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 CHEMICAL SYNTHESIS AND
CHARACTERIZATION OF BISMUTH FERRITE
NANOSTRUCTURES

Temporary Binding for Examination Purposes

Linfeng FEI

M.Phil

The Hong Kong Polytechnic University

2011
 The Hong Kong Polytechnic University
Department of Applied Physics

CHEMICAL SYNTHESIS AND CHARACTERIZATION

OF BISMUTH FERRITE NANOSTRUCTURES

Linfeng FEI

A thesis submitted in partial fulfillment of the requirements

for the degree of Master of Philosophy

December 2010
 CERTIFICATE OF ORIGINALITY

I hereby declare that this thesis is my own work and that, to the best of my

knowledge and belief, it reproduces no material previously published or written,

nor material that has been accepted for the award of any other degree or diploma,

except where due acknowledgement has been made in the text.

_ _ _ _ _ _ _ _ _ _ _ (Signed)

_ _ _ _~F~E~I.ll:::!oLm~·~fe""-in~g_ _ _ (Name of student)

To my parents
 ABSTRACT

ABSTRACT

Motivated by the uniqueness of simultaneous antiferromagnetic and

ferroelectric ordering at room temperature and hence, a fascinating vista of

applications, research interest on perovskite bismuth ferrite (BiFeO3) could be

dated back to 1950s although it was almost impossible to produce pure crystals at

that time. The discovery of large remnant polarization and strong ferromagnetism

measured on BiFeO3 thin films in 2003 has led to the revival of research in this

area and many more studies have been conducted since then. On the other hand,

the continuous evolution of nanoscience and nanotechnology have resulted in the

fabrication of various bismuth ferrite nanostructures, including 0D nanoparticles,

1D nanowires, nanotubes and even 3D architectures. More importantly, these

novel structures are proved to possess significantly different properties from their

bulk or film counterparts because of the nanosized morphological characteristics.

The ability to understand the size-dependent physical and chemical properties of

these structures would help to ultimately integrate them as building blocks in

future generation electronic devices, offering multiple controlling degrees of

freedom.

In this thesis, systematic experimental work has been carried out to

synthesize and characterize bismuth ferrite nanostructures with a variety of

sizes/morphologies, as outlined below.

First, a low-temperature wet chemical route was adopted to synthesize

nanoparticles of BiFeO3. In the process, bismuth nitrate and iron nitrate were

employed as starting materials with excess tartaric acid and citric acid as chelating

agents. It was found that the crystallization temperature of BiFeO3 is dependent

on the chelating agent. Under optimized processing conditions, BiFeO3

nanoparticles with good quality of crystallization and sharp distribution of particle

FEI Linfeng I
 ABSTRACT

size could be obtained after a thermal treatment at ∼350 °C, which is one of the

lowest crystallization temperatures ever achieved. Structures and

physical/chemical properties of BiFeO3 nanoparticles with different sizes

distributions were also characterized.

Second, a sol-gel based electrospinning process was developed which enabled it

to synthesize bismuth ferrite nanofibers at a relatively large scale. The annealing

temperature after the electrospinning was significantly lowered by introducing

appropriate chelating agent in the precursor solution. Nanofibers prepared under

optimized conditions were found to be well crystallized, uniform in diameter and

exhibit excellent ferroelectric properties when tested under piezoelectric force

microscope.

Third, uniform and phase-pure perovskite BiFeO3 crystallites with different

predominantly exposed facets were successfully synthesized via a facile one-pot

hydrothermal approach at 200 °C in the presence of potassium hydroxide and

polyethylene glycol. Pills and rods with dominant {111}c facets and cubes with

{100}c exposed facets were obtained by adjusting the alkaline conditions of the

precursor solution. Due to the distinct dominant facets of BiFeO3 crystallites, {111}c

dominant pills and rods were found to grant a significant enhanced visible light

response, suggesting that the designed structures can give rise to better performance

in future photovoltaic and photocatalytic applications of BiFeO3.

In summary, bismuth ferrite with controllable sizes and morphologies have been

developed and characterized. The nanostructures are expected to be useful in the

basic and applied research related to multiferroic nanomaterials.

FEI Linfeng II
 LIST OF PUBLICATIONS

LIST OF PUBLICATIONS

1. Y. M. Hu, L. F. Fei, Y. L. Zhang, J. K. Yuan, Y. Wang, and H. S. Gu,

―Synthesis of Bismuth Ferrite Nanoparticles via a Wet Chemical Route at Low

Temperature‖, Journal of Nanomaterials, Volume 2011, Article ID 797639.

2. L. F. Fei, J. K. Yuan, Y. M. Hu, C. Z. Wu, J. L. Wang, and Y. Wang, ―Visible

Light Responsive Perovskite BiFeO3 Pills and Rods with Dominant {111}c

Facets‖, accepted by Crystal Growth & Design.

3. L. F. Fei, J. K. Yuan, Y. M. Hu, and Y. Wang, ―A Study of Synthesis Process

and Conditions: Multiferroic Bismuth Ferrite Nanofibers via Sol-gel Based

Electrospinning‖, submitted to Journal of Materials Chemistry.

4. L. F. Fei, J. K. Yuan, Y. M. Hu and Y. Wang, ―Synthesis of Multiferroic

Bismuth Ferrite Nanoparticles and Nanofibers via Solution-Based

Approaches‖, presented at European Material Research Society 2010 Spring

Meeting, Strasbourg, France, 7-11 June 2010.

5. G. Y. Gao, Y. Wang, Y. Jiang, L. F. Fei, N. Y. Chan, H. L. W. Chan and W. B.

Wu, ―Epitaxial Growth and Rectification Characteristics of Double Perovskite

Oxide La2NiMnO6 Films on Nb-SrTiO3 Single Crystal Substrates‖, accepted

by Thin Solid Films.

6. Z. J. Shen, Y. M. Hu, K. Li, L. F. Fei, W. P. Chen, H. S. Gu, Y. Wang and H.

L. W. Chan, ―Photocatalytic Behavior of YBa2Cu3O7-x Nanoparticles

Obtained through Soft-Chemical Route,‖ accepted by Chemical

Communications.

FEI Linfeng III

 ACKNOWLEDGEMENT

ACKNOWLEDGEMENT

I would like to extend my thanks to a number of people who have

contributed so much to my M.Phil study at PolyU.

First of all, I would like to express my sincere gratitude to my supervisors,

Drs. Y. Wang and J. K. Yuan, for their guidance, encouragement and offering me

the opportunity to conduct research in such a fascinating field. I also highly

appreciate it that they always give me trust and support in the research.

I would also like to thank all these faculty members of our department,

especially Profs. H. L. W. Chan, K. H. Wong, S. P. Lau, Drs. J. Y. Dai, K. Z.

Baba-kishi, X. M. Zhang and F. Yan for their assistance on my research and

coursework studies.

I would also like to thank Drs. Y. M. Hu, C. Z. Wu, J. Q. Qi, and Prof. W. P.

Chen for providing invaluable support and suggestion to this project.

I would like to thank Drs. J. L. Wang (NTU, Singapore), X. M. Liu (USTC,

China), Y. Zhao (CityU, Hong Kong), H. T. Zhang (NIMS, Japan), S. Peng

(BrownU, United States), S. H. Xuan and Mr. F. Wang (CUHK, Hong Kong) for

helpful discussions, suggestion and help they offered to me.

I sincerely thank Dr. K. Zhang and Mr. Y. Jiang who are my friends and

colleagues. They have been teaching me so much since the time when I was still a

―freshman‖ in our group. My thanks also go to many other friends and colleagues

in AP, espeically Drs. G. Y. Gao, W. Huang, J. Ye, G. Y. Wang, Z. J. Shen, D. F.

Li, L. Sun, M. Zeng, X. Fu, J. Zhang, N. Y. Chan, L. Yan, J. H. Li, F. Cao, P. Lin,

Z. P. Wu and J. Liu.

FEI Linfeng IV
 ACKNOWLEDGEMENT

I thank Dr. W. Lu and Mr. M. N. Yeung from Materials Research Center for

the technical assistance.

Financial support from The Hong Kong Polytechnic University Research

Studentship is gratefully acknowledged.

Finally, I give my special appreciation to my beloved parents, who raised me

up so laboriously, for the education and edification they gave me during the past

years.

FEI Linfeng V
 TABLE OF CONTENTS

TABLE OF CONTENTS

ABSTRACT................................................................................................................ I

LIST OF PUBLICATIONS ........................................................................................ III

ACKNOWLEDGEMENT .......................................................................................... IV

TABLE OF CONTENTS ........................................................................................... VI

LIST OF ABBREVIATIONS ..................................................................................... IX

CHAPTER 1 INTRODUCTION ................................................................................ 1

1.1 Research Background ................................................................................ 1

1.2 General Description of Perovskite Oxides ................................................. 3

1.3 Fundamentals of BiFeO3 ............................................................................ 4

1.3.1 Historical Briefs ................................................................................. 4

1.3.2 Crystallographic Information ............................................................. 6

1.3.3 Multiferroicity in BiFeO3 .................................................................. 7

1.3.4 Phase Decomposition and Impurities ................................................ 9

1.4 Synthesis of BiFeO3 Nanostructures via Chemical Approaches............. 10

1.4.1 0D Nanoparticles ............................................................................. 11

1.4.2 1D Nanowires and Nanotubes ......................................................... 14

1.4.3 Complex Nanostructures ................................................................. 16

1.5 Size Effects and Applications of BiFeO3 Nanostructures ....................... 18

1.5.1 Ferroelectricity and Piezoelectricity ................................................ 19

1.5.2 Magnetism and M-E Coupling ........................................................ 20

1.5.3 Photocatalytic Behavior ................................................................... 22

1.5.4 Other Characteristics ....................................................................... 24

1.5.4.1 Gas Sensor ................................................................................ 25

1.5.4.2 Heterogeneous Catalyst ............................................................ 25

1.6 Motivations of the Project ........................................................................ 26

1.7 Scope of the Work .................................................................................... 27

FEI Linfeng VI
 TABLE OF CONTENTS

CHAPTER 2 RESEARCH METHODOLOGY .......................................................... 29

2.1 Sample Preparations................................................................................. 29

2.1.1 Sol-gel Method ................................................................................ 30

2.1.2 Electrospinning Process ................................................................... 31

2.1.3 Hydrothermal Reaction .................................................................... 33

2.2 Structure Characterizations ...................................................................... 35

2.2.1 X-ray Diffraction (XRD) ................................................................. 35

2.2.2 Scanning Electron Microscopy (SEM) ............................................ 36

2.2.3 Transmission Electron Microscopy (TEM) ..................................... 37

2.2.4 Thermal Analysis ............................................................................. 39

2.3 Property Measurements............................................................................ 39

2.3.1 Piezoresponse Force Microscopy (PFM)......................................... 39

2.3.2 Vibrating Sample Magnetometer (VSM) ......................................... 41

2.3.3 UV/Vis-NIR Spectrophotometer...................................................... 41

CHAPTER 3 LOW TEMPERATURE SYNTHESIS OF BiFeO3 NANOPARTICLES BY

MODIFIED SOL-GEL METHOD ................................................................. 43

3.1 Introduction............................................................................................. 43

3.2 Experimental Details .............................................................................. 45

3.3 Results and Discussion ........................................................................... 47

3.3.1 Determination of Sintering Temperatures ........................................ 47

3.3.2 Structure Characterizations .............................................................. 48

3.3.3 Proposed Precursors & Formation Mechanism ............................... 52

3.3.4 Investigation of Size-dependent Magnetism ................................... 54

3.4 Summary ................................................................................................. 55

FEI Linfeng VII

 TABLE OF CONTENTS

CHAPTER 4 SYNTHESIS OF BiFeO3 NANOFIBERS VIA ELECTROSPINNING ........ 56

4.1 Introduction............................................................................................. 56

4.2 Experimental Procedure.......................................................................... 58

4.2.1 Preparation of Precursor Solution .................................................... 58

4.2.2 Electrospinning and Annealing........................................................ 58

4.2.3 Structure Characterizations and Measurements ............................... 59

4.3 Results and Discussion ........................................................................... 59

4.3.1 Physicochemical Characterization ................................................... 59

4.3.2 Microstructures under Annealing .................................................... 63

4.3.3 Influence of Accelerating Voltages & PVP Concentrations ............. 65

4.3.4 Measurement of Piezoelectricity ..................................................... 67

4.4 Summary ................................................................................................. 69

CHAPTER 5 SYNTHESIS OF BiFeO3 PILLS AND RODS WITH DOMINANT {111}C

FACETS .......................................................................................... 70

5.1 Introduction............................................................................................. 70

5.2 Experiments ............................................................................................ 73

5.2.1 Hydrothermal Synthesis................................................................... 73

5.2.2 Characterizations and Measurement ................................................ 73

5.3 Results and Discussion ........................................................................... 74

5.3.1 Crystallographic Investigation ......................................................... 74

5.3.2 Microstructure Analysis ................................................................... 75

5.3.3 Formation Mechanism Reasoning ................................................... 78

5.3.4 Optical Adsorption Measurement .................................................... 80

5.4 Summary ................................................................................................. 81

CHAPTER 6 CONCLUSIONS ................................................................................ 83

REFERENCES ......................................................................................................... 85

FEI Linfeng VIII

 LIST OF ABBREVIATIONS

LIST OF ABBREVIATIONS

Abbreviation Description

0D Zero Dimension(al)

1D One Dimension(al)

2D Two Dimension(al)

3D Three Dimension(al)

AFM Atomic Force Microscopy(e)

BFO Bismuth Ferrite, BiFeO3

EDS Energy Dispersed Spectrum

M-E Magnetoelectric

NF Nanofiber

NP Nanoparticle

PFM Piezoresponse Force Microscopy(e)

RT Room Temperature

SAED Selected Area Electron Diffraction

SEM Scanning Electron Microscopy(e)

TC Curie Temperature

TEM Transmission Electron Microscopy(e)

TG-DSC Thermogravimetric Analysis & Differential Scanning Calorimetry

TN Neel Temperature

UV-Vis Ultraviolet-Visible

VSM Vibrating Sample Magnetometer

XRD X-Ray Diffractions

FEI Linfeng IX
CHAPTER 1 INTRODUCTION

CHAPTER 1
INTRODUCTION

1.1 Research Background

―There’s plenty of room at the bottom!‖1

On December 29, 1959, physicist Richard P. Feynman gave an influential

lecture in an American Physical Society meeting at Caltech entitled with this

famous sentence, creatively considering the possibility of direct manipulation of

individual atoms as a more powerful form of synthetic chemistry than those used

at that time. Today after 50 years, it is of common view that the lecture should

undoubtedly be the initial fuel of nanoscience and nanotechnology, and proudly, it

is no longer a wild fancy to a certain extent. In 1981, the development of scanning

tunneling microscope not only earned its inventors, Gerd Binnig and Heinrich

Rohrer (@IBM Zurich), the Nobel Prize in Physics of 1986, but also provided the

capacities of imaging and manipulating single atoms within materials.2 From then

on, nanotechnology rather enjoyed a major exploding and has been extending to

such diverse, ranging from extensions of traditional device physics to completely

new approaches based upon molecular self-assembly, from developing new

materials with dimensions on the nanoscale to investigating whether we can

directly control matter on the atomic level.

