced. Powder X-ray diffraction revealed the crystal structure to be single-phase tetragonal perovskite, and high temperature studies showed the position of the TC. Electron probe microanalysis and energy dispersive X-ray analysis confirmed the chemical composition grown, and scanning electron microscopy confirmed the absence of cracks. Promising electrical properties are reported including capacitance, dielectric loss, dielectric strength, permittivity- temperature and piezoelectric coefficient (d33).

43
MICROSTRUCTURE AND MOS CAPACITOR PROPERTIES OF Bi2Fe4O9 FILMS GROWN ON Si(001)

C. Dubourdieu1, N. Aetukuri2, E Cartier1, J. Bruley1, J. Jordan-Sweet1, T. Arruda3, S. Kalinin3, M. Samant2, M.M. Frank1, S.S.P. Parkin2, V. Narayanan1 1. IBM T.J. Watson Research Center, Yorktown Heights, NY 10598, USA 2. IBM Almaden Research Center, San Jose, CA 95120, USA 3. Oak Ridge National Laboratory, Oak Ridge, TN 37831 USA
Bi2Fe4O9 has been extensively studied in the past decades for its potential application as a semiconductor gas sensor and a high performance catalyst. It has an orthorhombic crystalline structure (a=7.965, b=8.440 and c=5.994) with space group Pbam. Because the structure is centro-symmetric, ferroelectricity is not expected. However, recent studies1,2 have claimed ferroelectricity in polycrystalline samples but the hysteresis loops that they show can not be considered as a proof for ferroelectricity. A recent study3 on single crystals has precluded ferroelectricity but has shown a coupling between magnetic and dielectric properties. As far as thin films are concerned, Bi2Fe4O9 is usually obtained as a secondary phase in BiFeO3 films and little is known about its properties. In this work, we investigate the microstructure and electrical properties of polycrystalline Bi2Fe4O9 films grown on Si (001). Films with thicknesses of ~ 50 and 300 nm were prepared by pulsed laser deposition using a BiFeO3 target. Films were deposited at a growth temperature of 675C on various surfaces: HF-last Si, SiO2 (0.8 nm thick chemical oxide) and HfO2 (2 nm) buffer layer. A post-deposition annealing was performed at 500C under 600 Torr of O2 for 1 hour. X-ray diffraction measurements (National Synchrotron Light Source) show that the films consist of polycrystalline Bi2Fe4O9, with diffraction peaks corresponding to the bulk orthorhombic structure but with a slight distortion of the unit cell. The microstructure and composition of the films were analyzed by transmission electron microscopy (TEM), energy-dispersive x-ray spectrometry (EDX) and electron energy loss spectroscopy (EELS). When grown on HF-last Si, the films of nominal thickness 50 nm consist of an interfacial ~2 nm SiO2 layer, an amorphous ~15 nm Bi-Fe-silicate and a ~45 nm thick polycrystalline Bi2Fe4O9 layer (Fig. 1.a) The composition of the amorphous layer is graded with a strong deficiency of iron at the SiO2 interface. Iron migration to the top surface of the growing layer might account for the formation of Bi2Fe4O9 rather than the BiFeO3 phase. The microstructure of the films with and without a HfO2 buffer layer will be discussed. Electrical measurements were performed on MOS structures using TiN top electrodes. A clockwise hysteresis loop is observed for the capacitance-voltage curves, with a memory window of ~0.7 V for 50 nm films deposited on the HF-last surface (Fig. 1.b). The width of the hysteresis depends on the starting surface and it increases with increasing film thickness. Charge trapping in dielectric oxides deposited on p-type Si typically leads to a counter-clockwise hysteresis. A clockwise hysteresis is expected for a ferroelectric oxide in a MOS capacitor. However, based on electrical measurements (frequency dependence of CV characteristics, dependence on the stress conditions) as well as piezo-force microscopy spectroscopy, we will also discuss other possible origins for such a hysteresis, including ionic motion. (a) (b)
Capacitance (pF)
40.0p
Vmin
(c)
0.8
Vfb (V)
0.7 0.6 0.5 0.4 0.3 0.2 0.1
20.0p
Sweep range [+4,Vmin,+4]

-6 -4 -2 0
0.0
100 kHz
0.0
-4
-3
-2
-1
Gate bias (V)
Minimum sweep voltage Vmin (V)
Fig. 1: (a) Cross-section TEM image of a Bi2Fe4O9 sample grown on HF-last Si. A SiO2 layer is seen above this is a Bi-Fe-SiO interfacial layer and the crystalline Bi2Fe4O9 layer - (b): Capacitance as a function of gate voltage and (c) shift of the flatband voltage as a function of minimum ramp voltage Vmin, both for the same stack as in (a). 1. A.K. Singh et al, Appl. Phys. Lett. 92, 132910 (2008) 2. Z.M. Tian et al., J. Appl. Phys. 106, 103912 (2009) 3. Y.A. Park et al., Appl. Phys. Lett. 96, 092506 (2010)

70
STRUCTURE AND FERROELECTRIC PROPERTIES IN THE (1-X)BIFEO3-X(K0.5BI0.5)TIO3 PIEZOELECTRIC CERAMIC SYSTEM Author(s): Mr Jim Bennett Professor Andrew Bell University of Leeds Dr Tim Comyn University of Leeds Dr Tim Stevenson University of Leeds Abstract: We have developed a piezoelectric ceramic comprising of a solid solution of (1-x)BiFeO3x(Bi0.5K0.5)TiO3 where x = 0.1-0.9 . Contrary to behaviour observed in for example BiFeO3 and BiFeO3 PbTiO3, large electric field induced strains can be achieved at relatively (compared to BiFeO3) low electric field strengths. Encouraging results have been discovered in the region where x = 0.4-0.6 with response to Strain-Field studies where a high field d33 of 359 pC/N has been achieved and this rivals many of the current lead free systems. This material also displays a G-type antiferromagnetic structure at room temperature for the compositions x = 0.1, 0.2 and 0.3 and is also seen as extremely promising as a high temperature piezoelectric material, with a ferroelectric Curie point of > 600 C for 0.1<x<0.4. XRD has also been carried out across all regions of this material along with relative permittivity as a function of temperature, dielectric loss as a function of temperature and PE loops.

71
Dielectric, Magnetic, Multiferroicic Properties in Garnet Re3Fe5O12 ceramics
J.Su, X.B.Wu, J.T.Zhang , H.Sun , X.M.Lu and J.S.Zhu

Natil Lab of Solid State Microstructures, Nanjing University, Nanjing 210093, P. R. China e-mail: jszhu@nju.edu.cn
Abstract
Polycrystalline lutetium iron garnet Lu3Fe5O12 and holmium iron Ho3Fe5O12 garnet ceramics were prepared by a solid-state reaction method and their dielectric and magnetic properties were studied. The dielectric relaxor behaviour at low temperature in both garnets may come from the dipolar effects associated with the charge carrier hopping between Fe2+ and Fe3+. In addition, the multiferroic properties were also studied in both garnets. The anomalies of dielectric constant and loss at TN provide an evidence of ME coupling and the ME voltage coefficient () is about 50 mv/cm.Oe with an applied magnetic field of 7 kOe at room temperature in Ho3Fe5O12. Otherwise, the magnetodielectric (MD) properties were measured in Lu3Fe5O12 ceramics and the small magnetic fields can dramatically change its dielectric constants of at room temperature. The MD or ME effects may be attributed to the coexistence of Fe2+ and Fe3+, which results in a charged region with cation ordered and initiate local dipoles. The effect of Mg doping on the magnetic and dielectric properties of Lu3Fe5O12 ceramics was also studied.
1

76
THE EFFECT OF MN DOPING ON THE DIELECTRIC PROPERTIES AND DOMAIN WALL MOBILITY OF (Ba0.8Sr0.2)TiO3 THIN FILMS C. Borderon, R. Renoud and H.W. Gundel IREENA, EA 1770, University of Nantes, Nantes Atlantic Universities 2 rue de la Houssinire, Nantes, F-44322, France e-mail: caroline.borderon@univ-nantes.fr Ferroelectric thin films are attractive materials for tunable microwave devices such as electrically tunable filters, capacitors, oscillators, resonators or phase shifters. For this type of applications, the ferroelectric material needs to have a high dielectric permittivity and low losses. The dielectric properties are very sensitive to the defects and to the quality of the material structure. In the ferroelectric materials, oxygen vacancies are the most important defects and create conduction in the film. Hence the losses are important and it becomes necessary to dope the film to decrease the influence of defects. In the present work, Mn-doped Ba0,80Sr0,20TiO3 (BST) thin films are realized by Chemical Solution Deposition (CSD) on stainless steal substrates. Dielectric and electrical characteristics are investigated as a function of Mn content. Dielectric permittivity is measured under a low acelectric field and the response is fitted by a hyperbolic law [1]:
r = rl + r rev 2 + ( r E0 ) .
2
This law is based on reversible and irreversible domain wall motions and allows us to dissociate the domain wall and lattice contributions. rl is due to intrinsic lattice and r-rev to reversible domain wall vibrations and can be associated to a measure of domain wall mobility [2]. The parameter r represents domain wall pinning and is related to an irreversible modification of the local polarization [2, 3]. Both parameters depend on the crystal structure, but r also reflects the presence of impurities, dopants or defects [4]. All parameters are studied as a function of doping.
[1] [2] [3] [4]
C. Borderon, R. Renoud, M. Ragheb, H.W. Gundel, Appl.Phys.Lett. 98/1 (2011). D.V. Taylor, D. Damjanovic, Journal of Applied Physics 82/4 (1997) 1973. J.E. Garcia, R. Perez, A. Albareda, Journal of Physics: Condensed Matter 17/44 (2005) 7143. O. Boser, Journal of Applied Physics 62/4 (1987) 1344.

81
Memristive Switching utilizing the electronic bipolar resistive switching Titanium dioxide Kyung Jean Yoon,* Seul Ji Song, Kyung Min Kim, Min Hwan Lee, Gun Hwan Kim, Jun Yeong Seok, Jung Ho Yoon, and Cheol Seong Hwang WCU Hybrid Materials Program, Department of Materials Science and Engineering and Interuniversity Semiconductor Research Center, Seoul National University, Seoul 151-744, Korea *Electronic mail; rodwls88@snu.ac.kr Memristive switching showing various resistance states according to electrical stimulation was proposed using electronic bipolar resistive switching phenomena in titanium dioxide (TiO2, anatase structure) deposited by plasma enhanced atomic layer deposition (PEALD). Physical mechanism for bipolar resistive switching in TiO2 was investigated beforehand in order to apply it to the device design. The observed I-V behavior of electronically formed bipolar resistive switching in TiO2 shows switching among on and off state that are with the ohmic and rectifying state, respectively. Even though the precise mechanism for the phenomena is still yet to be clarified, due to the difficulties in understanding the coupled electronic and ionic transport phenomena, the observed switching behavior of TiO2 was inspected mainly by the ionic drift of oxygen ions and the corresponding vacancies under a sufficient bias of electric field.[1] TiO2 is known as n-type semiconductor in which oxygen vacancy act as a donor.[2] As extrinsic carriers are injected to the TiO2 thin film during the electroforming step with an appropriate current compliance, switching layer, or active layer, where the oxygen vacancy actions occur, is formed within the thin film.[3] According to the polarity of applied electric field, oxygen vacancies drift back and forth within the switching layer and the concomitant collapse and reconstruction of Schottky barrier on the contact between thin film and metal electrode is occurred. This can result in the reversible switching among the ohmic and rectifying states.[4] By manipulating the switching conditions as well as the configuration of the multiple electrically formed bipolar resistive switching TiO2 thin films, switching layers were set either on the top or bottom contact, or both of them. As a result, memristive switching among the four distinctive resistance states, which are ohmic, forward rectifying, reverse rectifying, and insulating, was performed in current-voltage sweep mode as well as in pulse mode. [1] Yang, J. J et. al., Nat.Nanotechnol. 3, 429 - 433 (2008) [2] L Ferro et. al., J. Appl. Phys. 633 (1994) [3] Kyung Min Kim et. al., Nanotechnology 21 305203 (2010) [4] Yang, J. J et. al., Advanced Materials 21 37543758 (2009)

110
ISIF-2011
Abstract
2D Multiferroic Photonic-Band-Gap Materials for Tunable and Absolute Electromagnetic Vacuum
Kai Chen1, Yong Wu1 , Wei Yang2 , Zelin Lu2 and J. S. Zhu2
1.Department of Physics, Nanjing University of Science and Technology, Nanjing 210094, P. R. China 2. National Laboratory of Solid State Microstructures and Department of Physics, Nanjing University, Nanjing
210093, P. R .China
e-mail: pacinonono@yahoo.com.cn
When multiferroic terbium manganite (TbMnO3) cylinders are periodically and squarely arranged in airthe resultant 2D materials exhibit the photonic band gaps (PBG). The remarkable feature of this system is that the absolute PBG, origining from the Mie resonance, is tunable from close to open by applying the external magnetic field., which is attributed to the magnetic-order rearrangement and the electromagnon depression. The tunable location of electromagnetic waves may be realized by controlling the magnetic structure transition of manganese spins in TbMnO3.
Identify: 1. The abstract will be presented under Topic 2; 2. Preference to poster presentation.

130
CHARACTERIZATION OF A COMMON-GATE AMPLIFIER USING FERROELECTRIC TRANSISTORS Mitchell Hunt1, Rana Sayyah1, Todd C. MacLeod2, and Fat D. Ho1
1
The University of Alabama in Huntsville, Department of Electrical and Computer Engineering, Huntsville, Alabama, 35899, USA 2 National Aeronautics and Space Administration, Marshall Space Flight Center, Huntsville, Alabama, 35812, USA ABSTRACT
In this paper, the empirical data collected through experiments performed using a ferroelectric transistor (FeFET) in the common-gate amplifier circuit is presented. The FeFET common-gate amplifier was characterized by varying all parameters in the circuit, such as load resistance, biasing of the transistor, and input voltages. Due to the polarization of the ferroelectric layer, the particular behavior of the FeFET common gate amplifier presents interesting results. Furthermore, the differences between a FeFET common-gate amplifier and a MOSFET common-gate amplifier are examined. Keywords: FeFET; FFET; ferroelectric transistor; common-gate amplifier

136
REACTIVE TEMPLATE GRAIN GROWTH OF BiFeO3-PbTiO3 BY USING Bi4Ti3O 12 AND PbBi4Ti4O15 AS TEMPLATE
Meghdad Palizdar, Timothy P Comyn and Andrew J Bell

Institute for Materials Research, University of Leeds, Leeds, UK e-mail: ml07m2p@leeds.ac.uk
Bismuth ferrite exhibits multiferroic properties at room temperature. It is a perovskite with a rhombohedrally distorted lattice and has a ferroelectric Curie point of 836 C. Lead titanate is a perovskite with a tetragonally distorted lattice and a ferroelectric Curie point of 490C. The solid solution between bismuth ferrite and lead titanate (xBiFeO3-(1-x)PbTiO3 or BFPT) possesses a morphotropic phase boundary (MPB) between the rhombohedral and tetragonal forms at x=0.7. It is of interest to investigate the influence of field-driven rhombohedral-tetragonal phase transitions across the MPB, to determine whether correctly oriented BFPT can provide both giant piezoelectric properties and significant magnetoelectric coupling. Here, we used reactive template grain growth (RTGG) technique to prepare crystallographically textured BTPT ceramics. Template grain growth (TGG) utilizes an oriented template as a seed to improve and increase preferred directional growth within a polycrystalline matrix. In this example, Bi4Ti3O12 and PbBi4Ti4O15 have been used separately as templates in the process of BFPT preparation. The samples were characterized using X-ray diffraction (from both laboratory and synchrotron sources), scanning electron microscopy, polarizationfield loops and Curie temperature measurements. Primary results show that PbBi4Ti4O15 has more stability at high temperature in comparison with Bi4Ti3O12. Synchrotron radiation experiments highlight significant differences between the surface and the bulk in terms of the phases present and their orientation.

137
SYNTHESIS OF ORIENTED BiFeO3-PbTiO3 BY MOLTEN SALT METHOD
Meghdad Palizdar, Tim P Comyn and Andrew J Bell

Institute for Materials Research, University of Leeds, LS2 9JT, Leeds, UK e-mail: ml07m2p@leeds.ac.uk
The solid solution between bismuth ferrite and lead titanate, which is a perovskite with either a tetragonal or rhombohedra distortion, exhibits antiferromagnetic and ferroelectric properties at room temperature. xBiFeO3-(1-x)PbTiO3, or BFPT, possesses a morphotropic phase boundary (MPB) between the rhombohedral and tetragonal forms around x=0.7, accompany with a spontaneous strain of 18% on the tetragonal side of the boundary. We have attempted to produce crystallographically textured BFPT ceramics in order to demonstrate coupling between its ferroelectric and magnetic order parameters near the MPB. The approach taken here is to employ the molten salt method to produce two different plate-like precursors: Bi4Ti3O12 and PbBi4Ti4O15. The platelets have been formed into pellets by iso-static pressing, which were sintered under a range of temperature and time conditions. Samples have been characterized by X-Ray diffraction, scanning electron microscopy and polarizationfield measurements. It is demonstrated that by using Bi4Ti3O12 and PbBi4Ti4O15 as precursors, a degree of texture in BFPT ceramics has been created.

