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Nanostructured Multiferroics
Nanostructured Multiferroics
Edited by
Raneesh Balakrishnan
P. M. Visakh
Editors All books published by Wiley-VCH are carefully
produced. Nevertheless, authors, editors, and
Dr. Raneesh Balakrishnan publisher do not warrant the information contained
Department of Physics in these books, including this book, to be free of
Catholicate College errors. Readers are advised to keep in mind that
Pathanamthitta statements, data, illustrations, procedural details or
Kerala 689 645 other items may inadvertently be inaccurate.
India
Library of Congress Card No.:
Dr. P. M. Visakh applied for
TUSUR University
Department of Physical Electronics British Library Cataloguing-in-Publication Data
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v
Contents
Preface xi
Editors’ Bio xiii
1 Nanostructured Multiferroics: Current Trends and Future

Prospects 1
P.M. Visakh and B. Raneesh
1.1 Single-phase Multiferroics 1
1.2 Multiferroic Study of Pure BiFeO3 Synthesized Using Various
Complexing Agents by Sol–Gel Method 2
1.3 Nanostructured Multiferroics 3
1.4 Multiferroic Systems of BiFeO3 and BaTiO3 Nanostructures: New Ideas
and Insights from Recent Magnetoelectric Advancements 5
1.5 Effective Properties of Multilayered Nanomultiferroics 6
1.6 Correlation between Grain Size, Transport, and Multiferroic Properties
of Ba-doped BiFeO3 Nanoparticles 7
1.7 Specific Heat and Magnetocaloric Properties of Some Manganite-Based
Multiferroics for Cryo Cooling Applications 8
1.8 Preparations, Characterization, and Applications of Multiferroic
Nanocomposites 10
1.9 Conclusions 11
References 11
2 Single-Phase Multiferroics 23
Piotr Graczyk and Emerson Coy
2.1 Introduction 23
2.1.1 Considerations on Single-phase Multiferroics 26
2.1.2 Ferroelastic Multiferroics 29
2.2 Analysis of the Multiferroicity in the Hexagonal Manganites 30
2.2.1 Ferromagnetism in Hexagonal Manganites 30
2.2.2 Ferroelectricity in Hexagonal Manganites 32
2.3 Investigation of Charge States and Multiferroicity in Doped Systems 32
2.3.1 Sensitive Ordering-doped Perovskite Manganites 32
vi Contents
2.3.2 Frustrated LuFe2 O4 – Multiferroism in Controversy 35

2.3.3 From the Dzyaloshinskii–Moriya Interaction to the Exchange
Striction 37
2.4 Multiferroic Phases of Lone-pair Ferroelectrics: Bismuth-Based
Compounds 38
2.5 Studies on Proper Geometric Ferroelectrics 41
2.6 Conclusions 44
Acknowledgments 44
References 45
3 Multiferroic Study of Pure BiFeO3 Synthesized Using Various

Complexing Agents by Sol–Gel Method 51
Vivek Verma, Neelam Singh, and Jarnail Singh Bangruwa
3.1 Introduction 51
3.2 Experimental 52
3.3 Results and Discussion 53
3.3.1 Structural Analysis 53
3.3.2 Morphological Analysis 54
3.3.3 FTIR Analysis 55
3.3.4 Magnetic Analysis 57
3.3.5 Ferroelectric Analysis 58
3.3.6 Dielectric Analysis 59
3.3.7 Leakage Current Analysis 60
3.4 Conclusions 61
References 62
4 Nanostructured Multiferroics 63
Heng Wu and Xinhua Zhu
4.1 Introduction 63
4.2 Multiferroic Nanoparticles 64
4.2.1 Solid-state Reactions 65
4.2.2 Molten-salt Synthesis (MSS) 66
4.2.3 Mechanochemical Synthesis 66
4.2.4 Wet Chemical Methods 68
4.2.4.1 Sol–Gel Process 68
4.2.4.2 Hydrothermal/Solvothermal Process 69
4.2.4.3 Microwave–Hydrothermal (M–H) Process 70
4.3 Nanocomposites 73
4.4 Core–Shell Nanostructures 75
4.5 Nanostructures and Thin Films for Multifunctional Applications:
Technology, Properties, and Devices 77
4.5.1 Fabrication Technologies 78
4.5.2 Physical Properties 79
4.5.2.1 Ferroelectric Properties 79
Contents vii
4.5.2.2 Magnetic Properties 81

4.5.2.3 Photocatalytic Properties 82
4.5.3 Multiferroic Devices 82
4.6 Thin Films for Photovoltaic Applications 84
4.7 Conclusions 87
Acknowledgments 88
References 88
5 Multiferroic Systems of BiFeO3 and BaTiO3 Nanostructures:

New Ideas and Insights from Recent Magnetoelectric
Advancements 95
K.C. Verma, R. K. Kotnala, and Navdeep Goyal
5.1 Introduction to Multiferroics 95
5.1.1 Multiferroic Approaches Toward Magnetoelectric Memories 96
5.1.2 Multiferroic Perovskites 97
5.1.3 Multiferroic Systems of BaTiO3 and BiFeO3 Nanostructures 99
5.1.3.1 BaTiO3 99
5.1.3.2 BiFeO3 100
5.1.3.3 Lone Pairs and Charge Ordering of Ferroelectric Activity 101
5.2 Crystalline Structure and Phase Transition 102
5.2.1 X-ray Diffraction (XRD) of BaTM0.01 Ti0.99 O3 [TM = Cr, Mn, Fe, Co, Ni,
Cu (1 mol% Each)] Nanoparticles 102
5.2.2 Crystalline Structure of BiFeO3 Nanostructures with Pb Doping 103
5.2.3 Nanostructural Approach Toward Multiferroics 105
5.2.3.1 Nanostructural Influence on Ferroelectric Polarization 106
5.2.3.2 Nanosize-dependent Phase Structure 106
5.2.3.3 Lattice Defects-related Nanostructures 107
5.2.4 Magnetic Ordering 108
5.2.4.1 TM Ion-substituted BaTiO3 108
5.2.4.2 Magnetic Ordering in BiFeO3 110
5.2.5 Multiferroicity and Magnetoelectric Coupling: How to Enhance 112
5.2.5.1 Multiferroic Composites 112
5.2.5.2 Multiferroic Thin Films and Nanostructures 116
5.3 Synthesis Methods of BaTiO3 and BiFeO3 Multiferroics 122
5.3.1 Sol–Gel: Synthesis 122
5.3.2 Chemical Combustion 123
5.3.3 Liquid-phase Deposition Route 123
5.3.4 Hydrothermal Synthesis 123
5.3.5 Metallo-organic Decomposition Method (MOD) for Thin-Film
Preparation 123
5.3.6 Modified Pechini Method 124
5.4 Conclusions 124
Acknowledgments 124
References 125
viii Contents
6 Effective Properties of Multilayered Nanomultiferroics 133

Ivan A. Starkov and Alexander S. Starkov
6.1 Introduction 133
6.2 Matrix Homogenization Method 134
6.2.1 Justification of the Matrix Homogenization Method 135
6.3 Laminate Nanocomposites 138
6.4 Fiber Nanocomposites 144
6.4.1 Basic Equations 144
6.4.2 Anti-plane Elasticity 147
6.4.3 Axial-symmetry Case 149
6.4.4 Maxwell–Garnett Theory 152
6.5 Core–Shell Nanostructures 153
6.5.1 Basic Equations 154
6.5.2 Homogenization Procedure for the Layered Hollow Sphere 156
6.6 Summary and Conclusions 159
Acknowledgments 159
References 160
7 Correlation Between Grain Size, Transport, and Multiferroic

Properties of Ba-doped BiFeO3 Nanoparticles 163
M. M. El-Desoky and M. S. Ayoub
7.2 Characterization of Ba-doped BiFeO3 Multiferroic Nanoparticles 165
7.2.1 X-ray Diffraction (XRD) 165
7.2.2 Scanning Electron Microscope (SEM) 167
7.2.3 Transmission Electron Microscope (TEM) 167
7.2.4 Fourier Transform Infrared (FTIR) Spectra 169
7.3 Transport Properties of Ba-doped BiFeO3 Multiferroic
Nanoparticles 170
7.3.1 Nature of Conduction Mechanism 172
7.3.2 Relation Between Activation Energy and Mean Distance Between Iron
Ions 174
7.3.3 Nature of Small Polaron-hopping (SPH) Conduction 176
7.3.4 Small Polaron-hopping (SPH) Parameters 176
7.3.5 Hopping Carrier Mobility and Density 177
7.4 Multiferroic Properties of Ba-doped BiFeO3 Multiferroic
Nanoparticles 178
7.4.1 Ferromagnetic Properties 178
7.4.1.1 Molar Magnetic Susceptibility (λM ) 178
7.4.1.2 Néel Temperature (TN ) 180
7.4.2 Ferromagnetic Hysteresis Loop 180
7.4.3 Ferroelectric Properties 184
7.4.3.1 Temperature Dependence 184
7.4.3.2 Frequency Dependence 187
Contents ix
7.4.4 Ferroelectric Hysteresis Loop 188

7.5 Conclusion 189
References 190
8 Specific Heat and Magnetocaloric Properties of Some

Manganite-Based Multiferroics for Cryo Cooling
Applications 193
N. Pavan Kumar, Elle Sagar, and P. Venugopal Reddy
8.1.1 Magnetic Refrigeration 193
8.1.2 Magnetocaloric Effect 194
8.1.3 Magnetocaloric Effect and Magnetic Transition 195
8.1.4 Manganites as Magnetocaloric Materials 195
8.1.5 Magnetocaloric Effect in Rare Earth-Based Multiferroic
Manganites 196
8.1.6 Methods for the Determination of Magnetocaloric Effect 196
8.1.6.1 Direct Measurements 196
8.1.6.2 Indirect Measurements 197
8.1.7 Properties of an Ideal Magnetic Refrigerator Material 198
8.2 Multiferroic Materials and Their Structure 198
8.2.1 Rare Earth-Based Multiferroic Manganites Based on Their
Structures 198
8.2.1.1 Hexagonal Manganite Multiferroics 199
8.2.1.2 Orthorhombic Manganite Multiferroics 199
8.3 Specific Heat and Estimation of Magnetic Entropy 200
8.3.1 Specific Heat 200
8.3.1.1 RMnO3 (R = Sm, Eu, Gd, Tb, and Dy) 200
8.3.1.2 Tb1−x Dyx MnO3 (x = 0, 0.1, 0.2, 0.3, and 0.4) 204
8.3.1.3 RMn2 O5 (R = Tb, Dy, and Ho) 205
8.3.2 Estimation of Magnetic Entropy 208
8.3.2.1 RMnO3 (R = Sm, Eu, Gd, Tb, and Dy) 208
8.3.2.2 Tb1−x Dyx MnO3 (x = 0, 0.1, 0.2, 0.3, and 0.4) 211
8.3.2.3 RMn2 O5 (R = Tb, Dy, and Ho) 211
8.4 Magnetocaloric Properties 213
8.4.1 RMnO3 Series 214
8.4.1.1 Orthorhombic NdMnO3 , SmMnO3 , and EuMnO3 214
8.4.1.2 Orthorhombic GdMnO3 , TbMnO3 , and DyMnO3 216
8.4.1.3 Hexagonal DyMnO3 220
8.4.1.4 Hexagonal HoMnO3 220
8.4.2 Group 2 Series (Doped Rare-earth Manganites) 221
8.4.2.1 Orthorhombic Dy-doped TbMnO3 221
8.4.2.2 h-YbMnO3 Doped with Transition Metals and Rare Earths 223
8.4.3 RMn2 O5 (R = Tb, Dy, and Ho) Series 224
8.5 Conclusions 227
References 228
x Contents
9 Preparations, Characterization, and Applications of