At the current stage, the fabrication of various nanostructures has been

regarded as one of the most popular highlight due to their spectacular properties

and great potential applications. According to its definition, nanostructures refer

to materials with morphological features on the nanoscale, with at least one of its

dimensions ranging from 1-100 nm, and thus it can be simply classified as: zero

FEI Linfeng 1
CHAPTER 1 INTRODUCTION

dimensional quantum dot (0D, all three dimensions at nanoscale such as

nanoparticles and nanoclusters), one dimensional quantum wire (1D, two

dimensions at nanoscale including nanowires, nanorods and nanotubes) and two

dimensional quantum well (2D, one dimension at nanoscale such as thin-films).

Nanostructures possess the intermediate size between molecular and microscopic

structures; and hence, definitely exhibit physical and chemical properties

significantly differ from both their bulk and molecular counterparts which

originate from their surface effect, small size effect, quantum size effect and

macroscopic quantum tunneling effect.3 Mostly, nanostructures are prepared

artificially nowadays, however, the existences of natural nanoparticles and

nano-solids have already been confirmed.

Actually, for the development of modern technology, it is quite a necessity to

have the ability of synthesizing or manufacturing these specific kinds of structures

with ultimate small sizes to meet the practical demands. Based on this firm

conviction, thousands of scientists contributed a lot in the past few decades to the

designed fabrication of numerous nanostructures, both physically and chemically,

namely top-down and bottom-up methods.

This work based on a systematical study of chemical synthetic approaches of

such a fascinating material, perovskite BiFeO3 (BFO), with its peerless characters

as being discussed in the following chapters. The work was originally stimulated

by the discovery of Wang et al. in 2003,4 which made this material so attractive in

the past few years. Before entering this charming area, I hereby would like to give

a brief introduction on perovskite oxides and the relevant multiferroicity in

perovskite oxides, especially in BFO. Subsequently, I will try to summarize the

contributing publications on the synthesis and characterizations of various BFO

nanostructures, together with their excellent properties and promising

applications.

FEI Linfeng 2
CHAPTER 1 INTRODUCTION

1.2 General Description of Perovskite Oxides

A perovskite oxide is any compound with the same kind of crystal structure

as that owned by calcium titanium oxide (CaTiO3), widely known as the

XII 2+VI 4+
perovskite structure, or A B O2-3 as its general formula, where A and B

denote a large cation and a small cation, respectively. The perovskite structure is

considered as one of the most common structures in complex oxides on our earth.

In the following part of the thesis, this family of ―amazing‖ compound with this

specific formula will be on the focus of our study.

Figure 1.1 Two typical views of the ABO3 ideal cubic perovskite structure unit

cell. (a) The A atom sits at cube corner positions (0, 0, 0), B atom sits at body

center position (1/2, 1/2, 1/2) while oxygen atom sits at face center position

(1/2, 1/2, 0); (b) ABO3 structure in terms of BO6 octahedra networks.

The simplest perovskite structure is of a standard cubic symmetry,

corresponding to a high temperature phase. It is shown in Figure 1.1(a), where the

A atom has 12 oxygen first neighbors, while B atom sits at the center of an

octahedron composed of six oxygen atoms. Meanwhile, in an alternative frame of

reference, the structure can also be outlined as a 3D network of corner sharing

BO6 octahedra as in Figure 1.1(b). However, the relative variation of ionic radius

FEI Linfeng 3
CHAPTER 1 INTRODUCTION

of A and B atoms will easily distort the cubic symmetry with simultaneous tilting

of the oxygen octahedral. In 1926, Goldschmidt defined a parameter, tolerance

factor t, to accurately describe the stability (deformability) of a perovskite

structure. The factor t which associates with the ionic radius is obtained upon the

concept of the well-known closed-packed theory.5 It is given as

where rA, rB and rO correspond to the ionic radius of A, B and O atoms,

respectively. Under the change of A and B atomic species and a following change

of t value, the crystallographic symmetry will be lowered and can be tuned to

orthorhombic, tetragonal or trigonal in many perovskites. Hence, a broad range of

extraordinary properties will be brought by the changes in molecular formula and

symmetric structures which are of absolutely essentiality in either fundamental or

practical.

1.3 Fundamentals of BiFeO3

1.3.1 Historical Briefs

A ferroelectric6 crystal possesses stable and switchable spontaneous

polarization which relies on the cooperative atom displacements while a

ferromagnetic crystal exhibits stable and switchable magnetization that arises

from the quantum mechanical phenomenon of exchange. The combination of

these two novel properties, known as ―multiferroicity‖, has long been desired by

scientists because of the additional degree of freedom it offers in microelectronic

design. According to its original definition, a single phase multiferroic material

should possess at least two of the so-called ―ferroic‖ properties, i.e. ferroelectricity,

ferromagnetism and ferroelsticity.7 In practice, such definition has been broadened

to include ―antiferroic‖ orders. Although there are only few single-phase materials

FEI Linfeng 4
CHAPTER 1 INTRODUCTION

in which ferroelectricity and ferromagnetism arise independently,8 this topic has

often been a highlight for scientific research over the past 50 years due to its

impact on either new fundamental physics or innovative device applications.

The basic concept of multiferroic or magneto-electric can perhaps be

originated to Pierre Curie in the late 19th century.9 After linear coupling of

magnetoelectricity was defined and predicted to occur in the specific Cr2O3 by

Dzyaloshinskii in 1957,10 the magnetoelectric (M-E) coupling coefficient αij was

experimentally measured to be non-zero by Astrov in 1960.11 Unfortunately, the

paraelectricity and antiferromagnetism of Cr2O3 make it impossible for industrial

applications. A small number of breakthroughs have taken place in this area

during the 1960s. Schmid demonstrated the first magneto-electric switching on his

work to boracites (Ni3B7O13I).12 However, since boracites only exhibits its

magnetoelectricity at extremely low temperature (below 60 K); it is again

impracticable for device applications.

Meanwhile Smolenskii pioneered a study on perovskite bismuth ferrite

(BiFeO3)13 in which it failed to obtain single crystals of BFO successfully and that

the ceramic samples obtained were found to be poor insulators even by doping

other ions into both A and B sites of the lattice.14, 15 Strong research interests on

BFO have revived since 2003; Wang et al. observed large remnant polarization

together with strong ferromagnetism from a BFO on SrTiO3 epitaxial thin film.4

The result was later confirmed in France through the measurements from single

crystals.16-18 BFO was then believed as the only possible candidate which shows

simultaneous large ferroelectricity and antiferromagnetism at RT. This finding had

led to a series of studies on this area from around the world and many more novel

properties of BFO were discovered including photovoltaic effect,19

light-induced photostrictive effect,20 and controllable ferroelastic switching.21

While most physics scientists focus on bulk (ceramics and single-crystals)

FEI Linfeng 5
CHAPTER 1 INTRODUCTION

and thin film samples of BFO to reveal its physical properties, inspired by its

potential in information storage in spintronic devices and sensors,22 other chemists

and material scientists have been working on BFO through its nanostructures, an

effective way to fully understand the chemical properties and applications of the

material. Recent research has focused on synthesizing nanostructures of BFO such

as nanoparticles, nanorods, nanowires, nanotubes and nanocubes with reference to

their size-dependent physical and chemical properties. Originally, the objectives

of all synthesis approaches are in urgent pursuit of monodispersity, high stability

and crystallinity with controllable morphologies, and significant progress has been

made in the case of perovskite bismuth ferrite. To fully illustrate the background

of my study, I will try my best to summarize the recent advancements in chemical

synthesis and properties of perovskite bismuth ferrite nanostructures in the

following paragraphs.

1.3.2 Crystallographic Information

To explore this material system, it would be essential to first study its basic

crystal structure. Under ambient conditions, bulk BFO belongs to the R3c point

group with a highly distorted perovskite structure in rhombohedral symmetry.23

The lattice parameter ar is 3.965 Å, with a rhombohedral angle αr equals to ca.

89.3-89.4°. Alternatively, the structure can be characterized in a hexagonal frame

of reference by connecting two perovskite cubes along with their body diagonal,

i.e., [001]hexagonal ǁ [111]pseudocubic as that indicated by Figure 1.2(a) . The hexagonal

lattice parameters are ah = 5.58 Å and ch = 13.90 Å.24, 25

It is worth noting that in the lattice of BFO, the FeO6 octahedra has a rotation

angle, a result from its extra large volume that it must buckle into the cell. In fact

the rotation angles of the two adjacent octahedras are +12°and -12°around the

polar [111]r axis, which was first discovered by Achenbach’s group with neutron

diffraction measurement,27 and later confirmed by Turov and Sosnowska.23, 28 This

FEI Linfeng 6
CHAPTER 1 INTRODUCTION

Figure 1.2 (a) Schematic of the crystal structure of BFO and the ferroelectric

polarization (arrow) and antiferromagnetic plane (shaded planes). (b)

Ferroelectric polarization loops measured on epitaxial BFO thin films with

different crystallographic orientations.26

rotation does not only determine its space group of R3c, but also indicates the

Fe-O-Fe angle to be ca. 154-156°which is of great importance in establishing the

magnetic ordering temperature.25

1.3.3 Multiferroicity in BiFeO3

In parallel with its specific crystal structure, BFO exhibits unique properties

especially its superior electrodynamicity. Under its Curie temperature (TC, Figure

1.3) of about 1100 K,4 BFO shows simultaneous piezoelectricity, pyroelectricity

and ferroelectricity along its polar axis (<111>r). Based on the result of

Rovillain,29 the linear piezoelectric coefficient of BFO is d33=16 pm/V, about 6

times greater than that of quartz. A pyroelectric coefficient of about 310-3

μC/cm2K was observed by Rakov, comparable with that of LiNbO3.30 The

ferroelectricity of BFO was once considered to be very weak,31 however,

Lebeugle16 and Shvartsman32 proved the opposite through their high-quality

single crystals and ceramics with ca. 60 μC/cm2 normal to (001) and almost 100

μC/cm2 along [111]r respectively, a result similar to Ramesh’s thin film results

(Figure 1.2b).4 Ab initio calculations further verified that the intrinsic polarization

FEI Linfeng 7
CHAPTER 1 INTRODUCTION

of bulk BFO is rather high, up to 90-100 μC/cm2.33

Figure 1.3 Differential thermal analysis traces demonstrate the

antiferromagnetic-paramagnetic (TN, 370 °C) and ferroelectric-paraelectric (TC,

830 °C) transitions. Inset: differential scanning calorimetric trace showing the

lambda-shape of the calorimetric trace for the antiferromagnetic phase

transition. Arrows denote the transition temperatures as the peak temperature of

the magnetic transition, and the onset temperature of the ferroelectric

transition.37

Below its Neel temperature (TN) of about 643 K (Figure 1.3),34 the

short-range magnetic ordering of BFO belongs to G-type antiferromagnetism with

magnetic point group 3m. Sosnowska35 discovered a long-range superstructure

superimposed on an incommensurate spin cycloid of the antiferromagnetically

ordered sublattice by utilizing neutron diffraction technique. This cycloid has a

very long period of ca. 62  2 nm, and a propagation direction as [110]h (Figure

1.2a).36 This perhaps is the root cause why BFO does not generally exhibit

detectable magnetism in its bulk form or nanostructures in contrast with other

iron-based materials.

FEI Linfeng 8
CHAPTER 1 INTRODUCTION

The multiferroic nature of BFO is of marked distinction from the classic

theory in which ferroelectricity originates from the B-sites ion with d0 electron,

whereas the magnets require dj electrons (j0).8 Indeed, it is now generally

acknowledged that the polarization comes from the A-site Bi3+ lone pair 6s2

electrons that distort the system symmetry and hence, ferroelectricity while

magnetization stems from the B-site Fe3+ through antiferromagnetic coupling of

two adjacent crystal planes (Figure 1.2a). Although they arise from different

sources, a magnetoelectric coupling coefficient is established to be around 3

V/cmOe across a temperature range of 77-300 K.38

1.3.4 Phase Decomposition and Impurities

Figure 1.4 Compositional phase diagram of Bi2O3-Fe2O3 system.34

One major drawback in the research of BFO bulk and thin films would be

impurities and this also applies to the development of BFO nanostructures. In

practice, most studies have failed to synthesize single phase BFO samples without

generating secondary phase such as Bi25FeO39 and Bi2Fe4O9. The initial solution

FEI Linfeng 9
CHAPTER 1 INTRODUCTION

was to let it react with excess Bi2O3 followed by leaching with diluted nitric acid

to wash away the secondary oxides and residual Bi2O3.39 Scientists later declared

that the protective atmosphere such as argon and nitrogen during heating process

was of help to reduce the secondary phases.40, 41 It has been argued that BFO is

metastable in air with respect to Bi2Fe4O9 and Bi25FeO39 based on thermodynamic

factors (Figure 1.4).42 Hence, a decomposition process will be resulted as follows

49 BiFeO3  12 Bi2Fe4O9  Bi25FeO39 (1)

On the other hand, Bi2O3 is widely known to evaporate easily when heated at high

temperature. Thus, this will lead to the generation of iron-rich phases such as

Fe2O3 or even Fe3O434, 43

2 BiFeO3  Fe2O3  Bi2O3 (2)

12 BiFeO3  4 Fe3O4  6 Bi2O3  O2 (3)

In this situation, the properties of the sample, especially the magnetic

characteristics, will be strongly affected by these impurities. To minimize such

problem, careful optimization of growth parameters including thermaldynamic

and kinetic conditions would be required. Meanwhile, upon this circumstance,

reaction in hermetic systems or low temperature is evidently favorable in

obtaining phase-pure perovskite samples.

1.4 Synthesis of BiFeO3 Nanostructures via

Chemical Approaches

Traditional solid state reaction, which is grounded on oxides or carbonates of

metal components, was proved to be futile when applied to BFO system upon

thermal treatment around 800-830 °C. As discussed above, the preparation of

single-phase BFO is a highly critical task and in solid state reaction, the presence

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CHAPTER 1 INTRODUCTION

of impurity phase(s) in the final product seems inevitable.39 Most recently a ―rapid

liquid sintering‖ technique with a stoichiometric ratio of Bi2O3 and Fe2O3 as

starting materials was introduced to synthesize phase-pure BFO successfully. This

was achieved by rapidly heating the mixture of Bi2O3 and Fe2O3 to 1153 K

followed by 7.5 min of soaking time and rapid cooling to ambient temperature.44

However, such processes would require high sintering temperature, production of

coarse products and leaching in HNO3 to wash away unwanted oxides while

reproducibility remains low. Because of these shortcomings, new wet chemical

approaches have been found in facile synthesis of various BFO micro- and

nano-structures as these methods are highly controllable and tunable.

1.4.1 0D Nanoparticles

Current microelectronic companies obviously favorites to employ 0D

nanoparticles in their industrial designs and thus, a broad range of wet chemical

methods have been successfully utilized as synthetic approaches to generate BFO

0D nanoparticles in the past years. Among them, sol-gel method seems to be the

earliest and widest route employed worldwide, which involves dissolving bismuth

and iron salts (usually Bi(NO3)3 and Fe(NO3)3) in diluted acid to form solution,

adding chelating agents to form homogeneous polymeric precursor, ageing of the

precursor to get dried gel, and finally, heating the gel to yield nanoparticles. This

facile method exhibits a number of merits which can be delineated as (a) a mass

of nanoparticles with quasi-same sizes and properties can be produced, which are

originated from the uniformity of intimate mixing precursor at the molecular or

even atomic level, making doping of the system quite feasible; (b) the procedures

involved in the process are rather simple, resulting in high reproducibility; (c) the

sintering temperature required is definitely low with respect to solid state reaction,

thus, the approach is cost-effective; (d) the process is fairly controllable and

nanoparticles with tunable sizes can be regulated by varying sintering

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CHAPTER 1 INTRODUCTION

temperatures.45

Figure 1.5 XRD patterns of BFO powders (a) green (b) calcined at 400 °C (c)

calcined at 500 °C and (d) calcined at 600 °C and SEM micrograph of the BFO

powder after calcination at 400 °C.46

The most important variable in the sol-gel method would be the appliance of

chelating agents. During the sol-gel process of BFO nanoparticles, the chelating

agents are frequently chosen as carboxylic acids or occasionally as ethylene glycol

(EG). The species and quantities of chelating agents could strongly influence not

only the requisite sintering temperature but also the size and morphology of the

final product. Statically, oxalic acid,47 citric acid,48, 49 tartaric acid,46, 50, 51 ethylene

glycol (EG),50, 52, 53

poly(vinyl alcohol) (PVA),54 ethylenediamine tetraacetic

(EDTA)55, 56 etc. have all been used as chelating agents in various sol-gel systems.