141
1. The topic under which your abstract should be considered for presentation sif2011@tNon-Volatile Memories (RRAMs, MRAMs, FeRAMs, PCMs) 2. Presenting author's affiliation and email address : Pawankumarsolan@gmail.com, Department of Physics, Himachal Pradesh University, Shimla, India 3. Preference to oral or poster presentation : Poster
Ferromagnetic Ordering in Lanthanum Substituted Nano-Cobalt Ferrite at Room Temperature Pawan Kumar , Jagdish Chand , Sangeeta Thakur, M. Singh
Department of Physics, Himachal Pradesh University, Shimla, India.
Abstract. The effect of Fe3+ions substitution by rare earth La3+ ions on magnetic properties of nanocrystalline cobalt ferrite is investigated and reported in this paper. Coprecipitation method was used to prepare ultrafine particles of CoLaxFe2-xO4 (x=0, 0.10, 0.15). The samples have cubic spinel structure and average crystallite size of x=0, x=0.1 and x=0.15 are 49.84 nm, 27.73nm, 47.97 nm respectively. Structure has been investigated by XRD while magnetic properties have been studied using VSM and Mossbauer spectrometer. La3+ ions modulate significantly the magnetic properties of cobalt spinel ferrites. Keywords: Nano-crystalline; Cobalt ferrite; Saturation magnetization; Mossbauer spectra. PACS: 75.30.Cr; 75.50.Gg; 75.75.-c; 76.80.+y

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SOLID-SOLID SOLUTIONS OF BiFeO3: MECHANOCHEMICAL SYNTHESIS AND RAMAN STUDIES Maria Poomska1, Boena Hilczer1, Izabela Szafraniak-Wiza2 1 Institute of Molecular Physics, Polish Academy of Sciences, 60-179 Pozna, Poland, 2 Institute of Materials Science and Engineering, Pozna University of Technology M. Skodowskiej-Curie Sq.5 60-965 Pozna, Poland
Applications of multiferroics in novel devices require coexistence of ferroelectric and magnetic ordering at room temperature, low electric conductivity and larger magnetoelectric coupling. Between known multiferoic materials only BiFeO3 shows magnetic and ferroelectric phase transition well above room-temperature. However the other requirements are not fulfilled in case of pure compound. One of possible route to improve its properties is based on the doping by or preparations of solid-solid solutions. In this work we prepared and investigated properties of the solid-solution of BiFeO3 with LaFeO3 and BaTiO3. Recently it was shown that mechanochemical methods can be applied for preparation of broad range of nanocrystalline electroceramic materials exhibit perovskite structure (esp. BiFeO3). The BiFeO3 solid solutions were synthesized by high-energy milling in SPEX 8000 Mixer Mill. We used Bi2O3, Fe2O3, La2O3, BaO and TiO2 (99% purity from Aldrich) in different stoichiometric ratios of starting materials. The development of the synthesis was controlled by X-ray diffraction. The powders obtained after 120 h milling of the oxides were found to exhibit rhombohedrally distorted perovskite structure. As-prepared nanopowders were characterized by NIR Raman spectroscopy. FT NIR Raman spectra of the as synthesized nanopowders (with grains exhibiting core-shell structure) show broad bands. Thermal treatment (1 h at 500oC) results in the band narrowing and moreover, the structure of the Raman spectra becomes richer. Thermal treatment results in a disappearance of the shell and an increase in the grain size. Acknowledgements. This work was partially supported by COST Action MP0904, the respective Grant from the Ministry of Science and Higher Education in Poland and by the Foundation for Polish Science, Parent-Bridge Programme co-financed by the EU within the European Regional Development Fund.

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EFFECT OF SUBSTRATE INDUCED STRAIN ON THE MORPHOTROPIC PHASE BOUNDARY OF BiFeO3-PbTiO3 EPITAXIAL THIN FILMS R.Muralidharan, Faye Bygrave, Tim Comyn and Andrew Bell Institute for Materials Research, University of Leeds, Leeds LS2 9JT, United Kingdom Multiferroic compounds are attractive because of the interesting physics behind the ferroelectric and ferromagnetic coupling and because of its potential use in devices exploiting new functionalities. Particularly appealing is the electric field control of the magnetization. BiFeO3 is the rarest among the room temperature multiferroic material. Bulk BiFeO3 (BFO) has a rhombohedral R3c structure and the polarization axis is along a [111] direction. Very recently the epitaxial stabilization of a highly elongated tetragonal BFO phase, with high ferroelectric polarization, has been reported on LaAlO3(001) (LAO) substrates due to lattice induced strain [Bea et al., Phys. Rev. Lett. 102, 217603 (2009), R. J. Zeches et al. Science 977,326 (2009)]. Some major problems in the BFO is its leakage current and very narrow growth window due to the volatility of Bismuth. Solid solutions containing BFO with some well known insulating material have started attraction. Interestingly well before (Sov. Phy. Sol. Stat. 6 ,375 (1964) ) in the bulk form BiFeO3-PbTiO3(PTO) solid solution with a composition of 70:30 and subsequently on polycrystalline thin films (Acta Mater. 56 2110 (2008) ), a huge c/a ratio of 1.18 has been reported. In the present study we have prepared the BFO-PTO (70:30) films on various (001) oriented single crystal substrates to study the influence of lattice strain on the grown films. We chose 70:30 composition as it is close to the morphotropic phase boundary. By changing the substrate, the strain can be modified from compressive to tensile strain in the case of BFO-PTO thin films. The crystal structure and morphology of the grown films were analyzed by x-ray diffraction and atomic force microscopy. A tetragonal P4mm structure with huge c/a axial ratio has been stabilized under proper growth conditions, the experimental conditions and results will be presented in detail.

157
RANDOM TELEGRAPH NOISE IN Cu DOPED Ge0.3Se0.7 BASED RESISTIVE SWITCHING MEMORY CELLS
R. Soni,1,+,* P. Meuffels,1 A. Petraru,2 M. Weides,3 C. Kgeler,1 R. Waser,1 and H. Kohlstedt2
1 2
Institut fr Festkrperforschung, Forschungszentrum Jlich GmbH, Jlich 52425, Germany Nanoelektronik, Technische Fakultt Kiel, Christian-Albrechts-Universitt Kiel, Kiel 24143, Germany 3 Department of Physics, University of California, Santa Barbara, California 93106, USA
We report results on random telegraph noise (RTN) resistance fluctuations in Cu doped Ge0.3Se0.7 based RRAM cells. The influence of temperature and electric field on the RTN fluctuations is studied on different resistance states of the memory cells to reveal the dynamics of the underlying fluctuators. Our analysis indicates that the observed fluctuations could arise from thermally activated transpositions of Cu ions inside ionic or redox double-site traps triggering fluctuations in the current transport through a filamentary conducting path. Giant RTN fluctuations characterized by relative resistance variations of up to 50% in almost macroscopic samples clearly point to the existence of weak links with small effective cross-sectional areas along the conducting paths. Such large resistance fluctuations might hinder industrial applications of RRAM devices because huge bit-error rates during reading cycles can be expected.
*E-mail: soro@tf.uni-kiel.de + Present Address: Nanoelektronik, Technische Fakultt Kiel, Christian-Albrechts-Universitt Kiel, Kiel, 24143, Germany

177
FERROELECTRIC SWITCHING AND CYCLOIDAL ORDER IN o-YMnO3 THIN FILMS

I. Fina1, L. Fbrega1, X.Mart2, F. Snchez1 and J. Fontcuberta1 Institut de Cincia de Materials de Barcelona (ICMAB-CSIC), Campus UAB s/n, 08193 Bellaterra, Spain 2 Faculty of Mathematics and Physics, Charles University, Ke Karlovu 5, 121 16 Praha 2, The Czech Republic
.
Orthorhombic YMnO3 in bulk form displays an E-type antiferromagnetic structure. In remarkable contrast, an antiferromagnetic bc-cycloidal spin arrangement has been inferred for thin films, based on the study of ferroelectricity and magnetodielectric data on epitaxial o-YMnO3 thin films [1], However, some of the reported results remain puzzling. For instance, a finite remanent polarization is observed in zero-field cooling conditions, while under these conditions the two possible quirality values of the cycloidal domains should be equaly populated, and thus the spontaneous remanent polarization should be zero. The aim of this work is to deepen in the analysis of these puzzling features. First we will focus on the dissimilar dielectric and ferroelectric responses of c-textured and a-textured YMnO3 films as a function of magnetic field. We will show that the features indicative of magnetic field induced polarization switching, clearly visible in a-textured films, remain elusive in c-textured films; analysis of the data allows us to conclude that if a cycloidal order exists in the c-textured film, it can not be easily switched by a magnetic field up to 9T.
600 400 200
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14.7
24.4 kV/cm
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Elecric field (kV/cm)
Figure 1. (a) Pyrocurrent versus temperature, recorded upon cooling and heating through the Nel temperature (~40K) under zero electric field and different low magnetic fields. (b) Electric field dependence of permittivity.
Next, we will discuss on the selectivity of quiral values depending on cooling procedures. Pyrocurrent measurements (Fig.1) reveal clear ferroelectric signatures. Time integration of the measured current leads to polarization values that are of about 10% of the saturation polarization values measured by a P(E) loop. This indicates that in nominally zero-field conditions, about 10% of the cycloids and thus the ferroelectric domains are already oriented in a preferential direction. This result is not due to trapped flux in the superconducting magnet, since measurements performed at several low magnetic fields ( 10, 20, 30 Oe) do not reveal any change in either the absolute value or the sign of the pyrocurrent. We will discuss this result in connection with the observation of an imprint field, as shown in Fig.1b.
[1] I. Fina et al., Appl. Phys. Lett. 97, 232905 (2010)

181
PEROVSKITE-BASED OXIDE THERMOELECTRICS Susanne Stemmer, Bharat Jalan, Pouya Moetakef and Tyler Cain Materials Department, University of California, Santa Barbara, CA 93106-5050, USA Oxides were long believed to possess too low carrier mobilities to be considered seriously as promising candidates for thermoelectrics with a high figure of merit. The discovery that layered cobaltites can exhibit excellent thermoelectric properties was unexpected and has generated much excitement. Perovskite SrTiO3 has long been known to have a very large Seebeck coefficient and it can be doped to very high carrier concentrations to achieve high electrical conductivities. In this presentation we will show that La-doped SrTiO3 thin films grown by molecular beam epitaxy (MBE) show very high Seebeck coefficients (up to 980 VK !1 ). The maximum thermoelectric power 20 -3 factor is 39 Wcm !1K !2 (at a carrier concentration of 7 "10 cm ) and is comparable to that of commercial thermoelectrics. La-delta-doped superlattices were also characterized and exhibited Seebeck coefficients of ~ 500 VK !1 . The main shortcoming of doped ! SrTiO3 as a thermoelectric is its large thermal conductivity, which severely limits the thermoelectric figure of merit, ZT. In the second part of the presentation, we will discuss the thermoelectric properties GdTiO3/SrTiO3 superlattices grown by MBE. GdTiO3 is a Mott insulator that has a lower thermal conductivity than SrTiO3. We discuss the challenges in GdTiO3 growth, in particular avoiding the formation of the pyrochlore (Gd2Ti2O7) phase. We show that the electrical transport characteristics can be understood as being dominated by a conductive interface layer within the SrTiO3. We will discuss the role of the interfacial conduction in determining the thermoelectric properties of GdTiO3/SrTiO3 superlattices.

182
PFM STUDIES OF Bi1-xPrxFe0.95Co0.05O3 THIN FILMS DERIVED BY CHEMICAL SOLUTION DEPOSITION METHOD
Indrani Coondoo1*, Neeraj Panwar1, Venkata S. Puli2, R. S. Katiyar2 and A. L. Kholkin1

1
Department of Ceramics and Glass Engineering & CICECO, University of Aveiro, 3810-193 Aveiro, Portugal and
2
Department of Physics, University of Puerto Rico, San Juan-00931, PR, USA
*e-mail: indrani_coondoo@yahoo.com
Abstract Multiferroics exhibit ferroelectric, ferromagnetic and ferroelastic orders in the single phase or composites. These materials are potential candidates for applications in multifunctional devices. Recently, lead-free bismuth ferrite (BFO) has been extensively studied owing to its high ferroelectric Curie temperature and anti-ferromagnetic ordering. However, the large leakage current density in bismuth ferrite leads to an increase in conductivity which eventually hampers the visualization of saturated ferroelectric hysteresis loops. By suitable site engineering at Bi and Fe-sites, one can observe an improvement in the ferroelectric and magnetic properties. Scanning probe microscopy is one of most important techniques that allows for the visualization of piezocontrast and measurements of local hysteresis loops at the resolution of 10 nm level by detection of local piezoelectric deformation induced by an external electric field. Thin films of Bi1-xPrxFe0.95Co0.05O3 (x = 0,0.03, 0.05, 0.07 and 0.10 ) have been deposited by spin coating method on Pt(111)/TiO2/SiO2/Si(100) substrates. We have observed clear contrasts in the out-ofplane (OPP) and in-plane (IP) behaviour in Pr and Co substituted BiFeO3 thin films. Square patterns were written with different voltages ( 30V). Local piezoresponse hysteresis loops were acquired in the dc bias voltage range from -50 to +50 V. Effect of Pr and Co substitution has been investigated on the local domain structure and piezoresponse behaviour and the obtained results will be presented.

185
TAILORING FERROELECTRICITY IN CoFe2O4-BaTiO3 BILAYERS

I. Fina, N. Dix, R. Bachelet, L. Fbrega, F. Snchez, and J. Fontcuberta Institut de Cincia de Materials de Barcelona (ICMAB-CSIC) Campus UAB s/n, 08193 Bellaterra, Spain
Very few compounds are intrinsically magnetoelectric multiferroics. So far, composites made of ferromagnetic and ferroelectric materials are favourable candidates to observe room temperature magnetoelectric behaviour. The aim of this work is to study the ferroelectric behaviour of high quality bilayers made of BaTiO3 (BTO) and CoFe2O4 (CFO) as a function of the stacking sequence, relative thickness and bottom electrode, in order to optimize the functional properties. Atomically flat (001)-oriented bilayers composed by BTO and CFO (either CFO/BTO or BTO/CFO) were grown epitaxially on conducting electrodes (SrRuO3 (SRO) or La2/3Sr1/3MnO3 (LSMO)) by pulsed laser deposition monitored by in-situ reflection high-energy electron diffraction (RHEED). Ex-situ X-ray diffraction confirmed the epitaxial growth of the three films. Out-of-plane and in-plane lattice parameters of BTO were determined by reciprocal space maps. It was found that BTO grown on the metallic electrode (either SRO or LSMO) is more tetragonal than when grown on CFO: in this latter case, the tetragonality c/a is much reduced.
200
BTO25/CFO100 BTO80/CFO15
(a)
P (C/cm )
2
75 50 25 0 -25 -50 -75
(b)
bulk
100
I (A)
-100
-200 -1000 -500 0 500 1000
-1000
-500
500
1000
E (KV/cm)
E (KV/cm)
Figure 1. I-E characteristics (a) and extracted P-E (b) ferroelectric loops of BTO(25nm)/CFO(100nm) and BTO(80nm)/CFO(15nm) bilayers grown on SRO. The loops have been recorded at 1kHz and the loss
The main results regarding ferroelectric behaviour are common to heterostructures on LSMO and on SRO. All the studied bilayers are ferroelectric, thus indicating that ferroelectricity in BTO is preserved. The bilayers with BTO at the bottom, that is, BTO grown on the metallic electrode, display better ferroelectric properties than those with BTO grown on top of the ferromagnetic CFO layer. This experimental observation, that can be well understood based on epitaxy and strain effects, is an important guide for engineering multiferroic heterostructures. Remarkably, for the thinner BTO layers grown on the metallic electrode, polarization values significantly above the bulk one are obtained (Fig.1b). Finally, we will also show that the sign of the imprint is clearly depending on the stacking sequence; we will argue that this is a consequence of the opposite symmetry of the band diagram in the different heterostructures. From the analysis of these data we will discuss how to optimize ferroelectric behaviour in these layered heterostructures.

187
NOVEL PHASES INDUCED AT INTERFACES WITH FERROELECTRICS

R. Cherifi1*, S. Valencia2, A. Chanthbouala1, A. Crassous1, V. Garcia1, X. Moya3, L. Bocher4, S. Fusil1, K. Bouzehouane1, C. Deranlot1, A. Gloter4, N.D. Mathur3, M. Bibes1 and A. Barthlmy1
Unit Mixte de Physique CNRS/Thales, Campus de Polytechnique, 1 avenue Fresnel, 91767 Palaiseau, France 2 Helmholtz-Zentrum-Berlin fr Materialen und Energie, Albert-Einstein-Strasse 15, 12489 Berlin, Germany 3 Department of Materials Science, University of Cambridge, Cambridge, CB2 3QZ, UK 4 Laboratoire de Physique des Solides, Universit Paris-Sud, CNRS UMR-8502, 91405 Orsay, France
1
At the interface with a ferroelectric, materials can see their electronic properties (carrier density, resistivity, etc [1]) or even their ground state [2] (e.g. superconductivity [3]) modified due to the influence of polarizationinduced charges. In addition, interfaces between ferroelectrics and ferromagnets may display magnetoelectric coupling through which polarization act on the magnetic properties and, reciprocally, magnetism is induced in the ferroelectric [4]. Recently, first-principles calculations even predicted the possibility of turning a paramagnet like Pd into a ferromagnet at the interface with a ferroelectric [5]. These possibilities are appealing for electronics and spintronics as they enable to apply the non-volatile electricfield control of polarization existing in ferroelectrics to other charge- or spinbased functionalities [6]. In this presentation, we will present our efforts towards the generation and control of novel phases at the interface with a ferroelectric. In particular, we will show that in the most archetypal ferroelectric, BaTiO3, a sizeable spontaneous and hysteretic magnetization can be created at 300K by interface coupling with simple ferromagnets such as Fe or Co. We have used x-ray magnetic circular dichroism and x-ray resonant magnetic scattering to independently collect the magnetic signal of the different ionic species and find ferromagnetic-like responses for Ti and O, coupled with those of Fe or Co [7]. Ab initio calculations on realistic interface structures provide insight on the coupling mechanisms and the origin of the induced moments, suggesting strategies to unveil more interface-induced artificial ferroic functionalities.
[1] [2] [3] [4] [5] [6] [7] H.L. Stadler Phys. Rev. Lett. 14, 979 (1965) C.H. Ahn et al, Rev. Mod. Phys. 78, 1185 (2006) K.S. Takahashi et al, Nature 441, 195 (2006) C.G. Duan et al, Phys. Rev. Lett. 97, 047201 (2006) ; B 78 212406 (2008) Y. Sun et al, Phys. Rev. B 81, 064413 (2010) V. Garcia et al, Science 327, 1106 (2010) S. Valencia et al, submitted
M. Fechner et al, Phys. Rev.
* ryan.cherifi@gmail.com