Multiferroic Nanocomposites 233
P.M. Visakh
9.2 Preparation of Multiferroic Nanocomposites 235
9.3 Characterizations of Multiferroic Nanocomposites 238
9.4 Applications of Multiferroic Nanocomposites 240
9.5 Conclusions 241
References 241
Index 249
xi
Preface
The book Nanostructured Multiferroics: summarizes many of the recent research

accomplishments in the area of multiferroics. We discuss many topics such as
nanostructured multiferroics current trends, new challenges and opportunities,
structure and properties’ relationship in multiferroic systems. The book gives
a comprehensive account of single-phase multiferroics, multiferroic study of
pure BiFeO3 synthesized using various complexing agents by sol–gel method,
nanostructured multiferroics, multiferroic systems of BiFeO3 and BaTiO3 nanos-
tructures. New ideas and insights from recent magnetoelectric advancements;
effective properties of multilayered nanomultiferroics; correlation between grain
size, transport, and multiferroic properties of Ba-doped BiFeO3 nanoparticles;
specific heat and magnetocaloric properties of some manganite-based multiferroics
for cryo cooling applications; preparations, characterization, and applications of
multiferroic nanocomposites are also included in this book.
This book will be a very valuable reference source for university and college
faculties, professionals, research fellows, senior graduate students, researchers
in R&D laboratories working in the area of nanostructured multiferroics. The
various chapters have been contributed by prominent researchers from industry,
academia, and government/private research laboratories across the globe. It covers
an up-to-date record on the major findings and observations in the field of multifer-
roic nanocomposites. The first chapter discusses about, scope, state of art, current
trends new challenges, and opportunities of multiferroic nanosystems.
Second chapter titled “Single-phase Multiferroics” gives a better review on
structure-property relationships. The authors discuss many topics such as impor-
tance of single-phase multiferroics, ferroelastic multiferroics, analysis of the
multiferroicity in the hexagonal manganites, ferromagnetism in hexagonal man-
ganites, ferroelectricity in hexagonal manganites, investigation of charge states
and multiferroicity in doped systems, frustrated LuFe2 O4 , multiferroic phases of
lone-pair ferroelectrics, and studies on proper geometric ferroelectrics. Chapter 3
deals with multiferroic study of pure BiFeO3 synthesized using various complexing
agents by sol–gel method. In this chapter, the authors discuss experimental method,
structural analysis, morphological analysis, FTIR analysis, magnetic analysis,
ferroelectric analysis, dielectric analysis, and leakage current analysis of BiFeO3
multiferroics.
xii Preface
The fourth chapter is titled “Nanostructured Multiferroics.” Following an intro-

duction to the multiferroic nanoparticles, the chapter goes on to discuss different
synthesis method, core shell nanostructures and multifunctional applications of
nanostructures thin films. The fifth chapter “Multiferroic Systems of BiFeO3 and
BaTiO3 Nanostructures: New Ideas and Insights from Recent Magnetoelectric
Advancements”. In which the multiferroic approach toward magnetoelectric mem-
ories, multiferroics based on BaTiO3 and BiFeO3 nanostructures, multiferroicity
and magnetoelectric coupling, and synthesis methods for BaTiO3 and BiFeO3
multiferroics are criticality analyzed.
The sixth chapter the authors explain the effective properties of multilayered
nanomultiferroics through matrix homogenization method, justification of the
matrix homogenization method, laminate nanocomposites, fiber nanocomposites,
basic equations, anti-plane elasticity, axial-symmetry case, Maxwell–Garnett theory,
core–shell nanostructures, and homogenization procedure for the layered hollow
sphere.
The seventh chapter of this book is titled “Correlation Between Grain Size,
Transport, and Multiferroic Properties of Ba-doped BiFeO3 Nanoparticles”. In
this chapter, the authors discuss main topics such as, transport properties, and
multiferroic properties of Ba-doped BiFeO3 multiferroic nanoparticles. Specific
Heat and Magnetocaloric Properties of Some Manganite-based Multiferroics are
discussed in chapter eight.
The final chapter presents an over view of – preparation of multiferroic nanocom-
posites, characterizations of multiferroic nanocomposites, and applications of mul-
tiferroic nanocomposites.
Finally, we would like to express our sincere gratitude to all the contributors of this
book, who gave excellent support to the successful completion of this venture. We
are grateful to them for the commitment and the sincerity they have shown toward
their contribution in the book. Without their enthusiasm and support, compilation
of this book would have not been possible. We would like to thank all the reviewers
who have given their valuable time to make critical comments on each chapter. We
also thank the publisher Wiley-VCH for recognizing the demand for such a book,
for realizing the increasing importance of the area of nanostructured multiferroics,
and their current trends and future prospects.
B. Raneesh
P.M. Visakh
xiii
Editors’ Bio
Dr. B. Raneesh is an Assistant Professor in the Depart-

ment of Physics, Catholicate College, Pathanamthitta, Ker-
ala, India. He received Ph.D. in Physics from Mahatma
Gandhi University, Kerala, India. His current research inter-
ests include multiferroics, thin films, nanocomposites, and
electron microscopy. He has published more than twenty
research articles in peer-reviewed international journals.
He also co-edited three books and co-authored four book
chapters. Source: Dr. B. Raneesh.
Dr. Visakh P.M. (MSc, MPhil, PhD) is a prolific editor

with more than 30 published books. He is working as assis-
tant professor in TUSUR University, Tomsk, Russia, since
2017. He did his post doc research in Tomsk Polytechnic Uni-
versity, Tomsk, Russia (2014–2017). He obtained his PhD,
MPhil, and MSc degrees from School of Chemical Sciences,
Mahatma Gandhi University, Kottayam, Kerala, India. He
has edited 30 books of Scrivener (Wiley), Springer, Royal
Society of Chemistry, Elsevier, and more than 10 books in
press (Wiley, Springer, Royal Society of Chemistry, and Elsevier). He has been invited
as a visiting researcher to Russia (2014 to present), Portugal (2013, 2014), Czech
Republic (2012, 2013), Italy (2009, 2012), Argentina (2010), Sweden (2010, 2011,
2012), Switzerland (2010), Spain (2011, 2012), Slovenia (2011), France (2011), Bel-
gium (2012), and Austria (2012) for his research work. He has visited 12 countries,
and 15 universities in Europe. He has 20 publications, 4 reviews, and more than 30
book chapters to his credit. He has attended and presented at more than 28 con-
ferences, has 1339 citations, and his h-index is 17. He acts as guest editor for 4
international journals. Source: Dr. Visakh P.M.
1
Nanostructured Multiferroics: Current Trends and Future

Prospects
P.M. Visakh 1 and B. Raneesh 2
1
Department of Physical Electronics, TUSUR University, Tomsk, Russia
2
Department of Physics, Catholicate College, Pathanamthitta, Kerala, India
1.1 Single-phase Multiferroics
In ferroics, at least two metastable states can be found. These states are related to
the directional arrangement and crystalline limitations of the materials, providing
reversible “stored states” that can be switched by external fields. For example, in
ferromagnets, an external magnetic field can flip the direction of the material mag-
netization to align parallel to the field direction. This phenomenon has found several
applications nowadays, especially in electronics and information storage devices,
both for ferroelectric and ferromagnetic materials [1]. Multiferroics are special class
of materials which possess more than one of the primary ferroic properties in the
same phase. Multiferroic materials are of great interest in the electronics industry
for application as memory storage devices [2, 3], spintronics [4], components [5],
and sensors [6]. The perovskite structure is perhaps the most common crystalline
structure for multiferroic materials studied so far. Its simplicity is due to its rather
straightforward organization and chemical constitution. The general perovskite for-
mula is ABX3 , where A and B are cations and X is an anion, typically oxygen, but
also others, like fluorine, are sometimes considered. Materials in which multiple
ferroic ordering take place had been already studied, as early as 1960s. Those early
studies focused on the synthesis of compounds with extremely complex stoichiome-
try, such as (1 − x)PbFe0.66 W0.33O3 – xPbMg0.5 W0.5 O3 [7] and nickel iodine boracite,
(Ni3 B2 O13 I) [8], both of which present too large ionic interactions and crystalline dis-
tortions to be able to determine the true origin of their multiferroic behavior. Never-
theless, the methodology was conceptually simple: it aimed to replace d0 B cations, in
ferroelectric perovskite oxides, by magnetic dn cations [9]. To understand magnetic
interactions in perovskites, it is important to discuss the Goodenough–Kanamori
rule. It was first formulated by Goodenough in 1955, and more rigorous mathemat-
ical underpinning was subsequently provided by Kanamori (1959). It is applied to
interatomic spin–spin interactions between two atoms that are mediated by virtual
electron transfers, for example in the Ni2 + –O–Mn4+ chain [10, 11].
Nanostructured Multiferroics, First Edition. Edited by Raneesh Balakrishnan and P.M. Visakh.
© 2021 WILEY-VCH GmbH. Published 2021 by WILEY-VCH GmbH.
2 1 Nanostructured Multiferroics: Current Trends and Future Prospects
Ferroelectricity and ferromagnetism seemed at the beginning to be mutually

exclusive in most cases; much effort has gone to overcome this problem the search
for single-phase materials, which can allocate two or more ferroic orders, is still
of high scientific interest. One way to achieve this goal is to adopt the so-called
lone pairs of big stereochemical active atoms such as Bi3+ or Pb2+ [12–15]. Mag-
netic and electric ferroic states are mostly independent of each other. Finding a
material in which the electric field can affect not only the polarization but also
the magnetization (E[P,M] ) and, in equal manner, a material in which the magnetic
field also affects magnetization and polarization (H [M,P] ), are highly desirable
in the industry. Several studies have shown ferroelastic switching in thin films
[16–18] to exhibit the potential applicability of these materials in multifunctional
heterostructures [19, 20] or artificial multiferroic architectures [21]. Moreover, in
materials such as BiFeO3 , PbTiO3 , and BaTiO3 , the ferroelastic domains are known
to play an important role in facilitating the coupling between the polarization and
the magnetization via the ferroelastic switching [22, 23], an aspect that is highly
desirable in nonvolatile memories [24, 25]. Additionally, domain walls have been
shown to have a very strong effect on heat flow and phonon scattering, which can
dramatically affect device performance [26]. The compounds considered above
belong to the class of type I multiferroics, where the charge order and ferroelectricity
is of “electric” origin. e.g. HoMnO3 which has an E-type magnetic order [27, 28].
In type II multiferroics, the magnetism causes the ferroelectric polarization, thus,
implying a strong magnetoelectric coupling.
There are two mechanisms that govern charge order through magnetic order
[29, 30]. The first is the inverse Dzyaloshinskii–Moriya interaction (DMI). This effect
is a relativistic correction (spin–orbit interaction) to the superexchange between
two TM magnetic ions through the oxygen. It has been observed in RMn2 O5
compounds, where it induces spiral magnetic order. The second mechanism of
magnetically driven ferroelectricity is the exchange striction.
1.2 Multiferroic Study of Pure BiFeO3 Synthesized Using

Various Complexing Agents by Sol–Gel Method
Due to long-term technological aspirations in this field, a lot of research work has
been reported. The surge of interest in multiferroic materials over the past 15 years
has been driven by their fascinating physical properties and huge potential for
technological applications. So, there has been the search for a particular material to
fulfill the requirement to be a good multiferroic material. Wang et al. [31] worked
to enhance polarization and related properties in hetero-epitaxially constrained
thin films of the multiferroic BiFeO3 (BFO). The film displays a room-temperature
spontaneous polarization (50–60 μC/cm2 ), almost an order of magnitude higher
than that of the bulk (6.1 μC/cm2 ). The Curie temperature (T c ) and the Neel
temp (T N ) of BFO are 1103 and 673 K, respectively, due to which it acts as a
good multiferroic material at RT [14]. Subhash Sharma et al. [32] reported the
comparative studies of pure bismuth ferrite prepared by sol–gel method versus
1.3 Nanostructured Multiferroics 3
conventional solid-state reaction method. This group found that sol–gel method is
better compared to solid-state method for preparing pure phase of BFO at low tem-
peratures. The precursors used are Bi(NO3 )3 ⋅5H2 O, Fe(NO3 )3 ⋅9H2 O, and distilled
water. Different complexing agents like citric acid, oxalic acid, glycine, and malonic
acid in 1 : 1 M ratio of metal ions were added in stoichiometric solution of above
precursors with constant stirring. The grains of BFO samples using different acids
are rectangular and the type of structure is rhombohedral [33]. BFO is reported as
G-type antiferromagnetic due to local spin ordering of Fe3+ at RT. At the same time,
there are several reports that show ferromagnetic-like magnetic hysteresis in pure
bismuth ferrite. Bismuth ferrite, prepared using citric acid, may be a good candidate
for further studies. It can be observed that BFO prepared by sol–gel technique using
citric acid as complexing agent shows good ferroelectric properties as compared
to other methods, and it exhibits a rhombohedral perovskite structure with less
impurity [34].
Dielectric properties of BFO samples, prepared by using various complexing
agents and annealed at 600 ∘ C, as a function of frequency have been measured in
the range of frequency 102 –106 Hz. It can be observed that the dielectric constant
decreases on increasing frequency and becomes independent at higher frequencies.
The decrement in 𝜀’ is attributed to the dielectric relaxation. The variation of
leakage current for applied electric field of BFO for different acids annealed at
600 ∘ C. This gives an idea of leakage current of samples for applied electric field.
The leakage current is in the range of 10−5 –10−10 A/cm2 for maximum applied field
4000 V/cm. In BFO, oxygen vacancies can be produced by the vaporization of Bi or
the presence of lower-valence Fe2+ ions, which lead to the formation of a trap level
at 0.6 eV below the bottom edge of the conduction band. X-ray diffraction patterns
and Fourier transform infrared analysis of various samples show the degree of
formation of required phase. Ferroelectric and magnetic study of samples prepared
at 600 ∘ C shows their comparative multiferroic properties. Samples show good
magnetic and ferroelectric properties at RT, which are the fundamental requirement
for any multiferroic material.
1.3 Nanostructured Multiferroics