For instance, Popa et al. synthesized BFO at 600 °C with citrate as chelating agent

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CHAPTER 1 INTRODUCTION

and EG as polymerizing agent.57 Ghosh et al. have reported the preparation of

BFO nanoparticles with their sizes tunable in the range of 3-16 nm, using tartaric

acid as chelating agent, and BFO crystallized into pure perovskite phase at 400 °C

(Figure 1.5).46 This is probably the lowest sintering temperature used in sol-gel

process on phase-pure BFO nanoparticles.

However, these sol-gel processes pose a number of limitations such as the

long synthetic duration (up to several days or even weeks), expensive raw

materials (especially some organic salts), and more importantly, the toxicity of

some emergent gases (such as NOx from the decomposition of metal nitrates)

along with large volume of contraction during the decomposition of chelating

compound. This has led to the search for other chemical approaches towards BFO

nanoparticles. For example, hydrothermal methods were applied extensively

either with or without surfactants to acquire BFO nanoparticles.58-65 In this type of

closed reaction system, the evaporation of Bi2O3 will be exhaustively prohibited,

and the crystallization temperature will be effectively decreased due to

autogenous pressure. Thus, the formation of perovskite BFO will be more

desirable. Cho et al. reported that with the aid of triethanolamine (TEA), pure

BFO nanoparticles could be synthesized at 130 °C.61 Luo et al. produced

SrTiO3-coated BFO nanoparticles via hydrothermal process by utilizing the pretty

surface activity of BFO nanoparticles in their system.58 Wang et al. argued that

alkali metal ions (K+, Na+ and Li+) played an important role in the selective

formation of a series of bismuth ferrite, namely rhombohedral BiFeO3,

orthorhombic Bi2Fe4O9 and cubic Bi12(Bi0.5Fe0.5)O19.5 by means of changing the

solubility of Bi3+ and Fe3+ hydroxides.60

Apart from hydrothermal process, co-precipitation method,66 molten-salt

assistant technique,67, 68
autocombustion approach,69-72 sonochemical route73, 74

and microemusion system74 have all been employed in synthesizing BFO

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CHAPTER 1 INTRODUCTION

nanoparticles even though some of them can only obtain nearly phase-pure

products and traces of secondary phases can be detected. Interestingly, a recent

work by Wu et al. announced a self-catalyzed fast reaction process, which

generated about 100 nm BFO ferromagnetic nanoparticles at RT compared with

traditional antiferromagnetic behavior.72 This study assumed the origin of the

unusual ferromagnetism corresponded to the point defects of oxygen vacancies

during the extremely fast exothermic reaction. Although the products displayed

visible impurities with much room for improvement, the possibility of room

temperature ferromagnetic and ferroelectric orders in pure BFO nanoparticles

creates a blueprint for strong magnetoelectric coupling and thus, device

applications.

1.4.2 1D Nanowires and Nanotubes

Since the discovery of carbon nanotubes by Iijima,75 1D nanostructures have

received great research interests. Based on 1D nanostructures and/or 1D arrays,

many revolutionary and promising areas continue to develop including

nanofabrication,76 nanodevices,77 nanobiology,78 and multiferroic BFO is of no

exception. A rapid-growing body of research has been devoted to the manufacture

and characterization of BFO 1D nanotubes and nanowires in recent years. The

first work was reported by Park et al. who used pressure-filter variation of a

template synthesis involving sol-gel techniques.79 They applied pressure on the

precursor sol grounded on porous anodic alumina template (AAO), followed by

calcination and immersion in NaOH solution in order to completely remove the

alumina template, leaving out the nanotubes into a pile which would otherwise be

impossible to characterize physically. Morphologically, the as-synthesized

nanotubes exhibited diameters of 200-300 nm with lengths up to 50 μm. In our

department, Zhang et al. utilized the nanochannel alumina template (NCA)

combined with a similar sol-gel technique and successfully synthesized BFO

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CHAPTER 1 INTRODUCTION

nanotube arrays, which would be much simpler for use and characterization.80 The

nanotubes possessed diameters of about 250 nm and lengths of about 6 μm

(Figure 1.6). The electrical measurement on this nanotube array gave a perfect

piezoelectric hysteresis loop and the array was proved to be ferroelectric.

Interestingly, BFO nanotube Y-junctions were discovered later by Li et al. while

conducting a similar process.81 Zhang et al. also fabricated highly ordered BFO

nanowire arrays using a kindred approach.82 Gao et al. continued their study and

measured the optical properties of random BFO nanowires,83 as further discussed

below.

Despite the ineluctable complex procedures, one major obstacle of serious

template-based synthesis is the complete elimination of the template after

annealing, which so far has been inadequate by using wet chemical etching. The

interdiffusion during the heating process has often led to certain amount of

amorphous content in the final products. Consequently, many other chemical

Figure 1.6 SEM images of the nanochannel alumina (NCA) template and BFO

nanotubes: (a) NCA template, (b) top view of the nanochannel porous alumina

filled with BFO nanotubes, (c) oblique view of BFO nanotube arrays, and (d)

XRD pattern of the BFO nanotube arrays.80

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CHAPTER 1 INTRODUCTION

routes were tested. Zhang et al. reported a facile polymer-directed solvothermal

route which caused BFO nanoparticles to aggregate into rod-like structures,

imposing upon the interaction between polymer moleculars.84 Xie et al. published

their results of nanocrystalline BFO nanofibers via a sol-gel combined with

electrospinning method although the pure perovskite phase seemed slightly

difficult.41

Nevertheless, there is a common defect in all existing approaches, i.e. all the

as-synthesized BFO 1D nanostructures are of polycrystalline nature. However, it

was once predicted that in its single crystalline 1D structures, the small diameter

of the products would significantly affect the ferroelectric critical temperature of

the ferroelectric state through the stress generated from the curvature; when the

ferroelectric critical temperature goes down to the magnetic one, the

magnetoelectric coupling can be enhanced by several orders of magnitude.85 So

the theoretical calculation still awaits experimental confirmation, and thus, would

be rather powerful in both fundamental and industry.

1.4.3 Complex Nanostructures

To meet the diverse demands in either technological or fundamental fields,

other approaches towards perovskite BFO complex nanostructures and even

architectures have been developed. Han et al. realized a tunable hydrothermal

synthesis of a large family of bismuth ferrites with various morphologies,

including sillenite- and perovskite-type compounds.86 Well defined

Bi12Fe0.63O18.945 crystals and nano- and submicrometer-sized BiFeO3 and Bi2Fe4O9

particles with different regular shapes have been obtained by carefully tuning the

hydrothermal parameters (Figure 1.7). Among those, single-crystal BiFeO3

spindles with their lengths of nearly 600 nm and thickness of about 300nm can be

selectively prepared (Figure 1.7D). Followed this, Chen et al. carried out

comparable reactions with focus on perovskite BFO, in which detectable

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CHAPTER 1 INTRODUCTION

impurities were found and the morphologies were of irregularity.87 Very recently,

Joshi et al.88 and Li et al.89 employed the microwave-assistant and hydrothermal

approaches to fabricate BFO cube-like structures, respectively, with their

objectives mainly on their optical properties which will be explained in the

ensuing chapters.

Similar to the work of Joshi and Li, core-shell concept has also been applied

to BFO. Luo et al. engineered SrTiO3-coated BFO core-shell structure

nanoparticles, which were roughly spherical and of about 100-200 nm in sizes, to

act upon their interests of sensitizing the SrTiO3 shell to visible light.58 Nan’s

Figure 1.7 SEM images of A) Bi12Fe0.63O18.945 (approx. pH 12, heating

temperature, Th = 180 °C); B) Bi12Fe0.63O18.945 (approx. pH 10, Th = 180 °C);

C) Bi12Fe0.63O18.945 (approx. pH 8, Th = 180 °C); D) BiFeO3 (Th = 200 °C); E)

Bi2Fe4O9 (Th = 180 °C); F) Bi2Fe4O9 (Th = 270 °C).86

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CHAPTER 1 INTRODUCTION

group made another choice of anatase titania-coated perovskite bismuth ferrite

heterostructures by using hydrothermal reaction followed by hydrolysis

precipitation processing.63

I would like to add here that compared with other counterparts of BFO such

as ceramics and thin films, few publications have devoted to its doped

nanostructures.73, 90-92 The use of intentional impurities, or dopants, to control the

behavior lies at the heart of many fields, especially on the application of

semiconductors.93 Through doping on A-site or B-site or both of them,

enhancements of multiferroicity of BFO nanostructures can be achieved.73, 90, 91

For example, reinforcement on the optical properties of BFO nanoparticles was

achieved through manganese doping.92 However, to my thinking, the relevant

experiments and theoretical studies regarding enhancement of various properties

should be strongly encouraged to meet the future practical applications.

1.5 Size Effects and Applications of

BiFeO3 Nanostructures

The application of various BFO nanostructures depends strongly on the

latter’s multifunctional properties, such as ferroelectricity, ferromagnetism,

magnetoelectric effect, gas sensing and optoelectronics, which all carry potential

for future generation nanodevices, e.g., memory devices, tetrahertz radiation,

spintronics and so on. Tests and characterizations of multifunction properties

inside diverse nanostructures are of primary importance so as to ultimately

integrate them as building blocks into modern nanotechnology. Grounded on a

solid base of studies that lasted over half a century, some interesting phenomena

and properties of BFO have been revealed. As more novel size-dependent or

morphology-dependent properties of BFO nanostructures are being discovered,

this implies that a certain ―property‖ may be tuned to desired value in future

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CHAPTER 1 INTRODUCTION

industrial designs. In this section, I will list a number of multifunctional properties

of BFO nanostructures that have been measured either macroscopically or

microcosmically, together with their size effects and ultimate application fields.

1.5.1 Ferroelectricity and Piezoelectricity

Figure 1.8 Piezoelectric hysteresis loop of a single BFO nanotube measured by

piezoresponse force microscopy.80

As discussed in the previous part, the large intrinsic polarization of BFO has

been confirmed both theoretically and experimentally through results obtained

from high-quality ceramics, thin films and single crystals, and recently verdicts

from nanostructures have been highly demanded. In 2005, Dr. Dai’s group in AP

demonstrated the ferroelectric characteristics of the BFO nanotube arrays by

measuring the piezoresponse d33 hysteresis loop of an individual nantube (Figure

1.8).80 The experiment was carried out using a conductive atomic force

microscope tip and a lock-in amplifier, with a 16.5 kHz ac electric field and a

swept dc voltage. The decrease in d33 at high electric field (Figure 1.8) is believed

to be a result of the field-induced lattice hardening. Subsequently, BFO nanorods

were fabricated using a sonochemical technique and their electric field hysteresis

loops (P-E) were measured by the modified Sawyer-Tower circuit at a 1 kHz ac

frequency on a 5 mm diameter pellet with sputtered gold as top electrode and

silver paste as bottom electrode.73 At a maximum applied electric field of  500

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CHAPTER 1 INTRODUCTION

V/cm, there was no saturation of polarization. The remnant polarization (Pr) was

0.21 mC/cm2 and the coercive field (Ec) was 155 V/cm. The reported Pr value is

much less than that reported in case of BFO nanoparticles and thin films, but

higher than that observed in case of bulks.

To everyone’s astonishment, as a well-known RT multiferroic material, the

first application of BFO which may be available in the market focuses on its

ferroelectricity and piezoelectricity rather than its multiferroicity. The remnant

polarization of BFO is extremely large, over 100 μC/cm2 along the [111]c

direction. This value represents the largest switchable polarization among all

perovskite ferroelectrics, and is almost twice as large as that of PZT, which is now

most widely used in commercial ferroelectric memories.34 Another crude

advantage of BFO compared with PZT is the lead-free nature, an important factor

for health and environmental concern. Therefore it would be reasonable for

ferroelectric memories manufacturers such as FUJITSU (Japan) to regard BFO as

the unchallengeable candidate for ferroelectric capacitor in their next generation

ferroelectric random access memories (FeRAM) in a 90-nm technology node and

beyond.94 However, apart from the achievements of ultra large remnant

polarization (90-110 μC/cm2) together with low leakage current level (10-4 A/cm2)

by FUJITSU R&D teams, few obscure flaws may need to be fixed to make BFO

more practical such as its decomposition under voltage stressing43 and tendency to

fatigue in certain direction.95

1.5.2 Magnetism and M-E Coupling

As discussed earlier in this chapter, BFO is a commensurate ferroelectric and

an incommensurate antiferromagnet at RT. In contrast to its strong ferroelectricity,

the antiferromagnetic behavior of BFO seems rather complicated because of

Dzyaloshinsky-Moriya interaction which results in a long-wavelength (62 nm)

spin spiral.35 Thus, for bulk BFO, the magnetic hysteresis loop exhibits a typical

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CHAPTER 1 INTRODUCTION

antiferromagnetic curve with zero coercivity.69 Consequently, the linear M-E

coupling effect also averages to zero. Driven by breaking the spiral-modulated

spin structure and hence, recovering the linear M-E coupling, many methods have

been adopted since 1990s including application of large magnetic fields up to 20 T,

chemical doping, and induction of thin film constraints.22 As the new century

unfolds, the newly emerging nanotechnology on BFO recommended a facile and

inexpensive approach by controlling its dimensions down to 62 nm. This would

bring a distinctive enhancement in both ferroelectric and magnetic polarization

due to the combined action of exchange and spin-orbit interactions that produces

spin canting.52 As a result, more and more publications have contributed to this

domain in order to discover the nature of size-dependent magnetism and M-E

coupling in various BFO nanostructures,70, 73, 83, 89

in particular nanoparticles

smaller than 62 nm.49, 52, 64, 66, 69, 96-99

Park et al. reported their systematical studies on size-dependent magnetic

properties of single-crystalline BFO nanoparticles in 2007.52 They noted that the

magnetic properties of BFO nanoparticles with a mean size of 245 nm

experienced a remarkable similarity to that of the bulk sample which was not so

highly significant. When the size of the system is less than 95 nm, the magnetic

response can be initialed whereas the magnetic response of BFO nanoparticles

increased rapidly in the range of 270-460% for sample below 62 nm.

Superparamagnetism of 14 nm nanoparticles was also detected in their

experiments. Combined with their Mössbauer study, it is believed that the increase

of magnetization along with the decreasing particle size is primarily due to the

contribution of uncompensated spins at the surface, strain anisotropies, and

noncollinear magnetic ordering, leading to frustrated spin systems in addition to

an increased suppression of the material’s intrinsic spiral structure below a certain

threshold value of particle size. Moreover, their Raman results correlated with the

decreasing size attributes the enhanced coupling of magnetic, ferroelectric, and/or

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CHAPTER 1 INTRODUCTION

structure order parameters to size confinement and accompanying lattice

distortions.

