The single-phase multiferroic oxides: from bulk to thin film

Complex perovskite oxides exhibit a rich spectrum of properties, including magnetism, ferroelectricity, strongly correlated electron behaviour, superconductivity and magnetoresistance, which have been research areas of great interest among the scientific and technological community for decades. There exist very few materials which exhibit multiple functional properties; one such class of materials is called the multiferroics. Multiferroics are interesting because they exhibit simultaneously ferromagnetic and ferroelectric polarizations and a coupling between them. Due to the nontrivial lattice coupling between the magnetic and electronic domains (the magnetoelectric effect), the magnetic polarization can be switched by applying an electric field; likewise the ferroelectric polarization can be switched by applying a magnetic field. As a consequence, multiferroics offer rich physics and novel devices concepts, which have recently become of great interest to researchers. In this review article the recent experimental status, for both the bulk single phase and the thin film form, has been presented. Current studies on the ceramic compounds in the bulk form including Bi(Fe,Mn)O3, REMnO3 andthe series of REMn2O5 single crystals (RE =  rare earth) are discussed in the first section and a detailed overview on multiferroic thin films grown artificially (multilayers and nanocomposites) is presented in the second section.

[1]  V. Gopalan,et al.  Large optical nonlinearities in BiMnO3 thin films , 2003 .

[2]  M. Hervieu,et al.  Thin film deposition: a novel synthetic route to new materials , 1999 .

[3]  H. Schmid,et al.  Structure of a ferroelectric and ferroelastic monodomain crystal of the perovskite BiFeO3 , 1990 .

[4]  G. Gehring On the microscopic theory of the magnetoelectric effect , 1994 .

[5]  H. Ishiwara,et al.  Ferroelectricity of YMnO3 Thin Films on Pt(111)/Al2O3(0001) and Pt(111)/Y2O3(111)/Si(111) Structures Grown by Molecular Beam Epitaxy , 2001 .

[6]  V. Palkar,et al.  Observation of saturated polarization and dielectric anomaly in magnetoelectric BiFeO3 thin films , 2002 .

[7]  S. Cheong,et al.  Electric polarization reversal and memory in a multiferroic material induced by magnetic fields , 2004, Nature.

[8]  G. A. Smolenskii,et al.  REVIEWS OF TOPICAL PROBLEMS: Ferroelectromagnets , 1982 .

[9]  C. Rao,et al.  Charge ordering in the rare earth manganates: the experimental situation , 2000 .

[10]  Y. Tokura,et al.  Magnetic control of ferroelectric polarization , 2003, Nature.

[11]  S. Abrahams Ferroelectricity and structure in the YMnO(3) family. , 2001, Acta crystallographica. Section B, Structural science.

[12]  Y. Sun,et al.  Coupling between the ferroelectric and antiferromagnetic orders in YMnO 3 , 1997 .

[13]  Field-induced reentrant novel phase and a ferroelectric-magnetic order coupling in HoMnO3. , 2003, Physical review letters.

[14]  Xiaoqing Pan,et al.  Epitaxial growth and properties of metastable BiMnO3 thin films , 2004 .

[15]  B. Raveau,et al.  Stabilization of YMnO3 in a Perovskite Structure as a Thin Film , 1998 .

[16]  C. Rao,et al.  Orbital ordering as the determinant for ferromagnetism in biferroic BiMnO 3 , 2002 .

[17]  M. Wuttig,et al.  Exploration of artificial multiferroic thin-film heterostructures using composition spreads , 2004 .

[18]  V. Palkar,et al.  Effect of Mn substitution on magnetoelectric properties of bismuth ferrite system , 2003 .

[19]  Yasuhiro Tokura,et al.  Magnetocapacitance effect in multiferroic BiMnO 3 , 2003 .

[20]  P. Murugavel,et al.  Enhanced magnetoresistance in ferromagnetic Pr0.85Ca0.15MnO3∕ferroelectric Ba0.6Sr0.4TiO3 superlattice films , 2004, cond-mat/0410081.