Bismuth ferrite, BFO, as one of the very few single-phase multiferroics with a simul-
taneous coexistence of ferroelectric- and antiferromagnetic-order parameters at RT,
has attracted considerable attention since its discovery in 1960. Much work has
been carried out on the synthesis of pure BFO nanoparticles by numerous methods
(e.g. solid-state reactions [35–37], wet chemical synthesis, including sol–gel method
with the use of polymeric precursors [38–40], solution combustion methods [41, 42],
mechanical activation [43], mechanochemical synthesis [44–46], hydrothermal pro-
cess [47–49]). Park et al. [50] have also reported an increased magnetization value
at the nanoscale, while Mazumder et al. [51] have demonstrated that nanoscale
BFO depicts not only high saturation magnetization but also genuine ferromagnetic
behavior with finite coercivity at RT. Recently, multiferroic BFO nanoparticles and
La-doped BFO nanoparticles have been synthesized by MSS process in the NaCl
[52, 53], NaCl–KCl [54, 55], NaCl–Na2 SO4 [56], or KNO3 –NaNO3 [57] molten salt.
Perejon et al. [58] demonstrated that pure BFO nanoparticles were synthesized
via the direct mechanochemical reaction by grinding pure Fe2 O3 and Bi2 O3 in an
oxygen atmosphere at reaction times even less than 50 minutes. Crystallite size of
the BFO nanoparticles from 13 to 20 nm could be tailored by controlling the milling
conditions, particularly the milling power. Sol–gel process is a popular processing
route for the synthesis of perovskite oxide nanoparticles (e.g. BaTiO3 [59], PbTiO3
[60], BiFeO3 [61, 62]). This process involves the formation of a sol by dissolving
the metal oxides, metal–organic, or metal-inorganic salt precursors in a suitable
solvent, subsequent drying of the gel, followed by calcination and sintering at high
temperature.
The hydrothermal method, involves heating an aqueous suspension of insoluble
salts in an autoclave at a moderate temperature and pressure where the crystal-
lization of a desired phase takes place. Solvothermal synthesis is also defined as a
hydrothermal reaction that occurs in a nonaqueous solution in the hydrothermal
process of BFO nanoparticles, Bi3+ and Fe3+ ions are first transformed into hydroxide
Fe(OH)3 and Bi(OH)3 in the precursor, and then dissolved in the precursor with the
presence of alkaline mineralizers (e.g. KOH, NaOH, LiOH). When the ionic concen-
tration in the alkaline solution surpasses the saturation point, the BFO phase begins
to nucleate and precipitate from the supersaturated hydrothermal fluid, followed by
crystal growth [63, 64].
The term “microwave-hydrothermal process” was coined by Komarneni et al. [65]
in the early 1990s, and this process has been used for the rapid synthesis of numer-
ous ceramic oxides, hydroxylated phases, porous materials, and hematite powders
[66–68]. It offers many distinct advantages over conventional hydrothermal synthe-
sis, such as cost savings due to rapid kinetics time and energy, rapid internal heat-
ing, and synthesis of new materials. The morphologies of the component phases in
such vertical composite films containing either magnetic or ferroelectric nanopil-
lars varied markedly with the substrate orientation and phase fractions [69] was
inferred from their microscopy observations. Raidongia et al. [70] reported a compre-
hensive study on core–shell (CFO@ BTO) nanoparticles and nanotubes. Core–shell
type nanotubes exhibit a large saturation magnetization and remanent magnetiza-
tion as compared to the nanoparticles, since the nanotube provides a large inter-
facial area between two phases. The NiZnFe2 O4 @BTO core–shell nanostructures
were also extensively studied by Curecheriu et al. [71] and Testino et al. [72]. In
the past decades, there was widespread scientific interest in multiferroic nanostruc-
tures and thin films, owing to their fascinating multifunctional properties driven
by either interface-induced strain (typically in multiferroic thin films) [73–75] or
by an intrinsic size effect (in nanostructures), which provides the basis for devel-
oping the next-generation electronic devices. The top-down approach involves the
construction of small-sized structures from large ones through etching and removal
of parts [76, 77]. In this method, lithography usually is applied to produce nanos-
tructures with assistance from energy particles such as photons, ions, or electron
beams. Focused ion beam (FIB) milling and electron beam direct writing (EBDW)
1.4 Multiferroic Systems of BIFEO3 and BATIO3 Nanostructures 5
are popular techniques for fabrication of nanostructures with controlled size and
shape.
1.4 Multiferroic Systems of BiFeO3 and BaTiO3

Nanostructures: New Ideas and Insights from Recent
Magnetoelectric Advancements
Since BaTiO3 could exist in four different phases depending on the temperature – the
paraelectric cubic, ferroelectric tetragonal, orthorhombic, and rhombohedral
phases – the resulting displacement gives a polarization of 26 μC/cm2 along the
(0 0 1) direction [78]. The original cubic symmetry is distorted by lengthening of the
c lattice constant (c/a = 1.011) [79]. The perovskite BiFeO3 with high T c ∼ 1103 K
and T N ∼ 643 K attracts lot of attention because it has simultaneous ferroelectric
and antiferromagnetic ordering even at RT. This is because the ferroelectricity in
BiFeO3 originates from the 6s2 lone pair electrons of Bi3+ ions due to structural
distortion, while the magnetism occurs by Fe–O–Fe superexchange interactions.
As an overview, BiFeO3 has a disappointingly low spontaneous polarization and
saturation magnetization due to the superimposition of a spiral spin structure of
antiferromagnetic order [80]. In this spiral spin structure, the antiferromagnetic
axis rotates through the crystal with an incommensurate long wavelength period
of 62 nm, which cancels the macroscopic magnetization and also inhibits ME cou-
pling. Hence, for novel electronics of BiFeO3 , its magnetic and electric properties
must be enhanced. The superexchange between the octahedrally coordinated Fe3+
through the O ligand is responsible for the antiferromagnetism, but BiFeO3 has
been reported to have a weak ferromagnetic component at RT and is thus canted,
with a helical repeat of ∼620 Å [81].
Hund’s rule coupling would lead to spins of the TM 3d shell in parallel orientation
and this mechanism breaks the strong covalent bonds that are necessary for ferro-
electricity [82]. For example, in BiFeO3 and BiMnO3 , the ferroelectricity is due to the
lone pairs of nonmagnetic Bi, and in YMnO3 , it is due to tilting of almost-rigid MnO5
trigonal bipyramids [83]. The structure of the ferroelectric BiFeO3 phase has been
resolved experimentally using X-ray and neutron diffraction and found to possess a
highly distorted perovskite structure with rhombohedral symmetry and space group
R3c [84]. It creates an effective negative pressure that led to a volume expansion
[85]. The increase in c/a distortion leads to higher deformation of the TiO6 octa-
hedra [86]. The type of nanomaterials is not well defined in the literature, but it
is considered that at least one of its dimensions is below 100 nm [87]. The distri-
bution of nanomaterials is dependent upon its dimensionality; a system having all
three dimensions well below 100 nm (critical length) is considered as quantum dots
one main difference between ferroelectric nanostructures and bulk materials is the
presence of depolarizing field in the former because of the uncompensated charges
at the nanostructural surface [88]. The depolarizing field in nanosystems is able to
quench spontaneous polarization [89]. An external electric fields and short-circuit
boundary conditions are needed to screen the depolarizing field [90, 91]. Modified
Pechini method was also used to prepare BiFeO3 nanoparticles [92, 93]. The rhom-
bohedral distortion in BiFeO3 from cubic structure is reduced by decreasing particle
size accompanied by decreasing polarization inferred from atomic displacements.
The size-dependent atomic displacement in multiferroic nanostructure reflects the
effect of increasing depolarization field with decreasing crystallite size [94].
In small-sized nanostructures, the surface-to-volume ratio becomes so large that
it increases again with decreasing particle size. Cao et al. [95] reported a Co-doped
BaTiO3 system for which the Co-3d states, ranging from −6 eV to Fermi level, have
a strong hybridization with O-2p states. It involves double-exchange mechanism
of ferromagnetism. The bonding of the charge carriers mediates the exchange
interaction via oxygen vacancy within the local spins to contribute ferromagnetism.
Superimposition of ZFC/FC plots around 300 K and a clear separation between
FC/ZFC at low temperature, without blocking temperature, indicate that the TM
ions in BaTiO3 are not strongly antiferromagnetic [96]. It was predicted that the
hybridization between the TM 3d orbitals and the O2p is the origin of observed
magnetism [97]. These values of polarization are much larger than those observed
in pure BiFeO3 because of the formation of Bi2 Fe4 O9 phase, which causes lower
electrical resistivity [98, 99]. The doping of BaTiO3 is located at Fe site and acts
as acceptor for improving the electrical properties of BF–BT nanoparticles. For
this, the doped BaTiO3 acts as an acceptor to effectively compensate the charge
carriers to Fe2+ ions at the Fe site and induce lower oxygen vacancy. To modify
properties through size quantization such as the suppression of the spin spiral
in BiFeO3 and stabilizing phases that are inaccessible through conventional bulk
techniques, thin-film growth techniques provide the ability to vary the lattice
mismatch between the film and the substrate, so as to introduce epitaxial strain in
the thin-film material.
1.5 Effective Properties of Multilayered

Nanomultiferroics
The use of multiferroic materials is based on the magnetoelectric (ME) effect. This
effect consists in the appearance of an electric field under the action of an exter-
nal magnetic field and vice versa. In the natural multiferroic Cr2 O3 , the maximum
ME coefficient is observed at a temperature of 260 K and amounts to 3.7 pS/m [100].
Unfortunately, this value is insufficient for practical commercial applications. ME
coefficients greater by about two orders of magnitude were demonstrated for TbPO4
[101] and HO2 BaNiO5 [102]. The matrix homogenization method (MHM) presented
in this unit provides effective parameters of a layered structure without solution
of differential equations in partial derivatives [103–107]. To calculate the parame-
ters, only operations with the matrices entering into the equations are involved. The
method can be easily generalized for boundary conditions different from [110]. The
effective medium would possess the same anisotropy for monoclinic, orthorhom-
bic, tetragonal, and trigonal systems [111]. The effective structure with initial cubic
anisotropy is tetragonal, as a cubic medium is a particular case of the tetragonal one.
1.6 Correlation between Grain Size, Transport, and Multiferroic Properties 7
Fiber composites are the most common nanostructures and are in use in a variety
of systems [112]. Typically, they are modeled by a set of cylinders (inclusions),
which are coated with multiple layers of different materials and immersed in a
matrix of another material. The presence of an additional parameter – the curvature
of the cylindrical layer – gives hope to strengthen the interaction between the
electric, magnetic, and elastic fields. That is, by using fiber geometry, one may
be able to design nanocomposite multiferroics with larger ME, piezoelectric,
and/or piezomagnetic coefficients. Core–shell nanocomposites have been an
active research area in the past years because of their promising multifunctional
capabilities. These structures demonstrate novel characteristics that are different
from their single-component counterpart. Some applications can already be found
in bioimaging, cloaking, drug/gene delivery, nanophotonics, optics, and sensors
[113–121]. Multilayer nanoshells, or so-called nanomatryoshkas, are a particular
and very promising case of core–shell nanomaterials. The classical electromagnetic
theory is sufficient to estimate the optical parameters of nanomatryoshkas with
core–shell separations larger than a nanometer. Unfortunately, due to the bypass
of electron transport between the core and shell through the self-assembled mono-
layer [122], classical approach fails for the description of nanomatryoshkas with
subnanometer-sized gaps. Thus, there is need to employ a quantum approach for
the modeling of the small-sized nanomatryoshkas (less than 1 nm). Compared to
earlier published works [123–125], this approach does not require usage of special
functions like, e.g. spherical or Bessel functions.
The computational scheme is much simpler than the previously existing one, even
for the electrostatic problem. It allows finding solutions of more complex problems
accounting for the interaction of the fields of different nature [126]. For the determi-
nation of the material coefficients of this effective medium in the case of small total
thickness, it is recommended to use the MHM, which does not require the solution
of a complex system of magneto-electro-elasticity equations. The desired effective
characteristics are obtained using only operations with matrices characterizing the
properties of single nanolayers. This fact significantly simplifies the calculations and
allows multilayer nanosystems to be accurately and easily described.
1.6 Correlation between Grain Size, Transport, and

Multiferroic Properties of Ba-doped BiFeO3 Nanoparticles
BiFeO3 is one of the single-phase multiferroic materials with a distorted perovskite
structure ABO3 [127], which shows multiferroic behavior at RT having high
ferroelectric Curie temperature (T C ∼ 1100 K) and antiferromagnetic Néel tempera-
ture (T N ∼ 640 K) [128], and it continues to be the only compound with coexistence
of ferroelectricity and antiferromagnetism at RT [129]. The ferroelectricity and
magnetism in BiFeO3 is attributed to the Bi3+ 6s2 lone pair electrons and partially
filled d orbital of Fe3+ ion, respectively [130]; thus, the coupling between the
ferroelectric and magnetic ordering is usually considered to be rather weak [131].
The impurities, large leakage current, and antiferromagnetic nature are big hurdles
in BiFeO3 applications [132], and it is very difficult to obtain a single-phase BiFeO3

by using solid-state reaction at high sintering temperature [51]. Doping at A-site
affects the centrosymmetry of FeO6 octahedra, creates oxygen vacancies, and leads
to change in multiferroic properties of BiFeO3 . Furthermore, the leakage currents
are reduced by Ba2+ ion doping [133, 134]. Leakage current due to oxygen vacancies
or impurities is the major problem in BiFeO3 . It has been observed that doping
at A-sites reduces the leakage current in BiFeO3 and enhances the multiferroic
properties [135].
The substitution of Bi3+ by Ba2+ may cause two parallel phenomena with respect
to the concentration of oxygen vacancies: (i) the creation of oxygen vacancies to neu-
tralize the charge produced substituting Bi3+ by Ba2+ , (ii) decrease in concentration
of oxygen vacancies by filling the probable vacant volatilized Bi3+ sites [136]. The
spectra of 630 cm−1 are of strong metal oxygen-bending vibration of M–O4 [137, 138];
such band vibration is a possibility in impurity phase, since minor impurity phase
was seen on substitution in XRD. The magnetic properties of BiBaFeO3 multifer-
roic nanoparticles depend on particle size because of long-range spin arrangement.
The reduction in particle size below the periodicity of cycloidal spin structure will
enhance the magnetic properties. However, the weak ferromagnetic founding in
BiBaFeO3 multiferroic nanoparticles originated from canting in the Fe3+ moments
due to tilt of <FeO6 > octahedron and the distortion can suppress the spiral spin
structure and increase the weak ferromagnetism. Due to the small particle size,
the electron spins fluctuate; this results in decreasing Néel temperature as the fluc-
tuations create disorder. In addition, the reason may be related to the decrease of
magnetic exchange interactions with reduction in particle size [92].
The substitution of divalent metal ions Ba2+ at trivalent Bi3+ sites requires oxygen
deficiency for compensating charge, and this may destabilize the system [139]. It
is expected to suppress the cycloid spin structure [140]. The small particle sizes
observed in the samples of the order of 30 nm are excellent for efficient ferromag-
netic properties, due to the magnetic cycloid spin structure of 62 nm in this material
[141]. Lattice distortions, oxygen and bismuth vacancies, and defects at the inter-
faces as well as inside grains are the sources of space charges in BiFeO3 [142]. These
space charges are able to follow the applied field at lower frequencies, whereas they
cannot find time to undergo relaxation at high-frequency region [143, 144].
1.7 Specific Heat and Magnetocaloric Properties of