206
CHARACTERISTICS OF Gd2-xLaxO3 HIGH-K FILMS BY METAL-ORGANIC CHEMICAL VAPOR DEPOSITION
Liu-Ying Huang
Ai-Dong Li1, Ying-Ying Fu, Wen-Qi Zhang, Hui Li, and Di Wu
National Laboratory of Solid State Microstructures, Materials Science and Engineering Department, Nanjing University, Nanjing 210093, P. R. China
Gd2-xLaxO3 high-k films were deposited on Si substrates by low-pressure metal-organic chemical vapor deposition (MOCVD). The metal-organic precursors we used were Gd(thd)3 and La(thd)3 [thd=tris(2,2,6,6-tetramethyl-3-5-heptanedionato)]. The structure, band gap, composition and electrical properties of Gd2-xLaxO3 films have been investigated. X-ray diffraction patterns show that as-deposited thick Gd2-xLaxO3 films have formed cubic phase of solid solution. The band gap of the Gd2-xLaxO3 films can be calculated to be 5.78 eV using a UVvis-NIR spectrophotometer. X-ray photoelectron spectroscopy depth profile analyses reveal that there exists an interfacial layer of Gd-La-Si-O silicate and the La element is rich in interfacial layer. The equivalent oxide thickness (EOT) of 1.08 nm has been obtained with the flatband voltage (Vfb) of 1.0 Vfor Gd2-xLaxO3 (x=1.29) films of 8nm physical thickness after 800 oC post-annealing.
Fig.1. XRD patterns of Gd2-xLaxO3 thick films deposited on Si Fig.2. XPS depth profiles of (c) O element in at 600 oC for 45 min with various La/Gd source flux ratios. the Gd2-xLaxO3 films after 800 oC post-annealing Presenting author: Ai-Dong Li, E-mail: adli@nju.edu.cn, topic 6: High-K dielectrics and polymers; poster

209
TRAPPING PROPERTIES OF LiNbO3 /AlGaN/GaN METAL-FERROELECTRIC-SEMICONDUCTOR HETEROSTRUCTURE CAPACITORS BY CONDUCTANCE MEASUREMENTS
H.Z. Zeng,a) W. Huang, Y. Lin, L.Z. Hao, W.B. Luo, and Y.R. Li State Key Laboratory of Electronic Thin Films and Integrated Devices University of Electronic Science and Technology of Chin Chengdu 610054, Peoples Republic of China
Ferroelectric LiNbO3/AlGaN/GaN heterostructure capacitor was fabricated by a pulsed laser depsotion method. It shows memory characteristics in capacitance-voltage (C-V) measurements, with a hysteresis window of 0.3~12.1 V. The trapping properties of the ferroelectric LiNbO3 /AlGaN/GaN heterostructure capacitors were characterized by temperature dependent capacitance and conductance measurements. In a wide temperature range (200~450 K), two kind of traps were identified by the conductance measurements. One is the interface trap with the density of 1.11012 to 1.41010 cm2eV1, which shows an exponential dependency of time constant on the bias applied to the heterostructure. The other is the bulk trap with a lower density, about (1~4) 1010 cm2eV1, which manifests at higher temperatures. It is found that the trapping density significantly affects the C-V hysteresis and leackage properties of the ferroelectric LiNbO3/AlGaN/GaN capacitors.
a) Email: huizhongzeng@gmail.com Prefered to ORAL presentation at ISIF2011 under topic 11.DEVICES.
ISIF 2011 Poster Session A - Tuesday 2 August, 12:20 - 13:30 212
STUDY OF STRUCTURAL, MAGNETIC AND FERROELECTRIC ON Bi5FeTi3O15 AND Bi5Fe0.5Co0.5Ti3O15 CERAMICS
Xiangyu Mao, Wei Wang, Xi. Hu, Yalin Lu and Xiaobing Chen
College of Physics Science and Technology, Yangzhou University, Yangzhou 225002, Peoples Republic of China Leser and Optics Research Center, Department of Physics, US Air Force Academy, Colorado 80840, USA
The compounds Bi5FeTi3O15 (BFTO) and Bi5Fe0.5Co0.5Ti3O15 (BFCT) were prepared by incorporating BiFeO3(BFO) and BiFe0.5Co0.5O3 (BFCO) into the host Bi4Ti3O12 using the solid state reaction technique. The X-ray diffraction and Raman shift data indicate that the as-prepared materials are of the four-layer Aurivillius phases with an orthorhombic symmetry. At room temperature and under a driving electric field of 230 kV/cm, the half substitution of Fe-O layer by Co-O layer is found to result in the increase in the 2Pr by about 35% and simultaneously the decrease in 2Ec by about 41%, respectively[Fig. 1]. The magnetic moment at least tripled its value by substituting half Fe ions by Co ions. The remnant magnetization (2Mr) and the coercive field (2Hc) were about 7.8 memu/g and 410 Oe, respectively[Fig. 2]. The 2Mr of BFCT is about three thousand times the value of BFTO. The magnetization below 275 oC is relaxation like and its magnetic Curie temperature (TcM) is at ~ 345 oC.
Fig. 1. At RT, the ferroelectric loops of BFTO and BCFT samples.
Fig. 2. At RT, magnetic hysterrsis of BFTO and BCFT samples, inset: the enlarged central part of the MH curve for BFTO.
Corresponding Author. Email: xbchen@yzu.edu.cn.

1

215
EFFECTS OF ANNEALING ATMOSPHERE ON STRUCTURE AND ELECTRICAL PROPERTIES OF (Bi0.9Eu0.1)(Fe0.9Mn0.1)O3- THIN FILMS
J. W. Kim, G. H. Kim, Y. R. Bae, E. S. Kim, H. J. Kim, C. M. Raghavan, D. Do, W. J. Kim, Y. S. Sung1, M. H. Kim1, T. K. Song1 and S. S. Kim* Department of Physics, Changwon National University, Changwon, Gyungnam 641-773, Republic of Korea
1
School of Nano and Advanced Materials Engineering, Changwon National University, Changwon, Gyungnam 641-773, Republic of Korea *E-mail; sskim@changwon.ac.kr
Rhombohedral bismuth ferrite (BiFeO3, BFO) has been reported as an outstanding candidate for the room temperature ferroelectromagnetic applications. It has high ferroelectric (Tc ~810oC) and magnetic (TN ~380oC) transition temperature. Even though, BFO shows superior ferroelectric properties, the low electrical resistivity by the large leakage current has much influence on the device quality. The low resistivity is mainly related to the oxygen nonstoichiometry and the existence of chemical fluctuation in the Fe valencies (Fe3+/Fe2+). It is strongly suggested that the defect engineering concept has been applied to reduce the leakage current and to improve the ferroelectric properties in the BFO thin film. In this presentation, we have mainly focused on the effect of annealing atmosphere (air, N2 and O2) on the electrical properties of (Eu, Mn)-co-doped BiFeO3 thin film. Euand Mn-co-doped BiFeO3
[(Bi0.9Eu0.1)(Fe0.9Mn0.1)O3-, (BEFMO)] thin film was deposited on Pt(111)/Ti/SiO2/Si substrates by using a chemical solution deposition method. The coated films were annealed under air, N2 and O2 atmospheres at a temperature of 550 oC for 30 min. Effects of annealing atmosphere on the structure, ferroelectric properties and leakage current behavior of the BEFMO thin film were investigated. The single-phase rhombohedral perovskite crystal structure of all the samples was confirmed by X-ray diffraction. From the electrical studies, the BEFMO thin film annealed under air atmosphere showed better electrical properties than O2 and N2 atmosphere annealed samples. The remnant polarization as large as 81.1 C/cm2 at an applied electric field of 1435 kV/cm was obtained in the BEFMO thin film and the film showed improved leakage current behavior.
1. Topics; BiFeO3 and Multiferroics 2. E-mail; jinwonk@changwon.ac.kr (J. W. Kim, Changwon National University) 3. Prefer to poster presentation

216
STRUCTURE AND ELECTRICAL PROPERTIES OF RARE-EARTH SUBSTITUTED Bi(Fe0.975Cu0.025)O3- THIN FILMS PREPARED BY CHEMICAL SOLUTION DEPOSITION
D. Do, J. W. Kim, G. H. Kim, Y. R. Bae, E. S. Kim, H. J. Kim, C.M. Raghavan, Y. S. Sung1, M. H. Kim1, T. K. Song1 and S. S. Kim* Department of Physics, Changwon National University, Changwon, Gyungnam 641-773, Republic of Korea
1
Multiferroic materials have been widely investigated for the fabrication of integrated devices such as memories, spintronics and sensors. Among the existing materials, bismuth ferrite (BiFeO3, BFO) is a well known single phase room temperature magnetoelectric compound having high Curie Tc (~810oC) and Neel TN (~380oC) transition temperatures. BFO has a rhombohedral perovskite crystal structure with R3c space group. Occurrence of high leakage current density in BFO thin films limits effective utilization for the practical applications. There are plenty of research on the reduction of leakage current density and improving ferroelectric properties in BFO thin films by defect-structure engineering (substitution of rare earth metal ions on the Bi3+ site and transition metal ions on the Fe3+site). In addition to suppress oxygen vacancies, substitution of rare earth and transition metal ions also changing lattice constant(lattice distortion) in the BFO thin films, which may reduce the leakage current density and increases the ferroelectric properties. In this presentation, pure BFO and (Bi0.9A0.1)(Fe0.975Cu0.025)O3- (A=Dy, Eu, Nd, La, represented as BDFCO, BEFCO, BNFCO, BLFCO) thin films were prepared by using a chemical solution deposition method. For all samples, single phase rhombohedral perovskite crystal structure was confirmed by XRD analysis. The enhanced ferroelectric properties have been observed for the co-doped BFO thin films compared to pure BFO thin film. The remnant polarization (2Pr) of 68.8 C/cm2 at an applied electric field of 1336 kV/cm was obtained in the BEFCO thin film and the film showed improved leakage current behavior.
1. Topics; BiFeO3 and Multiferroics 2. E-mail; ddo@changwon.ac.kr (D. Do, Changwon National University) 3. Prefer to poster presentation

217
ENHANCEMENT OF FERROELECTRICITY IN RARE EARTH AND MANGANESE IONS CO-DOPED BiFeO3 THIN FILMS VIA CHEMICAL SOLUTION DEPOSITION METHOD
C. M. Raghavan, S. S. Kim*, J. W. Kim, W. J. Kim, D. Do, Y. S. Sung1, M. H. Kim1 and T. K. Song1 Department of Physics, Changwon National University, Changwon, Kyungnam 641-773, Republic of Korea
1
Bismuth ferrite (BiFeO3, BFO) is the most widely studied multiferroic material. It has simple rhombohedral crystal structure with high ferroelectric and magnetic transition temperatures (Tc ~810oC and TN ~380oC). However, large electrical leakage current in the BFO thin films causes high coercive field which leads to the difficulty in measuring hysteresis loops at room temperature. In this presentation, pure BFO and rare earth and manganese ions co-doped BiFeO3 [(Bi0.9A0.1)(Fe0.9Mn0.1)O3- (A=Nd, Sm, Ce and Tb, represented as BNFMO, BSFMO, BFCMO, BTFMO)] thin films were prepared by a chemical solution deposition method. Among them, the BNFMO thin film showed better electrical properties at room temperature. The remnant polarization as large as 95 C/cm2 at an applied electric field of 1194 kV/cm was obtained in the BNFMO thin film and the thin film showed improved leakage current density. The dielectric constant and loss factor for the thin film was found to be 139 and 0.038, respectively, at a frequency of 1 kHz. The result indicates that rare-earth and Mn-co-doped BFO thin films can effectively use for the ferroelectric memory applications.
1. Topics; BiFeO3 and Multiferroics 2. E-mail; cmragavan@changwon.ac.kr (C. M. Raghavan, Changwon National University) 3. Prefer to poster presentation

239
LIGHT CONTROLLED RESISTIVE SWITCHING IN AMORPHOUS AL2O3 FILMS

M. Ungureanu1, R. Zazpe1, R. Llopis1, F. Casanova1,2, L.E. Hueso1,2
1
CIC nanoGUNE Consolider, Tolosa Hiribidea 76, 20018 San Sebastian, Spain 2 IKERBASQUE, Basque Foundation for Science, 48011 Bilbao, Spain
Resistive random access memory, based on the change in the electrical resistance of an insulator under suitable applied voltage pulses, is seen as a promising candidate for the next generation of non-volatile memory devices. We investigated the resistive switching characteristics of aluminum oxide for memory applications. Amorphous Al2O3 films with thicknesses between 10 and 50 nm were prepared by atomic layer deposition (ALD) on Si/SiO2 substrates. Pd or Pd/Ti top metal contacts were deposited by magnetron sputtering after photolithography patterning. The current (I)-voltage (V) curves show a highly reproducible hysteresis when the sample is illuminated with visible light, as shown in figure 1. However, when external illumination is switched off, the samples present a very weak non-hysteretic response to applied voltages.
Figure 1: Characteristic I-V curves for a Pd/Al2O3/SiO2/Si memory stack illuminated with white light. The device can be switched between two states, corresponding to the increasing and decreasing branches of the hysteresis loop. From the observed I-V characteristics, the resistive switching could be attributed to the formation and rupture of conducting filaments in the Al2O3 film.

241
CHARACTERISATION OF NiO EPITAXIAL FILMS DEPOSITED BY MOLECULAR BEAM EPITAXY

G. Cheglakov1, Adrian Ionescu1, A. Bagnall1, L. Rokhinson2 and C.H.W. Barnes1
2
Thin Film Magnetism, Cavendish Laboratories, Cambridge, UK Department of Physics, Purdue University, West Lafayette, Indiana 47907 USA
Resistive Random Access Memory (RRAM) is seen as an attractive alternative to flash memory that currently is approaching its limits. Conceptually, RRAM devices are based on the electronic switching of an insulator element between two metals [1]. NiO films are promising candidates for RRAM as they can exhibit both unipolar and bipolar resistiveswitching properties (i.e. the switching operations between the low resistance state and the high resistance state have to be performed using opposite voltage polarity) [2]. In bulk NiO is an antiferromagnetic insulator that crystallises in a fcc structure with a lattice parameter of 4.18 , a Nel temperature of 525 K and a resistivity of 104 cm at room temperature [3-5]. Here we present results on high quality NiO epitaxial thin films grown by molecular beam epitaxy on MgO (100) and MgO (111) substrates. X-ray reflection (Fig. 1) and diffraction (Fig. 2) measurements indicate almost stoichiometric films with a lattice parameter matched to the underlying substrate. The interface roughnesses in the structures are below 2 . X-ray photoelectron spectroscopy results indicate in some of the films a slight Ni excess which leads to an increased magnetic susceptibility as compared to bulk. SQUID magnetometry measurements also show a decrease of the Nel temperature due to a change in the lattice parameter, in good agreement with the previous work [6]. Finally we will present temperature and thickness dependent resistivity measurements of these heterostructures.
Figure 1: XRR measurements of 65 nm of NiO(100)/MgO(100).
Figure 2: XRD measurements of 65 nm of NiO(100)/MgO(100).
References [1] Nishi, Y., Japanese Journal of Applied Physics 50, 015802 (2011). [2] Goux, L. et al., Journal of the Electrochemical Society 157, G187 (2010). [3] Fievet, F et al., Journal of Applied Crystallography 12, 387 (1979). [4] Kittel C., Introduction to Solid State Physics, printed by John Wiley & Sons, New York, 2005. [5] Nagakura S., Iwanami Dictionary of Physics and Chemistry, printed by Iwanami, Tokyo, 1998 (in Japanese). [6] Altieri S. et al., Physical Review B 79, 174431 (2009).

242
FABRICATION AND CHARACTERISATION OF Fe/GaAs ELECTRICAL SPIN INJECTION DEVICE

J. Y. Kim1, K. Lee1, S. N. Holmes2 and C. H. W. Barnes1
2
Thin Film Magnetism, Cavendish Laboratory, J J Thomson Avenue, Cambridge, U.K. Toshiba Research Europe Ltd., 208 Cambridge Science Park, Milton Road, Cambridge, U.K.
A basic model for a spin-based field effect transistor requires abilities to inject, manipulate and detect spin-polarised carriers in a single device [1]. In 2007, Lou et al. demonstrated a system with Fe contacts deposited on bulk n-type gallium arsenide, where spin-polarised carriers can be injected into the GaAs, manipulated with external magnetic fields and detected by the Fe contacts [2]. In this project, similar lateral injection devices were fabricated by depositing epitaxial Fe films on GaAs (001) surfaces. Low Energy Electron Diffraction (LEED) measurements confirmed epitaxial growth of Fe films. After the films were deposited, magnetic characterisation of films was performed by magnetooptical Kerr effect measurements, which are in excellent agreement with previous results [3]. After a series of optical lithography steps, devices were produced as shown in Fig. 1. Two Fe bars (200 m x 10 m) were patterned on top of a GaAs mesa structure (200 m x 800 m) and electrically contacted with Ti/Au contacts climbing sides of GaAs mesa. Figure 2 shows in-plane anisotropic magneto-resistance measurements of the Fe bars, where magnetisation switching were observed at around 70 Oe. Three-contact Hanle measurements were performed and will also be presented.
Figure 1. Optical microscope image of device Inset: SEM image of Ti/Au contact on a side of GaAs mesa.
Figure 2. AMR measurement of a Fe bar with applied magnetic field along the direction of the bar.
References
[1] S. Datta and B. Das, Appl. Phys. Lett. 56, 665 (1990). [2] X. Lou et al., Nature Physics 3, 197 (2007). [3] M. Gester, Ph.D. thesis, University of Cambridge (1994).