[21]  M. T. Casais,et al.  High Oxygen Pressure Preparation, Structural Refinement, and Thermal Behavior ofRMn2O5(R==La, Pr, Nd, Sm, Eu) , 1997 .

[22]  R. Vickery,et al.  Crystallographic and Magnetochemical Studies on ABO3 Group Compounds of Lanthanon and Manganese Oxides , 1957 .

[23]  J. Son,et al.  Writing polarization bits on the multiferroic BiMnO3 thin film using Kelvin probe force microscope , 2004 .

[24]  A. Haghiri-Gosnet,et al.  In situ monitoring of the growth and characterization of (PrMnO3)n(SrMnO3)n superlattices , 2003 .

[25]  M. Muñoz,et al.  MAGNETORESISTANCE IN EXCESS OF 200% IN BALLISTIC NI NANOCONTACTS AT ROOM TEMPERATURE AND 100 OE , 1999 .

[26]  Y. Tokura,et al.  Control of the ferroelectric properties of Dy Mn 2 O 5 by magnetic fields , 2004 .

[27]  R. Ramesh,et al.  Epitaxial BiFeO3 Multiferroic Thin Film Heterostructures , 2003, Science.

[28]  R Ramesh,et al.  Multiferroic BaTiO3-CoFe2O4 Nanostructures , 2004, Science.

[29]  C. Fermon,et al.  Magnetoresistance in nanocontacts induced by magnetostrictive effects , 2004 .

[30]  E Steichele,et al.  Spiral magnetic ordering in bismuth ferrite , 1982 .

[31]  C. Nan,et al.  Effect of magnetic bias field on magnetoelectric coupling in magnetoelectric composites , 2003 .

[32]  Zu-liang Liu,et al.  Room-temperature saturated ferroelectric polarization in BiFeO3 ceramics synthesized by rapid liquid phase sintering , 2004 .

[33]  M. Okuyama,et al.  Structural and multiferroic properties of BiFeO3 thin films at room temperature , 2004 .

[34]  O. Carp,et al.  New synthesis routes for obtaining dysprosium manganese perovskites , 2003 .

[35]  J. H. Yeom,et al.  Magnetic properties of helimagnetic YMn2−x(Fe,Co)xO5−δ (0.0⩽x⩽1.0) for the room temperature ferroism , 2004 .

[36]  A. Filippetti,et al.  Coexistence of magnetism and ferroelectricity in perovskites , 2002 .

[37]  Y. Syono,et al.  Magnetic Properties and Crystal Distortions of BiMnO3 and BiCrO3 , 1968 .

[38]  A. Filippetti,et al.  Why are there any magnetic ferroelectrics , 2002 .

[39]  Francis S. Galasso,et al.  Structure, Properties and Preparation of Perovskite Type Compounds , 1969 .

[40]  J. V. D. Boomgaard,et al.  Piezoelectric-piezomagnetic composites with magnetoelectric effect , 1976 .

[41]  D. R. Terrell,et al.  An in situ grown eutectic magnetoelectric composite material , 1974 .

[42]  S. Cheong,et al.  Colossal magnetodielectric effects in DyMn2O5. , 2004, Physical review letters.

[43]  T. Yoshimura,et al.  Ferroelectric properties of YMnO3 epitaxial films for ferroelectric-gate field-effect transistors , 2003 .

[44]  Th. Lonkai,et al.  Magnetic two-dimensional short-range order in hexagonal manganites , 2003 .

[45]  T. Oguchi,et al.  First-principles study on the electronic structure of bismuth transition-metal oxides , 2004 .

[46]  S. Abrahams,et al.  Crystal Structure of Paramagnetic DyMn2O5 at 298°K , 1967 .

[47]  Ferroelectric properties of c-oriented YMnO3 films deposited on Si substrates , 1998 .

[48]  J. Rivera,et al.  Magnetic field induced magnetoelectric effects, (ME)H, in the perovskites Pb2CoWO6 and Pb2FeTaO6 , 1988 .