Some Manganite-Based Multiferroics for Cryo Cooling
Applications
Due to the restrictions and disadvantages of the vapor compression technique,
the scientific community is looking at new refrigeration technologies, viz. ther-
moelectric cooling [145], adsorption refrigeration [146], absorption refrigeration
[147], thermoacoustic refrigeration, and solid-state magnetic refrigeration. In
recent times, the large magnetic entropy change found in perovskite manganites
[148] suggests that these materials might be exploited for magnetic refrigeration
1.7 Specific Heat and Magnetocaloric Properties of Some Manganite-Based Multiferroics 9
applications. Apart from this, the rare earth manganites exhibiting multiferroic
behavior have attracted attention due to their potential applications in magnetic
refrigeration industry [15, 149]. Although research on colossal magnetoresistance
and multiferroic manganite materials was initiated almost two decades back, this
method was used for the calculation of magnetocaloric effect by using temperature
dependence of specific heat data at different magnetic fields [150, 151]. It has been
reported that the magnetocaloric effect (MCE) determined by this method has the
same accuracy as that from magnetization measurements. Further, the accuracy of
this method is better than that of the direct methods. At the transition temperature,
an anomaly in the dielectric behavior has also been observed, indicating correlation
between these behaviors [152]. Based on the neutron diffraction studies [153], it
was reported that the sinusoidal ordering of Mn3+ moments transforms into an
incommensurate spiral order at this transition, where Mn3+ moments are locked.
The transformation of sinusoidal to spiral magnetic ordering results in breaking
center of symmetry, which, in turn, leads to the polarization in the material. The
transition is also observed in dielectric constant data of the present investigation
[154], which is attributed to the ferroelectricity. Based on the results of neutron
diffraction measurements of TbMnO3 sample, it is reported that the sinusoidal
ordering of Mn3+ moments transforms into an incommensurate spiral order, which
breaks the center of symmetry of the system leading to the spontaneous polariza-
tion. In the specific heat studies of present investigation, yet another transition
observed at 24, 27, and 18 K is influenced by the magnetic field. At this transition
temperature, the commensurate phase becomes low-temperature incommensurate
phase. The signature of this magnetic transition can also be seen in dielectric
constant behavior of the present investigation [155]. Therefore, this is called second
ferroelectric transition (T C2 ).
Sagar et al. [156] calculated ΔSM , ΔT ad , and RCP of EuMnO3 at different fields
using a simple theoretical approach [157]. Only temperature-dependent magne-
tization data (M versus T) are needed in this method. It was observed that with
increasing field, MCE parameters increase linearly [157]. Several scientific groups
also worked on MCE of GdMnO3 , TbMnO3 , and DyMnO3 samples in their single
and polycrystalline forms. Aditya A Wagh et al. [158] investigated MCE properties
of GdMnO3 single crystal. They used magnetic and magnetothermal measurements
along the three crystallographic axes for the investigation of MCE properties.
DyMnO3 , which crystallizes in hexagonal form, was also studied by Balli et al.
[159]. And calculated ΔSM along the c-direction and in ab plane at different applied
magnetic field variation. In c-direction, when varying the magnetic field from 0 to
2 T, 0 to 5 T, and 0 to 7 T, the maximum variation of the entropy reaches values of 5,
10, and 13 J/kg-K, respectively. Sattibabu et al. [160] also investigated the influence
of Er doping on magnetocaloric performance of YbMnO3 sample at different
fields. They used two samples with compositional formula Yb0.9 Er0.1 MnO3 and
Yb0.8 Ho0.2 MnO3 and calculated using heat-capacity data. MCE parameters of this
system increase with rise in doping concentration and field, and are comparable
with reported values. For the first sample in this series, the ΔSM values are 1.81,
3.27, 5.45, and 7.26 J/Kg-K at 2, 4, 6 and 8-T fields. Multiferroic manganites with
orthorhombic and hexagonal structure show high magnetic entropy and adiabatic
temperature changes at below 20 K, which is very useful for liquefaction of gases
for cryo cooling applications. The ΔS distribution of the samples is uniform, and it
is desirable for an Ericsson-cycle magnetic refrigerator, which is beneficial for the
household application of active magnetic refrigerant materials.
1.8 Preparations, Characterization, and Applications of

Multiferroic Nanocomposites
Many preparation methods have been adopted in order to produce high-quality
materials exhibiting multiferroic properties at room temperature. Salami et al. [161]
prepared (1 − x)Bi2 Fe4 O9 − xCoFe2 O4 (0.0 ≤ x ≤ 1.0) multiferroic nanocomposites;
these nanocomposites have been prepared by wet chemical procedures combining
reverse chemical coprecipitation and Pechini-type sol–gel techniques followed by
mechanical blending process. The authors have characterized all nanocomposites
with XRD and SAED, and the results show that the diffraction patterns were
perfectly indexed to the constituent phases present in composite samples. Also,
the characteristic peaks in FTIR spectra confirmed formation and purity of all
specimens. Many preparation methods have been adopted to produce artificial
high-quality materials exhibiting multiferroic properties at RT [162–165]. One
interesting approach is to synthesize composite materials with one component
being ferroelectric and the second one being ferromagnetic at RT [166–168].
Mitra et al. [169] have combined phases of GdMnO3 (GMO) and CoFe2 O4 (CFO)
in the nanocomposite state and showed some limitations as multiferroics. The
authors have reported high dielectric loss, though magnetic ordering is found
at RT, while the TiO2 matrix hosts the GMO and CFO where the dielectric loss
has been remarkably lowered and the dielectric and ferroelectric ordering (below
∼13 K) of GMO along with the magnetic phase of CFO are utilized to develop the
multiferroic. Mandal et al. [170] investigated ME coupling, dielectric, and electrical
properties of xLa0.7 Sr0.3 MnO3 (LSMO) − (1 − x) Pb(Zr0.58 Ti0.42 )O3 (x = 0.05 and 0.1)
multiferroic nanocomposites. Duong et al. [171] discussed about the growth of 79%
Bi2 Fe4 O9 –21%Fe3 O4 nanocomposite films on LaAlO3 substrates using molecular
beam epitaxy. X-ray diffraction and field emission scanning electron microscopy
confirmed that the nanocomposites consisted of an orthorhombic phase of lamellae
Bi2 Fe4 O9 .
Rajesh Babu and Koduri Ramam, [172] reported synthesis, structural, magnetic,
and dielectric studies of Ruthenium (Ru)-doped BKFO (BiKFe2 O5 ) multiferroic
nanocomposite. Ajith et al. [173] prepared and characterized ME multiferroic
BCZT–CFO nanocomposites that were synthesized via sol–gel route. XRD measure-
ments and TEM measurements were conducted, and they indicate that the majority
of particles formed, have core–shell structure. Tang et al. [174] prepared enhanced
ME response for La0.67 Sr0.33 MnO3 /PbZr0.52 Ti0.48 O3 multiferroic bilayer thin film
at RT; these nanocomposites have been prepared using pulsed laser deposition
method. Vivek Verma et al. [175] proposed improved magnetic properties of
References 11
Bi0.9 Pr0.1 FeO3 in their composites of BPFOx NZFO. For the composites sample
BPFO–NZFO 1, the Ms. and Mr. are higher than those measured for the BPFO
and continuously increase with the increasing weight percentage of NZFO in
composites. Mahalakshmi et al. [176] prepared and characterized the multiferroic
composites of CoFe2 O4 and BaTiO3 . These nanocomposites have been synthe-
sized by coprecipitation method. Hajlaoui et al. [177] prepared and characterized
high-quality Ba2 NdFeNb4 O15 -based multiferroic nanocomposite films that were
grown on Pt/MgO(100) single crystalline substrates. Tuning of ME coupling in
multiferroics is of great fundamental and technological importance due to the
potential applications of ME effect in advanced devices, such as ME read-head
sensors [178, 179], data storages [1, 180, 181], and spintronic devices [12, 107].
Multiferroic nanocomposites can find various applications in magnetic materi-
als covering sensitive H sensors, including biomedical sensing, navigation, magne-
toresistance (MR) applications, and many more complex applications in spintronics
[182].
1.9 Conclusions
Nanostructured Multiferroic materials offer great prospects at many application

levels owing to their unique properties. In this chapter, we have reviewed the
various multiferroic materials and preparation, characterizations, and applications.
We have also reviewed each chapter through a detailed abstract.
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23
Single-Phase Multiferroics
Piotr Graczyk 1,2 and Emerson Coy 2
1
Adam Mickiewicz University in Poznan, Faculty of Physics, Umultowska 8561-614, Poznan, Poland
2
Adam Mickiewicz University, NanoBioMedical Centre, Wszechnicy Piastowskiej 361-614, Poznan, Poland
2.1 Introduction
Ferromagnets, ferroelectrics, and ferroelastics (ferroics) are widely studied mate-

rials that have been attracting the attention of researchers and industry since the
mid-twentieth century. Among the most interesting group of materials are those
in which changes in symmetry are observed as a function of temperature [1]. Such
alterations result from the thermal variation of the equilibrium positions of atoms
or charges in the complex electronic structure. The equilibrium positions are degen-
erated in high temperature and split into multiple equivalent states in low temper-
ature, leading to the distortive phase transition. The long-range order within those
equivalent states is driven by the dynamic interactions propagating over large dis-
tances, which may be attributed to phonons (soft modes, see Section 2.5). Distortive
phase transitions are called ferroics, unless translational symmetry is the only struc-
tural change.
Because of the changes in symmetry, ferroics possess exciting and unique
physical–chemical properties that ultimately have led to their diverse applicability,
ranging from macroscopic devices, like electrical transformers; through medium
devices, like actuators; to microscopic ones like sensors, used in integrated circuits
or as a storage device in modern memories [1]. It is important to remark that
although ferroic materials derive their name from the Latin word ferrum – meaning
“metallic iron” – they are not defined by the presence or absence of iron. They
were so named due to the similarity of magnetic properties of iron, which is the
first ferromagnetic (FM) material known to mankind, and the electric and elastic
properties of ferroelectrics and ferroelastics.
Although not limited to, among the most interesting properties of ferroic materi-
als are their hysteretic nature and nonzero remanence [2]. In ferroics, at least two
metastable states can be found. These states are related to the directional arrange-
ment and crystalline limitations of the materials, providing reversible “stored states”
that can be switched by external fields. For example, in ferromagnets, an external
Nanostructured Multiferroics, First Edition. Edited by Raneesh Balakrishnan and P.M. Visakh.
© 2021 WILEY-VCH GmbH. Published 2021 by WILEY-VCH GmbH.
24 2 Single-Phase Multiferroics
magnetic field can flip the direction of the material magnetization to align paral-
lel to the field direction. This phenomenon has found several applications recently,
especially in electronics and information storage devices, both in ferroelectric and
FM materials [3].
There has been interest in studying the possibility of coexistence of two or more
ferroic orderings in a single material, especially in the same crystalline phase. From
the technological and industrial points of view, the need and demand of multifunc-
tional materials has propelled the expansion of functionalities in devices and compo-
nents, making single functional materials increasingly less desirable. These so-called
multiferroic materials are of great interest in the electronics industry for application
as memory storage devices [4, 5], spintronics components [6, 7], and sensors
[8, 9].
The first ferroelectric material with nonzero remanence – the Rochelle salt
(sodium potassium tartrate tetrahydrate) – was discovered in 1920, although
piezoelectric response was observed in this material as early as 1824 [10, 11].
However, it wasn’t until 1945 when a much simpler oxide material, namely barium
titanate BaTiO3 (BTO), was found to have similar ferroelectric response. BTO is
perhaps the most well-known and studied member of the perovskite family of
oxides, having been analyzed for more than 70 years [12]. Its popularity can be
partially attributed to the large applicability in the industry and the relative easy
integration of the perovskite structure to oxide-based electronics [13]. Barium
titanate is in a tetragonal ferroic phase at room temperature (RT) with nonzero
remanent polarization. It has been well established that below RT, BTO undergoes
a series of transitions to other phases, all of them being ferroelectric. Fortunately,
all of the changes of the structure at the phase transition can be easily under-
stood and described as slight changes or “octahedral tilting” in the perovskite
formula.
The perovskite structure is perhaps the most common crystalline structure for
multiferroic materials studied so far. Its simplicity is due to its rather straightforward
organization and chemical constitution. The general perovskite formula is ABX3 ,
where A and B are cations and X is an anion, typically oxygen, but also others, like
fluorine, are sometimes considered. In the ABO3 structure, the B site is at the cen-
ter of an oxygen octahedron (BO6 ), while the A atom is in the center of the unit
cell (Figure 2.1a). Most of these perovskites follow cubic symmetry, although some
of them show a distorted crystallinity to a lower symmetry, such as in the case of
orthorhombic TbMnO3 [16–18] (Figure 2.1b). In the ideal case, such as the para-
electric phase of BaTiO3 , the octahedrons are aligned, retaining the simple cubic
structure. This is observed when the A cation fits perfectly in the center of the cubic
structure, without deforming it or changing the bounding lengths #[19]#. On the
other hand, when the A atom is smaller, the whole unit cell twists to reach mini-
mum energy state. This leads to the so-called octahedron tilting and changes in the
lattice symmetry [20]. Therefore, as shown in the BTO phase diagram in Figure 2.1c,
the paraelectric (prototypic) phase is of a simple cubic structure, while the ferroelec-
tric phase results from the octahedral tilting, which allows for the polar organization
of unit cell, and therefore the spontaneous polarization appears [19, 21].
2.1 Introduction 25
(a) Cubic (b) Orthorhombic
Rhombohedral (R) Orthorhombic (O) Tetragonal (T) Cubic (C)