More recently, signatures of spin-phonon and M-E coupling were also found

in ~50-60 nm BFO crystallites.100 Wu et al. announced the strong ferromagnetism

at RT of ~100 nm BFO nanoparticles via a self-catalyzed low temperature fast

solid state raction.72 They stated that the finding can be attributed to the effect of

point defects associated with oxygen vacancies, which may require further

verification. Combined with the results of upper observations, these are promising

results with respect to the feasibility of making small multiferroic devices basing

on strong M-E coupling in BFO nanosystem.

In addition, as nanotechnology progresses with each passing day, novel BFO

nanostructures were also magnetically investigated. Polycrystalline nanowires

exhibit a weak ferromagnetic order at RT which may be resulted from the

significant spin relaxation of the spatially modulated antiferromagnetic

configuration.83 BFO microspheres and micro-/submicro- cubes were compared

magnetically and the former exhibited slightly larger magnetization at low

temperature (5 K).89 The magnetic and M-E coupling properties in BFO

nanostructures would of significant assistance to meet the original motivations

behind most of the applied research on this material, such as spintronics,101 chief

among those would be memories which can be written using a voltage and read

using a magnetic field.

1.5.3 Photocatalytic Behavior

Research on semiconductor photocatalyst was initially fueled and promoted

by the discovery of TiO2 photochemical electrodes for splitting water under the

luminescence of ultraviolet light in 1972 (Honda-Fujishima Effect).102 During the

following years, extensive and comprehensive studies have been carrying out in

search of a highly efficient, low cost and nontoxic photocatalyst with excellent

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CHAPTER 1 INTRODUCTION

photochemical stability. For large-scale practical applications, it is gradually

emphasized that the active region of the photocatalyst should be planned at

visible-light wave band, to maximize the utilization of natural light.

Recently, scientists begin to take notice of BFO as one of their potential

candidates. Its great optical performance originates from its small bandgap,

nontoxicity and good chemical stability during the photocatalytic process when

compared with other narrow bandgap semiconductors such as CdS.58 The reported

values of bandgap for BFO at RT range from ~2.2-2.8 eV.103-108 According to

certain authors, this bandgap is direct,107, 108 while other argue that an indirect one

is present which is roughly 0.4-1.0 eV smaller than the direct bangap.104, 105 After

the introduction as visible light sensitizer in SrTiO3 system for water spliting,58

further studies have taken place in BFO by utilizing various nanostructures to

improve its visible light photocatalytic property.46, 63, 64, 88, 89

Since their discovery of photo-induced oxidization ability for polycrystalline

nanowires to produce O2 in AgNO3/H2O system with considerable efficiency,83

Prof. Liu’s group was inspired by the thought that BFO nanostructures might be

useful for photocatalytic decomposition of organic contaminants, who soon

published their work on the degradation of Methyl Orange by BFO

nanoparticles.53 Although a trace of impurities can be identified in their XRD

patterns, as-synthesized BFO nanoparticles (80-120 nm, bandgap 2.18 eV)

presented significant enhanced visible light induced photocatalytic ability than

that of bulk sample with outstanding photochemical stability. On top of that,

various BFO nanostructures were characterized to confirm their photocatalytic

activity. Nanocubes from microwave synthesis88 and microcrystals via

hydrothermal reaction89 were successively proved to possess useful activity under

visible light irradiation. In order to bring new insight into the design of highly

efficient photocatalysts, anatase TiO2 coated BFO core-shell nanocomposites were

FEI Linfeng 23
CHAPTER 1 INTRODUCTION

synthesized and tested to possess good visible-light adsorption properties which

should be induced by Fe or Bi/Ti interdiffusion in the interfaces.63 Hence, the

BFO/TiO2 nanocomposites show good photocatalytic activities in visible-light

region, which should be ascribed to the increase in the charge separation rate.

Furthermore, the fascinating size effect of photocatalytic behavior was

recently studied by Li et al. using BFO nanoparticles with different sizes (Figure

1.9).64 Their results strongly support that an increase in the bandgap of the

crystallites with a reduced particle size and the photocatalytic activity can be

dramatically enhanced by decreasing the particle size.

Figure 1.9 (A) UV-Vis diffuse reflectance spectroscopy of BFO with different

particle sizes. The inset shows the energy band gap of BFO samples as a

function of particle size. (B) Photocatalytic properties of various BFO samples

for degrading CR solution under visible-light irradiation.64

1.5.4 Other Characteristics

Because of its popularity and continuous development, more and more new

properties of BFO nanostructures have been identified, and undoubtedly, some are

still remaining waiting. In this section, I will shortly mention two newly

developed properties and applications concerned with BFO nanostructures.

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CHAPTER 1 INTRODUCTION

1.5.4.1 Gas Sensor

Perovskite oxides have long been regarded as promising candidates for gas

sensors due to their higher stability and reliability when compared with other

popular simple metallic oxides such as WO3, SnO2 and ZnO, especially when

working under a humid environment.109 Taking BFO into consideration, Yu et al.

in our group, reported the excellent gas-sensing properties of its nanoparticles for

the first time.51 It was found that BFO nanoparticles are surprisingly sensitive to

several organic gases (e.g., acetone and alcohol) with an ultra low detection limit,

rapid response, fast recovery as well as good selectivity.

1.5.4.2 Heterogeneous Catalyst

In organic synthesis, the acylation of alcohols, phenols and amines is one of

the most useful and versatile transformations.110 Among them, protection and

conversion of hydroxyl or amino group into the corresponding acetate or

acetamide is essential for its medical applications.71 Conventional ways of

acetylation of alcohols and phenols or amines are usually performed with the help

of certain homogeneous catalysts,111, 112 which present a number of drawbacks.

This results in the development of facile process using heterogeneous catalysts

under solvent-free conditions in terms of economical and environmental

feasibilities.113

In 2009, after preparing ~42 nm BFO nanoparticles via combustion method

using sucrose as a fuel, Farhadi et al. employed as-synthesized nanoparticles as

reusable heterogeneous catalyst in their acetylation reaction under solvent-free

conditions.71 Efficient and selective acetylation of various amines, alcohols and

phenols was carried out over BFO nanoparticles by using acetic anhydride and/or

acetyl chloride as the acetylating agents at RT under solvent-free conditions. This

method was proved not only highly chemoselective, but also efficeient, high

yielding, clean, safe, and cost-effective. It is also compatible with substrates with

FEI Linfeng 25
CHAPTER 1 INTRODUCTION

other functional groups and is very suitable for practical organic synthesis.

1.6 Motivations of the Project

Upon the systematical literature review and overlook of what has been done

in the studies of BFO nanostructures as above, it can be concluded that it is both

theoretical and experimental interest together with application perspectives which

draw scientists’ attention in this specific domain. Hence more than many efforts

have been contributed to seek the applicable synthetic approaches to various BFO

nanostructures and try to open up the abundant connotations, either physically or

chemically, so as to satisfy the final device integration. However, in despite of

significant progress achieved on controllable synthesizing of diverse

nanostructures, a few basic issues on this unique material are still regarded to

deserve further addressing in our opinion. For instance, as for the most attractive

BFO nanoparticles, it is yet of challenge to gain pure phase samples, while fine

controlling of dispersity and uniformity is remained quite a blank. Intensive

investigations are highly requested to develop more novel nanostructures, in order

that the structure-property relationship can be understood in-depth. Few if any

attempt has been carried to comprehend the growth mechanism and function of

process parameters inside most synthetic approaches. Much more useful

properties are expected to be recognized or enhanced to expand the practice

ranges of BFO nanostructures.

To try to overcome these obstacles, we must perform some experiments to

designedly synthesize varieties of novel BFO nanostructures, with our special

concentration on phase and morphology controlling, together with the relevant

size effect in their physical and chemical properties. These experiments may

reveal the fundamentals of BFO nanostructures and help to further understand

BFO-based systems, even provide sufficient guidance to the designedly synthesis

FEI Linfeng 26
CHAPTER 1 INTRODUCTION

of other perovskite oxides. In this project, the following chemical approaches are

introduced in the fabrications of BFO nanostructures, which are directly

motivated by the above problems.

[1] To the most interested BFO nanoparticles, it is definitely of prime importance

to optimize the synthesis strategy so as to obtain uniform and well-dispersed

phase-pure crystallites. Thus we selected here the most widely-used sol-gel

method as an example; in order to facile harvest BFO nanoparticles with

tunable sizes.

[2] More novel nanostructures are expected by scientists to meet the future

diverse application demands, and the related physical and chemical properties

should be thoroughly studied. In this project, we tried other chemical methods

such as electrospinning technique and hydrothermal reaction, aiming to

produce fascinating structures based on comprehensive recognitions of their

formation mechanisms.

1.7 Scope of the Work

The overall objective of this thesis is to fully study the chemical approaches

and the resulted BFO nanostructures by means of structural characterizations and

property measurements, as well as trying to understand the chemical process and

mechanism during fabrication.

Chapter 1 is mainly literature review which gives a brief introduction on

perovskite oxides, fundamentals of BFO and recent synthetic contributions on

BFO nanostructures.

Chapter 2 briefly describes the chemical synthetic approaches that have been

employed in this study, including sol-gel method, electrospinning technique and

hydrothermal reaction. Information about structural characterization techniques

FEI Linfeng 27
CHAPTER 1 INTRODUCTION

and measurement setups is also given in this chapter.

Chapter 3 presents the synthesis of bismuth ferrite via a facile sol-gel method.

We carefully optimized the synthesizing process, in pursuit of a lower

crystallization temperature involved in the method, and the well uniformity

together with dispersity. This section concludes with a study of interesting

size-dependent magnetic phenomena.

Chapter 4 exhibits experiments on the sol-gel based electrospinning process

to the generation of continuous BFO nanofibers. We realized a non-protective

synthesizing of pure BFO nanofibers. And significant piezoresponse from an

individual nanofiber is also shown in this part.

Chapter 5 mainly concerns about our comprehensive study of the

hydrothermal approach to novel BFO 3D crystallites. With variation of the

reaction parameters, we achieved a controllable synthesis of BFO microcrystals

with different dominant facets. Despite the thoroughly understanding of their

formation mechanism, the morphology-dependent visible-light responses of

as-synthesized crystallites were explored respectively.

We make a conclusion of the whole thesis in Chapter 6 with the important

results and achievements attained in the present investigation, and some future

perspectives are suggested on BFO as well as other perovskite oxides.

FEI Linfeng 28
CHAPTER 2 RESEARCH METHODOLOGY

CHAPTER 2
RESEARCH METHODOLOGY

The realization of our objectives lies on a number of professional synthetic

methods and characterization facilities, which can be generally categorized into

the following four groups:

I Sample preparation techniques: sol-gel method, electrospinning process and

hydrothermal method.

II Structure characterizations: X-ray diffraction (XRD), scanning electron

microscopy (SEM) and transmission electron microscopy (TEM).

III Thermal analysis: thermogravimetric analysis & differential scanning

calorimetry system (TG-DSC).

IV Electrical, magnetic and optical measurements: piezoresponse force

microscopy (PFM), vibrating sample magnetometer (VSM) and UV/Vis-NIR

spectrophotometer.

This chapter will give a brief introduction of these techniques and facilities,

and the background theories of these methods will also be stated one by one.

2.1 Sample Preparations

In pursuit of BFO nanostructures with diverse morphologies, I selectively

employed homologous chemical approaches for satisfaction, which included

sol-gel method, electrospinning process and hydrothermal reaction. The basic

principles and experiment procedures of these approaches are outlined as below.

FEI Linfeng 29
CHAPTER 2 RESEARCH METHODOLOGY

2.1.1 Sol-gel Method

As the merits and drawbacks of sol-gel method have been discussed in

section 1.4.1 along with its appliance in BFO system, I will just illuminate it here

with a short introduction.

Figure 2.1 Flowchart of multiple applications of sol-gel method.

Sol-gel method is a wet chemical approach which has been widely used in

the fields of material science and ceramic engineering in recent years. The

appliance of such method primarily aims to synthesize functional materials

starting from a chemical solution (sol) that acts as the precursor for an integrated

network (gel) of either discrete particles or polymer networks. Generally, the

precursors are metal alkoxides or inorganic salts, which experience certain

hydrolysis and polycondensation process to form either a metal-organic network

or a colloidal suspension – a system composed of discrete fine particles and a host

of liquid. Consequently, the precursor sol can be deposited on a substrate to form

a film, poured into a given container (for fabrications of monolithic ceramics,

fibers, membranes and aerogels) or used to synthesize micro-/nano-sized particles,

as schemed in Figure 2.1.

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In the case of metal oxide particles, apart from metal salts and solvents, the

precursor sol should also involve chelating agent as an important role, which

bridges the metal ions to form a metal-organic complex in solution. The

employment of the chelating agent would make the solution not only stable but

also homogeneous. After an ageing process, the sol evolves to a diphasic gel

system (liquid and solid phases). The formation of oxide particles requires a

further drying (even sintering) to completely remove the liquid phase and

crystallize into desired particles, which is typically accompanied by a significant

amount of shrinkage and densification.

2.1.2 Electrospinning Process

Figure 2.2 (a) Sketch of deposition principle of electrospinning; inset refers to

the formation of Taylor cone; (b) image of our electrospinning setup in lab.

At first glance, electrospinning is perhaps the only technique which allows

the production of continuous 1D structure with diameter down to several

nanometers.114 This method was originally utilized to the fabrication of either

natural or synthetic polymers, however, recent efforts have made it possible to

generate nanostructures of metals and ceramics.115 The scope of its applications,

in fields as diverse as optoelectrics, sensors, catalysis, filtration and even medicine

delivery, is such broad.

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As shown in Figure 2.2, the whole setup of electrospinning impresses so

facile and controllable. In a typical assembly, a precursor solution is pumped

through a thin metallic nozzle with its inner diameter on the orders of 100

micrometer. The nozzle simultaneously works as a positive electrode which is

connected to a high-voltage dc source, and the counter electrode which also works

as sample collector is grounded and placed in a distance of 5-30 cm. Meanwhile,

the electric field between two electrodes is adjusted in the range from 100-3000

kV/m. In most cases, in order to feed the solution at a programmed rate, a syringe

pump is also combined with the system.

During the electrospinning process, firstly, a liquid droplet becomes charged

when a sufficient strong electric field is applied, thus the electrostatic repulsion

counteracts the surface tension and the droplet is gradually stretched. At a critical

point (which is named as Taylor cone, refer to inset of Figure 2.2a), a stream of

liquid erupts from the surface. Due to the high molecular cohesion of the liquid, a

charged liquid beam can be launched and consequent dried out itself during flight,

until it finally deposits on the grounded collector. There are a great set of

parameters which play significant roles in the whole process, i.e. property of the

solution (viscosity, conductivity and surface tension), distance between the nozzle

and collector, the electric potential, feeding rate and ambient parameters

(temperature, humidity and air velocity in the chamber). And additionally, the

motion of collector can also have an important impact. Despite the simple setup

and operation of electrospinning, the mechanism behind is rather intricate and is

still being argued vehemently. In the present posture of ceramic fibers, it has to

rely on the use of spinnable precursors which should contain polymeric

component so as to increase the viscosity. We can generally divide the typical

experiment into 3 steps: (i) Preparation of a precursor solution containing a matrix

polymer and alkoxide or inorganic salt. (ii) Electrospinning the solution and hence

produce composite nanofibers composing of the matrix polymer and precursor. (iii)

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Calcination, sintering or chemical conversion of the precursor into the desired

ceramic nanostructures at an elevated temperature, that is, completely removal of

all organic components from the precursor fibers as well as crystallization.