[49]  Nicola A. Spaldin,et al.  The origin of ferroelectricity in magnetoelectric YMnO3 , 2004, Nature materials.

[50]  D. Többens,et al.  Development of the high-temperature phase of hexagonal manganites , 2004 .

[51]  E. Golovenchits,et al.  Magnetic and magnetoelectric dynamics in RMn2O5 (R = Gd and Eu) , 2004 .

[52]  Hans Schmid,et al.  Multi-ferroic magnetoelectrics , 1994 .

[53]  Y. Tokura,et al.  Ferroelectricity and giant magnetocapacitance in perovskite rare-earth manganites. , 2004, Physical review letters.

[54]  E. Ascher,et al.  Some Properties of Ferromagnetoelectric Nickel‐Iodine Boracite, Ni3B7O13I , 1966 .

[55]  W. James,et al.  The precision determination of the lattice parameters and the coefficients of thermal expansion of BiFeO3 , 1972 .

[56]  T. Choi,et al.  Bi modification for low-temperature processing of YMnO3 thin films , 2004 .

[57]  M. Fiebig,et al.  Magnetoelectric Behaviour of Domain Walls in Multiferroic HoMnO3 , 2004 .

[58]  W. David,et al.  Diffuse X-ray scattering from benzil, C(14)H(10)O(2): analysis via automatic refinement of a Monte Carlo model. , 2001, Acta crystallographica. Section A, Foundations of crystallography.

[59]  V. Palkar,et al.  Observation of room-temperature magnetoelectric coupling in pulsed-laser-deposited Bi0.6Tb0.3La0.1FeO3 thin films , 2004 .

[60]  E. F. Bertaut,et al.  Substitution dans les hexaferrites de l'ion Fe3+ par Al3+ , Ga3+, Cr3+ , 1959 .

[61]  B. Raveau,et al.  Tailored superlattices containing distinct oxide and oxycarbonate blocks grown by pulsed laser deposition , 1997 .

[62]  J. V. D. Boomgaard,et al.  A sintered magnetoelectric composite material BaTiO3-Ni(Co, Mn) Fe2O4 , 1978 .

[63]  Ueda,et al.  Ferromagnetism in LaFeO3-LaCrO3 superlattices , 1998, Science.

[64]  Junling Wang,et al.  Epitaxial BiFeO3 thin films on Si , 2004 .

[65]  M. Fiebig,et al.  Observation of coupled magnetic and electric domains , 2002, Nature.

[66]  H. Ishiwara,et al.  Epitaxial Growth of Ferroelectric YMnO3 Thin Films on Si (111) Substrates by Molecular Beam Epitaxy , 1998 .

[67]  C. Nan,et al.  Resonance magnetoelectric effect in bulk composites of lead zirconate titanate and nickel ferrite , 2004 .

[68]  T. Yoshimura,et al.  Epitaxially grown YMnO3 film: New candidate for nonvolatile memory devices , 1996 .

[69]  M. Fiebig Revival of the magnetoelectric effect , 2005 .

[70]  Ch. Simon,et al.  Magnetocapacitance effect in perovskite-superlattice based multiferroics , 2005 .

[71]  Pseudo moiré dislocations appearing in x‐ray diffraction topography , 1996 .

[72]  Ramamoorthy Ramesh,et al.  Three-dimensional heteroepitaxy in self-assembled BaTiO3–CoFe2O4 nanostructures , 2004 .

[73]  R. Prasher Planck blackbody emissive power in particulate media , 2005 .

[74]  Influence of magnetic on ferroelectric ordering in LuMnO3 , 2004, cond-mat/0402465.

[75]  J. Banys,et al.  Glass behaviour in the solid solution of deuterated betaine phosphate0.15 betaine phosphite0.85 , 2000 .

[76]  K. Ohoyama,et al.  Structure determination of ferromagnetic perovskite BiMnO3 , 1999 .