Ps//[111] Ps//[011] Ps//[001] Ps = 0
ε
O
Dielectric constant
6000
Ti
3000 Ba
181K 196K 279K 394K
BaTiO3 401K
285K
[100] Tc
0
0 100 200 300 400 500
T(K)
(c)
Figure 2.1 Schematic representations of crystalline structure of a standard cubit

perovskite (a), such as BTO or CaTiO3 and the tilting of octahedrons associated with (b) the
orthorhombic structure. Source: (a,b) Atta et al. [14]. Licensed under CC BY 3.0. (c) Shows the
dielectric permittivity of BTO as a function of temperature and the associated crystalline
phase and polarization direction. Source: (c) Fu and Itoh [15]. Licensed under CC BY 3.0.
Because of the simplicity of the perovskite formula, it is possible to substitute a

wide variety of elements, such as Co, Fe, Ni, Mn, Mo, Nb, Bi, Pb, Y, and virtually all
rare-earth elements, in a controllable manner. It is important to mention that doping
often results in the so-called double perovskite structure with formula A2 BB’O6 in
the case of B-site ordering or A(Bx B’[1−x] )O3 for mixtures. Although there is great
flexibility in choosing the dopants, there is a general rule that allows to identify the
compatibility of ions with the formula. The stability of the unit cell is determined
by the Goldschmidt tolerance factor. This factor considers all ionic radii and gives a
qualitative result of the compatibility of the atoms.
The Goldschmidt tolerance factor (t) is a dimensionless number obtained from the
following formula [22]:
r + r0
t= √ A
2(rB + r0 )
where r A , r B , and r 0 are the ionic radii of A, B, and oxygen atoms, respectively. The
result of this calculation is t = 1 for a perfect cubic perovskite (Figure 2.1a) and t < 1
for an orthorhombic or rhombohedral symmetry due to the tilting of the octahedron
(Figure 2.1b). It is also assumed that for t > 1, the unit cell would become a closely
packed hexagon, especially for small r A values. In similar fashion, when doping is
considered, like in the case of the double perovskite, it is also possible to estimate
its stability by the Goldschmidt tolerance factor. The equation changes slightly due
to the nature of the mixed atoms, and the modified formula is described as follows
[23]:
r + r0
t= √ A
2(<rB > + r0 )
where the <r B > stands for the average of the B and B′ bounding lengths. According
to D. Serrate et al. [23], for double perovskites, the tolerance factor works in a rather
different way, for t > 1.05 a hexagonal structure is adopted, for 1.05 > t > 1.00 the
compound becomes cubic within the Fm3m space group, for 1.00 > t > 0.97 the most
likely structure corresponds to the I4/m tetragonal space group, and finally, if t < 0.97
the compound becomes either monoclinic (P21 /n) or orthorhombic. The last one is
the most common structure in A2 (Mn, Co, Ni, Ti)O6 mixtures [24–26].
2.1.1 Considerations on Single-phase Multiferroics

Materials in which multiple ferroic orderings take place had been already studied,
as early as 1960s. Those initial studies focused on the synthesis of compounds with
extremely complex stoichiometry, such as (1 − x)PbFe0.66 W0.33 O3 –xPbMg0.5 W0.5 O3
[27] and nickel iodine boracite (Ni3 B2 O13 I) [28], both of which present too large
ionic interactions and crystalline distortions to be able to determine the true origin of
their multiferroic behavior. Nevertheless, the methodology was conceptually “sim-
ple”: it aimed to replace d0 B cations, in ferroelectric perovskite oxides, by magnetic
dn cations [1].
The main complication in this approach is the inherent competition between fer-
romagnetism and ferroelectricity [29]. In perovskites, the FM ordering is typically
associated to the B site of the ABO3 formula, providing FM or antiferromagnetic
(AFM) interactions [30]. To understand the origin of the magnetism in the ABO3
and A2 BB’O6 formula, let us examine the magnetic interaction in the A2 (NiMn)O6
perovskite family [24–26, 31–37].
To understand magnetic interactions in perovskites, it is important to discuss the
Goodenough-Kanamori rule. It was first formulated by Goodenough in 1955, and
more rigorous mathematical underpinning was subsequently provided by Kanamori
(1959). It is applied to interatomic spin–spin interactions between two atoms that
are mediated by virtual electron transfers, for example in the Ni2+ —O—Mn4+ chain
[25, 38]. In the La2 NiMnO6 double perovskite, the FM interactions are provided by
the half-filled e2 and filled t6 orbitals on Ni2+ and the empty e0 and half-filled t3
orbitals in the Mn4+ ions [39–41]. In this type of perovskites, the superexchange is
mediated/interrupted by oxygen anions; thus, the direct exchange is weakened, but
as compensation the interaction shows FM ordering.
In an ideal cubic perovskite, where the bonding angle between B—O—B atoms
is 180∘ , superexchange interactions are easily achieved. However, due to the equal
eg orbital filling of both B sites, such interactions are commonly AFM, as shown
in Figure 2.2a–c. In the A2 BB’O6 perovskites, the FM ordering can be promoted
2.1 Introduction 27
eg eg Electric field
AFM
t2g t2g E
d Orbitals p Orbital d Orbitals Ferroelectric
(half-filled eg) O2– (half-filled eg)
(a) B B Polarization
P
eg eg
Ferroelastic
t2g t2g AFM Ferromagnetic
d Orbitals p Orbital d Orbitals
(empty eg) O2– (empty eg) Magnetization
Strain
(b) B B
ε M
eg eg
t2g t2g
FM σ H
d Orbitals p Orbital d Orbitals Stress Magnetic field
(empty eg) O2– (half-filled eg)
B B
(c) (d)
Figure 2.2 Schematic representations of superexchange interactions in ABO3 and A2 BB’O6

perovskites, showing how this can lead to (a), (b) AFM and (c) FM interactions [42, 43]. (d)
Diagram of the multifunctional nature of multiferroic materials and the desired
interdependences between ferroelectric and ferromagnetic orderings. Source: Adapted and
reimagined from Refs. [3, 44, 45]; Texas Instruments; Everspin Technologies Inc.
if one B site has empty eg orbital, while the eg orbital of the other is half-filled
(Goodenough–Kanamori rule). However, it is important to notice that the total
magnetization of the system will be strongly influenced by the tilting of the octahe-
drons in the unit cell, thus deviating the Ni—O—Mn angle from its maximum/ideal
FM contribution. Nevertheless, the centrosymmetric ideality of the FM ordering in
perovskites is not compatible with the ferroelectric ordering, which is negated in
unit cells with symmetry inversion [39]. Symmetry inversion breaking is a key for
the appearance of the polar state.
Although ferroelectricity and ferromagnetism seemed at the beginning to be
mutually exclusive in most cases, much effort has been done to overcome this
problem and, as we will see, the effort has started to pay off. The search for
single-phase materials, which can allocate two or more ferroic orders, is still of
high scientific interest. One way to achieve this goal is to adopt the so-called lone
pairs of big stereochemical active atoms such as Bi3+ or Pb2+ [3, 16, 39, 46, 47].
Lone–pair electrons are electrons that are at the outermost orbitals (6 s) and do not
participate in chemical interactions, since the lower unoccupied levels (p-states),
[Xe]4f14 5d10 6s2 6p0 , form covalent bonding with the surrounding oxygens. They
shift the Bi or Pb atom away from the centrosymmetric position, forming local
electric dipoles, effectively breaking the inversion symmetry and inducing the
ferroelectric polarization.
In BiFeO3 , AFM order coexists with ferroelectricity. To explain in more detail at
this point, as the mechanisms responsible for those orders have different origins,
multiferroicity in those compounds does not differ much from the piece of iron
and lead zirconate titanate (PZT) enclosed together in a single box. Magnetic and
electric ferroic states are mostly independent of each other. Finding a material in
which the electric field can affect not only the polarization but also the magneti-
zation (E[P,M] ) and, in equal manner, a material in which the magnetic field also
affects magnetization and polarization (H [M,P] ) are highly desirable in the industry.
This interdependence between magnetic and electric degrees of freedom is com-
monly referred as “magnetoelectric coupling” (MEC), and it is responsible for the
wide industrial and scientific interest in multiferroic materials, Figure 2.2d.
Based on the origin of their multiferroic properties, single-phase multiferroic
materials can be classified into the following subgroups:
Type I multiferroics: This group of multiferroics is the most numerous; the mate-
rials exhibit both ferromagnetism and ferroelectricity, usually with a rather large
polarization; however, both ferroic orderings have distinctive temperature and ori-
gin mechanisms. Due to this fact, the MEC between ferroic orders is very weak. This
group can be further divided into three small subgroups according to the origin of
the ferroelectricity.
(i) Ferroelectric polarization due to long paired electrons: This group of perovskites
takes advantage of the ABO3 (also in A2 BB’O6 ) formula to promote the ferro-
electric polarization. As mentioned before, the B site of the perovskite formula
is responsible for the magnetic ordering of the structure, while the A site is
selected to promote ferroelectricity. The selected atoms are cations of long pair
electrons (i.e. Bi3+ , Pb3+ , etc.); long pair electrons are electrons that do not take
part in any chemical bounding and are responsible for the electric polarization
of these materials. Examples of this group are BiFeO3 , BiMnO3 , PbMnO3 , and
Bi2 NiMnO6 [31, 48, 49].
(ii) Ferroelectricity due to charge ordering (CO): CO can occur when cations in the
same structural site have difference in valence. This mechanism relies on the
simultaneous presence in equivalent sites and bonds. However, how strong the
MEC in this case will be, is still an open question. This mechanism works, e.g.
in RNiO3 nickelates and TbMn2 O5 [50, 51].
(iii) “Geometric” ferroelectricity: These are materials known as hexagonal mangan-
ites, and examples are YMnO3 (YMO) and LuMnO3 . In these compounds, the
tilting of the MnO5 polyhedrons generates a closer packaging in the perovskite.
As a result, there is a displacement of the oxygen ions to a closer position toward
the A ions, thus promoting the dielectric dipole [52].
Type II multiferroics: This group of materials is one of the most promising due to
the origin of the multiferroicity. Here, magnetism causes ferroelectric polarization,
thus implying a strong MEC. However, ferroelectric polarization has always low val-
ues and appears at rather lower temperature than the magnetic ordering (typically
AFM).
(i) Spiral magnets: Ferroelectricity appears in conjunction with a spiraling mag-
netic phase, mostly of the cycloid type. In this case, ferroelectricity arises in
the plane in which the cycloid is perpendicular to its propagation vector [53].
This is due to the so-called inverse Dzyloshinsky–Moriya interaction (DMI),
∑
P = A rij × (Si × Sj ), where r ij is the connecting vector between Si and Sj spins
and A is spin–orbit interaction [16].
(ii) Collinear magnets: In this group, all the magnetic moments are aligned along a
particular axis in up–up–down–down arrangement (↑↑↓↓). Due to an exchange
2.1 Introduction 29
striction, the distortion of ferro and antiferro bounds (↑↑ and ↑↓) is different, and
thus the material becomes ferroelectric, due to the ordered dipoles. This case is
observed in Ca3 CoMnO6 [54], HoMnO3 [55], and lately in Y2 NiMnO6 [56, 57].
2.1.2 Ferroelastic Multiferroics