2.1.3 Hydrothermal Reaction

Figure 2.3 (a) Sectional view of a hydrothermal reaction autoclave: (1)

stainless steel autoclave, (2) precursor solution, (3) Teflon liner, (4) stainless

steel lid and (5) spring; (b) a series of autoclave with different capacities in our

lab.

Due to the incomparable merit brought by the mild reactive conditions in a

single step, hydrothermal reaction has been extensively utilizing for the synthesis

of various compounds such as oxides, sulfides, halides, zeolites and other

microporous solids since its pioneering works from 1960s to 1980s.116 Recently,

scientists particularly focus on its effective application of synthesizing many

micro-/nano-sized crystals with specific size and shape.117-119

The apparatus for hydrothermal reaction is so simple and cheap, which

consists of a steel pressure vessel named autoclave (as shown in Figure 2.3). In

order to carry out chemical reactions, the stainless autoclave requires a suitable

liner which is practically determined as Teflon. This polymer exhibits its unique

superiority as excellent resistance to chemical reaction, corrosion, and stress

cracking even at high temperature. On the other hand, as the temperature rises

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during the hydrothermal reaction, the Teflon liner expands and hence hermitic

sealing can be obtained.

General procedure of a hydrothermal reaction starts from the preparation of

precursor solution. Then the solution is transferred into the Teflon liner and sealed

in the autoclave. During hydrothermal reaction, the evaporating solvent generates

a pressure inside the sealed vessel at a temperature beyond its boiling point, and

this pressure, due exclusively to the refluxing solvent, is always called as

―autogenous‖ pressure. Consequently, the autoclave is cooled down and thus the

pressure is released. The as-synthesized powder is washed to get rid of ions in the

solvent and any possible impurities. Finally, the well-crystallized product can be

harvested after drying in the air. We must add here that the reaction pressure is

determined not only by temperature but also the degree of precursor filling.

What’s more interesting and challenging is the mechanism inside this ―small‖

autoclave. Generally speaking, the basic mechanism can be understood either by a

―dissolution/precipitation process‖ or an ―in-situ transformation process‖.116

Sequentially, dissolution/precipitation process involves dissolving the reactant

particles, supersaturating the solution phase, and eventually precipitating out the

product crystals. All these reactions are driven by the difference in solubility

between the least soluble reactant and the objective product. In some cases,

mineralizer such as KOH should be added because of the extremely low solubility

of some reactants, otherwise product will form via another in-situ transformation

process. However, the accurate mechanism of specific reaction remains such a

blank due to the poor available data of supercritical region of water-based system.

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2.2 Structure Characterizations

2.2.1 X-ray Diffraction (XRD)

The as-synthesized sample should be well prepared for X-ray diffraction

(XRD, Bruker D8 Advance) measurement, where Cu-Kα radiation (λ=0.154 nm)

is used and usually operates at 40 kV/40 mA. In our experiments, all XRD

patterns were recorded by the θ-2θ scanning mode while 2θ ranged between

20-85°at a step-width of 0.05°and 1 sec/step.

XRD technique is now commonly utilized in the analytical characterization

to gain crystallographic information of crystals. The main function of the

instrument concentrates on the determination of phase structure. Since each

material possesses its own unique XRD spectra, as a result, qualitative and

quantitative analysis can be conveniently conducted by comparing the as-obtained

XRD profile to the standard database. After simple calculations, a wealth of

information, such as lattice parameter and particle size, can be also extracted.

Figure 2.4 Schematic diagram of the typical arrangement of a XRD working

under θ-2θ scanning mode.

Figure 2.4 schemes a typical arrangement of θ-2θ XRD system. The X-ray

tube irradiates an X-ray beam towards the sample, while the sample and the

detector rotate slowly in the same direction, at a speed of θ and 2θ, respectively.

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And hence, the detector records the reflected counts from the sample at each step

to produce the diffraction spectrum. Basically, the diffraction follows the famous

Bragg’s law,

nλ=2dhklsinθ

where n is an integer, λ is the wavelength of the X-ray, dhkl is the lattice spacing

between (hkl) planes and θ is the angle between incident beam and (hkl) plane.

2.2.2 Scanning Electron Microscopy (SEM)

Figure 2.5 Sketch of electron beam–sample interactions under SEM and TEM.

The morphology and size of the as-synthesized samples can be determined

by scanning electron microscopy (SEM, JEOL 6335F Field Emission System,

usually works at an accelerating voltage of 15 kV). The powder or bulk sample is

simply fixed on a flat holder by conductive rubberized fabrics, and then, a thin

layer of gold particles is deposited onto the sample to enhance its conductivity

before SEM observation. By scanning the sample with an energetic electron beam

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in a raster scan pattern, SEM can image the surface of the sample with extremely

high resolution.

During the scanning process, the electrons strike the sample surface which

makes the sample producing signals that contain information about the surface

topography, chemical composition and other properties. As shown in Figure 2.5,

the reactions occur on the top side are utilized under SEM while the reactions on

the bottom side are generally examined under transmission electron microscopy

(TEM, as discussed in the following section). Firstly, the productions of

backscattered electron (BSE) and secondary electron (SE) are exceedingly

topography related. They enable the imaging of the morphology of the sample,

with great depth of field, at either low or high magnifications. The difference

between BSE and SE is noted as that, the BSE is more sensitive to the sample’s

atomic number. Secondly, after the production of each SE, the atom of the sample

would de-energize and thus emit X-ray. Meanwhile, the X-ray is so characteristic,

which is unique to the element from which it originated, and hence can be

collected and sorted to obtain the information of specimen’s composition.

2.2.3 Transmission Electron Microscopy (TEM)

Prior to TEM investigations, our powder samples need to be dispersed to

ethanol and fixed on a copper-support ultra-thin carbon film. Similarly but

furthermore, transmission electron microscopy (TEM, JEOL 2011, works at 200

kV) is a powerful analytical technique on microstructure investigation whereby an

electron beam transmits through an ultra-thin sample, and interacts with the

sample as it passes through. With the aid of a series of sophisticated

electromagnetic lens, the signals brought by the interactions can be either utilized

to form a magnified image with its resolution up to a few angstroms, or

transferred into an electron diffraction spectrum to determine the microscopic

crystallographic structure at such a fine scale, which is sketched in Figure 2.6.

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We now go back to Figure 2.5; the amount of transmitted unscattered

electrons is inversely proportional to the specimen thickness and atomic number,

thus can be used to generate the morphological mass-thickness contrast image,

either bright field or dark field. Since all elastically scattered electrons follow

Bragg’s law, and thus all incident electrons that are scattered by the same atomic

spacing would be scattered by the same angle. And these electrons with ―similar

angle‖ can be collated to form a pattern of spots, whereby each spot

corresponding to a specific atomic spacing, and hence yield information about the

orientation, atomic arrangement and phase. Finally, the in-elastically scattered

electrons can be gathered to extract both compositional and bonding information

in the area being examined, by accessories such as electron energy loss

spectroscopy (EELS).

Figure 2.6 Sketch of image and diffraction mode within TEM arrangement.

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2.2.4 Thermal Analysis

Thermal analysis is a wide branch of materials science where the properties

of materials are investigated as they change with temperature; among them,

Thermogravimetry (TG) and Differential Scanning Calorimetry (DSC) are invited

in our project for analytical purpose. TG is generally used to determine the

amount and the rate of weight change in a material as a function of temperature,

or time, in a controlled atmosphere, while DSC is employed to determining the

quantity of heat that is either absorbed or released by a substance undergoing a

physical or a chemical change.

The simultaneous application of TG and DSC to one and the same sample in

a single instrument provides much more information than separate measurements

due to the perfectly identical test conditions (TG-DSC, NETZSCH STA 449 C

Jupiter®). By the combination of TG & DSC, the analyzability of the signals is

greatly improved since two sets of information concerning sample behavior are

always synchronous available (same atmosphere, gas flow rate, vapor pressure of

the sample, heating rate, thermal contact to the sample crucible and sensor,

radiation effect, etc.).

2.3 Property Measurements

2.3.1 Piezoresponse Force Microscopy (PFM)

Under atomic force microscopy (AFM) as that in Figure 2.7a, the

information such as 3D surface topography is gathered by simply ―feeling‖ the

surface with a mechanical probe by means of monitoring the actions of the

scanning tip with a laser beam. Furthermore, as the most important variant of

AFM, piezoresponse force microscopy (PFM, Veeco Multimode SPM system with

Nanoscope IV controller) allows directly imaging and manipulation of

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ferroelectric domains from relatively large area i.e. 100100 μm2 down to the

nanoscale.

Figure 2.7 (a) Block diagram of atomic force microscopy (AFM); and (b)

piezoresponse of parallel and anti-parallel domains under piezoresponse force

microscopy (PFM).

The objectives of PFM are realized by bringing a sharp conductive tip into

contact with a ferroelectric surface and adding a swept alternating current (AC)

bias to the conductive tip so as to excite the deformation of the sample via the

converse piezoelectric effect. As sketched in Figure 2.7b, top line exhibits an

in-phase piezoresponse to the driving voltage while the bottom line shows a 180°

out-of-phase one. From the definition of piezoelectric effect, the alignment of

electric field (E) and polarization orientation (P, top right) results in an expansion

of the domain, which gives a positive deformation as measured by the standard

split photodiode; when the bias is negative the domain contracts and thus gives a

negative deformation as measured meaning that the piezoresponse will always be

in-phase with the applied voltage. Contrarily, the anti-alignment of E & P as that

schemed in bottom right, a positive bias results a contraction of the domain and

hence gives negative deformation as measured by the photodiode therefore the

piezoresponse is 180° out-of-phase with the driving voltage. The resulting

deformations of the probe as the domain are further modulated by using a

lock-in-amplifier, and so, the surface topography and the ferroelectric domains

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can be recorded simultaneously within high resolution. Quantificationally, the

polarization value of domain can be simply calculated by

P=A•cosθ

where P refers to polarization, A refers to amplitude and θ refers to phase.

2.3.2 Vibrating Sample Magnetometer (VSM)

The magnetic behaviors of the sample were characterized by a vibrating

sample magnetometer (VSM, LakeShore 7407) combined with a liquid helium

cryostat (model 74018) which can reduce the temperature of the sample down to

almost 4.2 K.

In this test, the sample is vibrated with a sinusoidal motion while a known

external magnetic field H is applied with its frequency (ω), thus the change of

magnetic flux in the sample induced a voltage in the pick-up coil, which follows

the Faraday’s law,

V = -N = -NA = -NAμ0 (H+M)

where Φ refers to the magnetic flux through the coil; A and N are the area and

number of the coil, respectively; V is the induced voltage; B is the magnetic field

of the sample, μ0 is the vacuum permeability, and M is the magnetization. Hence,

the output voltage can be directly converted into magnetic moment of the sample,

on the basis of calibrating our system with a reference.

2.3.3 UV/Vis-NIR Spectrophotometer

Ultraviolet/visible-near infrared spectrophotometer (UV/Vis-NIR, Shimadzu

SolidSpec-3700DUV) refers to instruments which can read out absorption

spectroscopy in the ultraviolet-visible-near infrared spectral region. Practically,

we use the UV-Vis frequency range in our experiments, and we directly measure

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the diffused reflection behavior of as-synthesized powders. However, for the

convenience of analysis, the diffused reflection spectra have been transformed

into the absorption ones based on the well-known Kubelka-Munk theory.120

The spectrophotometer simply measures the intensity of light passing

through a sample (I), and compares to the intensity of light before it passes

through the sample (I0), the absorbance (A) of the sample can be calculated based

on the Beer-Lambert’s law,

A=-log =ε•c•l

where ε stands for extinction coefficient, c is concentration of the absorbing

species, and l refers to the pathlength through the sample.

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CHAPTER 3
LOW TEMPERATURE SYNTHESIS OF BiFeO3
NANOPARTICLES BY MODIFIED SOL-GEL METHOD

Sol-gel method is of vital importance both fundamentally and practically in

the study of BFO nanostructures, brought by its large-scale production ability and

relatively facile industrial processes. Learning from the literatures as in section

1.4.1, it seems that weaker chelating agents, such as tartaric acid and EG, can

make the fabrication of BFO nanoparticles (NPs) much easier in a sol-gel

approach. In this chapter, we optimized this excellent wet chemical route so as to

synthesize nanoparticles of multiferroic bismuth ferrite with narrow size

distributions and good uniformity, by using bismuth nitrate and iron nitrate as

starting materials and excess tartaric acid and citric acid as chelating agent,

respectively, followed by thermal treatment. It was found that BFO NPs

crystallized at ∼350 °C when using citric acid as chelating agent. Such

crystallization temperature is much lower than that of reported chemical process

in which other types of chelating agent are used. BFO NPs with different sizes

distributions show obvious ferromagnetic properties, and the magnetization is

increased with reducing of the particle size.

3.1 Introduction

The interest on BFO in the past few years was initially fueled by Wang et al.

with their exciting results from perfectly epitaxial thin-films,4 and this business

was further promoted by fruitful achievements from high quality single-crystals.16,

17
However, among current febrile atmosphere of BFO investigations, more and

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more concentrations are devoted to polycrystals as well as substrate-free

nanostructures such as low-dimensional nanostructures, especially

zero-dimensional structures like NPs.51, 55, 59, 68, 121, 122 Meanwhile, studies on finite

size effect of BFO have been carried out by different groups and some interesting

properties (e.g., shift of Neel temperature, lattice parameters, etc.) have been

revealed.52, 61, 64, 66

Previous studies have demonstrated that synthesis of BFO NPs through a

traditional solid-state method produces poor reproducibility and causes formation

of coarser powders as well as Bi2O3/Bi2Fe4O9 impurity phase.44 Up to date,

several chemical routes (e.g. hydrothermal treatment, mechanochemical synthesis

method, and microemusion methodology, etc.) have been successfully employed

for fabricating BFO nanoparticles. However, these approaches have certain

shortcomings such as impurities in the final products. Ghosh et al. reported a

ferrioxalate precursor method to synthesize BFO NPs through solutions of some

specific salts at a temperature of 600 °C.47 Despite the efforts made through

enhancing sintering temperature to avoid impurities, a small amount of Bi2O3 was

found in the final product. Han et al. have accomplished the morphologies tunable

synthesis of bismuth ferrites using a hydrothermal method;86 the resulting size of

BFO NPs was sometimes large (up to several hundred nanometers) although no

impurities were found in the final products. Using the same method, Chen et al.

prepared pure phase BFO nanocrystallites at 200 °C using KOH concentration of

4 M. In this study, impurity phases of Bi2Fe4O9 and Bi25FeO40 were easily formed

with only a slight change in the KOH concentration.87 Selbach et al. synthesized

BFO NPs through a modified Pechini method using nitrates as metal precursors.98

Although pure phase BFO was obtained in this study, contaminant produced by

decomposition of the precursor was present. Ghosh et al. synthesized nanosized

bismuth ferrite using a soft chemical route with tartaric acid as a template material

and nitric acid as an oxidizing agent.46 However, the crystallinity of the resulting

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BFO NPs was unsatisfactory and the existence of an impure Bi2O3 amorphous

phase in the host at low temperature product of 400 °C was evident. To deal with

the issues mentioned above, our recent research suggests that excess tartaric acid

and/or citric acid to be added in the solution so that the crystallinity of BFO NPs

can be improved as presented in this chapter. Herein, we demonstrated a general

wet chemical route for synthesizing uniform BFO NPs at about 350 °C. To our

best knowledge, this is the lowest temperature employed in the literatures for BFO

fabrication with the exception of certain high pressure techniques such as

hydrothermal or solvothermal methods. In addition, the magnetic properties were

also investigated for BFO NPs with different size distributions.