243
CO ADSORBATE INDUCED SPIN-REORIENTATION TRANSITION OF Co/Cu(110)

S. L. Chin1, R. Reeve1, A. Ionescu1, J. Cheng2 and C.H.W. Barnes1
1. Cavendish Laboratory, University of Cambridge, JJ Thomson Avenue, Cambridge, CB3 0HE, U.K. 2. Chemistry Department, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, U.K. Introduction Small amounts of residual gas such as N2, O2 and CO were found experimentally and theoretically to have profound effects on the surface magnetic properties [1-3]. Such effect has attracted attention in diverse research areas. For example, this effect is of paramount importance in controlling the process environments for spintronic devices fabrication. We present here a combined theoretical and experimental study of CO on Co/Cu(110) using in-situ Mott polarimetry and density functional theory (DFT) calculations. Decoupling of the spin-orbital magnetic moment Hope et al. studied the adsorption of CO on Co/Cu(110) using in-situ magneto-optical Kerr effect (MOKE) and o found that as little as 0.08ML of CO was enough to cause a spin reorientation transition (SRT), i.e. a 90 in-plane rotation of the magnetic easy axis from the [001] direction to [110] [4]. Recently, we extended this experiment by combining in-situ MOKE and Mott polarimetry [5]. Both the coercivity obtained from the MOKE and the secondary electron spin polarisation (SESP) from the Mott polarimtery measured along the initially magnetic easy axis vanished after being exposed to CO. DFT calculation showed that adsorption of 0.5ML CO partially quenched the surface magnetic moment which indicated that the SRT may be due to quenching of magnetic moments at the adsorption sites. Although both the SESP and coercivity were expected to vanish, they did not do so simultaneously. Since Mott polarimetry measures only the spin contribution, whereas MOKE measures both the spin and orbital contributions of the magnetic moment, this indicated that during the SRT the spin and orbital moments did not rotate at the same time and therefore decoupling of spin-orbital magnetic moment occurred. Electron beam switch-back and bit patterning The SRT can be reversed by extended exposure to an electron beam [5]. The switch-back was believed to be caused by the dissociation of the CO bond by the electron beam, leaving C on the adsorption sites. Not only did the C prevented a reoccurrence of the SRT by blocking the CO adsorption site, it also caused the SESP signal to be lower than the clean Co/Cu(110) surface (Fig. 1). Local tuning of the surface magnetic anisotropy was possible by carefully exposing the Co/Cu(110) surface at two separate locations (Fig. 2). Therefore we conclude that bit patterning is possible by using an electron beam to alter the magnetic anisotropy locally.
e beam exposure
Fig. 1: Electron beam exposure reversing the SRT for different film thicknesses
Fig. 2: Coercivity along the [001] direction shows local tuning of the magnetic anisotropy.
References [1] K.P. Kopper, et al., Physical Review B, 80, 052406 (2009). [2] D. Gunn, et al., Surface Science, 603, (6), p. L54-L48 (2009). [3] S. Pick, et al., Phys. Rev. B, 75, 195446 (2007) [4] S. Hope, et al., Physical Review B, 57, p. 7454 (1998) [5] R. Reeve, et al., IEEE Trans. on Magnetics, 47, (6), (in press 2011)

249
COMPARATIVE STUDY ON STRUCTURE AND FERROELECTRIC PROPERTIES OF DIFFERENT RARE-EARTH SUBSTITUTED MULTIFERROIC BiFeO3
Yongyuan Zang, 1) Dan Xie, 2) Mohan Li, 3) Xueguang Han, 2) Tingting Feng, 2) Xiao Wu, 2) Tianling Ren, 2) and David Plant 1)
1
Electrical and Computer Engineering, McGill University, Montreal, Quebec, H3A 2T8, Canada Tsinghua National Laboratory for Information Science and Technology (TNList), Institute of Microelectronics,
Tsinghua University, Beijing, 100084, P. R. China

3
Chemical Engineering, McGill University, Montreal, Quebec, H3A 2B2, Canada
Multiferroic material BiFeO3 (BFO) with a high remnant polarization, coexistence of ferroelectric and antiferromagnetic orders, is considered as a perspective candidate for many technologically demanding applications. However, high conductivity nature due to the Fe ions valence fluctuation and Bi atoms volatile nature is a major problem for the BFO room temperature application. Many cation substitutions for Bi and Fe have been introduced to reduce the electrical leakage problem. In this paper, we report a comparative study between different rare-earth substituted BFO materials and an optimized substation pattern is concluded from the structural and ferroelectric characterization. BiFeO3, Bi0.95Nd0.05Fe0.95Nb0.05O3, Bi0.95Nd0.05Fe0.95Mn0.05O3, and Bi0.95La0.05Fe0.95Nb0.05O3 thin films are deposited on Pt/Ti/SiO2/Pt substrate by sol-gel process. XRD patterns show well defined pervoskite phase with few secondary phase in the doped BFO thin films. Moreover, highly intensive (110) peak without any structural distortion is observed in the (La, Nd) doped BFO crystal, indicating a preferred orientation due to the increased lattice parameters and an improved crystallinity. Morphology of the doped BFO thin films is measured by AFM. It can be concluded that the small grains are merged and surface roughness decreases with rare-earth substitution. (Nd, Nb) doped BFO exhibits the smallest surface roughness in the measurement due to grain-merging during the nucleation process. Current density-voltage (J-V) characteristics are also investigated and a remarkable leakage current improvement is observed in the (Nd, Nb) doped BFO thin film, namely, 110-8 A cm-2 in the lower electric filed region and 510-6 A cm-2 in the saturated region, which is 4 order of magnitude lower than the undoped BFO. This improvement can be attributed to the significant reduction of oxygen vacancies caused by Nd and Nb substitution. Meanwhile, (La, Nb) doped BFO also exhibits well leakage density in the range of 10-5 A cm-2 when applied with lower electric filed. Substitution dependence of leakage density model and mechanics is extracted from the above J-V characters. Frequency dependence (1 KHZ-1 MHZ) of relative dielectric constant and loss tangent factor and other fundamental ferroelectric properties for different rare-earth doped BFO thin film are also detailed and compared in this paper.
Fig.1 Current density-voltage characteristics of different rare-earth doped BFO thin films.
1

250
TEMPERATURE CONTROL OF P(VDF-TRFE) COPOLYMER THIN FILMS DERIVED BY SOL-GEL PROCESS Tingting Feng, 1) Dan Xie, 1) Yongyuan Zang, 2) Mohan Li, 3) Xueguang Han, 1) Xiao Wu,1) Tianling Ren, 1) and David Plant 2)
1
Tsinghua National Laboratory for Information Science and Technology (TNList), Institute of Microelectronics,

2 3
Electrical and Computer Engineering, McGill University, Montreal, Quebec, H3A 2T8, Canada Chemical Engineering, McGill University, Montreal, Quebec, H3A 2B2, Canada
To furthure understand the effects of annealing temperature (Ta) in the preparation process of spin-coated ferroelectric poly(vinylidene fluoride/trifluoroethylene) [P(VDF-TrFE)] copolymer thin film, the mircostructure and morphology of P(VDF-TrFE) (70/30) thin films annealed at different temperatures (70C -160C ) were investigated. As indicated in atom force microscope (AFM), it can be observed that the morphology of P(VDF-TrFE) thin films change greatly with annealing temperature. With the increase of Ta, the crystallites of P(VDF-TrFE) thin film grow from small spheroids into larger particles, and further grow longer to be the popular structure of ferroelectric phase. When Ta exceeds 140C, the ferroelectric grains merge into large rod-like structures, leading to the P(VDF-TrFE) thin film with high surface roughness and low coverage of substrate, leading to a short leakage problem which many researchers have encountered. When Ta exceeds the melting point of P(VDF-TrFE), the crystal grains began to melt, forming a relatively dense film. XRD measurements show that the crystallinity of ferroelectric phase is also affected by Ta. As the annealing temperature increases, the crystallinity of ferroelectric phase increases at first, and then reduces when Ta is larger than the melting point.
Fig. 1 Microstructures of P(VDF-TrFE) thin films processed at different annealing temperatures.
Fig. 2 XRD patterns of P(VDF-TrFE) copolymer thin film processed at different annealing temperatures.

251
Copper ions induced resistance switching in ZnO thin films

Tran Le1, Duc Hoang Tran2, Thi Kieu Hanh Ta2, Tuan Tran2, Van Hieu Le2, Hoang Cao Son Tran2, Jaichan Lee3 and Bach Thang Phan2,3,* Faculty of Physics and Physics Engineering, University of Science, Vietnam National University, HoChi Minh City, Vietnam 2 Faculty of Materials Science, University of Science, Vietnam National University, HoChi Minh City, Vietnam 3 Advanced Materials Science and Engineering, Sungkyunkwan University, Suwon, South Korea
1
We investigated resistance switching behavior of ZnO thin films deposited by using Magnetron sputtering. The ZnO thin films were sandwiched between the metallic electrodes in metal oxide metal structures with different electrode materials (Pt, Ti, Al, Ag, ITO and Cu). The Cu ZnO Cu structure showed the good unipolar switching behavior. The additional experiments strongly figured out the role of copper ions in inducing the resistance switching.
Key words: Resistance switching, ZnO, Copper ions, Magnetron sputtering
Corresponding author:
pbthang@skku.edu pbthang@hcmus.edu.vn

252
Dong Jin Yoon, Jai-Yeoul Lee, and Hee Young Lee* School of Materials Science and Engineering, Yeungnam University, Gyeongsan, Korea e-mail : hyulee@yu.ac.kr Abstract
Multiferroic properties of BaTiO3-CuFe2O4 thin films grown on highly-textured Pt(111)/TiO2/SiO2/Si(100) substrates were studied. Sintered BaTiO3 and CuFe2O4 pellets prepared by the conventional mixed oxide process were used as targets during deposition by the pulsed laser deposition technique. The film structure is of bi-layer type, where BaTiO3 layer lies underneath of CuFe2O4 layer. Ferroelectric and electrical properties were measured using TF-analyzer 2000, Keithley 6430, and Agilent 4294A. The magnetic hysteresis (M-H) behavior at room temperature was measured using vibration sample magnetometer (VSM). We have previously reported the multiferroic behavior of the similar structure, i.e. BaTiO3-Fe bi-layer thin films, in which the possibility of ferroelectric-ferromagnetic coupling was suggested as a result of interfacial reaction between the layers. Top Fe layer, however, is not chemically stable in an oxidizing atmosphere, and as a result CuFe2O4 spinel film replaced Fe layer in this study.
Corresponding author: Hee Young Lee, School of Materials Science and Engineering, Yeungnam University, Gyeongsan 712-749, Korea. Tel: +82-10-9812-2562, Fax: +82-53-810-4628, E-mail: hyulee@yu.ac.kr
Submitting authors name Institution Address e-mail Topic Preferred mode of presentation
Dong Jin Yoon School of Materials Science and Engineering 214-1 Dae-Dong, Gyeongsan, 712-749, Korea felix3@hanmail.net BiFeO3 and Multiferroics Poster

255
Resistive switching characteristics and different forming states of Ti/ Pr0.48Ca0.52MnO3 junctions
C. Park1*, A. Herpers1, R. Dittmann1, R. Bruchhaus1, J. Verbeeck3, G. van Tendeloo3, R. Waser1,2
1 Peter Grnberg Institut, Electronic Materials (PGI-7) and Jlich-Aachen Research Alliance, Fundamentals of Future Information Technology (JARA-FIT), Research Center Jlich, Germany 2 Institut fr Werkstoffe der Elektrotechnik 2 (IWE II), RWTH Aachen University, Germany 3 EMAT, Electron Microscopy for Materials Science University of Antwerp, Belgium
We investigated the resistive switching (RS) characteristics in epitaxial Pr0.48Ca0.52MnO3 (PCMO) thin films sandwiched between a SrRuO3 (SRO) bottom electrode and a Ti top electrode. Hysteretic current-voltage characteristics, i.e., RS effects, were observed for Ti/PCMO junctions after a first forming procedure, which changes the initial resistance state to the high resistance state (HRS). The initial state and the HRS after the first forming show a clear the area dependence which hints on a homogeneous current distribution in both cases. After the first forming step, we observed a strong asymmetric switching hysteresis curves which are dominated by the p-n-junction at the Ti/PCMO interface. By performing crosssectional transmission electron microscope (TEM) and electron energy loss spectroscopy (EELS), we found that there exists a TiOx and a CaTiyOz layer at the as-prepared Ti/PCMO interface and the thickness of the CaTiyOz layer slightly increases after the first forming step. Moreover, we were able to perform a second forming step which changes the HRS to the low resistance state (LRS), when a higher bias than the bias which is needed for the first forming is applied in the Ti/PCMO junctions. After the second forming step, we observed a stable hysteresis behavior in both bias regions, but the area dependence disappeared. This implies that conducting filaments might form at the Ti/PCMO interface after the second forming step. Concerning the driving mechanism, resent studies in metal/PCMO junctions have indicated that the electrochemical migration of oxygen vacancies induces the RS effect. However, the Ti/PCMO interface is more complicating due to mixed interfaces and an oxygen-deficient PCMO layer. We will discuss possible scenarios for the microscopic mechanisms for the observed homogeneous and filamentary switching types.

257
RARE EARTH SUBSTITUTED MULTIFERROIC BiFeO3

Christopher M. Kavanagh Department of Chemistry, University of St Andrews, St Andrews, KY16 9ST BiFeO3 is one of the most widely studied multiferroic materials because of its magnetoelectric properties (i.e. ferroelectric, with a high Curie temperature, T C ~ 810 830 C, and antiferromagnetic with TN ~ 370 C)1. The study and application of BiFeO3 is hindered by its thermal metastability and overriding electrical conduction due to nonstoichiometry2. One common approach to improve the properties is by substitution of the volatile Bi3+. In this case we dope BiFeO3 with lanthanum (Bi1-xLaxFeO3) and neodymium (Bi1-yNdyFeO3). This results in improve stability of the perovskite phase. We have investigated structural transitions as a function of temperature and degree of doping using a number of different techniques including XRD and electrical impedance spectroscopy. We propose a series of transitions from R3c - Imma (x = 0.3) - Pbnm (x 50) within the lanthanum doped system (BLFO). In contrast the neodymium doped system shows the existence of a Pbam phase (R3c Pbam Pbnm). Electrical characterisation of the materials are also discussed.
1 2
G. Catalan & J.F Scott, Adv. Mater., 21 (24), 2463, 2009. W. Eerenstein, F.D. Morrison, J. Dho, M.G. Blamire, J.F. Scott & N.D. Mathur, Science, 307 (5713), 1203a, 2005.

259
ELECTRICAL PROPERTIES OF ZnO THIN FILMS ON DIFFERENT SUBSTRATES M. Echizen et al., Samco Corp., Kyoto, Japan We have fabricated ZnO thin films via pulsed laser deposition (PLD). Those deposited on MgO have Schottky-limited currents that are symmetric with respect to polarity. Those deposited directly on Si have diode-behavior which is highly asymmetric with respect to voltage polarity. IV(V) characteristics and losses are compared in detail.

3
HIGH Q-FACTOR Ba0.25Sr0.75TiO3 THIN FILM BULK ACOUSTIC WAVE RESONATORS: GROWTH CONDITIONS AND CORRELATIONS WITH MICROSTRUCTURE
A. Vorobiev, S. Gevorgian, M. Lffler, E. Olsson Chalmers University of Technology, SE-41296 Gothenburg, Sweden
The electrically tunable thin film bulk acoustic wave resonators (FBARs), utilizing electric field induced piezoelectric effect in paraelectric phase ferroelectrics, enable development of novel reconfigurable/adaptable circuit architectures. However, the practical applications are hindered by their relatively low acoustic Q-factor which is limited by extrinsic loss mechanisms associated with structural imperfections. The Qf product of the best reported tunable BaxSr1-xTiO3 (BSTO) FBARs are in the range 400-600 GHz. In this work correlations between microstructure and Q-factor of tunable solidly mounted BSTO FBARs are studied using analysis of the test structures prepared at different growth temperatures of the BSTO films varying in the range 450-650 C. The BSTO films are deposited by magnetron sputtering in onaxis configuration at 2 mTorr gas pressure. These deposition conditions support formation of the films with low grain misorientation which, in turn, reduces the generation of shear waves leaking through the Bragg reflector. The observed changes in the Q-factor with growth temperature are correlated with related changes in microstructure including the grain size, texture misalignment, interfacial amorphous layer, surface roughness and deterioration of the Bragg reflector layers. The correlations are established through analysis of corresponding extrinsic acoustic loss mechanisms including Rayleigh scattering at localized defects, acoustic attenuation by amorphous layer, generation of the shear waves leaking into the substrate, wave scattering by surface roughness and resonance broadening by local thickness variations. The observed drop in the Q-factor with growth temperature above 590 C is associated mainly with sharp increase in the roughness (Fig. 1) at top (Fig. 2) and bottom (Fig. 3) interfaces and corresponding acoustic losses due to wave scattering and resonance broadening by local thickness variations. The dashed line in Fig. 1 is a simulated quality factor taking into account loss associated with scattering by top interface roughness. The increase in the roughness is caused by a deformation of the Pt bottom electrode (Fig. 3) during heating up to the BSTO film growth temperature due to large differences in the thermal expansion coefficients of the Pt and the SiO2 layers of the Bragg reflector below. The FBAR utilizing BSTO film grown at 585 C reveals series resonance at 5.15 GHz with Q=360 (Qf=1854), tunability of the resonance frequency 1% and electromechanical coupling coefficient 2.5% at 25V dc bias.
Fig. 1. Quality factor (circles) and surface roughness of the BSTO films (squares) vs. growth temperature.
Fig. 2. AFM image of a BSTO film grown at 610 C.
Fig. 3. TEM cross-section image of the bottom interfacial area of a BSTO film grown at 625 C.