Not much attention has been devoted to ferroelectric and ferroelastic coupling and
their applicability in nonvolatile memory devices or other electronic applications.
One of the main concerns has been the substrate-clamping effect, in which stress
and ferroelectric polarization is suppressed by the epitaxial strain from the substrate
[58]. Nevertheless, several studies have shown ferroelastic switching in thin films
[59–61], exhibiting the potential applicability of these materials in multifunctional
heterostructures [62, 63] or artificial multiferroic architectures [64]. Moreover, in
materials such as BiFeO3, PbTiO3 , and BaTiO3 , the ferroelastic domains are known
to play an important role in facilitating the coupling between the polarization and
the magnetization via the ferroelastic switching [65, 66] – an aspect that is highly
desirable in nonvolatile memories [67, 68]. Additionally, domain walls have been
shown to have a very strong effect on heat flow and phonon scattering, which can
dramatically affect device performance [69]. Nevertheless, these traditional ferro-
electrics have very limited ferroelastic behavior, mainly due to the need of epitaxial
strain in their thin-film stabilization, which renders the polarization switching only
observable in multidomain structures, which clearly points out to a clamping sub-
strate of effect with negative implications for electronics [61, 70].
One of the oldest and most well-known ferroelectric and ferroelastic materials,
gadolinium molybdate Gd2 (MoO4 )3 (GMO) [71–74], can be of great use. GMO
is a full ferroelectric–ferroelastic material with a complex phase diagram [75]
and effective polarization of P(001) : 2μC/cm2 and coercive stress of 1 MPa [76].
The complex phase diagram is due to its high oxygen content, a critical aspect of
the rare-earth molybdates (Re2 ((MoO4 )3 ), which is worsened by the stability of
several off-stoichiometric phases. Nevertheless, the orthorhombic phase of GMO
(β’-GMO), with lattice parameters a = 1.388 nm, b = 1.042 nm, and c = 1.07 nm [77],
remains the most studied one. Nowadays, GMO is being extensively used as optical
material in electronics [78–81]; however, due to the aforementioned concerns,
very little literature has dealt with stabilizing GMO in thin films and much less
for β’-GMO [80–83]. Sol–gel attempts have proven somehow to be successful;
although the use of high temperature was needed to stabilize a fully orthorhombic
film (>700 ∘ C), no conclusive proof of ferroelectricity was provided. This was
attributed to short cuts in the film [82], supported by the fact that cracks are a
common problem in sol–gel thin films [84]. Moreover, although sol–gel is regarded
as low-temperature technique [85, 86], the use of high temperature, without a
careful study of temperature annealing on the crystalline quality of the films,
leaves much space for investigation and development. Nevertheless, low oxygen
pressure PLD experiments have recently achieved the stabilization of β’-GMO on
silicon substrates [87]. Although the morphology of the films does not fulfill the
standards of other thin-film ferroelectrics, it is an important step toward further

integration.
2.2 Analysis of the Multiferroicity in the Hexagonal

Manganites
2.2.1 Ferromagnetism in Hexagonal Manganites
Hexagonal manganites of the RMnO3 family, with R = Y, Dy, Ho, Er, Tm, Yb, Lu,
or Sc, are part of the Type I (ii) multiferroics, an early group of materials, which
showed a polar lattice, assigned to the P63 cm (no. 185) space group and that puz-
zles researchers to this day. With a sevenfold coordination group, this perovskite
shows a “tight” structure, which differs from the ideal cubic perovskite. In fact,
its structure is so distorted that instead of octahedrons (BO6 ), the perovskite forms
bipyramids (BO5 ) along the a–b plane [88], Figure 2.3a. As an example, in the case of
the YMO3 perovskite, the magnetic interactions between Mn3+ follow the superex-
change interactions, making the whole system AFM. Due to the geometrically frus-
trated triangular structure, the spins are rotated 120∘ from their neighbors, allowing
the Mn3+ —O—Mn3+ superexchange [89], Figure 2.3a. Although the origin of ferro-
electricity in this compound has been widely discussed [16, 52, 90–92], it has been
established that it was caused due to the BO5 packaging, which pushes the Y ion to
move along the c-axis, providing a strong and spontaneous polarization at RT, and
where transition temperature is usually found at very high temperatures [93, 94]. Let
us discuss some of the main aspects of the multiferroicity of this group of materials
in detail.
In contrast to the orthorhombic YMO3 perovskite structure [95–97], where
the Mn3+ ions are coordinated to their surrounding four (4) Mn3+ atoms, in the
hexagonal structure, the coordination is reduced to a noncollinear three (3)-spin
arrangement, which, in time, constrains the bounding angles to ≈120∘ . It is
important to remark that the FM ordering of YMO takes place at much lower
temperature, 70–90 K, well below the ferroelectric ordering [52, 89, 98, 99]. Taking
into account the aforementioned geometric considerations, the AFM in hexagonal
manganites is expected in-plane, while in the out-of-plane directions (c-axis)
the superexchange is not observed. Similarly, in the orthorhombic structure,
the out-of-plane interactions comprehend an extra oxygen (Mn—O—O—Mn)
exchange, rendering this feature extremely weak, especially when compared with
the in-plane order. Thus, two important aspects can be observed, (i) the interplane
interactions are not constrained by geometry and (ii) the in-plane arrangement
of the Mn3+ spins can vary, with respect to the crystal directions. I will then
theorize that any of these scenarios could lead to the AFM ordering of the YMO
perovskite. To understand and distinguish these effects, Fiebig et al. [100] used
second harmonic generation (SHG) measurements, which allowed them to identify
the governing scenario [101, 102]. In contrast, neutron diffraction experiments
resulted in inconclusive results regarding the magnetic structure of YMO, due to
2.2 Analysis of the Multiferroicity in the Hexagonal Manganites 31
MnO5
a b
(a)
Φ
(b) (c)
Figure 2.3 (a) Structure of the hexagonal YMnO3 (110) showing the bipyramids (BO5 ) and
(b) the spin arrangement parallel and antiparallel, respectively. Source: Lorenz [88].
Licensed under CC BY 3.0.
the similarity in the patterns expected for both scenarios [103, 104]. Nevertheless,
Fiebig et al. [105] concluded that interplane interactions among spins in the same
crystal direction are FM, although weak. Nevertheless, the tilting of spins remained
an open question.
Geometrically speaking and taking into account the FM alignment of the spins
between the out-of-plane layers, there are two possibilities to arrange the spin orien-
tation between two superposed Mn3+ layers. Their alignment strongly depends on
the relative orientation of the pairs of spins and the cooperative orientation between
layers along the edges of the magnetic unit cell; these two scenarios are shown in
Figure 2.3b,c [88]. In these geometries, the spin alignments are confined to a range
of tilting angles (𝜑): 90∘ ≥ 𝜑 ≥ 0 ∘ [105]. In the case of YMnO3 , 𝜑 = 0 ∘ , the entire AFM
regime is observed. In contrast, R = Er–Yb shows a spin arrangement of 𝜑 = 90 ∘ .
In the case of Ho- and LuMnO3 , the AFM ordering corresponds to 𝜑 = 90∘ at high
temperatures, but it flips to 𝜑 = 0∘ as temperature decreases. This phenomenon is
caused due to the magnetic interaction of the rare earth ions and their interference
with the Mn3+ arrangements, leading to another magnetic phase transition at low
temperatures, involving mainly the rare earth magnetic moments. Notice that there
are two important repercussions for hexagonal RMnO3 perovskites, first, the inter-
planar interactions between R ions thus cannot be fully neglected [105] and, second,
many phase transitions of rearrangements can be induced by an external magnetic
field.
2.2.2 Ferroelectricity in Hexagonal Manganites

The hexagonal YMO3 perovskite is of great interest to understand the ferroelectric,
and in many aspects the FM, properties of the hexagonal RMnO3 family. This is par-
tially because of the lack of lone-pair electrons in Bi or Pd ions, thus ensuring firstly
that the ferroelectric polarization does not fall in the Type I (i) case; and secondly,
because of the lack of magnetic ions in the R position, making its multiferroic prop-
erties ideal for fundamental studies [106]. As mentioned previously, the polar axis of
the YMO, and essentially all the RMnO3 perovskites, resides along the [0001] direc-
tion or the c-axis. The ferroelectric transition temperature has been found to be as
high as 1000 K [93, 94], with a spontaneous polarization and coercive field of around
≈5.5 μC/cm2 and 10 kV/cm, respectively [93].
YMO3 perovskite belongs to the Type I multiferroics and contrary to that observed
in the group of so-called proper ferroelectrics, its ferroelectric polarization is because
the atomic displacements of the Y ion are ultimately responsible for its polarization.
Nevertheless, the physico-chemistry and geometry of YMO does not follow the two
most well-stabilized driving mechanisms in perovskites. With an Y3+ ion in the A
site, and Mn3+ (3d4 ) in the B site, it lacks the lone-pair electrons and 3d0 orbitals
needed in traditional ferroelectrics. Nevertheless, it does fulfill the properties of “im-
proper” ferroelectrics (see also Section 3.5). It was shown that in the paraelectric
regime, YMO belongs to the P63 /mmc, which is a centrosymmetric space group;
thus, as mentioned before, it prevents the ferroelectric polarization. However, below
transition temperature, in the ferroelectric regime, it belongs to P63 cm (no. 185)
space group, a noncentrosymmetric group [52, 92, 100, 107]. This effect is caused
due to the less abundant kinetic energy available, which allows for the tilting of
the bipyramids, pushing the Y atoms, thereby effectively forming a buckled trian-
gular lattice in the ferroelectric state. Since the charges are not equal, spontaneous
ferroelectric polarization occurs.
2.3 Investigation of Charge States and Multiferroicity

in Doped Systems
The field of multiferroics has been developing rapidly in the last few decades. Dozens
of new materials have been synthesized and suggested to possess multiferroic prop-
erties. We will focus on the compounds that were most extensively studied recently.
Even then, the results are usually not conclusive. As we will see, the structural, elec-
tronic, magnetic properties, underlying mechanisms of multiferroicity, or even its
existence are still an open question for some of these materials. Therefore, this must
be an unfinished story perforce.
2.3.1 Sensitive Ordering-doped Perovskite Manganites

Doped manganites of the formula R1−x Cax MnO3 , where R = Pr (PCMO) or La
(LCMO), are the most frequently listed representatives of charge-ordered multifer-
roics [92]. The half-doped insulating Pr0.5 Ca0.5 MnO3 has an orthorhombic structure
2.3 Investigation of Charge States and Multiferroicity in Doped Systems 33
a b c
Figure 2.4 Spin (top) and charge (bottom) order in PCMO in (a) site-centered CE order, (b)
bond-centered ∟ order, and (c) mixed order. Source: Efremov et al. [108]. © 2004 Springer
Nature.
of the space group Pnma at RT. At T CO = 230 K, it undergoes a phase transition