3.2 Experimental Details

Figure 3.1 Flow chart of synthesis procedure in our experiment (Tartaric acid

is employed here as an example).

All the reagents were of analytical grade and were used without further

purification. Following is a typical procedure, bismuth nitrate [Bi(NO3)3 •5 H2O]

and iron nitrate [Fe(NO3)3 •9 H2O] were weighed in stoichiometric proportions

and dissolved in deionized water to make a solution with an independent

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concentration of 0.2 M before adding 20 mL diluted nitric acid (65~68% HNO3)

to the mixture. Then 10 g of citric acid (C6H8O7) were added to the solutions as

chelating agent. The light-yellow-colored transparent solution was heated under

vigorous stirring until no liquid was left in the beaker to form gel deposit. Each

beaker with solid deposit was kept in the oven at 150 °C for another 2~3 h.

Subsequently, powders were quarterly divided and calcined in the oven for 2 h at

350, 450, and 550 °C, respectively, to obtain well-crystallized BFO NPs with

controllable sizes. For comparison, another group of powders were synthesized by

modifying a typical soft chemical route by using excess tartaric acid as chelating

agents.46 The whole process is sketched here as Figure 3.1, using tartaric acid as

an example.

The gel (intermediate product) was subjected to thermal analysis in order to

determine the subsequent sintering temperature with simultaneous

Thermogravimetric Analysis & Differential Scanning Calorimetry (TG-DSC)

system (NETZSCH STA 449 C Jupiter®). After heat treatment, the sample was

characterized using X-ray diffraction (XRD) with a Bruker AXS D8 ADVANCE

X-ray diffractometer under Cu Kα radiation (λ=0.154178 nm ) at ambient

conditions. Fourier transformation infrared (FT-IR) spectra were obtained on a

Perkin-Elmer Spectrum one FT-IR spectrometer at a resolution of 4 cm−1 with an

HgCdTe detector. Transmission electron microscopy (TEM) images and

high-resolution transmission electron microscopy (HRTEM) images were

obtained on a JEOL 2011 transmission electron microscope at an acceleration

voltage of 200 kV. Magnetization measurements were taken place on a LakeShore

Vibrating Sample Magnetometer (VSM) system.

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3.3 Results and Discussion

3.3.1 Determination of Sintering Temperatures

Figure 3.2 TG-DSC curves of the gel reminders acquired by using (a) tartaric

acid and (b) citric acid as chelating agent.

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The TG/DSC curves of the precipitated and dried powders were carried out

and shown in Figure 3.2. Since tartaric acid and citric acid can form different

chelating compounds with Bi3+ and Fe3+ ions (as schematically shown in Figures

3.6(a) and 3.6(b)), different thermal behaviors were observed from the curves.

However, there are four weight-loss segments in both Figures 3.2(a) and 3.2(b). It

can be deduced that the first and last segments are due to the evaporation of

crystalline water and the crystallization process of BFO. The major mass loss of

the two intermediate segments in tartaric acid precursor are derived from

volatilization of excess tartaric acid, decomposition of chelating complex, and a

small amount of nitrate. However, in the citric acid precursor, this loss is caused

by the decomposition process only. The analysis results provided us a detailed

guidiance to our subsequent heat treatment process, which showed that citric acid

precursor has a relatively lower crystallization temperature (indicated by red

arrows in Figure 3.2), that is, nearly 100 °C lower than that of the tartaric acid

precursor. More importantly, to our best knowledge, a crystallize temperature of

about 350 °C is far lower than those reported in the literature.

3.3.2 Structure Characterizations

XRD measurements were performed to characterize the crystal structure of

the calcined powders. As shown in Figure 3.3, all the XRD patterns can be

indexed to a pure rhombohedral perovskite structure, which are in good agreement

with the powder data of JCPDS Card number 20-169. After heat treatment at

350 °C, the sample from citric acid precursor begins to generate pure phase BFO

while another sample from tartaric acid precursor is still of amorphous feature. It

is clear that the crystallization of BFO completed at a temperature of 350 °C for

citric acid precursor while 450 °C for tartaric acid precursor, which is in good line

with the TG-DSC analysis. Meanwhile, the particle size of BFO changed

remarkably after further heat treatment. Calcined at temperatures above 450 °C,

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Figure 3.3 XRD patterns of BFO samples synthesized by wet chemical route

using different chelating agents followed by calcination at 350 °C, 450 °C and

550 °C, respectively. Note that (a) Tartaric acid and (b) citric acid.

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well-crystallized and pure phase BFO can be obtained for either precursor. As

discussed in early literatures, the grain sizes of BFO NPs grow up with increasing

the temperature in soft chemical routes.52, 98 This can also be confirmed by the

peak sharpening of XRD curves.

Figure 3.4 TEM images of BFO NPs at low and high magnification, and

corresponding SAED patterns: (a), (b), and (c) for nanoparticles from tartaric

acid and calcined at 450 °C, while (d), (e), and (f) for NPs from citric acid and

calcined at 350 °C.

The morphology of the calcined BFO nanoparticles was examined with the

assistance of TEM. Typical TEM images are shown in Figure 3.4. It is clear that

the spherical NPs formed from both precursors are sufficiently fine and uniform

on copper grid, and the particle sizes are about 12 and 4 nm, respectively. Hardly

any aggregation could be found in our samples compared with traditional

approaches. The corresponding selected area electron diffraction (SAED) patterns

(as shown in Figures 3.4(c) and 3.4(f)) suggest that our NPs are well crystallized;

and both can be indexed to pure BFO rhombohedral crystal structure. The

HRTEM image of individual BFO NP (Figure 3.4(b)) clearly shows an interplanar

spacing of 2.778Å, corresponding to the (110) crystal planes. Furthermore, we can

acquire NPs with an average particle size of about 4, 12, 30, and 80 nm through

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keeping the calcination temperatures at 350, 450, 550, and 650 °C, respectively.

Figure 3.5 FTIR spectra of BFO precursors formed by tartaric acid (a) and

citric acid (b), respectively.

Figure 3.5 shows the FTIR spectra of BFO precursors using tartaric acid and

citric acid as chelating agent, respectively. As shown, eight characteristic IR peaks

appeared for BFO precursor (tartaric acid), while four characteristic IR peaks

together with some weak peaks appeared for BFO precursor using citric acid as its

chelating. Both samples have two sharp and one wide IR peaks, which correspond

to the stretching vibrations of C=O and –OH. The IR wide peaks located at 3466

cm-1 in (a) and (b) were assigned to the stretching vibrations of structural

hydroxyl (OH) groups, and the intense peaks at 1628–1672 cm-1 were assigned to

the stretching vibrations of C=O (corresponding to the groups of tartaric and citric

acid). The IR peaks located at 1374 cm-1 were attributed to the symmetry bending

vibration of C–H. In addition, a sharp IR peak located at 1278 cm-1 was assigned

to the stretching vibration of single bond of C–O for tartaric acid precursor sample,

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while it cannot be observed for citric acid precursor sample. The IR peaks below

1000 cm-1 (such as 492, 806, and 902 cm-1 for tartaric acid precursor, 477, 551,

613, 858, and 910 cm-1 for citric acid precursor) were corresponding to the

vibration bonds of Bi–O or Fe–O, respectively.

3.3.3 Proposed Precursors & Formation Mechanism

Figure 3.6 Schematic for different chelating complex formed by tartaric acid

(a) and citric acid (b), where purple sphere stands for Bi, blue sphere for Fe,

red sphere for oxygen, and gray spheres for carbon atoms. (c) Possible

formation processes of BFO NPs under wet chemical environment using

tartaric acid and citric acid as chelating agents, respectively.

A possible mechanism for the formation of BFO NPs was proposed based on

previous contributive analysis (as shown in Figure 3.6). Firstly, Bi(NO3)3•5 H2O

and Fe(NO3)3•9 H2O along with chelating agents were added to the deionized

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Figure 3.7 TEM image of BFO NPs calcined at 650 °C and the corresponding

SAED pattern (inset), which recorded from the area indicated by the black

square.

water and formed the complex of Bi and Fe (Figures 3.6(a) and 3.6(b)). Secondly,

sol-like precursor and irregular particles come into being followed by aqueous

solution were dried (which can be inferred from FRIR spectra of BFO precursors

using tartaric and citric acid as chelating, as shown in Figure 3.5). Finally, the

precursor decomposed and BFO NPs started to generate accompanied by the

calcination stage under different temperature. It is believed that the chelating

compounds plays an important role in controlling shape and size of particles and

the decomposition temperatures of the precursor will partially determine the

crystallization temperature of BFO NPs in our synthesis. The investigations show

that the grain size of the BFO NPs increases with increasing calcination

temperature, implying a facile way to BFO NPs with controllable sizes. The

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geometry of the grains becomes more complicated with higher temperature, a

result of better crystallization under high temperature. Higher temperatures cause

the grains to grow much bigger so that we can obtain sharper monocrystal SAED

image as shown in Figure 3.7.

3.3.4 Investigation of Size-dependent Magnetism

Figure 3.8 Magnetization hysteresis loops of BFO NPs with different particle

size distributions; (a) 4 nm, (b) 12 nm, and (c) 30 nm.

The magnetization hysteresis loops of BFO NPs samples with three different

particle sizes were measured over at room temperature, as shown in Figure 3.8.

All loops exhibit a finite exchange bias field and vertical asymmetry with visibly

greater saturation magnetizations compared to what has been reported

previously.52 This could be a result of uniform particle sizes and the additional

lattice strains caused by the large amount of surfaced atoms from small grain

size.69 According to the theory of BFO system’s ferromagnetism, magnetization

drops as its grain size increases.52 As the calcination temperature rises, the

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magnetization of BFO NPs with diameters of 12 and 30 nm decreases as expected.

One possible explanation may be that some grains may not have spontaneous

magnetic moments and therefore fail to contribute to the magnetization. The

possibility of superparamagnetic behaviors in BFO NPs can be ruled out from the

finite coercivity and the finite exchange bias field at room temperature (varies

within 60 to 90 Oe), which confirms the ferromagnetic order as well as spin

pinning at the ferromagnetic—antiferromagnetic interfaces. The magnetization is

nearly linear with the external magnetic field for the sample heat treatment at

650 °C, which means the NPs has almost lost its ferromagnetic property. This

finding matches well with what have been found previously, that is, crystallites

larger than 62 nm display bulk lattice parameters and hence do not present any

ferromagnetic property, namely, the hysteresis loop.

3.4 Summary

In summary, pure phase BFO nanoparticles with average diameter ranging from 4

to 30 nm were synthesized by a simple soft chemical route using citric acid as

chelating agent followed by calcination at a relatively low temperature. TG/DSC,

XRD, and TEM were used to determine the phase and size distribution of the

nanoparticles. It was found that nanoparticles obtained in our research were

featured with a narrow size distribution together with good dispersity. VSM was

utilized to measure the size-dependent magnetic behaviors of the as-prepared

nanoparticles. The mechanism for the synthesis of crystallized nanoparticles under

such low temperatures was discussed.

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CHAPTER 4
SYNTHESIS OF BiFeO3 NANOFIBERS VIA
ELECTROSPINNING

Apart from nanoparticles, nanofibers of bismuth ferrite are also of interest for

materials scientists as such one-dimensional structure may be employed as

building blocks to construct three dimensional functional materials and/or

components. Due to the high-symmetry crystal structure of bismuth ferrite, it is

not easy to synthesis nanofibers or nanowires of this oxide via conventional

processes (such as hydrothermal method) despite that there are successful cases in

the literature. Comparatively, the electrospinning technique offers a more

convenient alternative through which the morphology control becomes very easy.

This chapter presents the synthesis of bismuth ferrite via electrospinning. As to be

demonstrated, nanofibers of bismuth ferrite of high quality of crystallization have

been successfully developed and their structures characterized.

4.1 Introduction

To develop and study low-dimensional bismuth ferrite is motivated by the

facts that interesting properties were observed in bulk ceramics and epitaxial thin

films of bismuth ferrite123-126 and, more importantly, there is strong evidence that

the structure and properties of bismuth ferrite (e.g. lattice parameters, N’eel

temperature, magnetic polarization, etc.) are size dependent.52, 66, 79, 82, 98

Nanowires and nanofibers are very important nanostructures for bismuth ferrite;

however, there is much technical difficulty in the synthesis of such structures

mainly due to the high-symmetry of the crystal structure. For example,

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hydrothermal method is often employed to synthesize 1-D nanostructures of

metallic oxides (such as zinc oxide) but it is not much suited for the synthesis of

bismuth ferrite nanofibers. Based on our experience, bismuth ferrite tends to grow

at a same rate along all crystallographic direction, giving rise to the formation of

nanoparticles as final products.41, 59, 68, 82, 127

Fortunately, there are a few synthesis

techniques which offer constraint of the morphology of the final products. Among

them the electrospinning technique is easy to control and low cost and thus

employed in the present research.

Up to now, electrospinning is perhaps the only technique that is suited for

fabricating continuous nanometer- and sub-micrometer-sized fibers. In this

method, an electrical field is applied to draw fibers from a liquid such as solutions

or melts.128, 129
The electrospinning method was originally developed for

producing polymer fibers; until very recently, it was successfully introduced to

some certain ceramic systems.130, 131 So far more than 20 ceramic systems were

developed in this method to generate amorphous, polycrystalline, dense, porous or

even hollow fibers.131 However, there is limited work on electrospinning of BFO

NFs originated from its impractical phase-control in synthesizing,41 much less the

detailed studies of the synthesis process and conditions although such momentous

problems should be seriously addressed. Grounded on the comprehensive study of

sol-gel method in BFO system as described in the chapter 3, we further developed

as here a sol-gel combined electrospinning process in order to produce BFO NFs,

with accurately and simultaneously controlling over its perovskite structure and

morphology.

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4.2 Experimental Procedure

Figure 4.1 A schematic diagram showing the sequence of steps in the

fabrication of BFO NFs by electrospinning.

4.2.1 Preparation of Precursor Solution

All of the chemicals were of analytical grade and were used as received.

Firstly, 1.20 g bismuth nitrate [Bi(NO3)3·5H2O] and 1.00 g iron nitrate

[Fe(NO3)3·9H2O] were weighed and dissolved into a mixture of 10 ml acetone

and 5 ml distilled water, followed by exposed to ultrasound for 5 minutes to give a

suspended solution. Then 1 ml nitric acid (67 %~68 %, mass ratio) was added

dropwise until the suspended solution became transparent. After that, a 7.5 g

solution of 10% (mass concentration) poly (vinyl pyrrolidone) (PVP, molecular

weight of about 1 300 000) in ethanol was added dropwise and stirred for 30

minutes. Finally, 1 ml of 2, 4- pentanedione (99+ %) was added dropwise to the

solution to form our precursor solution.

4.2.2 Electrospinning and Annealing

The precursor solution was carefully loaded to a syringe with its capacity of

5 cc for electrospinning. The distance between the capillary and the collector was

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fixed at about 10 centimeters, the accelerating voltage was set at 14 kV, and the

feeding rate of the solution was controlled at 0.5 ml/h. The fibers spun were

collected either on an aluminum foil or on an Au/SiO2/Si wafer. The as-spun

fibers was dried at 120 °C for 2 h, and then followed by thermal annealing at 550

°C for 2 h in ambient conditions before characterization. The schematic diagram

of the whole process is shown in Figure 4.1.

4.2.3 Structure Characterizations and Measurements

The precursor solution was dried and the gel remainder was subjected to

thermal analysis in order to determine the subsequent annealing temperature with

simultaneous Thermogravimetric Analysis & Differential Scanning Calorimetry

(TG-DSC) system (NETZSCH STA 449 C Jupiter®). After annealing, the sample

was characterized using X-ray diffraction (XRD) with a Bruker AXS D8

ADVANCE X-ray diffractometer under Cu Kα radiation (λ = 0.154178 nm).