[77]  S. Cheong,et al.  Structural anomalies and multiferroic behavior in magnetically frustrated TbMn2O5. , 2004, Physical review letters.

[78]  H. Yakel,et al.  On the crystal structure of the manganese(III) trioxides of the heavy lanthanides and yttrium , 1963 .

[79]  Junling Wang,et al.  Dramatically enhanced polarization in (001), (101), and (111) BiFeO3 thin films due to epitiaxial-induced transitions , 2004 .

[80]  Anthony K. Cheetham,et al.  Evidence for the likely occurrence of magnetoferroelectricity in the simple perovskite, BiMnO3 , 2002 .

[81]  Mahesh Kumar,et al.  Relaxor behavior in BaTiO3 , 2000 .

[82]  L. E. Cross,et al.  Destruction of spin cycloid in (111)c-oriented BiFeO3 thin films by epitiaxial constraint: Enhanced polarization and release of latent magnetization , 2005 .

[83]  Karin M. Rabe,et al.  FIRST-PRINCIPLES INVESTIGATION OF FERROMAGNETISM AND FERROELECTRICITY IN BISMUTH MANGANITE , 1999 .

[84]  Ning Cai,et al.  Dielectric, ferroelectric, magnetic, and magnetoelectric properties of multiferroic laminated composites , 2003 .

[85]  K. Kohn,et al.  Structure and Ferroelectricity of RMn 2 O 5 , 2002 .

[86]  Ram Seshadri,et al.  Visualizing the Role of Bi 6s “Lone Pairs” in the Off-Center Distortion in Ferromagnetic BiMnO3 , 2001 .

[87]  Robert Zannetti,et al.  Landolt-bornstein, new series , 1974 .

[88]  N. Spaldin,et al.  Ab initio prediction of a multiferroic with large polarization and magnetization , 2004, cond-mat/0410268.

[89]  M. Blamire,et al.  Epitaxial and oriented YMnO3 film growth by pulsed laser deposition , 2004 .

[90]  P. Lecoeur,et al.  Colossal magnetoresistive manganite thin films , 2001, cond-mat/0111363.

[91]  D. Jayatilaka,et al.  Wavefunctions derived from experiment. II. A wavefunction for oxalic acid dihydrate. , 2001, Acta crystallographica. Section A, Foundations of crystallography.

[92]  T. Yoshimura,et al.  Influence of Schottky and Poole–Frenkel emission on the retention property of YMnO3-based metal/ferroelectric/insulator/semiconductor capacitors , 2003 .

[93]  Young K. Park,et al.  Memory window of highly c-axis oriented ferroelectric YMnO3 thin films , 1999 .

[94]  Determination of the magnetic structure of hexagonal manganites RMnO3 (R=Sc, Y, Ho, Er, Tm, Yb) by second-harmonic spectroscopy , 1999 .

[95]  Nicola A. Spaldin,et al.  Weak ferromagnetism and magnetoelectric coupling in bismuth ferrite , 2005 .

[96]  Xiaoqing Pan,et al.  Bismuth manganite: A multiferroic with a large nonlinear optical response , 2004 .

[97]  J. Gregg,et al.  Spin electronics—a review , 2002 .

[98]  A. Maignan,et al.  Effect of A -site cation size mismatch on charge ordering and colossal magnetoresistance properties of perovskite manganites , 1997 .

[99]  T. Yoshimura,et al.  Ferromagnetic and ferroelectric behaviors of A-site substituted YMnO3-based epitaxial thin films , 2003 .

[100]  Pavlov,et al.  Determination of the magnetic symmetry of hexagonal manganites by second harmonic generation , 2000, Physical review letters.

[101]  W. Sun,et al.  Hydrogen bonds in the framework of bis(2-[bis(2-aminoethyl)amino]ethanol)nickel(II) diperchlorate. , 2001, Acta crystallographica. Section C, Crystal structure communications.

[102]  C. Lokhande,et al.  Synthesis and dielectric properties of Bi1−xNdxFeO3 perovskites , 2004 .