13
CO IMPLANTATION OF Pb(Mg1/3Nb2/3)O3-PbTiO3 SINGLE CRYSTALS: EFFECT ON THE FERROELECTRIC DOMAIN CONFIGURATION
Jess Ricote1, Mara Torres1, Harvey Amorn1, Miriam Jaafar1, Norbert Nemes2, Susana Holgado3, Juan Piqueras4, Agustina Asenjo1, Mar Garca-Hernndez1 and Miguel Alguer1
1Instituto 2GFMC,
de Ciencia de Materiales de Madrid, CSIC. Cantoblanco, 28049 Madrid, Spain
Departamento de Fsica Aplicada 3, Universidad Complutense de Madrid, 28040 Madrid, Spain

3Escuela
Politcnica Superior, Universidad Autnoma de Madrid, 28049 Madrid, Spain
4Laboratorio
de Microelectrnica, Facultad de Ciencias, Universidad Autnoma de Madrid, 28049 Madrid, Spain Presenting author: jricote@icmm.csic.es
Ion implantation of magnetic species into semiconductor substrates has successfully been used to prepare dilute magnetic semiconducting layers for spintronics, and clustering has been described at high doses [1]. In this communication, we report our results on the application of the same concept to prepare magnetoelectric thin film composites [2]. In the experiments here reported, high increasing doses of 11016, 21016, 51016 and 11017 Co ions cm-2 were implanted into commercial Pb(Mg1/3Nb2/3)O3-PbTiO3 single crystals (TRS X2B) at 200 kV. Simulation with SRIM2008.04 resulted in a projected range of 79 nm with a longitudinal straggling of 44 nm. Therefore, average Co concentrations between 1x1021 and 1x1022 cm-3 are anticipated in a surface layer of 100 nm. Changes of the surface topography and of the ferroelectric domain configuration were studied by piezoresponse force microscopy. A drastic modification was found, which is further analyzed by high resolution and scanning transmission electron microscopy of cross-section specimens. The appearance of ferromagnetism is also studied by SQUID magnetometry, and locally by magnetic force microscopy.
[1] N. Akdogan et al., J. Appl. Phys. 105, 043907 (2009) [2] C.A.F. Vaz et al., Adv. Mater. 22, 2900 (2010)
Implantations were carried out at Forschungszentrum Dresden-Rossendorf (Germany) under the EC I3 contract no. 227012 (SPIRIT). International Symposium on Integrated Functionalities ISIF 2011 Topic 3.Magnetic and Ferroelectric Nano-Domains & PFM Preference to poster presentation

14
Temperature dependent electric and dielectric analysis of BST films with blocking and injecting electrodes
Thorsten J. M. Bayer, Shunyi Li, Cosmina Ghinea, Robert Schafranek, Andreas Klein Department of Materials and Earth Science Technische Universitt Darmstadt Petersenstr. 32 64287 Darmstadt, Germany
Abstract: The interface formation of (Ba,Sr)TiO3 thin films with different electrodes like platinum and transparent conducting Sn-doped indium oxide (ITO) has been studied by photoelectron spectroscopy with in situ sample preparation via RF magnetron sputtering. The energy level alignment indicates a very small barrier height at the ITO/BST interface compared to the barrier height at the Pt/BST interface. Current-voltage measurements have been performed on BST thin films with parallel-plate structure using Pt bottom and either Pt or ITO top electrodes to investigate the charge transport through the BST film. Thereby a strong influence of electrode materials on the electrical properties of the BST films is observed. BST capacitors with Pt electrodes show a back-to-back diode behavior and a relatively low leakage current. In contrast, the BST films with ITO top electrodes show high leakage currents and a space-charge limited current (SCLC) behavior with slopes above 2 in forward bias direction. The space charge also leads to a relaxation in the frequency dependence of the dielectric response. The current voltage and low frequency dielectric behavior are strongly depending on the carrier mobility, which is significantly lower than the carrier mobility of doped (Ba)SrTiO3 single crystals reported in literature.
The topic under which your abstract should be considered for presentation Tunable Dielectrics for RF Applications and Devices Presenting author's affiliation and email address Darmstadt University of Technology, Germany tbayer@surface.tu-darmstadt.de Preference to oral or poster presentation Oral presentation

25
TWO DIMENSIONAL DISTRIBUTION OF THE RELAXATION TIMES OF RELAXORS

Juras Banys1, Andrejus Mikonis1, Robertas Grigalaitis1, Anthony Kania2
1 2
Faculty of Physics, Vilnius University, Lithuania
August Chelkowski Institute of Physics, University of Silesia, Poland e-mail: juras.banys@ff.vu.lt
Relaxors and dipolar glasses show very broad distribution of the relaxation times. Due to that the usual models, such as Cole Cole equation or Davidson Cole or Havriliak Negami equations are working not very well especially at low temperatures, where the distribution of the relaxation times becomes extremely
broad. To address these shortcomings a calculation program was created, which allowed to extract one dimensional
0.6
distribution of the relaxation times. If we

E / eV
0.3 0.0 -20 -10 0
assume, that each relaxation time follows the Arrhenius law, with certain activation energy and attempt relaxation time, we can obtain two dimensional distribution function of attempt relaxation times and activation energies. Such calculations have been
lg( / s)
performed for different materials, such as classical dipolar glasses BP/BPI, classical relaxors PMN (Fig.1) and PLZT. The
Fig.1 Two dimensional distribution of activation energies and attempt relaxation time of PMN crystal measured from 10-3 Hz to GHz frequency range.
graphs allow us to distinguish between dipolar glasses and relaxors. Also, the results confirmed Meyer Neldel law with different values of the linear coefficients. The differences and common features of these two classes of materials will be presented.

33
FERROELECTRICANDPIEZOELECTRICPROPERTIESOFMULTILAYERCOMPOSITETHIN FILMSBASEDONMPBPb(Mg1/2Nb2/3)O3PbTiO3 H.ElHoisnyali,1R.Jimnez,1J.Ricote,1J.PrezdelaCruz,2J.R.A.Fernandes2,3andM.L. Calzada1
Instituto de Ciencia de Materiales de Madrid (CSIC). Cantoblanco. 28049 Madrid. Spain. 2 INESCPorto,UOSE,RuadoCampoAlegre,687,4169007Porto.Portugal. 3 Universidade de TrsosMontes e Alto Douro, Apartado 1013, 5001-801, Vila Real, Portugal. One of the most widely studied piezoelectric material is the (1x)PbMg1/3Nb2/3O3 xPbTiO3(PMNT)solidsolution,neartotheMorphotropicPhaseBoundary(MPB).1This is due to the ultrahigh piezoelectric activity observed in bulk materials at these compositions,2 with reported piezoelectric coefficients (d33) of 2500 pm/V. The integrationof these compounds into microelectronic devices requires the fabrication of thin films. However, a strong reduction in the properties of these materials is observed when they are prepared in thin film form onto metalized Sibased substrates.3 Therefore, new strategies for the fabrication/architecture of relaxor ferroelectric MPBPMNT films should be investigated in order to enhance the remanence of the properties in the device. In this work, we propose a multilayer configuration that uses layers of a poled ferroelectric material with large remnant polarization (Pr), such as PbTiO3 (PT), to generate a stable internal electric field on PMNTlayersburiedbetweenthem.Thisinternalelectricfieldwillinduceapolarization in the PMNT layers that will remain even without the application of any external electric field, effectively increasing the remanence of the material properties.4 Following this idea, we have prepared multilayer composite (MLC) thin films of alternating layers of PT and PMNT onto Pt/TiO2/SiO2/Si(100) substrates, by Chemical Solution Deposition (CSD). Ferroelectric and dielectric properties of the above mentioned MLC thin films have been studied in comparison with those of the single phase PT and PMNT films. In addition, the macroscopic and local piezoelectric responsesofthesematerialshavebeenmeasuredbyusinganopticalinterferometry and Piezoresponse Force Microscopy techniques, respectively. The feasibility of the integration of these MLC MPBPMNTbased films as piezoelectric elements in microelectromechanicalsystemsisdiscussed.
1. Z.G.Ye,MRSBull.34,277(2009). 2. S.E.ParkandT.R.Shrout,J.Appl.Phys.82,1804(1997) 3. J. H. Park and S. TrolierMcKinstry, J. Mater. Res., 16(1) (2001). M.L.Calzada, M.Alguer,A.Santos,M.Stewart,M.G.CainandL.Pardo.J.Mater.Res.,2,24(2009). 4. H. El Hosiny Ali, R. Jimnez, J. Ricote, M. Alguer and M.L. Calzada, Thin Solid Films (submitted). ThisworkhasbeensupportedbythespanishprojectMAT201015365 Topic7.PiezoelectricsandOptoElectronicsforSensors,Actuators&Transducers

51
HYDROSTATIC PRESSURE EFFECT ON PHASE TRANSITIONS IN TlIn(S0.97Se0.3)2 FERROELECTRIC
R.R. Rosul1, P.P.Guranich1, O.O.Gomonnai1, M.Yu.Rigan2, I.Yu.Roman 3, A.G.Slivka1, V.M. Rubish2 and A.V. Gomonnai3
1
Uzhhorod National University, Pidhirna St. 46, 88000 Uzhhorod, Ukraine, 2Uzhhorod
Scientific and Technological Centre for Materials of Optical Information Carriers, Institute for Information Recording, Ukr. Nat. Acad. Sci., Zamkovi Skhody 4, 88000 Uzhhorod, Ukraine, 3Institute of Electron Physics, Ukr. Nat. Acad. Sci.,Universytetska St. 21, 88000 Uzhhorod, Ukraine Studies of presure-induced physical effects in complex ferroics of different dimensionality enable a deeper insight into the nature of formation of incommensurate modulated structures and appearance of polycritical points in their phase diagrams as well as a targeted search for materials to become a base for pressure and temperature gauges, pyroelectric detectors of electromagnetic radiation [1]. TlIn(S1-xSex)2 crystals belong to this class of materials and are interesting to be studied since they are characterized by the existence of an incommensurate phase and polycritical phenomena. It should be noted that in the (p, T) phase diagram of TlInS2 crystal pressure-induced structural transformations to nonpolar phases are observed [2]. Besides, a Lifshitz-type point is observed in the (x, T) phase diagram of TlIn(S1-xSex)2 solid solutions at x = 0.05 [3]. TlIn(S0.97Se0.3)2 single crystals were grown by Bridgman technique. Dielectric constant and dielectric loss were measured at the measuring field frequencies of 1 MHz and 1 kHz along the [100] and [001] crystallographic directions as well as pyroelectric current. The sample temperature was measured by a copper-constantane thermocouple. At atmospheric pressure, in the temperature dependences of the dielectric constant in TlIn(S0.97Se0.3)2 crystal an anomaly is observed in the temperature range 200-210 K. With the pressure increase to 540 MPa, the anomaly of the dielectric constant is observed to shift towards higher temperatures. The positive sign of the pressure-related shift of the temperature of the anomaly means that the corresponding phase transformation can be treated as a phase transition of order/disorder type. The relevant pressure coefficients are determined. In the pressure range p > 560 MPa a qualitative change of the (T) dependence is observed, related to polycritical phenomena. At pressure p=560 MPa two anomalies are observed at the temperatures T1= 222 K and T2= 236 K, corresponding to first-order phase transitions induced by pressure. Based on the experimental results, the (p, T)-phase diagram of TlIn(S0.97Se0.3)2 crystal is built, its specific features being discussed. [1] A.M. Panich, J. Phys.: Condens. Matter. 20, 293202 (2008). [2] O.O. Gomonnai, P.P. Guranich, M.Y. Rigan, I.Y. Roman, A.G. Slivka, High Pressure Research 28, 615 (2008). [3] M.H. Yu. Seyidov, R.A. Suleymanov, F. Salehli, Physics of the Solid State, 51, 2513 (2009)

60
INTEGRATED THICK FILM ACOUSTIC EMISSION SENSOR FOR STRUCTURAL HEALTH MONITORING A Pickwell, R.A. Dorey, D. Mba Microsystems and Nanotechnology Centre, Cranfield University, Cranfield, UK, MK43 0AL The ability to monitor the condition of complex engineering structures is an important aspect of modern engineering, eliminating unnecessary work and enabling planned maintenance, preventing failure. One method to achieve real time continuous monitoring is through the use of Acoustic Emission (AE) testing. In addition to being a continuous monitoring technique it also has advantages of being non destructive and capable of in situ monitoring in a variety of environments. A novel thick film (17.6m) AE sensor, with the potential for integration into engineering structures, is presented. Piezoelectric lead zirconate titanate (PZT) thick films were fabricated directly onto stainless steel test beds using a powder/sol composite ink deposition technique and mechanically patterned to form a discrete, thick film piezoelectric AE sensors. The thick film sensors were benchmarked against a commercial AE device and found to exhibit comparable responses to simulated Acoustic Emissions. This work presents an overview of the fabrication process along with comparison results showing the performance of the thick film sensor relative to the commercially available sensor.

64
DIELECTRIC PROPERTIES OF PZT THIN FILMS UNDER A LOW AC-ELECTRIC FIELD AT DIFFERENT BIAS FIELDS
R. Renoud, C. Borderon, M. Ragheb and H.W. Gundel IREENA, EA 1770, University of Nantes, Nantes Atlantic Universities 2 rue de la Houssinire, Nantes, F-44322, France e-mail: raphael.renoud@univ-nantes.fr
Functional ferroelectric thin films present a great interest for telecommunication applications. In particular, the tunability of the dielectric constant under an applied electric field allows realizing of intelligent devices. The non linear variation of the permittivity is attributed to domain wall motion. The movement of domain walls under the influence of a low ac electric field corresponds either to a vibration around the equilibrium position (pinning centers) or to a jump towards another equilibrium position. The first mechanism corresponds to a reversible process whereas the second is related to an irreversible modification of the local polarization. For the permittivity, that results in the hyperbolic law that is an improvement of the Raleight law [1]. We present here a study of the parameters of the hyperbolic law as a function of the bias fields, i.e. at different points of the hysteresis cycle. We are in particular interested by the ratio between the reversible and the irreversible contributions to the permittivity. Experiments concern the real part of the permittivity but also the imaginary part which is related to losses phenomena. [1] C. Borderon, R. Renoud, M. Ragheb, H.W. Gundel, Appl.Phys.Lett. 98/1 (2011).

83
CHARACTERIZATION OF AN AUTONOMOUS NON-VOLATILE FERROELECTRIC MEMORY LATCH Caroline S. John1, Todd C. MacLeod2, Joe Evans2 and Fat D. Ho1
1
The University of Alabama in Huntsville, Department of Electrical and Computer Engineering, Huntsville, Alabama, 35899, USA 2 National Aeronautics and Space Administration, Marshall Space Flight Center, Huntsville, Alabama, 35812, USA 2 Radiant Technologies Inc., Albuquerque, New Mexico, 87107, USA ABSTRACT
Non-volatile memory forms an integral part of computer systems and its applications. Nonvolatile memory using ferroelectric components is more desirable over the other available memories due to its high endurance and high speed writing. The properties of the material to store an electric polarization in the absence of an electric field make the device non-volatile. In this paper we present an autonomous non-volatile ferroelectric memory latch using the principle that when an electric field is applied to a ferroelectric capacitor, the positive and negative remnant polarization charge states of the capacitor are denoted as either data 0 or data 1. The latch holds the new data as long as power is applied and returns automatically to that state when the power is removed and reapplied ensuring non-volatility. Further the memory latch is autonomous as it operates with the ground, power and output node connections only. The unique quality of this latch circuit is that it can be written when powered off. The circuit was laid out using discrete components which was used to characterize the design. This paper analyses the electrical characterization and the data retention of the circuit. Keywords: Ferroelectric capacitor; non-volatile; autonomous; memory latch
Topic: Presenting Author: Affiliation: Email: Type:
Non-Volatile Memories Caroline S. John The University of Alabama in Huntsville carolinesangeetha@gmail.com Poster Presentation

88
CHARACTERISTICS OF A NONVOLATILE SRAM MEMORY CELL UTILIZING A FERROELECTRIC TRANSISTOR Cody Mitchell1, Crystal Laws1, Todd C. MacLeod2, Fat D. Ho1
1
The University of Alabama in Huntsville, Department of Electrical and Computer Engineering, Huntsville, Alabama 35899, USA 2 National Aeronautics and Space Administration, Marshall Space Flight Center, Huntsville, Alabama 35812, USA Abstract
The SRAM cell circuit is a standard for volatile data storage. When utilizing one or more ferroelectric transistors, the hysteresis characteristics give unique properties to the SRAM circuit, providing for investigation into the development of a nonvolatile memory cell. This paper discusses various formations of the SRAM circuit, using ferroelectric transistors, n-channel and p-channel MOSFETs, and resistive loads. With varied source and supply voltages, the effects on the timing and retention characteristics are investigated, including retention times of up to 24 hours.
Keywords: SRAM, nonvolatile, ferroelectric

99
Topic: Ferroelectric Materials: Theory & Experiments Preference to oral presentation (invited talk if possible)
REVISIBLE MODIFICATION OF PHOTOLUMINESCENCE IN FERROELECTRICS
Jianhua Hao*, Yang Zhang, Xianhua Wei Department of Applied Physics and Materials Research Center, The Hong Kong Polytechnic University, Hong Kong, China apjhhao@inet.polyu.edu.hk Abstract Ferroelectric control of electric and magnetic properties have recently been reported and gained substantial interest because of additional degree of freedom in the design of multifunctional materials and devices. To date, modification of the photoluminescence (PL) in the materials excited by a given excitation source can only be achieved by changing the composition of host materials and/or doping metal ions, which is essentially an irreversible process, thus limiting our understanding of the detailed process of luminescence and applications. Although co-existence of PL and ferroelectricity is known in metal ion-doped ferroelectrics, there has been no report on the reversible modification of PL under electric field, which could open up a new avenue not only for understanding the fundamentals of luminescence, but also for exploring novel ferroelectric applications. This work firstly demonstrates an enhancement and modulation of PL emission by applying a low bias voltage to the ferroelectric sample. The emission intensity of the ferroelectric material under a low bias voltage at 10 V is significantly enhanced. Moreover, the PL intensity can be modulated with ac electric field as shown in Fig.1, which is in contrast to conventional chemical and plasmonic approaches. This work provides a real-time and dynamic way to control PL under an electric-field, which should be expected to unlock a realm of new possibilities in the field of ferroelectric-luminescence multifunctional materials and devices.
Figure 1. Sinusoidal ac electric field that applied to a ferroelectric sample. The PL intensity response at the wavelength of 523 nm as a function of time.

102
ISIF-2011
Submitted to Topic 1 for Consideration of oral presentation
Stability and crossover of 109 and 71 domains influenced by thickness and depolarization field in rhombohedral ferroelectric thin films
Chuanwei Huang, Zuhuang Chen and Lang Chen*

School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798, Singapore Presenters Email address: langchen@ntu.edu.sg
The stability of domain patterns in rhombohedral ferroelectric films was studied using the free energy condition consisting of electrostatic and elastic energies, and including the converse piezoelectric effect from the depolarization field. The 109 domain is more stable in the opencircuit condition compared with 71 domain which has larger depolarization energy. By gradually decreasing the depolarization energy, the domain pattern changes from 109 to 71 at a critical film thickness. This critical thickness of crossover of 109 and 71 domains is predicted to decrease with a smaller residual depolarization field and/or a larger effective piezoelectric constant.
The figure shows the film thickness dependent depolarization field energy Fd (dash lines) of 71 domain pattern with asymmetric electrical parameter A and total energy Ft(solid lines) of 109 domain pattern. (Inset) A critical thickness tc for the crossover between 71 and 109 domain patterns as a function of A. The shadow of inset is the coexistence range of 71 and 109 domain patterns.