Scanning electron microscopy (SEM) observations were carried out on a JEOL

6335F system. Transmission electron microscopy (TEM) images and EDS

spectrums were obtained on JEOL 2011 & JEOL 2010F (field emission)

transmission electron microscopes at an acceleration voltage of 200 kV. And the

atomic force microscopy (PFM) topography and the piezoresponse tests were

taken on a Veeco Multimode SPM system with Nanoscope IV controller.

4.3 Results and Discussion

4.3.1 Physicochemical Characterization

An indispenpensable step in electrospinning of ceramic structures is the

thermal treatment of as-spun products, so as to completely remove the thickening

agent and crystallize the final ceramic. To handle it properly, thermal analysis of

the as-spun fibers must be carried out in advance to determine the annealing

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Figure 4.2 TG-DSC curves of the as-spun BFO fibers.

conditions. We thus assessed the thermal behavior of our samples from a

simultaneous TG-DSC system (30-800 °C ranges, result is shown as Figure 4.2).

A series of minor peaks before 350 °C in DSC curve together with successive

weight loss in TG ought to be issued to the loss of solvents/combined-water and

succeeding decomposition of the nitrates/complex-compounds in our precursor.

Furthermore, the following major weight loss and wide-deep endothermic peak

directly result in the inference that there bears a BFO crystallization temperature

at about 364 °C (denoted by star) and a PVP fully volatilization temperature of

about 520 °C (denoted by arrow), which would be such instructive and

meaningful to our subsequent thermal treatment.

Next, a SEM image of the typical BFO sample (Figure 4.3a) obtained after

thermal treatment shows primary fiber-like structure at a radial size ranging from

100-200 nm with excellent continuity and flexibility. However, the NFs manifest

remarkably rough but dense surface due to the poly-crystalline nature from the

electrospinning process. Figure 4.3b shows the TEM image from an individual

BFO NF, which indicates that the fiber is composed of many small crystallites

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with their average size distributed within 10 to 20 nm. The crystalline phase of

BFO was further determined by XRD measurement and the result is also given in

Figure 4.3c. It is well know that phase-pure BFO is hard to synthesize and

impurity phases are often present, especially when the sample need to be annealed

at a high temperature.40, 127 Here in our work, all the peaks from the pattern can be

indexed to rhombohedral perovskite structure of BFO with its point group R3c as

shown, and we cannot detect any noticeable peak belonging to secondary phases;

that is to say, we obtained phase-pure BFO NFs from a normal stoichiometric

ratio of precursors and without any protective atmosphere during annealing at

550 °C for the 1st time so far.

Figure 4.3 (a) SEM image of the as-synthesized BFO NFs; (b) the TEM image

of an isolated NF; (c) XRD pattern of the as-synthesized NFs.

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The crystalline nature of ultrafine BFO NF is further examined by a

high-resolution TEM combined with an energy dispersed spectrum (EDS) system,

as shown in Figure 4.4. When we magnified stepwise on a single fiber like shown

in Figure 4.4a, b and c, it is observed that the fiber is made up of uniform

Figure 4.4 High resolution TEM analysis of a single BFO NF; (a), (b) and (c)

are gradual magnified images, (d) and (e) are the corresponding

selected-area-ED pattern and HR-image; and (f) is the EDS spectra obtained

from it.

nanoparticles, such as which indicated by the dashed ovals in Figure 4c. Particles

are spherically shaped with facetted morphology, exhibiting certain dispersion of

particle size around the average value between 10-20 nm. Figure 4.4d and 4.4e are

the selected-area electron diffraction (SAED) pattern and the corresponding

high-resolution image; both can be well indexed to the perovskite structure of

BFO as shown. The EDS result is shown as in Figure 4.4f (all the un-indexed

peaks are caused by the copper grid used in TEM analysis), from which we can

calculate that the atomic ratio of Bi: Fe is almost 1: 1. All the analysis from the

HRTEM is consistent with the XRD; suggest that phase-pure BFO NF has been

fabricated in our study.

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4.3.2 Microstructures under Annealing

Figure 4.5 The SEM images of NFs obtained by annealing at different

temperatures for 2 h; (a) 400 °C; (b) 450 °C; (c) 500 °C and (d) 550 °C.

Furthermore, in order to go insight of the process, we carefully carried out a

detailed study of temperature-dependent morphology and crystallinity-changing

under SEM and TEM. Accompanied by the higher annealing temperature, the

average diameter of the NF gradually shrinks (Figure 4.5, SEM images with scale

bars); meanwhile, the surface of the NF gradually becomes rough, and the

crystallinity also changes regularly. As shown in Figure 4.6a, after 120 °C drying,

the sample exhibits excellent fiber-like structure but remains amorphous in the

light of the ED pattern. Upon annealing at 400 °C (Figure 4.6b), the fiber shrinks

and gives only a little crystalline while still has a smooth surface. But after 450 °C

annealing (Figure 4.6c), a quasi-core/shell structure begins to form. The reason

can be easily supposed to the volatilization of PVP content in the fiber. That is to

say, along with the heat treatment, the PVP content evaporates and the

diminishing PVP shrinks to the core part, so the fiber becomes a little hollow as

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checked. Meanwhile, the remained BFO at the shell part starts its crystallization.

The evidence is the SAED pattern below acquired from the shell part, which not

only indicates a good crystalline, but also exhibits no diffusion caused by any

organic component. When the annealing temperature goes up to 500 °C (Figure

4.6d), we can clearly see that the PVP content almost disappear, only remains a

little on the surface of the fiber which we can easily recognize from the diffused

contrast of the image and the SAED pattern. Finally, when we employ a further

550 °C annealing, the fiber becomes phase-pure BFO and the diffraction rings in

the SAED pattern turn to be so bright, sharp and uniform, and the surface of the

fiber becomes a little rough but dense simultaneously. However, when we further

increase the temperature to 600 °C, the particles on the fiber grow too large, and

in this situation, we even cannot acquire continuous diffraction rings from the

fiber.

Figure 4.6 TEM images and the corresponding SAED patterns of (a) the

as-spun NF dried at 120 °C and the NFs obtained by annealing at different

temperatures for 2 h; (b) 400 °C; (c) 450 °C; (d) 500 °C; (e) 550 °C and (f)

600 °C.

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Thus, our work exhibits not only a phase-pure product of BFO, but also an

obvious lower crystallization temperature than all previous work.46 The reason

should be ascribed to the employment of 2, 4- pentanedione (acetylacetone, or

acacH, and C5H8O2) as chelating agent in our precursor solution. This diketone

often acts as bidentate ligand in solution systems to forms complexes with

practically all metals, and the functionality here is to reduce the complexity of the

reactions as well as to stable the sol system. It is known that acacH is able to

bridge (μ-bonding) metal ions although it is not the preferred process in general,

and the complex has relatively low thermal decomposition temperatures, giving

metal oxide as the primary product.132, 133 Since the mole ratio of acacH over

metal ions (Bi3+ & Fe3+) is about 2, it can be deduced that all the Bi3+ and Fe3+

cations are bound to the acacH. So the crystallization process here is actually

synchronous with the decomposition process of Bi3+-(acacH)-Fe3+ compound

under annealed conditions, which significantly lowered the crystallization

temperature of BFO than previous studies.

4.3.3 Influence of Accelerating Voltages & PVP Concentrations

To further understand the whole process, we also studied the influences of

some key parameters during the electrospinning procedure, such as the

accelerating voltages and the PVP concentrations. In Figure 4.7, we show a series

of SEM images recorded at different accelerating voltages varying from 12 kV to

18 kV. Generally speaking, the increase of the accelerating voltage will generate

NFs with smaller diameters, however, when the accelerating voltage is too high,

the as-synthesized samples will become not so uniform and continuous. For

example, we can find the fibers in Figure 4.7a exhibit not so uniform in axial and

a little big in radial. But in Figure 4.7c, the as-synthesized fibers become

segmental after annealing at 550 °C. And in Figure 4.7d, we can even identify

many droplets on the collector, which implicate that the static charge force is too

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high to maintain the continuous fluid out of the capillary. Only when we use an

accelerating voltage of 14 kV like in Figure 4.7b, we can obtain uniform and

continuous NFs both before and after annealing.

Figure 4.7 The NFs synthesized at different accelerating voltages after 120 °C

drying, (a) 12 kV; (b) 14 kV; (c) 16 kV and (d) 18 kV; the insets are the

morphologies after annealing at 550 °C; all the scale bars represents for 2 µm.

To study the influence of PVP amount in the precursor solution, Figure 4.8 is

induced at different X values (X is defined as the weight ratio of PVP over

Fe(NO3)3•9H2O in the solution), where X=0.6, 0.75 and 0.9. When X equals to 0.6

as in Figure 4.8a, due to the low viscosity of the solution, we can hardly obtain

continuous NFs, and consequently, there will be some big droplets generated on

the collector because of the disjointed fluid during the electrospinning process.

However, when there is excessive PVP, as shown in Figure 4.8c, the NFs will

shrink seriously after annealing, and they will break into segments easily. So here

in this situation, we optimized X=0.75 to be the most proper parameter.

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Figure 4.8 The SEM images of NFs from different PVP amounts in the

solution; (a) X=0.6; (b) X=0.75; (c) X=0.9. The insets are corresponding

magnified images.

Therefore, through this study of the influences of accelerating voltages and

PVP concentrations during the process, we can not only find out the optimized

parameters but also make sense of the condition-dependent morphologies. Thus, it

is quite liable to obtain qualified NFs with different diameters and lengths for

different potential applications by slightly adjusting these key parameters around

their optimized values.

4.3.4 Measurement of Piezoelectricity

For the multiferroic BFO, piezoelectricity and ferroelectricity need to be

verified, as it is well-known that the big switchable ferroelectric polarization of

BFO will be its first application in memory devices, which is now under

developing globally by several leading companies. We employed here the high

voltage piezoresponse force microscopy (PFM), as shown in Figure 4.9. Figure

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Figure 4.9 (a) The AFM topographic image of NFs and (b) the ferroelectric

properties of a single NF. The inset of (a) is the PFM phase image on a single

fiber, and insets in (b) are the PFM phase-voltage hysteresis loop and the

amplitude-voltage butterfly loop, respectively.

4.9a is the AFM topographic image of NFs on a gold-coated silicon wafer. In

accordance with the SEM results, the AFM image shows wonderful flexible and

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uniform fiber-like structure with its average diameter of about 100 nm. In the

PFM phase image (inset of Figure 4.9a), a clear ferroelectric domain structure can

be identified. In most regions of the fiber, an obvious signal of PFM can be

recognized when a sufficient voltage is applied, separated by boundaries where

the signal approaches zero and the phase of the signal flips. These boundaries are

interfaces and domain walls which separate sizeable of different polarization

directions.41, 134 It is noted that some domains in the image can be as large as

50-80 nm, which means that the domain walls should expand across several

particles. Furthermore, after we applied a high swept dc voltage on one isolated

fiber, we can switch the polarization and the phase-voltage hysteresis loop

together with the amplitude-voltage butterfly loop (insets of Figure 4.9b) can be

recorded. Then we can calculate the polarization using P = A•cosθ (where P refers

to polarization, A refers to amplitude and θ refers to phase) to acquire the

polarization hysteresis loop as shown in Figure 4.9b, which confirmed the

undoubted ferroelectricity of our fiber.

4.4 Summary

In summary, ultrafine and continuous BFO NFs have been developed via a

facile sol-gel based electrospinning process combined with a follow-up annealing.

With acetylacetone used as chelating agent in the precursor solution, the process

has made it possible to obtained well crystallized nanostructures via an ultra-low

temperature annealing. The influence of processing factors (e.g. annealing

temperature, accelerating voltage and PVP concentration) on the final product

structure was examined. Piezoelectric force microscopy measurements were

conducted through which room temperature ferroelectricity in the as-synthesized

nanofibers were confirmed.

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CHAPTER 5 WITH DOMINANT {111}C FACETS

CHAPTER 5
SYNTHESIS OF BiFeO3 PILLS AND RODS WITH
DOMINANT {111}C FACETS

Constraint of the growth directions or exposed facets of micro-/nano-

structures has been long regarded as a popular research topic due to the various

anisotropic properties of crystals. We present here, for the first time, not only

uniform and phase-pure but also tunable perovskite BiFeO3 crystallites with

different predominantly exposed facets that have been successfully synthesized

via a facile one-pot hydrothermal approach at 200 °C under the presence of

potassium hydroxide and polyethylene glycol. Pills and rods with dominant

{111}c facets and cubes with {100}c exposed facets have been obtained by

adjusting the alkaline conditions of the precursor solution. Furthermore, due to the

distinct dominant facets of BiFeO3 crystallites, {111}c dominant pills and rods

grant a significant enhanced visible light response, suggesting that the designed

structures can give rise to better performance in future photovoltaic and

photocatalytic applications of BiFeO3.

5.1 Introduction

The unique morphological characteristics of snow crystals have made them

known as ―the letter from the sky‖. In scientific research, developing techniques

of controlling the growth directions or exposed facets of functional materials on a

nanometer- or micrometer- scale is of great importance because of its significance

in determining the electrical, magnetic and optical properties brought by spatial

geometry effect.135-137 Remarkable progress has been made in controlled

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fabrication or self-organization of various compounds. For examples, anatase TiO2

has been studied extensively to gain highly exposed {100} facets because of the

promising high reactivity in heterogeneous reactions;138-140 while Co3O4 nanorods

have been proved to possess excellent low temperature catalytic ability with

predominant {110} planes.141 However, little attention has been paid to complex

oxides such as perovskite materials despite their high values in both scientific and

technological fields.

Perovskite oxides and related compounds have been attracting increasing

research interests over the past decade because of their potential applications in

thin film capacitor, nonvolatile memory, nonlinear optics and

photo-electrochemical cell originated from their multiferroic, photocatalytic or

magnetic properties.34, 142, 143

Among them, perovskite-type bismuth ferrite

(BiFeO3) has currently received most attention as a rare multiferroic material that

shows simultaneous ferroelectric and G-type antiferromagnetic orderings well

above room temperature.144, 145 As well discussed in chapter 1, at RT and 1 atm,

BFO shows a rhombohedrally distorted perovskite structure with point group

R3c.23 The perovskite unit cell has a lattice parameter, arh, of 3.965 Å and a

rhombohedral angel, αrh, of ca. 89.3 °- 89.4 °at room temperature. Alternatively,

the unite cell can be described in a hexagonal frame of reference, with its c-axis

parallel to the diagonal of the perovskite cube, i.e. [001]hexagonal ǁ [111]pseudocubic.

The hexagonal lattice constants are ahex= 5.58 Å and chex= 13.90 Å.25 For its

multiferroicity, BFO exhibits both spontaneous polarization (Ps) and

antiferromagnetic order along the [001]hex/[111]c.146 However, it exhibits no

detectable magnetism because of a spiral magnetic spin cycloid with a periodicity

of about 62 nm.147 Nevertheless, BFO nanostructures continue to be regarded as

primary building blocks for a wide range of future nanodevices due to their

unique properties such as magneto-electric effect,4 gas-sensing properties51 and

photovoltaic property.19 In photocatalysis research, the small band gap (reported

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Figure 5.1 Plan-view and side-view (insets) of (a) {100}c and (b) {111}c facets

of BFO supercell structure.

value: ~2.2-2.8 eV) and good chemical stability of BFO make it an effective

photocatalyst in UV and visible light region during the photocatalytic process.53

Many techniques have been developed to fabricate various BFO nanostructures to

meet this demand, which suggests that BFO should make a competitive candidate

in intending photocatalysts and optoelectronic devices. Yet until now it remains a

challenge to produce phase-pure BFO41, 86, 122 and to tune the dominant facets of

the crystallites to enhance its performance.