to a charge-ordered state. The material consists of equal amounts of Mn ions of
different valencies: Mn4+ , which are related to the Ca2+ cations, and Mn3+ , related
to the La3+ cations. They form site-centered CO of the checkerboard (CB) type. It
has been shown that charge order exists down to the doping level of x = 0.4 and
up to x = 0.9. At T N = 180 K, the material undergoes orbital ordering to a CE-type
antiferromagnet, i.e. spins form FM zigzag chains on the ab plane, which are
coupled antiferromagnetically (see Figure. 2.4).
The image of CB CO in half-doped PCMO seems to be quite simple. However,
site-centered CO does not break inversion symmetry and cannot induce ferro-
electricity. It has been proven that for the doping level of x = 0.4, the CO is of
bond-centered type, i.e. the position of the charge is between Mn ions. At the
intermediate doping level, the CO is of mixed site- and bond-centered type (see
Figure. 2.4). That breaks the inversion symmetry and the FM state appears. At x
between 0.4 and 0.5, the PCMO is thus multiferroic.
Although the value of the spontaneous polarization in PCMO is expected to be
quite large, up to few μC/cm2 , experimental proof for its ferroelectric character has
caused much trouble due to poor resistivity of the material. Thus, so far, mainly indi-
rect evidence for (anti)ferroelectric order is available [109]. Nevertheless, significant
value of the MEC in homologous La0.5 Ca0.5 MnO3 of 2.4 mV/cm Oe has been already
reported [110]. As we will see, the high MEC results from the magnetic origin of the
charge order.
That the exact picture of the charge order for the doping level is different from
x = 0.5 in PCMO has been a matter of debate in the literature since 1990s. The
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And after the prayer the Archpriest openeth the book of the
apostles over the head of the reader. And the subdeacons conduct
him from the Archpriest, and place him in the middle of the church,
with his face towards the east, and give him the book of the apostles,
and he readeth thus, The reading of the message of the holy apostle
Paul to the Romans (or, to others). And he readeth the portion of the
epistle that is appointed, from the beginning to the end, and turneth
himself and boweth thrice to the Archpriest according to rite. And the
subdeacons take off from him the phelonion, and conduct him to the
Archpriest. And the Archpriest again signeth his head thrice with the
hand. And they bring the sticharion to the Archpriest, and he signeth
the sticharion with his hand over the cross. And he that hath been
appointed, having signed himself with his hand, kisseth the cross
upon the sticharion, and the hand of the Archpriest; and the
subdeacons vest him with the sticharion. And the Archpriest
addresseth him on this wise,
Child, the first degree of the priesthood is that of reader. Therefore
it becometh thee to read every day in the divine scriptures, that they
that hear, considering thee, may receive edification, and that thou, in
nowise shaming thine election, mayest prepare thyself for a more
advanced degree. For, living temperately, holily, and righteously, thou
shalt gain the mercy of the man-loving God, and make thyself worthy
of a higher ministry, in Christ Jesus our Lord, to whom be glory to
ages of ages. Amen.
Then the Archpriest saith on this wise,
Blessed be the Lord, lo, the servant of God, name, becometh
reader of the most holy church, name, in the name of the Father, and
of the Son, and of the Holy Ghost.
And the Archpriest giveth him a lamp, and he standeth before the
Archpriest with the lamp in the indicated place.
And if there be several readers to receive the laying
on of hands they receive this together,
and the prayer is said in the
plural.
THE OFFICE THAT IS USED AT THE LAYING ON
OF HANDS OF A SUBDEACON.
Now if on the same day he is to receive the laying on of hands for
the subdiaconate, after the investing with the sticharion, the
subdeacons bring a sticharion-girdle to the Archpriest. And the
Archpriest maketh the sign of the cross upon the girdle, and he that
is to receive the laying on of hands kisseth the girdle, and the hand
of the Archpriest, and they gird him. And the Archpriest signeth him
with the hand upon the head thrice. After this the protodeacon saith,
Let us pray to the Lord. And the Archpriest, having laid his hand
upon him, saith this prayer.
O Lord our God, who through one and the same holy Spirit,
distributest gifts to them whom thou hast chosen, bestowing various
orders in thy church, and appointing degrees of service therein for
the ministration of thy divine and spotless mysteries, who, in thine
unspeakable foreknowledge, dost also appoint this thy servant to be
worthy to serve in thy holy church; do thou thyself, O Master,
preserve him blameless in all things, and grant unto him to love the
beauty of thy house, to stand at the doors of thy holy temple, to
kindle the lamp of the tabernacle of thy glory; and plant him in thy
holy church as a fruitful olive-tree that beareth fruit of righteousness;
and, at the time of thine advent, declare thy servant perfected to
receive the reward of them that have been acceptable unto thee.
Exclamation.
For thine is the kingdom, and the power, and the glory, of the
Father, and of the Son, and of the Holy Ghost, now and ever, and to
ages of ages. Amen.
And after the prayer the subdeacons give a ewer to him that is
receiving the laying on of hands, and lay a towel upon his shoulder;
and the Archpriest washeth his hands. And he that is receiving the
laying on of hands for subdeacon poureth water on the hands of the
Archpriest. After this he that is receiving the laying on of hands, and
the other subdeacons, kiss the Archpriest’s hand, and betake
themselves from him to the indicated place. And he that is receiving
the laying on of hands for subdeacon standeth, holding the ewer,
and the wash-hand basin, together with the towel, until the cherubic
hymn. And he saith, Trisagion. O most holy Trinity.... Our Father....
Lord, have mercy. I believe in one God.... Forgive, remit.... and
whatever else he is minded to say secretly. And during the cherubic
hymn he is conducted before the royal doors to the Archpriest; and
the Archpriest washeth his hands according to rite, and saith the
prayer. Then he signeth the water with his hand crosswise thrice.
And the Archpriest with this sanctified water wetteth his eyes, ears,
nostrils, and lips. And at the great introit he walketh behind all the
ministers. And when the Archpriest taketh up the holy things, and all
the ministers proceed into the altar, he that is receiving the laying on
of hands for subdeacon boweth to the Archpriest, and beareth water
to the right and left choirs, and to the people, and they all splash
themselves with this water. And they conduct him back to the altar,
and they pour the water that remaineth into the piscina. And, being
conducted, he remaineth before the royal doors, and standeth in the
indicated place according to rite. And when the Archpriest hath said,
And may the mercies.... after this exclamation he is conducted into
the altar by the subdeacons according to rite, and, having received a
blessing from the Archpriest, he standeth with the subdeacons.

OF HANDS OF A DEACON.
After the Archpriest hath said,
And may the mercies of the great God.... the subdeacons bring
forward the throne, and place it before the holy table, but somewhat
on the left side, so that they may not turn their backs towards the
holy things. And the Archpriest seateth himself thereupon, and they
take him that is to receive the laying on of hands from the middle of
the church, two subdeacons holding him between them, each of
them laying one hand upon his neck, and with the other hand holding
him by the hands, and they bow him down as lowly as possible. And
a deacon in the altar saith, Bid. Then, having advanced somewhat,
they bow him down as before. And another deacon saith, Bid ye.
Then they come nigh unto the holy gates of the altar, and bow him
down before the Archpriest.
And the protodeacon saith,
Bid, right reverend master.
And the subdeacons leave him that is to receive the laying on of
hands at the royal gates, and two receive him, a protodeacon and a
deacon, one by the right and the other by the left hand, and he
boweth himself to the Archpriest. And the Archpriest signeth him with
the hand crosswise, and they conduct him round the holy table, they
that lead him and the others singing,
O holy martyrs, who valiantly contended, and are crown’d; pray ye
the Lord for mercy on our souls.
Then they that are without sing the same once. And he that is
receiving the laying on of hands kisseth the four corners of the holy
table, and the hand of the Archpriest, and his knee. Then they
conduct him round again, singing,
Glory to thee, Christ God, apostles’ boast, and martyrs’ joy, whose
preaching was the consubstantial Trinity.
And the choir without singeth the same once. And he that is
receiving the laying on of hands again kisseth the holy table in like
manner as before, and the Archpriest’s epigonation, and his hand.
Then again they conduct him round, singing,
Rejoice, O Esaias, the virgin is with child, and bringeth forth a son,
Emmanuel, God and man: the orient is his name, whom magnifying,
we call the virgin blessed.
And they make the rite, as before written. And they sing the same
without. Then the Archpriest riseth, and they remove the throne, and
he that is receiving the laying on of hands goeth to the right side of
the Archpriest, and boweth himself before the holy table thrice,
saying, O God, cleanse me, a sinner. And, bending the right knee,
he placeth his palms crosswise on the holy table, and layeth also his
forehead between his hands on the holy table. The Archpriest
placeth the end of the omophorion on the head of him that it
receiving the laying on of hands, and blesseth him upon the head
thrice. And the protodeacon or the deacon having said, Let us
attend, the Archpriest, holding his hand upon his head, readeth
aloud in the hearing of all them that stand in the altar,
The divine grace, which always remedieth that which is feeble,
and supplieth that which is lacking, layeth hands upon, name, the
most pious subdeacon to be deacon: let us therefore pray for him,
that the grace of the all-holy Spirit may come upon him.
And the priests within sing, from the right hand side, Lord, have
mercy, thrice. Then again, from the left hand side, the same thrice.
And the singers without, in the right and left choirs, Kyrie eleison,
antiphonally thrice slowly, while the Archpriest readeth the prayer.
Then the Archpriest blesseth him upon the head thrice, holding his
hand upon the head of him that is receiving the laying on of hands.
The protodeacon saith, Let us pray to the Lord, in a low voice.
And the Archpriest saith the prayer secretly.
O Lord our God, who, by thy foreknowledge sendest the gift of thy
holy Spirit on them that are destined, by thine unsearchable might, to
be ministers, and to serve at thy spotless mysteries; do thou thyself,
O Master, preserve in every virtue this man whom thou art well-
pleased to lay hands upon by me for the ministry of the diaconate,
he holding the mystery of the faith in a pure conscience. Give unto
him the grace which thou gavest to thy protomartyr Stephen, whom
thou didst first call to the work of thy ministry; and make him worthy
to use, as may be acceptable unto thee, the degree which, by thy
goodness, is given unto him (for they that minister well prepare for
themselves a good degree); and do thou declare him thy perfect
servant.
Exclamation.
For thine is the kingdom, and the power,
and the glory, of the Father, and of
the Son, and of the Holy Ghost,
now and ever, and to
ages of ages.
Amen.
And the protodeacon readeth that which is of peace in a low voice.
In peace let us pray to the Lord. And they answer to each petition,
Lord have mercy, once. For the peace that is from above.... For the
peace of the whole world.... For our archpriest, name, for his
priesthood, assistance, continuance, peace, health, salvation, and
for the work of his hands, let us pray to the Lord. For the servant of
God, name, now receiving the laying on of hands for deacon, and for
his salvation, let us pray to the Lord. That the man-loving God may
bestow on him a spotless and blameless diaconate, let us pray to the
Lord. For our Most Pious, Autocratic Great Lord, THE EMPEROR
ALEXANDER ALEXANDROVITCH of all Russia, and for all HIS
palace and army, let us pray to the Lord. For this city.... For our
deliverance.... Help us, save us, have mercy on us....
Commemorating our most holy, most pure.... They answer, To thee,
O Lord.
And the Archpriest, holding his hand on the
head of him that is receiving the laying on of hands,
saith the second prayer.
O God our Saviour, who, by thine incorruptible voice, didst appoint
the law of the diaconate unto thine apostles, and didst declare the
protomartyr Stephen of such rank, and proclaim him the first to fulfil
the work of a deacon, as it is written in thy holy gospel, Whosoever
desireth to be the first among you, let him be your minister; do thou,
O Master of all, fill this thy servant, whom thou hast made worthy to
enter on the ministry of a deacon, with all faith, and love, and power,
and sanctification, through the visitation of thy holy and life-creating
Spirit (for it is not by the imposition of my hands, but by the presence
of thy compassions, that grace is given unto them that are worthy of
thee), that he, being without any sin, may stand blameless before
thee in the fearful day of thy judgment, and may receive the unfailing
reward of thy promise.
Exclamation. For thou art our God, and to thee we ascribe glory, to
the Father, and to the Son, and to the Holy Ghost, now and ever, and
to ages of ages. Amen.
Then they raise him up, and loosen his girding. And the Archpriest,
taking the orarion, layeth it upon his left shoulder saying with a loud
voice, Axios. And they sing in the altar thrice, Axios. And in like
manner without by both choirs. Then the maniples are given him,
and the Archpriest saith, Axios. And they sing the same in the altar
thrice, and in like manner without. Then the fan is given him, and the
Archpriest saith, Axios. And they sing in the altar and without
according to custom. And he kisseth the Archpriest on the shoulder,
and placeth himself by the altar, and fanneth the holy things.
THE OFFICE THAT IS USED AT THE

APPOINTMENT OF AN ARCHDEACON AND A
PROTODEACON.
He that is to be appointed an archdeacon is led by a protodeacon
and a deacon unto the right reverend Archpriest in the middle of the
church, where the Archpriest is standing at the time of the introit with
the gospel; and he inclineth himself to his girdle before the
Archpriest thrice, and boweth his head. And the Archpriest, sitting,
signeth him with the hand on his head crosswise, thrice; and, rising,
he layeth his hand upon his head. And the deacon having said, Let
us pray to the Lord,
the Archpriest saith this prayer.
Master, Lord our God, who, by thine unspeakable providence, hast
given to our race archdeaconship, that they that are endued
therewith may command and serve, with the subordinate ministers at
thy divine mysteries; do thou thyself endue with this grace of
archdeaconship thy present servant, name, and adorn him with thy
virtue to stand at the head of the deacons of thy people, and to be a
good example to them that are under him. And make him to attain
unto a ripe old age to glorify thy majestic name, of the Father, and of
the Son, and of the Holy Ghost, now and ever, and to ages of ages.
Amen.
Then the Archpriest signeth his head crosswise, saying, Blessed
be the Lord, lo, the servant of God, name, is archdeacon (or
protodeacon) in the name of the Father, and of the Son, and of the
Holy Ghost.
And the Archpriest, laying his hand upon his head, exclaimeth,
Axios, thrice. And the singers sing, Axios, thrice. And they enter the
altar according to rite.