113
LEAKAGE CURRENT BEHAVIORS OF SrTiO3/BiFeO3 MULTI-LAYERS FABRICATED BY PLUSED LASER DEPOSITION S. W. Kim1, H. I. Choi1, D. Do1, M. H. Lee2, S. S. Kim1, T. K. Song2, M. H. Kim2, W. J. Kim1,*
1
Department of Physics, Changwon National University, Changwon 641-773, Korea and
School of Nano & Advenced Material Engneering, Changwon National Univerisity, Changwon 641-773, Korea
It has been well known that BiFeO3(BFO) exhibits two interesting physical properties simultaneously; ferroelectricity with a Curie temperature of TC = 1130K and antiferromagnetism with a Nel temperature of TN = 643K. This invoked multi-ferroic device applications to change electrical properties by controlling magnetic properties of the BFO or vice versa. However, BFO has a few draw-backs, such as a high leakage current density, which may be attributed to bismuth and/or oxygen vacancies in the structure. In order to improve the leakage current properties, partial substitution of Bi to lanthanides and/or Fe to 3d transition metals have been extensively investigated. In this study, thin layer of dielectrics, such as SrTiO3(STO), have been deposited on top of BFO films to control the leakage current densities of pure and substituted BFO thin films. Both BFO and STO films have been deposited by pulsed laser deposition with optimized conditions. Electrical properties were measured from the Pt/BFO/Pt and Pt/STO/BFO/Pt capacitors for comparison. Improved leakage current behaviours were observed from the STO capped BFO thin films. Structural and electrical properties of BFO and STO/BFO will be presented in details. Furthermore, ferroelectric properties of BFO and STO/BFO will be discussed in the presentation.
Session: Multiferroics and Magnetoelectrics: Theory & Experiments

*
Department of Physics, Changwon National University, e-mail: kwj@changwon.ac.kr
Poster Presentation

120
DOMAIN BUNDLE BOUNDARIES IN SINGLE CRYSTAL BaTiO3 LAMELLAE: SEARCHING FOR NATURALLY FORMING DIPOLE FLUX-CLOSURE / QUADRUPOLE CHAINS
L. J. McGilly, A. Schilling and J. M. Gregg Centre for Nanostructured Media, School of Maths and Physics, Queens University Belfast, University Road, BELFAST, BT7 1NN. U.K. In single crystal {100}pseudocubic faced BaTiO3 lamellae discrete bundles of 90 aa domains, which naturally form on cooling through the Curie Temperature, have been characterised by both Piezoresponse Force Microscopy (PFM) and Scanning Transmission Electron Microscopy (STEM). Using a form of vector PFM, in which information is obtained from the flexure or buckling modes of the cantilever, allows bundle macroscopic polar orientation to be ascribed. In meso-scale dots produced by means of Focused Ion Beam (FIB) patterning, 90 aa domain bundles [1] are observed to form into bands which have been measured as a function of structure lateral size as seen in Fig. 1. Behaviour consistent with a Landau-Kittel-like scaling relationship has been observed below a certain lateral size but which is poorly defined in the case of larger dots (Fig. 1(e)). From this observation the origin of bundle bands, composed of 90 aa stripe domains, seems to lie in a drive to minimise in-plane depolarising fields that act across the sidewall faces of the dot through 180 variations in the band polar orientation. Detailed interpretation of the dipole configurations present at boundaries between two 90 aa domains bundles (using data taken from PFM) shows that, in the vast majority of cases, they are composed of simple zigzag 180 domain walls. Occasionally topological information from STEM shows that domain bundle boundaries can support chains of dipole flux closure [2] and quadrupole nanostructures , but these kinds of boundaries are comparatively rare; when such chains do exist, it is notable that singularities at the cores of the dipole structures are avoided. The symmetry of the boundary shows that diads and centres of inversion exist at positions where core singularities should have been expected. 1 white line
Figure 1: Domain band formation in small scale structures of BaTiO3. Free-standing isolated structure seen in the topography image (a) and corresponding flexural PFM amplitude (c) and phase (d) show a series of 180 bundle bands similar to that depicted diagrammatically in (b). Scaling of band width, w, with lateral size, deff , is plotted in (e).
References: [1] L. J. McGilly and J. M. Gregg, Appl. Phys. Lett., in press (2011). [2] L. J. McGilly, A. Schilling and J. M. Gregg, Nano Lett., 10, 4200 (2010).

122
ADDRESSABLE METAL-FERROELECTRIC-METAL NANOCAPACITOR ARRAYS FABRICATED BY FOCUSED ION BEAM MILLING

Ying Dai and Lei Yang State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan, 430070, China Longhai Wang, Bin Tian, Lianying Zou, Hao Cheng, Danxia Huang School of Electrical and Electronic Engineering, Wuhan Institute of Technology, Wuhan, 430073, China
1. Topic:3. Nanoscale Ferroelectrics and 3-D Geometries for High Density Memories. 2. Presenting authors email address: Ying Dai, daiying@whut.edu.cn Longhai Wang, wlonghai66@yahoo.com.cn 3. Preference to poster presentation. The ferroelectric RAM has a great potential for a wide range of applications. In order to obtain ultrahigh-density ferroelectric memories, nanoscale and individually addressable metalferroelectricmetal capacitors arrays are required. Many processes were attempted to fabricate nanoscale ferroelectric structures, such as self-patterning, conventional nanoimprint lithography-based patterning and electron-beam techniques, but they are unfortunately not appropriate to fabricate addressable metalferroelectricmetal capacitors arrays. Focused ion beam milling offering advantages of compatible with CMOS technique have been employed to fabricate smaller capacitors or islands ferroelectric structures, however two-dimensionally (2D) periodic and addressable large-area capacitors arrays did not attempted. In this work we report on the fabrication and properties of two-dimensionally (2D) periodic and addressable large-area metalferroelectricmetal capacitors arrays.
2.0
Displacement (nm)
1.8 1.6 1.4 1.2 1.0 -10 -5 0 5 10
Applied Voltage (V)
Fig.1 SEM image of nanocapacitor (a) nonuniform and (b) uniform arrays, (c) piezoelectric displacement-voltage loops of uniform arrays. Acknowledgments The project supported by State Key Laboratory of advanced Technology for Materials Synthesis and Processing (Wuhan University of Technology) (No. 2010-KF-8) and Nature Science Foundation of Hubei Province (No. 2009CDB195).

123
LEAKAGE CURRENT AND DIELECTRIC PROPERTIES OF INTEGRATED FERROELECTRIC CAPACITOR ETCHED IN NON-CRYSTALLINE PHASE
Longhai Wang, Bin Tian, Lianying Zou, Hao Cheng, Danxia Huang School of Electrical and Electronic Engineering, Wuhan Institute of Technology, Wuhan, 430073, China Ying Dai and Lei Yang State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan, 430070, China
1. Topic:3. Nanoscale Ferroelectrics and 3-D Geometries for High Density Memories. 2. Presenting authors email address: Longhai Wang, wlonghai66@yahoo.com.cn Ying Dai, daiying@whut.edu.cn 3. Preference to poster presentation. Ferroelectric capacitors have generated a great interest for their applications in memory devices. In order to fabricate integrated ferroelectric capacitors with high properties, the etching process is innovated to reduce etching-damaged. The innovated process is as following: after the proper thickness non-crystalline phase films were prepared, they were not annealed for crystallization, but directly deposited top electrode and etched in one-mask-patterned process. The patterned capacitors with non-crystalline phase films were annealed for crystallization in the last. So the ferroelectric films were etched in non-crystalline phase. The detailed process and ferroelectric properties of the capacitor were described formerly, but, other reliability properties are not investigated. In this work, the leakage current, dielectric, dielectric loss and time dependent dielectric breakdown (TDDB) are measured. The possible mechanisms responsible for the leakage current and dielectric loss are discussed, and the correlations between them are studied.
Fig.1 Currenttime plots with various DC voltage (a) and staircase DC voltage (b). Acknowledgments The project supported by Nature Science Foundation of Hubei Province (No. 2009CDB195) and State Key Laboratory of advanced Technology for Materials Synthesis and Processing (Wuhan University of Technology) (No. 2010-KF-8). Especially, the authors deeply appreciate professor Jun Yu (Huazhong University of Science and Technology) for the assistance in the experiments.

125
DIELECTRIC SPECTROSCOPY OF NANOGRAIN PSN CERAMICS Maksim Ivanov1, Martynas Kinka1, Saulius Rudys1, Juras Banys1, C. Bogicevic2, Jean-Michel Kiat2,3 1 Laboratory of Phase Transitions Dielectric Spectroscopy, Faculty of Physics, Vilnius University, Sauletekio str. 9 III 817, LT-10222, Vilnius, Lithuania 2 Laboratoire Structures, Proprits, Modlisation des Solides (UMR 8580) Ecole Centrale Paris, Grande Voie des Vignes 92295 Chtenay-Malabry Cedex 3 Laboratoire Lon Brillouin, CE Saclay CNRS-UMR 12, 91991 Gif-Sur-Yvette Cedex, France e-mail: maksim.ivanov@ff.stud.vu.lt Ferroelectric materials are of high interest for both researchers and engineers due to their remarkable properties, which makes them great targets of fundamental research for scientists and materials of choice for a variety of devices [1]. As a result, nanoscale size effects became of interest in both scientific and technological fields. Size has clear influence on dielectric properties of the material, as can be seen from figure 1. Firstly, maximum of dielectric permittivity diminishes and dispersion region shifts to lower temperatures with smaller grain sizes. Furthermore, no relaxor-normal ferroelectric phase transition at 370 K is observed, which is typical for bulk ceramics [2]. However, this graph shows remnant anomaly in imaginary part around 370 K for grains bigger than 60 nm. This must mean that in this case some weak interaction between polar nanoregions (PNR) still takes place. At smaller grain sizes PNRs likely become smaller due to confinement inside grains, thus giving smaller contribution to Fig.1 Temperature dependencies of the real part (top) value of dielectric permittivity. The and imaginary part (bottom) of complex dielectric experimental results are in good agreement constant for different grain sizes at 1.21 kHz frequency. with other works [3, 4].
References 1. C. H. Ahn, K. M. Rabe, and. J.-M, Triscone, Science 303, 488 (2004). 2. F. Chu, I. M. Reaney, and N. Setter, J. Appl. Phys. 77, 1671 (1995). 3. Z. Zhao, V. Buscaglia, M. Viviani, M.T. Buscaglia, L. Mitoseriu, A. Testino, M. Nygren, M. Johnsson, and P. Nanni. Phys. Rev. B 70, 024107 (2004). 4. J. Banys, R. Grigalaitis, M. Ivanov, J. Carreaud, J.M. Kiat. Integrated Ferroelectrics 99, pp. 132139 (2008).

126
LARGE PIEZOELECTRIC RESPONSE IN NANOTWINNED BATIO3 REVISITED P. Marton, P. Ondrejkovic, and J. Hlinka Institute of Physics, Academy of Sciences of the Czech Republic, Na Slovance 2, 18221 Praha 8, Czech Republic Ferroelectric materials are used in various applications for their outstanding electromechanical properties, which are, to a large extent, determined by their complicated ferroelectric-domain microstructure. Control of the ferroelectric domain structure provides an additional possibility for tuning of their material properties for specific purposes, which is utilized e.g. in nonlinear optics etc. Recently, Wada and Tsurumi [1] discovered that the piezoelectric coefficients in a frustratively poled BaTiO3 crystal (the poling direction is [111]) can be strongly enhanced by increasing the density of domain walls. The enhancement is approximately proportional to the inverse of domain thickness. Such increase of piezoelectric properties by domain engineering is indeed very tempting from the perspective of applications, but the underlying mechanism for the enhancement, necessary for full exploitation of such phenomenon, has been not yet satisfactorily understood. Results of Wada and Tsurumi indicate that not only the domain properties, but also the properties of domain walls themselves may be important for the overall response of the sample with decreasing domain sizes. In this talk we address several mechanisms proposed in order to explain the observations. For this sake we use the Ginzburg-Landau-Devonshire-model-based phase-field simulations of ferroelectric domain structure under applied electric field. First, the mechanisms proposed by Rao and Wang [2], such as domain wall broadening and polarization tilt within the domain wall are discussed and quantified using simulations. Next, we revisit our recently reported results on the influence of domain-walls proximity on piezoelectric coefficient [3]. Finally, a recently presented model by Sluka et al. [4], which incorporates an additional effect of stress-assisted phase transition in elastically incompatible domain structure of BaTiO3 with charged domain walls, will be addressed. This work has been funded by the Czech Science Foundation (Project GACR P204/10/0616). [1] S. Wada and T. Tsurumi, Br. Ceram. Trans. 103, 93 (2004). [2] W. F. Rao and Y. U. Wang, Appl. Phys. Lett. 90, 041915 (2007). [3] J. Hlinka, P. Ondrejkovic, and P. Marton, Nanotechnology 20, 105709 (2009). [4] T. Sluka, D. Damjanovic, A. K. Tagantsev, and N. Setter, 10th International Symposium on Ferroic Domains and Micro- to Nanoscopic Structures, Praha (2010).

128
HIGH TEMPERATURE MEASUREMENT OF ELASTIC MODULI OF BULK (0001) FREE-STANDING GaN AND RELATED SUBSTRATES M. J. Edwards1, 2, E. Le Boulbar2, C. R. Bowen1 and D. W. E. Allsopp2
2
Department of Mechanical Engineering, University of Bath, UK, Department of Electronics and Electrical Engineering, University of Bath, UK,
GaN is a piezoelectric semiconductor with a wide band gap and good thermal properties, making it a suitable material for piezoelectric sensing applications at high temperatures. The accurate determination of the elastic moduli of GaN and substrate materials as a function of temperature is necessary in order to correctly calculate the thermal and lattice misfit stress of GaN epilayers. This paper reports the theoretical and experimental elastic moduli data obtained on (111) silicon, (0001) sapphire and of in-plane free-standing (0001) bulk GaN. Dynamic Mechanical Thermal Analysis (DMTA) measurements were carried out on these materials up to 550C. First measurement on free standing (0001) GaN along the [11-20] direction has shown a modulus (1/s33) of 364 GPa, which is close to literature values. Temperature dependent DMTA measurements show a near-linear decay of 1/s33 (fig 1). In order to minimise the error associated with geometry, the GaN samples were laser cut from a 2 free-standing (0001) bulk GaN wafer. Additional samples were laser cut between the angles of 0 to 30 anti-clockwise from the [11-20] direction in order to determine any deviation in 1/s33 with respect to orientation.
Figure 1: Temperature dependent modulus (1/s33) of free standing GaN (0001) along the [11-20] direction obtained by DMTA measurements

133
Improvement of piezoelectric response in (Pb(Mg1/3Nb2/3)O3)0,74-(PbTiO3)0,26 ferroelectric relaxor near the morphotropic phase boundary
Nikola Novak1, George Cordoyiannis1 and Zdravko Kutnjak1

1
Jozef Stefan Institute, Jamova 39, 1000 Ljubljana, Slovenia e-mail: nikola.novak@ijs.si
In last few decades the production of electronic devices is directed in minimization, speed, efficient and high performance. To achieve all this, the materials used in electronic elements have to exhibit large value of different physical properties like electrical polarization, dielectric permittivity and electromechanical or piezoelectric response. Especially the giant piezoelectric response, which was found in ferroelectric relaxors, has attracted considerable attention due to the improvement of new generation actuators, sensors, ultrasonic and telecommunication devices which are based on piezoelectric effect. Ferroelectric relaxor Pb(Mg1/3Nb2/3)O3-PbTiO3 (PMN-PT) exhibit large electromechanical response observed near the morphotropic phase boundary. It is known for some time, that the proximity of morphotropic phase boundary in ferroelectric relaxors enhances piezoelectric response due to the polarization rotation between different phases. Recently, it was shown experimentally and later theoretically confirmed that the proximity of the liquid-vapor type critical point has significant impact on the enhancement of the piezoelectric response [1,2]. We investigate PMN(1-x)-PTx sample with composition near the morphotropic phase boundary, x=0.26. Temperature and frequency dependence of the complex dielectric constant as a function of the bias electric field for [100] crystal axis was measured to show the influence of the electric field on the monoclinic phase sequence. Frequency dependence of the complex dielectric constant at different temperatures and various bias electrical fields was measured to obtain the behavior of piezoelectric coefficient. The temperature dependence of the piezoelectric coefficient at different electrical fields is presented. It is shown that in both [110] [3] and [100] axis the piezoelectric response exhibit significant weakening within the temperature range of monoclinic phases. [1] Z. Kutnjak, J. Petzelt, R. Blinc, Nature 441, 956-959 (2006). [2] M. Porta, T. Lookman, A. Saxena, J. Phys.: Condens. Matter 22, 345902 (2010). [3] Z. Kutnjak, R. Blinc, Y. Ishibashi, Phys. Rev. B 76, 104102 (2007).

144
Effects of Additives on Dielectric and Piezoelectric Properties of (Na0.53K0.47)(Nb0.55Ta0.45)O3 Ceramics
G. H. Ryu, J. H. Lee, Y. S. Sung, J. H. Cho, T. K. Song, M. H. Kim* School of Nano & Advanced Materials Engineering, Changwon National University, Changwon 641-773, Korea
(Na,K)NbO3 (NKN) with high piezoelectric properties is one of Pb-free materials for replacing Pb(Zr,Ti)O3 (PZT). Unlike other piezoelectric ceramic, NKN-based ceramics have polymorphic phase transition (PPT) as well as morphotropic phase boundary (MPB). High piezoelectric properties are observed especially in the case that the phase transition temperature from orthorhombic to tetragonal phases (TO-T) is around room temperature. However, NKN-based ceramics exhibit low dielectric and piezoelectric properties compared with those of PZT. Moreover, their poor sinterability due to evaporation of Na and K is still a problem that needs to be improved. In our previous work, the variation of PPT with B-site ratio between Nb and Ta in (Na0.53K0.47)(Nb1-xTax)O3 was investigated to improve piezoelectric properties as shown in Fig. 1. High piezoelectric constant (d33) around 300 pC/N was obtained at the composition of x = 0.45, (Nb0.55Ta0.45). In this study, the effects of various additives such as ZnO and CuO, etc. are investigated to further enhance dielectric and piezoelectric properties of (Na0.53K0.47)(Nb0.55T0.45)O3. Sintering temperatures for various additives were determined by difference thermal analysis (DTA). Phase and structural evolution in relation with the additives are examined in terms of dielectric and piezoelectric properties.
Dielectric Constant
TC TO-T 1000
0.0 0.30 0.45 0.50 0.6
100 0
100
200
300
400
o
500
Temperature ( C)
Fig. 1. Effects of Ta substitution x on PPT in (Na0.53K0.47)(Nb1-xTax)O3 ceramics.
The 7th topic E-mail address; mhkim@changwon.ac.kr Poster presentation is preferred.

145
Effects of A-site Non-Stoichiometry on Dielectric and Piezoelectric Properties of (Na0.50+xK0.50+y)(Nb0.55Ta0.45)O3 Ceramics
J. H. Lee, G. H. Ryu, Y. S. Sung, J. H. Cho, T. K. Song, M. H. Kim*
School of Nano & Advanced Materials Engineering, Changwon National University, Changwon 641-773, Korea
Lead-based Pb(Zr,Ti)O3 (PZT) ceramics have very good piezoelectric properties. However, PZT ceramics have environmental and human health problems. Therefore extensive research has been investigated into lead-free materials to replace PZT. The search for alternative piezoelectric materials is now being focused on (Na,K)NbO3 (NKN)-based materials. However, not much progress has been made in terms of either reproducing or understanding properties of NKN. A phase diagram shown in Fig. 1 represents one of our experimental results of dielectric properties as a function of Ta substitution in (Na0.53K0.47)(Nb1-xTax)O3. Piezoelectric coefficient (d33) up to 309 pC/N was obtained at x=0.45. Therefore, in this study, the effects of Na and K content is investigated in (Na0.50+xK0.50+y)(Nb0.55Ta0.45)O3 considering piezoelectric properties can be improved by A-site nonstoichiometry. The variations in dielectric and piezoelectric properties are coupled with the compositional variations.
(Na0.53K0.47)(Nb1-xTax)O3
Dielectric Constant
TC TO-T
0.0 0.30 0.45 0.50 0.6
1000
100 0
100
Temperature (oC)
200
300
400
500
Fig. 1. Effects of Ta substitution on polymorphic phase transition (PPT) in (Na0.53K0.47)(Nb1-xTax)O3 ceramics.
The 7th Topic Email address; mhkim@changwon.ac.kr Poster presentation is preferred.