Previous work contributed to crystallites with exposed {100}c crystal planes

are shown in Figure 5.1a.88, 89 However, based on the consideration of crystal

structure of BFO, [111]c/[001]hex does not only act as the directions of Ps and

antiferromagnetic ordering but also works as the closest packing direction, thus,

possessing the highest atomic density as sketched in Figure 5.1b. Therefore it is

quite likely that with highly exposed {111}c facets, it will be much easier for the

atoms to interact with photons so as to exhibit quality optical properties. In this

chapter, we will demonstrate a simple and controllable approach to create

perovskite BFO pills and rods with dominant {111}c facets which leads to an

obvious enhancement in light response, especially at the visible light region when

compared with that of {100}c exposed cubes. The synthetic strategy presented

here may not only be suitable for potential large-scale applications of BFO but

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also provide an effective means to synthesize other perovskite crystals with

tunable exposed facets.

5.2 Experiments

5.2.1 Hydrothermal Synthesis

All chemicals were of analytical grade and were used without further

purification; and all samples were prepared via the following hydrothermal

process. Typically, 2 mmol of Fe(NO3)3·9H2O and Bi(NO3)3·5H2O together with

0.8 g polyethylene glycol (PEG, Mw = 4 000) were dissolved in a 40 mL of

deionized water. The pH value of the solution was adjusted by adding certain

amount of KOH, which also served as a mineralizer. After being stirred for about

30 min, the suspension was carefully transferred into a Teflon-lined steel

autoclave. The autoclave was then sealed and heated at 200 °C for 3 days. The

temperature was increased at a rate of 1 °C/min. The product was collected from

the bottom of the autoclave after it was furnace-cooled to RT. After being washed

with distilled water and absolute ethanol to remove possible residues and dried at

60 °C, powder products were obtained.

5.2.2 Characterizations and Measurement

The obtained sample was characterized using X-ray diffraction (XRD) with a

Bruker AXS D8 ADVANCE X-ray diffractometer under Cu Kα radiation (λ =

0.154178 nm). Scanning electron microscopy (SEM) observations were taken

place on a JEOL 6335F field emission system. Transmission electron microscopy

(TEM) images and high resolution TEM (HRTEM) images were captured on

JEOL 2011 & JEOL 2010F (field emission) transmission electron microscopes at

an acceleration voltage of 200 kV for both instruments. The absorption properties

in UV and visible light region were measured by a Shimadzu

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 SYNTHESIS OF BiFeO3 PILLS AND RODS
CHAPTER 5 WITH DOMINANT {111}C FACETS

SolidSpec-3700DUV UV/Vis-NIR spectrophotometer.

5.3 Results and Discussion

5.3.1 Crystallographic Investigation

Through the experiment, we obtained three kinds of products in this

PEG-assisted hydrothermal reaction by utilizing different alkaline conditions. The

X-ray diffraction (XRD) patterns of as-synthesized samples are presented in

Figure 5.2. As it is shown, all peaks can be perfectly indexed to a rhombohedral

lattice with the space group of R3c (JCPDS card No. 86-1518). No noticeable

Figure 5.2 Evolution of XRD patterns from the as-synthesized samples under

different KOH concentrations: (a) pills (1 M KOH); (b) rods (2 M KOH) and

(c) cubes (15 M KOH).

peak from other impurity phases was detected, demonstrating that single-phase

and well-crystallized BFO has been successfully obtained under these conditions.

It is worth noting that in this series of patterns, the intensity of (012)hex and
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CHAPTER 5 WITH DOMINANT {111}C FACETS

(024)hex peaks for BFO samples C was clearly strengthened, suggesting that

{012}hex/{100}c planes should be dominant. As for the other two samples, the rise

of (202)hex/(111)c peak can be identified which suggests that the anisotropic

growth is perhaps preferential. These observed phenomena indicate that the

products may have microscopically undergone a morphological evolution.

5.3.2 Microstructure Analysis

Scanning electron microscopy (SEM) measurement was performed to

characterize the morphology and uniformity of all samples. Figure 5.3 shows the

results of the product from 1 M KOH. High yield and well-defined BFO pills can

be recognized with their average diameter of ~0.5–1 μm and an average thickness

of ~100–300 nm. The surfaces of these pills are quite flat while the side faces

seem slightly irregular.

Figure 5.3 SEM images of BFO pills obtained at: (a) Low magnification and (b)

high magnification.

We further examined the crystallographic nature of the pills using high

resolution transmission electron microscopy (HRTEM). The results were shown in

Figure 5.4. As schemed in Figure 5.4a, for crystals with such unique dimensions,

there are two typical incident directions for electron beam. Morphologically,

plan-view 5.4b exhibits a quasi-circular geometry for all pills; and the uniform

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 SYNTHESIS OF BiFeO3 PILLS AND RODS
CHAPTER 5 WITH DOMINANT {111}C FACETS

Figure 5.4 TEM analysis of BFO pills: (a) schematic of two typical projected

directions, and (b)-(e) are from axial direction: (b) plan-view of pills, (c)

corresponding SAED pattern, (d) and (e) are high resolution TEM image and

the associated contrast profile; while (f)-(g) are from radial direction: (f) and

(g) are side-view of a single pill and SAED pattern, respectively..

contrast on them verifies the flat surface of the pills while the ripple-like contrast

would be a result of the strain and bending of the crystal.148 Selected area electron

diffraction (SAED) patterns as either Fig. 5.4c or 5.4g can be well indexed to

perovskite BFO and simultaneously suggest that the axial direction of pills

belongs to [111]c. In HRTEM image 5.4d and the corresponding contrast profile

5.4e (acquired along the horizontal solid white line in 5.4d), the as-measured

lattice spacing of 0.23 nm corresponds to the distance between adjacent

{111}c/{202}hex planes which further confirms that the flat surfaces of the pills are

{111}c. Thus it would be rather easy to calculate that the BFO pills have over 60%

exposed {111}c facets according to the basic surface area formula of a cylinder.

Moreover, we can declare here that all crystallites are of good single-crystal as

repeated observations were made on many other crystallites during our

experiment.

The same characterizations were carried out on products obtained from 2 M

KOH as shown in Fig. 5.5. Summarized from SEM images, these rods possess an

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 SYNTHESIS OF BiFeO3 PILLS AND RODS
CHAPTER 5 WITH DOMINANT {111}C FACETS

Figure 5.5 SEM images of rods at (a) low- and (b) high-magnifications;

together with TEM analytical results as that of (c)-(g): (c) side-view of an

isolated rod, (d) and (e) are SAED pattern and corresponding HRTEM image,

while (f) and (g) are contrast distribution profiles from (e) (indicated by solid

white line), respectively.

average diameter of ~0.5–1 μm associated with an average length of ~1–2 μm.

About the crystallographic specifications under TEM, both the SAED and

HRTEM images suggest a growth direction of [111]c, i.e. the rods are simply

―elongated‖ from the pills and hold only about 20% exposed {111}c facets based

on similar calculations.

However, another sample from relatively high alkaline concentration (15 M)

is shown in Figure 5.6 which presents distinct results from the above. The

as-synthesized crystals display as such excellent cubes under SEM observation

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 SYNTHESIS OF BiFeO3 PILLS AND RODS
CHAPTER 5 WITH DOMINANT {111}C FACETS

Figure 5.6 (a) Low magnification and (b) highly magnified SEM images of

BFO cubes.

with relatively rough surfaces and an edge length ranging from 5-10 μm. Although

the large dimensions of the cubes make it impossible to be examined by our TEM

instrumentations, their well-developed morphologies suggest an undoubtedly high

crystallinity of the as-synthesized sample. According to the symmetries of

perovskite BFO and other relevant works,88, 89 all the surfaces of cubes can be

ascribed to {100}c crystal faces. In other words, the cubes show almost 100%

{100}c exposed facets.

5.3.3 Formation Mechanism Reasoning

Figure 5.7 A series of SEM images from the BFO samples after (a) 6 hours, (b)

24 hours and (c) 72 hours hydrothermal treatment with 15 M KOH.

In our fabrication process of BFO cubes, there is something rather worthy of

noting; when samples from different reaction intervals were observed under SEM,

an interesting formation process was detected as presented here in Figure 5.7.

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CHAPTER 5 WITH DOMINANT {111}C FACETS

Figure 5.7a shows some large and almost amorphous crystallites (20-30 μm) after

6 hours of hydrothermal treatment. When the treatment time was extended to 24

hours (Figure 5.7b), the intermediate product generated shows an interesting

microstructure which resembles a Rubik's Cube with an edge length of about 10

μm. Finally, perfect cubes with sharp edges (length of ~10 μm) were produced

after a 72-hour hydrothermal treatment (Figure 5.7c).

Grounded on the above time-dependent morphology-evolution process, a

multi-step formation mechanism is suggested as following. First, BiONO3 is

formed by hydrolyzing of bismuth nitrate together with Fe(OH)3 resulted from the

reaction between iron nitrate and potassium hydroxide in our precursor solution.

When the solution is heated in an autoclave, these two compounds experience a

dissolution process under alkaline condition and autogenous pressure in our

closed reaction system. Subsequently, they nucleate to form BFO amorphous

colloids followed by a slow aggregation and crystallization of primary particles.149,

150
The reactions involved during this process are as follows.

BiONO3 + H2O ⇋ Bi3+ + 2OH- + NO3-

Fe3+ + 3OH- → Fe(OH)3 ⇋ FeO33- + 3H+

Bi3+ + FeO33- → BiFeO3 ↓

In the second step, since symmetry conservation would work better in this

situation ([KOH] = 15 M), the colloids slowly change into cubic shape crystallites

and oriented-attaches151 into bigger cubes. As the growth proceeds, micro-cubes

are gradually formed. The rough surface of the cubes should be associated with

the erosion effect of KOH to crystallites at such concentration level. On the other

hand, at lower KOH concentration levels (i.e. 1 M and 2 M), the symmetry break

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 SYNTHESIS OF BiFeO3 PILLS AND RODS
CHAPTER 5 WITH DOMINANT {111}C FACETS

will dominate the growth process to form pills or rods due to selective adsorption

of PEG on certain crystal planes. The schematic illustration of this growth

procedure is presented in Figure 5.8.

Figure 5.8 Formation and shape-evolution process during the reaction.

5.3.4 Optical Adsorption Measurement

To study the change of visible light response of our {111}c dominant pills

and rods, their optical absorption performance was characterized. As shown in

Figure 5.9a, the diffused reflection spectra have been transformed into the

absorption ones according to the well-known Kubelka-Munk theory.120

Interestingly, in contrast to the {100}c dominant cubes, the photo absorption edges

of BFO pills and rods enjoys a significant red-shift to visible light region, while

the absorption features below 400 nm remain almost unchanged. Furthermore, for

pills with extremely high exposed {111}c, an extra strong absorption can be

identified in ca. 600-700 nm region. Based on the results and our sample BFO

cubes, it is quite possible to calculate the bandgap from the plot of Kubelka-Munk

function ((ahv)2) VS. photon energy (hv) for direct bandgap semiconductors as

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 SYNTHESIS OF BiFeO3 PILLS AND RODS
CHAPTER 5 WITH DOMINANT {111}C FACETS

Figure 5.9 (a) UV-Visible absorption spectra from the three kinds of BFO

crystallites. (b) A plot of (ahv)2 VS. photon energy (hv) for cubes, where the

dot line is tangent of the linear part.

presented in Figure 5.9b. The slope of the linear part suggests a bandgap of ~2.1

eV, which is smaller than that of bulks or thin films. Similarly, the bandgap for

BFO pills and rods is estimated to be even smaller (~2.05 eV, not shown). On the

other hand, it was reported that the bandgap energy would increase with

decreasing crystalline size for BFO nanoparticles,64 but here in our situation, we

actually observed a weak diminution together with the reducing particle size

(cube > rod > pill) which further proved the effects of the highly dominant {111}c

facets. From the viewpoint of utilizing solar energy as in the applications of

photocatalyst and optoelectric devices, the results suggest that our pills and rods

may have greater advantage especially under the visible light wave band.

5.4 Summary

In summary, we have developed a facile and controllable route for one-pot

synthesis of phase-pure BFO products under different alkaline conditions in this

work. The as-synthesized samples exhibit as pills and rods with different

percentages of exposed {111}c facets. The superior phase purity and

single-crystalline nature were confirmed by a series of technical measurements.

Compared with that of {100}c dominant BFO cubes, such pills and rods show an

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 SYNTHESIS OF BiFeO3 PILLS AND RODS
CHAPTER 5 WITH DOMINANT {111}C FACETS

significantly enhanced visible light response which provides wide vista of

applications for this unique material. The developed method has the merits of

being so simple, reproducible and mass-producible.

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CHAPTER 6 CONCLUSIONS

CHAPTER 6
CONCLUSIONS

To conclude, the present research focused on controllable synthesis of

bismuth ferrite nanoparticles and nanowires with desired phase, size and

morphology via chemical approaches (in particular, the sol-gel, hydrothermal and

electrospinning techniques). Important results that can lead to a better

understanding of the processing-structure-property relationship for bismuth ferrite

have been obtained, they include:

(1) A modified sol-gel method has been developed for producing well

crystallized bismuth ferrite nanoparticles with different sizes. It was found

that, with the aid of proper chelating agents in the precursors, the

crystallization temperature of bismuth ferrite could be lowered and the lowest

one recorded in this work was ~350C. To the best of our knowledge, this is

also the lowest crystallization temperature reported in the literature. Using the

nanoparticles as samples, the size-dependent magnetism in bismuth ferrite

was also studied.

(2) An electrospinning technique for producing continuous nanofibers of bismuth

ferrite has been developed. Experiments were conducted to systematically

study the dependence of final product structure on processing conditions,

including chemical agents for the precursor solutions, accelerating voltage,

post-annealing temperature and etc. Nanofibers prepared under optimized

conditions were found to be well crystallized and uniform in diameter.

Ferroelectricity in these nanofibers was confirmed by measurements on

piezoelectric force microscope.

FEI Linfeng 83
CHAPTER 6 CONCLUSIONS

(3) A one-pot hydrothermal process has been developed for the synthesis of BFO

nanostructures with controllable morphologies. Uniform and phase-pure

BiFeO3 crystallites with different predominantly exposed facets have been

successfully developed. Pills and rods of bismuth ferrite with dominant

{111}c facets and cubes with {100}c exposed facets have been obtained by

adjusting the alkaline conditions of the precursor solution. Furthermore, due

to the distinct dominant facets of BiFeO3 crystallites, {111}c dominant pills

and rods grant a significant enhanced visible light response, suggesting that

the designed structures can give rise to better performance in future

photovoltaic and photocatalytic applications of BiFeO3.

In summary, different synthesis techniques have been developed and bismuth

ferrite nanostructures with different sizes and morphologies have been obtained.

The synthesized nanostructures are expected to be useful either as samples for

basic study of the structure-property relationship of this material or as building

blocks for construction of large-sized materials for electrical and environmental

applications.

Bismuth ferrite is an important material. While the present work has made it

possible to fabricate samples of desired sizes and morphologies, further study on

the structure and properties is necessary. In particular, investigation on physical

and chemical behaviors of bismuth ferrite exposed to visible and/or UV light is a

topic of both scientific and technological significance.

FEI Linfeng 84
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