OF HANDS OF A PRESBYTER.
After the conclusion of the cherubic hymn, he that is to be
appointed presbyter is conducted by an archdeacon, or by one of the
other deacons, through the royal gates unto the holy table before the
Archpriest on the right hand side. And the Archpriest signeth him
with the hand crosswise, and he is conducted round the throne
thrice, as it is written in the diaconal laying on of hands, while all in
the altar sing these troparia.
O holy martyrs, who valiantly contended and are crown’d; pray ye
the Lord for mercy on out souls.
Once.
Glory to thee, Christ God, apostles’ boast and martyrs’ joy, whose
preaching was the consubstantial Trinity.
Once.
Then, Rejoice, O Esaias, the virgin is with child, and bringeth forth
a son, Emmanuel, God and man: the orient is his name, whom
magnifying, we call the virgin blessed.
Once.
And he bendeth both knees, and placeth his palms crosswise on
the holy table, and layeth his forehead between his hands on the
holy table. The Archpriest placeth the end of the omophorion on the
head of him that is receiving the laying on of hands, and blesseth
him upon the head thrice. And the leading priest having said, Let us
attend, the Archpriest, holding his hand upon his head, readeth
aloud in the hearing of all them, that stand in the altar,
The divine grace, which always remedieth that which is feeble,
and supplieth that which is lacking, layeth hands upon, name, the
most pious deacon, to be presbyter: let us therefore pray for him,
that the grace of the all-holy Spirit may come upon him.
And the priests within sing, Lord, have mercy, thrice from the right
hand side. Then again thrice from the left hand side. Then in like
manner also the singers without in the right and left choirs, Kyrie
eleison, antiphonally thrice slowly, while the Archpriest readeth the
prayer. The Archpriest again blesseth him thrice, having his hand
lying upon the head of him that is receiving the laying on of hands.
And the protodeacon saith, Let us pray to the Lord, in a low voice.
The Archpriest saith the prayer secretly.
O God, unbeginning and unending, who art older than every created
thing, who honourest with the tide of presbyter them who are made
worthy in this degree to minister sacredly the word of thy truth; do
thou thyself, O Master of all, vouchsafe that this man, whom thou art
well-pleased to lay hands upon by me, may receive, in a blameless
conversation and in unswerving faith, this great grace of thy holy
Spirit, and declare him thy perfect servant, acceptable unto thee in
all things, and worthily exercising this great priestly honour
vouchsafed unto him by thy foreknowing power.
Exclamation.
For thine is the might, and thine is the kingdom,
and the power, and the glory, of the
Father, and of the Son, and of the
Holy Ghost, now and ever,
and to ages of ages.
Amen.
And the priest readeth that which is of peace in a low voice.
In peace let us pray to the Lord. They answer to each petition,
Lord, have mercy, once. For the peace that is from above.... For the
peace of the whole world.... For our archpriest, name, for his
priesthood, assistance, continuance, peace, health, salvation, and
for the work of his hands, let us pray to the Lord. For the Servant of
God, name, now receiving the laying on of hands for presbyter, and
for his salvation, let us pray to the Lord. That the man-loving God
may bestow on him a spotless and blameless priesthood, let us pray
to the Lord. For our Most Pious, Autocratic Great Lord, THE
EMPEROR ALEXANDER ALEXANDROVITCH of all Russia, and for
all HIS palace and army, let us pray to the Lord. For this city.... For
our deliverance.... Help us, save us.... Commemorating our most
holy, most pure.... They answer, To thee, O Lord.
The Archpriest, having his hand lying on the head of him that is
receiving the laying on of hands, prayeth thus,
O God, mighty in power, and unsearchable in understanding,
wonderful in counsels above the sons of men; do thou thyself, O
Lord, fill with the gift of thy holy Spirit this man, whom thou art well-
pleased should attain unto the presbyterial degree, that he may be
worthy to stand blamelessly at thine altar, to declare the gospel of
thy kingdom, to minister sacredly the word of thy truth, to offer unto
thee gifts and spiritual sacrifices, and to renew thy people by the
laver of regeneration, that he, meeting thee at the second coming of
the great God and our Saviour, Jesus Christ, thine only-begotten
Son, may receive the reward of a good stewardship of his order, in
the plentitude of thy grace.
Exclamation.
For blessed and glorified is thine all-revered and majestic name, of
the Father, and of the Son, and of the Holy Ghost, now and ever, and
to ages of ages. Amen.
Then they raise him up, and bring the epitrachelion, and taking the
orarion from him that hath received the laying on of hands, the
Archpriest giveth him the epitrachelion, having blessed it, and he that
hath received the laying on of hands kisseth the epitrachelion, and
the Archpriest’s hand. And the Archpriest layeth it upon his neck,
saying with a loud voice, Axios. And they sing in the altar thrice,
Axios. And the singers without sing the same in both choirs. In like
manner he giveth him also the girdle, and he kisseth it, and the
Archpriest’s hand, and girdeth himself. And the Archpriest saith,
Axios. And they sing in the altar and without in like manner. And they
do the same with the phelonion, and with the sloujébnik. And the
Archpriest saith with each, Axios. And they sing according to custom.
And, having kissed the omophorion and the Archpriest’s hand, he
that hath received the laying on of hands as priest goeth out and
kisseth the archimandrites, and all the co-ministrants on the
shoulder, and standeth with the priests.
THE ORDER OF THE OFFICE FOR THE MAKING

OF A PROTOPRESBYTER.
He that is to be appointed protopresbyter is conducted by a
protodeacon, or by two deacons, to the right reverend Archpriest in
the middle of the church, where the Archpriest standeth at the time
of the introit with the gospel. And he inclineth himself to his girdle
before the Archpriest thrice, and boweth his head. And the
Archpriest, sitting, signeth him with the hand on his head crosswise
thrice. And, rising, he layeth his hand upon his head. And the
protodeacon having said, Let us pray to the Lord,
Master, Lord Jesus Christ, our God, who hast bestowed priesthood
on our race, and hast endued us with the grace of this gift and
honour, and hast appointed us who are sufficiently pious to rule the
priestly order, and the other subordinate ministers of thy mysteries;
do thou thyself endue our brother, name, with thy grace, and adorn
him with virtue to stand at the head of the presbyters of thy people,
and make him worthy to be a good example to them that are with
him; and be thou pleased that he may finish his life in piety and
virtue unto a good old age; and, as the good God, have mercy upon
us all. For thou art the giver of wisdom, and all creation singeth thee
to ages of ages.
Then the Archpriest signeth his head crosswise, saying, Blessed
be the Lord, lo, the servant of God, name, becometh protopresbyter
of the most holy church of God, name, in the name of the Father,
and of the Son, and of the Holy Ghost.
And the Archpriest, laying his hand upon his head, exclaimeth,
Axios, iii. And the singers sing, Axios, thrice. Then they range the
protopresbyter with the other clergy according to rite, and they go
into the altar through the royal doors, and they act with the ministers
according to rite.

APPOINTMENT OF AN ABBOT.
He that is to be appointed abbot is conducted by a protodeacon, or
by two deacons, to the Archpriest in the middle of the church, where
the Archpriest standeth at the time of the introit with the gospel, if the
Archpriest himself be celebrating the liturgy. But if not, they bring to
the Archpriest the epitrachelion, the maniples, and the omophorion,
and he vesteth himself, standing in his place. And he that is to be
appointed abbot is conducted to his place, and inclineth himself to
his girdle before the Archpriest thrice, and boweth his head. And the
Archpriest, sitting, signeth him with the hand upon his head thrice.
And, rising, he layeth his hand upon his head, and the protodeacon
having said, Let us pray to the Lord,
O God, who ever makest provision for the salvation of men, and
gatherest together in one this thy rational flock; do thou, O Master of
all things, in thy measureless love to man, thyself preserve this same
blameless, keeping thy commandments continually, so that not one
sheep thereof may be lost, and be devoured by the wolf. And declare
this thy servant, whom thou art pleased to appoint abbot over it,
worthy of thy grace, and adorn him with all virtues, that he, by his
works, may be a good example to them that are under him, that they,
being emulators of his blameless conversation, may stand with him
uncondemned before thy fearful judgment-seat.
Exclamation. For thine is the kingdom, and the power, and the
glory, of the Father, and of the Son, and of the Holy Ghost, now and
ever, and to ages of ages. Singers. Amen.
Archpriest. Peace to all.
Singers. And to thy spirit. Protodeacon. Bow your heads to the
Lord. Singers. To thee, O Lord.
The Archpriest prayeth secretly.
Incline thine ear, O Lord, and hearken unto our prayer, and declare
this thy servant to be abbot of this honourable habitation, a faithful
and wise administrator over the rational flock committed to him by
thy grace, he doing thy will in all things, and becoming worthy of thy
heavenly kingdom.
Exclamation.
Through the grace, and compassions, and love to man of thine
only-begotten Son, with whom thou art blessed, together with thine
all-holy, and good, and life-creating Spirit, now and ever, and to ages
of ages. Amen.
And the protodeacon saith with a loud voice, Bid, master.
And the Archpriest saith with a loud voice,
The grace of the all-holy Spirit, through our mediocrity, appointeth
thee abbot of the honourable habitation of our Lord, God, and
Saviour, Jesus Christ, name, whatever title of him the temple may
be, or, of our most holy God-bearing Lady, whatever title of her the
temple may be, or, of Saint, name, to whom may be dedicated the
temple.
Then, laying his hand upon his head, the Archpriest exclaimeth,
Axios, thrice. And the singers sing, Axios, thrice.
After this he that hath been appointed abbot
kisseth the Archpriest’s omophorion on the right
and left shoulder; and, being conducted, he rangeth
himself with the other abbots according to rite; and
they go into the altar through the royal
doors, and he acteth with the
ministers according
to rite.

APPOINTMENT OF AN ARCHIMANDRITE.
He that is to be appointed archimandrite is conducted by a
protodeacon, or by two deacons, to the Archpriest in the middle of
the church where the Archpriest standeth at the time of the introit
with the gospel, if the Archpriest himself be celebrating the liturgy.
But if not, they bring the epitrachelion, the maniples, and the
omophorion to the Archpriest, and he vesteth himself standing in his
place. And he that is to be appointed archimandrite is conducted to
his place, and he inclineth himself to his girdle thrice before the
Archpriest, and boweth his head. And the Archpriest, sitting, signeth
him with the hand upon his head thrice. And if he that is to be
appointed archimandrite be not an abbot, the Archpriest saith over
him the prayers which are said over an abbot. But if he be already an
abbot the prayers for an abbot are not said over the archimandrite,
and the protodeacon only saith with a loud voice,
Bid, master.
And the Archpriest exclaimeth with a loud voice,
The grace of the all-holy Spirit, through our mediocrity, appointeth
thee archimandrite of the honourable habitation of our Lord, God,
and Saviour, Jesus Christ, or, of our most holy God-bearing Lady,
whatever temple of her it may be, or, of Saint, name, to whom may
be dedicated the temple.
Then the Archpriest, laying his hand on the head of him that is
appointed, exclaimeth Axios, thrice.
And the singers sing, Axios, thrice.
And if, by the command of our Most Pious,
Autocratic Great Lord, THE EMPEROR
ALEXANDER ALEXANDROVITCH of
all Russia, and with the blessing of the Most Holy
Governing Synod, the mitre be given to the archimandrite,
then after the procession from the altar
with the gospel at the divine liturgy, the archimandrite
is conducted to the Archpriest. And the
Archpriest doth not say the prayer, but only blesseth
the archimandrite with the hand. And he kisseth
the Archpriest’s hand, and the mitre; and they
place the mitre on the archimandrite. And, being
conducted, he rangeth himself with the archimandrites
and abbots according to degree,
and they go into the altar through
the royal doors, and he acteth
with the ministers
according to
rite.
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Nanostructured Multiferroics Raneesh Balakrishnan Full Chapter

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Nanostructured Multiferroics Raneesh

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© 2021 WILEY-VCH GmbH, Boschstr. 12, 69469

All rights reserved (including those of translation

Print ISBN: 978-3-527-34320-1

Typesetting SPi Global, Chennai, India

Printed on acid-free paper

1 Nanostructured Multiferroics: Current Trends and Future

2.3.2 Frustrated LuFe2 O4 – Multiferroism in Controversy 35

3 Multiferroic Study of Pure BiFeO3 Synthesized Using Various

4.5.2.2 Magnetic Properties 81

5 Multiferroic Systems of BiFeO3 and BaTiO3 Nanostructures:

6 Effective Properties of Multilayered Nanomultiferroics 133

7 Correlation Between Grain Size, Transport, and Multiferroic

7.4.4 Ferroelectric Hysteresis Loop 188

8 Speciﬁc Heat and Magnetocaloric Properties of Some

9 Preparations, Characterization, and Applications of

The book Nanostructured Multiferroics: summarizes many of the recent research

The fourth chapter is titled “Nanostructured Multiferroics.” Following an intro-

Dr. B. Raneesh is an Assistant Professor in the Depart-

Dr. Visakh P.M. (MSc, MPhil, PhD) is a prolific editor

Nanostructured Multiferroics: Current Trends and Future

1.1 Single-phase Multiferroics

Ferroelectricity and ferromagnetism seemed at the beginning to be mutually

1.2 Multiferroic Study of Pure BiFeO3 Synthesized Using

1.3 Nanostructured Multiferroics

1.4 Multiferroic Systems of BiFeO3 and BaTiO3

1.5 Effective Properties of Multilayered

1.6 Correlation between Grain Size, Transport, and

in BiFeO3 applications [132], and it is very difficult to obtain a single-phase BiFeO3

1.7 Speciﬁc Heat and Magnetocaloric Properties of

1.8 Preparations, Characterization, and Applications of

Nanostructured Multiferroic materials offer great prospects at many application

1 Spaldin, N.A. and Fiebig, M. (2005). The renaissance of magnetoelectric multi-

44 Szafraniak, I., Połomska, M., Hilczer, B. et al. (2007). Characterization of

116 Ghosh Chaudhuri, R. and Paria, S. (2011). Core/shell nanoparticles: classes,

Ferromagnets, ferroelectrics, and ferroelastics (ferroics) are widely studied mate-

(a) Cubic (b) Orthorhombic

Rhombohedral (R) Orthorhombic (O) Tetragonal (T) Cubic (C)

Figure 2.1 Schematic representations of crystalline structure of a standard cubit

Because of the simplicity of the perovskite formula, it is possible to substitute a

2.1.1 Considerations on Single-phase Multiferroics

Figure 2.2 Schematic representations of superexchange interactions in ABO3 and A2 BB’O6

2.1.2 Ferroelastic Multiferroics

standards of other thin-film ferroelectrics, it is an important step toward further

2.2 Analysis of the Multiferroicity in the Hexagonal

2.2.2 Ferroelectricity in Hexagonal Manganites

2.3 Investigation of Charge States and Multiferroicity

2.3.1 Sensitive Ordering-doped Perovskite Manganites

of the space group Pnma at RT. At T CO = 230 K, it undergoes a phase transition

THE OFFICE THAT IS USED AT THE LAYING ON

THE OFFICE THAT IS USED AT THE

THE OFFICE THAT IS USED AT THE LAYING ON

THE ORDER OF THE OFFICE FOR THE MAKING

THE OFFICE THAT IS USED AT THE

THE OFFICE THAT IS USED AT THE

Creating the works from print editions not protected by U.S.

START: FULL LICENSE

To protect the Project Gutenberg™ mission of promoting the free

Section 1. General Terms of Use and

1.B. “Project Gutenberg” is a registered trademark. It may only be

1.E. Unless you have removed all references to Project Gutenberg:

1.E.1. The following sentence, with active links to, or other