153
ROLE OF SINGLE-CRYSTAL PILLARS IN FORMING THE EFFECTIVE PROPERTIES AND FIGURES OF MERIT OF NOVEL 13 PIEZOCOMPOSITES R.W.C. Lewis1, C.R. Bowen1, V.Yu. Topolov2, D.W.E. Allsopp3
1 2 3
Department of Mechanical Engineering, University of Bath, Bath, BA2 7AY, UK
Department of Physics, Southern Federal University, 344090 Rostov-on-Don, Russia
Department of Electronic and Electrical Engineering, University of Bath, Bath, BA2 7AY, UK E-mail: R.W.C.Lewis@bath.ac.uk
This work examines the formation of submicron pillars that are made from (1 x)Pb(Mg1/3Nb2/3)O3 xPbTiO3 (PMN-PT) single crystal and LiNbO3 single crystal and expolited as an active component of modern 13 piezocomposites. These structures are of interest in sensor and actuator technologies, and most notably energy harvesting devices. This research area has seen recent growth in terms of interest with the advent of electronics with greater portability, wireless sensors etc. The fabrication of nanopillars on the single crystal surface will be investigated using a nanoimprint lithography (NIL) approach. The use of a disposable master allows the user to reproduce large area nanostructures. Dry etching then allows for the nanopillars to be formed. Theoretical modelling of the regular array structure allows for the evaluation of the piezocomposite behaviour, and is given in this work. Modelling of the 13 piezocomposite structure and its effective parameters [1] provides the predicted material characteristics based on the geometrical and materials parameters of the single crystal, epoxy and air. The
efficiency of the system to work as an energy harvester, sensor or actuator will be investigated with regards to the relevant piezoelectric coefficients such as the dij, gij and the electromechanical coupling factor kij. This work concludes with discussions with regards to the working figure of merits with respects to the role of the anisotropy of electromechanical properties of the single-crystal component and the 13 piezocomposite as a whole.
[1] V.Yu. Topolov and C.R. Bowen. Electromechanical Properties in Composites Based on Ferroelectrics (Springer, London, 2009).

164
MODELING OF SONOS MEMORY CELL ERASE CYCLE

THOMAS A. PHILLIPSa, TODD C. MACLEODa, and FAT DUEN HOb National Aeronautics and Space Administration, Marshall Space Flight Center, Huntsville, Alabama, 35812, U.S.A. b The University of Alabama in Huntsville, Department of Electrical and Computer Engineering, Huntsville, Alabama 35899, U.S.A.
a
ABSTRACT Utilization of Silicon-oxide-nitride-oxide-silicon (SONOS) nonvolatile semiconductor memories as a flash memory has many advantages. These electrically erasable programmable read-only memories (EEPROMs) utilize low programming voltages, have a high erase/write cycle lifetime, are radiation hardened, and are compatible with high-density scaled CMOS for low power, portable electronics. The SONOS memory cell erase cycle was investigated using a nonquasistatic (NQS) MOSFET model. During an erase cycle, a negative pulse is applied to the gate which causes Fowler-Nordheim tunneling between the floating gate and channel. The SONOS floating gate charge and voltage, tunneling current, threshold voltage, and drain current were characterized during this erase cycle. Comparisons were made between the model predictions and experimental data for the tunneling current and threshold voltage.

165
NOVEL HIGH-SENSITIVE COMPOSITES BASED ON FERROELECTRIC CERAMICS V.Yu. Topolov1, C.R. Bowen2, S.E. Filippov3, and A.A. Vorontsov3
Department of Physics, Southern Federal University, 344090 Rostov-on-Don, Russia Materials Research Centre, Department of Mechanical Engineering, University of Bath, BA2 7AY Bath, UK 3 Scientific Design &Technology Institute Piezopribor, Southern Federal University, 344090 Rostov-on-Don, Russia
2 1
Modern composites based on ferroelectric ceramics (FCs) are often applied as piezo-active materials with effective parameters that vary in some predictable ranges. It is possible to increase and tailor the piezoelectric sensitivity, electromechanical coupling and hydrostatic response of 13 FC / polymer composites as a result of the modification of the composite structure [1]; for example, with changes in the properties of the matrix surrounding the FC rods. In this work, we consider a new structure of the 13-type FC-based composite and study the important trends in increasing materials parameters related to the piezoelectric effect. The composite structure with 103 connectivity (Fig. 1, a) is characterised by the regular distribution of cylindrical FC rods and spheroidal FC inclusions in a polymer matrix. The shape of the isolated inclusion is given by the aspect ratio i = a1 / a3 that is assumed to be fixed over the composite sample. The determination of the effective electromechanical properties *(m, mi, i) of the composite is carried in two stages: (i) the effective properties of the 03-matrix are calculated as a function of mi and i, and (ii) the properties of the system FC rods matrix are evaluated as a function of m. The corresponding averaging procedure at both stages is carried out within the framework of the effective field method [1]. Among the FC compositions of E interest here are PCR-7M and modified PbTiO3 [1]. PCR-7M is a PZT-type FC with the large ratio of e33 / c33 E (e33 is the piezoelectric coefficient and c33 is the elastic modulus) and large piezoelectric coefficients d3j. The modified PbTiO3 FC is characterised by large anisotropy of d3j. Graphs in Fig. 1, b, c show changes in the effective parameters near their maximum points. Hereby it is possible to examine the important role of a matrix E E E E with oblate FC inclusions and the variable ratios of the elastic moduli c11, m / c33, m and c13, m / c33, m of the
* inclusions in forming a composite architecture with high piezoelectric sensitivity ( g 33 (300 ... 370) mV.m / N)
* and hydrostatic piezoelectric activity ( d h (300 ... 335) pC / N). In the PCR-7M-based composite, squared
* * * * figures of merit d 33 g 33 8.10-11 Pa-1 and d h g h 3.10-11 Pa-1 are achieved in ranges of 0.1 mi 0.3 and 1 i 100. A comparison to the performance of the conventional 13 FC / polymer composites [1] is drawn. Data on the maximum points and non-monotonous behaviour of the effective parameters (Fig. 1, b, c) can be of benefit for the optimisation and exploitation of the piezoelectric sensitivity, hydrostatic activity and other characteristics of the novel 103 composite that is suitable for modern hydroacoustic, sensor and other applications. [1] V.Yu. Topolov and C.R. Bowen. Electromechanical Properties in Composites Based on Ferroelectrics (Springer, London, 2009).
Fig. 1. Schematic of the 103 FC / FC / polymer composite (a) and behaviour of the longitudinal piezoelectric * coefficient g 33 (in mV.m / N) of the modified PbTiO3 / modified PbTiO3 / polyurethane composite (b) and the
* * * * hydrostatic piezoelectric coefficient d h = d 31 + d 32 + d 33 (in pC / N) of the PCR-7M / PCR-7M / polyurethane composite (c). In figure (a) OX3 is the poling axis. m and 1 m are volume fractions of the FC rods and the surrounding heterogeneous matrix, mi is the volume fraction of the isolated FC inclusions in the polymer medium, and a1 and a3 are semiaxes of the FC inclusion. In figure (b) mi = 0.1, and in figure (c) i = 100.

166
Preparation and characterization of BaTiO3 thin films using reactive sputtering method
Tsuyoshi Osumi1, Masamichi Nishide1, Hiroshi Funakubo2, Ken Nishida1, and Takashi Yamamoto1
1
Department of Communications Engineering, National Defense Academy, Yokosuka 239-8686, Japan
Department of Innovative and Engineered Materials, Tokyo Institute of Technology, Yokohama 226-8502, Japan
1. Introduction Barium titanate (BTO) is one of the typical ferroelectric material which has been widely investigated for many applications. The sintered body was mainly used and applied for dielectric material, for example multilayer ceramic capacitors (MLCC). However, BTO is required for form sintered body to thin film with decreasing of device size. BTO thin film are prepared using the sputtering method, the sol-gel method and the chemical vapor deposition. Among these techniques, sputtering method has been known as one of the most useful deposition methods because a equipment is relative simple and it has good reproducibility. However, there are some drawback. Since the ceramics target is used for sources, the composition control of film is difficult. Furthermore, a high temperature is necessary to improve crystalline. Then, we applied the reactive sputtering method for preparing BTO thin films. The composition of the thin films is changing by varying Ba and Ti metal target area. In addition, It is also able to grow at low temperature. However, there is no report to use Ba and Ti metal target because Ba metal is easily reacted with water in atomspher. In this work, BTO thin films with high quality were grown at low temperature using the reactive sputtering method. 2. Experimental procedure The BTO thin films were grown on (100)MgO substrates using RF magnetron sputtering equipment. The Ba metal area that were put on Ti metallic disc was use for target. The Ba/Ti ratio of the target was controlled by the number of Ba metal pieces. Growth conditions were as follows. Growth temperature was 460 , sputtering pressure 5-30 Pa, RF power 100 W and gas flow rate Ar:O2 = 1:1-1:3. The X-ray diffraction method and Raman scattering spectroscopy was used for structural analysis and the composition of film was measured by using and X-ray fluorescence. 3. Result and discussion Figure 1 shows the composition of ratio BTO thin film vs. the area ratio of the Ba/Ti metal. Composition of Ba in the thin film was increased with the area of the Ba metal increased and it was saturated to 0.16 of Ba/Ti target area ratio. Stoichiometric BTO film was obtained at the area ratio of Ba/Ti was 0.16. The X-ray diffraction pattern of the BTO thin film that the area ratio of Ba/Ti was grown at condition of 0.16 is shown in Fig.2. In Fig.2, the diffraction peak of tetragonal (001)/(100)BTO and (002)/(200)BTO is clearly observed and second phases were not observed. It is understood that BTO thin film was epitaxially grown on MgO substrate. Relative high quality BTO thin films were obtained by reactive sputtering method using Ba/Ti metal target even if the growth temperature was quite low, 460 .
1.00
Ba/(Ba+Ti) ratio of BTO films
0.50
0.25
0.00 0.05
0.10
0.15
0.20
0.25
0.30
20
(001)BTO (100)BTO
30
2 (deg.)
40
(002)BTO (200)BTO
0.75
Intensity (arb. unit)
(200)MgO
Pressure 20Pa
50
Ba/Ti area ratio of sputtering target
Fig.1
Composition ratio of BaTiO3 vs. Ba/Ti area ratio of sputtering target
Fig.2
X-ray diffraction spectrum of BaTiO3 thin film

170
Dry etching properties of Piezoelectric MEMS

Yoshiaki Yoshida, Masahisa Ueda, Yutaka Kokaze, Hiroki Kobayashi, Isao Kimura
Institute of Semiconductor and Electronics Technologies, ULVAC, Inc., 1220-1 Suyama Susono, Shizuoka 410-1231, Japan
yoshiaki1_yoshida@ulvac.com
Abstract: Pb(Zr, Ti)O3 (PZT) has large Piezoelectric constant, it is used for the MEMS device such as ink-jet printer head. We process the PZT element by dry etching, and to understand the etching properties contributes to producing MEMS devicies of the high quality. In this study, we report etching rate, PZT vs Pt electrode etching selectivity, hysteresis loops, as for etching properties. A PZT thin-film actuator consist of a top-electrode/1-m-thick-PZT film/bottom electrode on 6inch. The top and bottom Pt electrodes were deposited by DC magnetron sputtering. The PZT film was deposited by the RF magnetron sputtering using a sintered PZT ceramic target. Photoresist for etching mask was patterned on the top electrode. The top Pt electrode and PZT were etched by a dry etching tool. The top Pt electrode was etched by chlorine-based gas plasma, and the thick PZT film was etched by several kinds of halogen gas plasmas. Etching rate were evaluated by scanning electron microscopy (SEM) observation. Remanent polarization was measured by the piezoelectric evaluation system. In Fig. 1, dependence of PZT film and Pt film etching rate on process gas are shown. In the case of Ar gas etching, etching rate of PZT is low in 50nm/min. In the case of Cl2 or SF6 gas etching, chemical etching advances, so that the etching rate of PZT is more than 200nm/min. However etching selectivity of PZT vs Pt is low in 3. In the case of CF4 gas etching, etching selectivity of PZT vs Pt is the best in 6. In Fig. 4. hysteresis loops of the PZT films after etching are shown. The remanent polarization of PZT element which was etched by Cl2 or CF4 gas was 22C/cm2 with both. In the case of CF4 gas etching, a CF polymer accumulates on the surface of PZT and Pt. This CF polymer controls etching. During PZT etching, oxygen is emitted from the PZT, and the oxygen is combined with C or CF and turns into CO, CO2 and COF and volatilizes. On the other hands, when etching reached the bottom Pt electrode, the oxygen is not emitted from the Pt. Therefore the CF polymer remains at only Pt surface and Pt etching is restrained.

170

191
THE RETENTION LOSS OF FERROELECTRIC DOMAINS IN P(VDFP(VDF-TrFE) THIN FILMS Hyunwoo Choi,1,2 Seungbum Hong,2 Tae-Hyun Sung,3 Kwangsoo No1 Department of Materials Science and Engineering, Korea Advanced Institute of Science and Technology, Daejeon 305-701, Korea 2 Materials Science Division, Argonne National Laboratory, Lemont, Illinois 60439, USA 3 Department of Electrical Engineering, Hanyang University, 17 Haengdang-dong, Seongdong Hany dong, Seongdong-gu, Seoul 133-791, Korea Presenting authors e-mail address: bluestarcml@kaist.ac.kr resenting author domains trifluoroethylene) Retention loss of ferroelectric domain of poly(vinylidenefluoride-co-trifluoroethylene) [P(VDF-TrFE)] thin films were investigated using piezoresponse force microscopy. We found that the retention loss occurred by nucleation of opposite domains at the regions between the peak and valley with tention morphological gradients. The retention loss of ferroelectric domains showed a stretched exponential suggests relaxation behavior, which suggest that the loss occurs by random walk process. Considering not only domain low stretched exponential factor and large time constant but also higher remained dom fraction per totally lapsed time compared to other ferroelectric oxides, P(VDF-TrFE) can be a promising material for volatile devices. applications to flexible and non-volatile memory devices
TrFE) Change inthe normalized size of ferroelectric domains of P(VDF-TrFE) thin film as a function of time. eft (Left inset) Topography image corresponding to the ferroelectric domain ight (Right inset) PFM phase image of the ferroelectric domain
Topic : Ferroelectrics Experimental Preference to oral or poster presentation : POSTER presentation

195
Characteristics of BaNb2O6 Thin Films made by MOCVD using Ultrasonic Nebulization
CHOON-HO LEE, and MYUNG-HO PARK Dept. of Materials Engineering, Keimyung University, 2800 Dalgubeoldaero, Dalseo-Gu, Daegu 704-701, South Korea Presenting author's email address: chl594@kmu.ac.kr
Recently, dielectric thin films have been intensively studied for the applications. Especially, BaNb2O6-based ferroelectric materials (AxBa1-xNb2O6 (A= Sr, Er, Pb, , etc)) with tungsten bronze type structure exhibit excellent electro-optic and pyroelectric properties. In this study, BaNb2O6 thin films were deposited on Pt/Ti/SiO2/Si substrates by the MOCVD using ultrasonic nebulization and their deposition characteristics were investigated. The composition of thin films was controlled by changing the molar ratio of Ba/Nb source in the source solution and the deposition temperature. The BaNb2O6 single phase thin films could be prepared using a source solution with the concentration of 0.07 mol/l Ba-source and 0.105 mol/l Nb-source at the substrate temperature of 350. The dielectric constant of the film was about 86. The current density was 6.740x10-7A/cm2 at -10V and 1.075x10-6A/cm2 at +10V. Also, the remanent polarization was 0.302 C/cm2 and the coercive force was 31.523 kV/cm.

196
Preparation of Ba6Ti2Nb8O30 Thin Films by MOCVD using Ultrasonic Nebulization
CHOON-HO LEE, and DO-WOO KIM Dept. of Materials Engineering, Keimyung University, 2800 Dalgubeoldaero, Dalseo-Gu, Daegu 704-701, South Korea Presenting author's email address: hotnanro33@dreamwiz.com
Materials with tetragonal tungsten bronze (TTB) structure such as BaNb2O6-based ferroelectric materials (AxBa1-xNb2O6 (A= Sr, Er, Pb, , etc)) have attracted much attention as these materials show great potential in dielectric, ferroelectric, electro-optic, photorefractive, large pyroelectric and piezoelectric properties. In this study, Ba6Ti2Nb8O30 (abbreviated BTN) thin films were deposited on Pt/Ti/SiO2/Si substrates by the MOCVD using ultrasonic nebulization and their deposition characteristics were investigated. Single phase BTN films could be obtained by varying the mixing ratios of the source solutions for BaTiO3 and BaNb2O6 films at the deposition temperature range of 350400. The crystallinity of Ba6Ti2Nb8O30 films was enhanced by the RTA treatment. The BTN thin films showed the dielectric constant of 53.5(at 100 kHz). And the current density was 1.36110-4A/cm2 at +10V, and 1.42410-5A/cm2 at -10V. Also, the remanent polarization was 0.459C/cm2 and the coercive field was 36.865kV/cm.

198
MODEL OF FERROELECTRIC FBARs INCLUDING LONGITUDINAL AND SHEAR WAVES

S. Gevorgian, and A. Vorobiev Department of Microtechnology and Nanoscience, Chalmers University of Technology 412 96 Gothenburg, Sweden In parallel-plate Film Bulk Acoustic Resonators (FBAR) the acoustic oscillations generated in the film due to the piezoelectric (including DC field induced) effect may consist of both thickness longitudinal and shear waves. The shear waves are generated mainly due to the c-axis tilted nanocolumns in the ferroelectric films. ADS and Mason based circuit model of a solidly mounted FBAR is proposed. Both thickness mode longitudinal and shear waves are taken into account. Since the shear and longitudinal waves are normal modes the resonator is represented as two independent longitudinal and shear wave resonators connected in parallel. For both resonators the thicknesses of the layers are given for longitudinal mode. The corresponding longitudinal and shear acoustic velocities, impedances and losses are used in longitudinal and shear resonators (branches). SiO2/W reflector and Ba0.25Sr1-xTiO3 film as the piezoelectric are assumed in simulations. The simulated reflector transmittivity, T=10log(1-|S11|2), of the longitudinal and shear are shown in Fig.1. BSTO assumed to be infinite thick. Transmittivity of the shear modes is rather high. The relative power loss into the shear mode, Fig.2, is defined as 100Pshear/(Plong+Pshers), %. In this case kt2long=0.013 and kt2shear=0.001. The fraction of the shear mode at longitudinal resonant frequency of 5.16 GHz is minimum (0.35%). This is due to lower resonant impedance of the longitudinal mode as compared with the shear mode which is offresonance. The fraction of the shear mode increases with increasing shear mode coupling coefficient. Fig.3 compares measured and simulated performances of the resonator for kt2long=0.013 and kt2shear=0.001. These results are used to simulate/predict the performance of the resonator shown in Fig.4. The highest Q-factors of these resonances are achieved for certain coupling coefficients. The proposed ADS may be easily extended towards optimization of the Bragg reflector for efficient reflection of both longitudinal and shear modes. The work is partially supported by Swedish Research Council in the framework of the project VR FBAR.
Long.
Fraction of shear power, %
Fig.1 Transmittivty of longitudinal and shear modes.
Fig.2 Shear waves power at the input of the reflector.
Fig.3 Simulated and measured performances

5,2 5,15
fs, fp (GHz)
T, dB
Shear
kt2shear=0.001
500
f
p
400
Q f
p
5,05 5 4,95
Q
s
200 100 0 0,1
0,02
0,04 0,06 0,08 kt2long_input
Fig.4 Resonant frequencies and Q-factors of the series and parallel resonances vs. kt2long
Qs, Qp
5,1
300

214
VACANCY DEFECTS IN UNDOPED AND IRON DOPED STRONTIUM TITANATE THIN FILMS OBSERVED BY POSITRON ANNIHILATION LIFETIME SPECTROSCOPY D.J. Keeble1, S. Wicklein2, R. Dittmann2, L. Ravelli3, and W. Egger3
1
Carnegie Laboratory of Physics, University of Dundee, Dundee DD1 4HN, United Kingdom
2
Institut fr Festkperforschung, Forschungszentrum Jlich, 52425 Jlich, Germany and

3
Universitt Bundeswehr Mnchen, D-85577 Neubiberg, Germany e-mail: d.j.keeble@dundee.ac.uk
Positron annihilation spectroscopy measurements have been shown to have specific sensitivity to vacancy related defects, DFT calculations and measurements on bulk single crystal samples have established the lifetime values for the A-site and B-site cation vacancy defects in perovskite oxide titanates [1]. A recent study has shown that positron lifetime measurements performed using a high flux positron beam can identify vacancy defects in thin film perovskite oxides [2]. In this study we extend our earlier measurements [3] on a series of homoepitaxial SrTiO3 thin films deposited by pulsed laser ablation, with varying laser fluence, to films grown at different temperatures and with a wider fluence range. We also report on a study of Fe doped SrTiO3 thin films, where the concentration of Fe is varied from 0.1 to 10 %. For fluences between 90120 mJ/cm2 positron lifetime measurements identified both Sr and Ti vacancies. Positron trapping was dominated by Ti vacancies at low fluences, and by Sr vacancies for high values. This was consistent with the lattice constant variation, determined by x-ray diffraction, and provides additional direct evidence for nonstoichiometry accommodation by vacancy formation. Films deposited using fluencies < 90 mJ/cm2 showed additional positron trapping to vacancy cluster and nanovoid defects. The incorporation Fe is found to modify the cation vacancy defect content. [1] R. A. Mackie, S. Singh, J. Laverock, S. B. Dugdale, and D. J. Keeble, Phys. Rev. B 79, 014102 (2009) [2] D.J. Keeble, R. A. Mackie, W. Egger, B. Lwe, P. Pikart, C. Hugenschmidt, and T.J. Jackson, Phys. Rev. B 81, 064102 (2010) [3] D. J. Keeble, S. Wicklein, R. Dittmann, L. Ravelli, R. A. Mackie, and W. Egger, Phys. Rev. Lett. 105, 226102 (2010)

248
TEMPERATURE DEPENDENCE OF OPTICAL PROPERTIES OF ND-DOPED BISMUTH TITANATE THIN FILM FOR OPTICAL APPLICATION
Yongyuan Zang, 1) Dan Xie, 2) Mohan Li, 3) and David Plant 1)
1 2
Electrical and Computer Engineering, McGill University, Montreal, Quebec, H3A 2T8, Canada Tsinghua National Laboratory for Information Science and Technology (TNList), Institute of Microelectronics,

3
Chemical Engineering, McGill University, Montreal, Quebec, H3A 2B2, Canada
Ferroelectric materials are considered promising candidates for optical applications, such as optical waveguides and modulators, due to their remarkable electro-optic properties. Traditional ferroelectric materials LiNbO3 and PZT have been extensively applied in optical domain over the last several decades. Recently, novel ferroelectric material B3.15Nd0.85Ti3O12 (BNdT) has been reported with better ferroelectric properties compared to PZT. However, little attention has been paid to the optical properties of this brand new ferroelectric material. In this paper, we report an experimental investigation of the annealing temperature dependence of BNdT optical properties for the first time. The BNdT thin films are fabricated on optical graded fused quartz substrate by sol-gel process. Crystalline microstructure is characterized by XRD, SEM, AFM, and TEM. The BNdT thin film annealed at 650C exhibits a well defined pervoskite crystalline structure, which leads to a saturated polarization-voltage (PV) hysteresis with a remnant polarization of 46.5 C/cm2 and coercive field of 96 kV/cm at 5 V DC. A superior optical transparency T() of >80% is observed for wavelengths from 250 to 2000 nm indicating a high optical transparency. From an ellipsometry measurement, we extract material optical parameters such as reflective index n, extinction coefficient k, and band gap energy Eg, which are fundamental to the optical properties of BNdT thin films. The microstructure and annealing temperature dependence of T(), n, k, and Eg is also investigated. It can be understood that the transparency and reflective index variation can be attributed to the stress relaxation, glass transformation, and grain size variation during the annealing process. While the quantum-size effect and amorphous percentage are the factors of temperature and thickness dependence of band gap energy Eg of BNdT material. BNdT material with a good transparency, a high reflective index and a low transmission loss is a promising candidate for integrated optics applications.
Fig.1 Transmission spectra of BNdT thin films with thickness from 50 to 200 nm at different annealing temperatures.
Fig.2 Band gap energy of BNdT thin films with different thickness from 50 to 250 nm at different post annealing temperatures from 300C to 650C. 1

253
WET CHEMICAL ETCHING OF BaSrTiO3 FERROELECTRIC THIN FILMS FOR INTELLIGENT ANTENNA APPLICATION
S. Pavy, S. Baron, C. Borderon, H.W. Gundel IREENA, EA 1770, University of Nantes, Nantes Atlantic Universities 2 rue de la Houssinire, Nantes, F-44300, France E-mail: sabrina.pavy@univ-nantes.fr Due to its high tunable permittivity and low dielectric losses, (Ba1-xSrx)TiO3 (BST) thin films appear to be one of the most studied candidates among ferroelectric materials for the realization of intelligent microelectronics components. More particularly, the conception of innovative antenna devices may profit from the materials high-k property and from its tunability for miniaturization and functionalizing of embarked telecommunication systems, allowing the integration of an increased number of services while reducing size, weight and energy consumption. Antenna conception is based either on a coplanar or on a metal-insulator-metal (MIM) geometry. In both cases, integration of the thin films also needs etching of the ferroelectric material. In the present study, we investigate BST wet chemical etching. The etchant is prepared from buffered hydrofluoric acid (BHF) and nitric acid (HNO3), BHF being the reactive substance while HNO3 acts as a catalyst. The BST thin films were elaborated by a modified sol-gel process and the precursor solution is spin-coated either on insulating substrates (Si-wafers, Al2O3) or on metal (stainless steel substrates or underlying platinum electrode patterns). Classical photolithography technique, using a positive photo resist, was used for the transfer of the BST patterns. Despite of the isotropic wet etching procedure, the etching results show that a line roughness below 1 m can be obtained in the case of a 1 m thick BST ceramic thin film. Appropriate water dilution reduces the etching speed, thus allowing a better visual control of the process. No damage of the underlying layers (substrate or electrode) is observed.

254
PULSED LASER DEPOSITION OF EPITAXIAL PZT FILMS ON STO AND SI SUBSTRATES FOR NON-VOLATILE MEMORY APPLICATIONS
A.S. Borowiak1, G. Niu2, P. Lecoeur 3, V. Pillard3, D. Albertini1, N. Baboux1, B. Vilquin2, B. Gautier1
Institut des Nanotechnologies de Lyon, INSA de Lyon, 20, avenue Albert Einstein, 69621 Villeurbanne, France Institut des Nanotechnologies de Lyon, Ecole Centrale de Lyon, 36 avenue Guy de Collongue, 69134 Ecully cedex, France 3 Universit Paris-Sud, Institut dElectronique Fondamentale, Bt. 220, 91405 Orsay cedex, France. E-mail: alexis.borowiak@insa-lyon.fr
1
There has been an increasing effort to integrate ferroelectric thin films with silicon CMOS technology to enable commercially viable, high-density, non-volatile ferroelectric memories, and other technologies. Pb (Zr, Ti)O3 (PZT) and lead-based compounds constitute the best family of piezoelectric and ferroelectric materials suitable for integration in devices, such as piezoelectric actuators, sensors, and transducers [1,2]. Especially PZT thin films have been more attractive than other piezoelectric films due to their large piezoelectric coefficients (d33 and e31) and reliable performance. In this work, we compare the epitaxial growth and electrical properties of PZT thin films deposited by Pulsed Laser Deposition (PLD) on 2 different substrates: SrTiO3 (STO) and buffered Si(001). Previously to PZT growth, 40nm-thick (La,Sr)MnO3 (LSMO) layer is deposited to serve as electrical bottom electrode. The LSMO film epitaxy was optimized by PLD on STO and STO-buffered Si(001) [3]. The 200nm-thick PZT film growth was first optimized on LSMO-STO substrate by PLD. The deposition parameters were found to be: 600C and 100mTorr Oxygen. The XRD patterns indicate that the PZT film is monocrystalline with (001) orientation and rocking-curve value for PZT(002) about 0.54. Then using the same growth parameters a 200nm-thick PZT film was deposited on LSMO-STO-Si heterostructure. The STO-buffered silicon was fabricated by Molecular Beam Epitaxy (MBE). This UHV technology allows a good control of the oxide/Si heterointerface [4]. By using a conductive oxide bottom electrode LSMO, the polarization fatigue phenomenon can be largely reduced [5]. The PZT on silicon then shows a monocrystalline structure with (001) orientation and an in-plane epitaxy relationship between silicon and PZT: PZT[110] // Si[100]. The rocking curve measured on PZT(002) is still low, about 0.75, indicating a good quality of the ferroelectric film on silicon substrate. Ferroelectric properties at the nanoscale were carried out by Piezoresponse Force Microscopy (PFM) by applying -8V on a 55 m area to switch locally the polarization. Thereafter on the same surface and at the same point we have applied +8V on a surface of 2.52.5m to switch the polarization in the opposite direction. After the poling, 2 areas with different polarization are present on the surface. The high contrast of stable artificially poled, evidences the good ferroelectric properties of the PZT thin film. The comparison of the PZT/LSMO/STO/Si(001) and PZT/LSMO/STO structures proves that very good quality layers have been obtained for films grown on silicon substrate.
References [1]B. Jaffe, W. R. Cook, and H. Jaffe, Piezoelectric Ceramics (Academic, New York, 1971) [2]F. Levassort, P. Tran-Huu-Hue, E. Ringaard, and M. Lethiecq, J. Eur. Ceram. Soc. 21, 1361 (2001) [3]D. Esteve, K. Postava, P. Gogol, G. Niu, B. Vilquin, and P. Lecoeur Phys. Stat. Soli B 8, 1957 (2010) [4]G. Niu, G. Saint-Girons, B. Vilquin, G. Delhaye, J.L. Maurice, C. Botella, Y. Robach and G. Hollinger, Appl. Phys. Lett. 95, 062902 (2009)
[5]B. T. Liu, K. Maki, Y. So, V. Nagarajan, and R. Ramesh, Appl. Phys. Lett. 80, 25 (2002)

256
BaTiO3-BASED LEAD-FREE PIEZOELECTRICS

Sarah A. Turp Department of Chemistry, University of St Andrews, St Andrews KY16 9ST
With piezoelectric materials becoming increasingly important in a world which uses more electronic devices than ever, this work has been focused on bettering our understanding of the electrical properties of known piezoelectric materials and on the effects of cation doping. Due to the environmental concerns surrounding the use of lead, which is commonly found in current piezoelectrics such as PZT, this work focuses on the development lead-free barium titanate based compositions, in the hope of providing commercially viable lead-free alternatives. Barium titanate exhibits piezoelectric properties up to ~130C, showing a sharp peak in the dielectric maximum at this temperature, as well as smaller peaks at lower temperatures as the perovskite structures shifts through a range of lattice systems. Its perovskite structure is well suited to the incorporation of a variety of dopant species, often resulting in a broadening of the dielectric maxima and a shift in the Curie temperature. This work focuses of the used of both isovalent and aliovalent dopants to bring together this series of peaks in the dielectric constant, in order to form single broaden peaks, maximising the piezoelectric properties over a greater temperature range for use in commercial applications.

ISIF 2011 - International Symposium on Integrated Functionalities

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ISIF 2011 - International Symposium on Integrated Functionalities

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International Symposium on Integrated Functionalities

July 31 August 4 University of Cambridge, UK

ISIF 2011 Location of venues

Asylum Research - www.asylumresearch.co.uk

attocube systems AG - www.attocube.com

PI-KEM Ltd - www.pi-kem.com

Radiant Technologies Inc - www.ferrodevices.com

Physiology Lecture Theatre

Earth Sciences Lecture Theatre

Welcome - Jim Scott

Spintronics and electrical devices Plenary - Chair Stuart Parkin

Chair - Manuel Bibes and Moon-Ho Jo

Superlattices Chair - J.-M. Triscone and M. Dawber

Ferroelectrics theory Chair - A. J. Bell and R. A. Cowley

Xavier Marti - SPIN-VALVE-LIKE MAGNETORESISTANCE OF AN ANTIFERROMAGNET-BASED TUNNEL JUNCTION (218)

BiFeO3 and Multiferroics Chair - J. Fontcuberta & G. Catalan

Josep Fontcuberta - MAGNETOELECTRIC COUPLING IN EXCHANGE-BIASED MULTIFERROIC HETEROSTRUCTURES (233) 14:00

Plenary - Chair I. Dzyaloshinskii

R. Ramesh - COUPLING MAGNETISM TO ELECTRICITY IN MULTIFERROIC HETEROSTRUCTURES (231)

Chair - J. Fontcuberta & G. Catalan

Jan Seidel - PHOTOVOLTAIC AND ELECTROCHROMIC PROPERTIES OF BiFeO3 (228)

R. Blinc - CREATION OF POLAR NANOCLUSTERS IN RELAXORS (238)

Physiology Lecture Theatre

Earth Sciences Lecture Theatre

BiFeO3 and Multiferroics Chair - J. Fontcuberta & G. Catalan

M. Kenzelmann - MAGNETICALLY-DRIVEN ELECTRIC POLARIZATION IN MAGNETO-ELECTRICS AND MULTIFERROICS (237)

Eric Bousquet - UNEXPECTEDLY LARGE ELECTRONIC CONTRIBUTION TO MAGNETOELECTRICITY (9)

Electrocalorics Chair - Qi Zhang & S. Kar-Narayan

Lunch Lunch Poster sesssion A

Lunch Poster session A

Nanodomains and nanocrystals: Continuous media

Xavier Marti - SKIN LAYER OF BiFeO3 SINGLE CRYSTALS (219)

Q. Zhang - MOVING TOWARDS ELECTROCALORIC REFRIGERATION (146)

RRAM Plenary - Chair Sandwip Dey

Rainer Waser - REDOX-BASED MEMRISTIVE SWITCHING - SCALING BEYOND FLASH? (232)

Hermann Kohlstedt - TUNNEL JUNCTIONS FOR MEMORY APPLICATIONS (63)

BiFeO3 and Multiferroics Chair - J. Fontcuberta & G. Catalan

Anna Ggor - MAGNETO-ELASTIC EFFECT IN CuCrSe2 ANTIFERROMAGNET (48)

Nanodomains and nanocrystals: Nanopatterned media

Haidong Lu - ELECTRIC MODULATION OF MAGNETIZATION IN FERROELECTRIC-FERROMAGNETIC HETEROJUNCTIONS (54)

18:30 18:45 19:30

Physiology Lecture Theatre

Earth Sciences Lecture Theatre

RRAM Chair - H. Kohlstedt and A. Jiang

Graphene Plenary - Chair Neil Mathur

Roman Gorbachev - COULOMB DRAG IN GRAPHENE / BORON NITRIDE HETEROSTRUCTURES (151)

Lunch Lunch Poster sesssion B

rf and high frequency devices Plenary - Chair J. Banys

Chair - J. Banys and E. Rocas

Andrew J Bell - IMPEDANCE SPECTROSCOPY AND DIELECTRIC MODELLING OF (KxNa1-x)1/2Bi1/2TiO3 (28)

Juras Banys - INVESTIGATION OF 0.4Na1/2Bi1/2TiO3- (0.6-x)SrTiO3xPbTiO3 SOLID SOLUTIONS (109)

Chair - S. Ducharme and A. J. Bell

Wontae Chang - FERROELECTRICALLY ACTIVE ACOUSTIC WAVE PROPAGATION (69)

Devices Chair - Joe Evans and MacLeod

Physiology Lecture Theatre

Medical applications Plenary - Chair M. Goryll

Susan Trolier-McKinstry - MEDICAL APPLICATIONS OF PIEZOELECTRIC MICROELECTROMECHANICAL SYSTEMS (159) 9:45

Medical applications Plenary - Chair M. Goryll

Chair - D. Chrisey and M. Goryll

Devices Chair - Joe Evans and MacLeod

Ferroelectrics Experimental Chair - H. N. Lee