M - Sample Preparation For PFM

FERROELECTRIC DOMAIN STUDY BY
PIEZORESPONSE FORCE MICROSCOPY
ZHAO XIN
M. PHIL.
THE HONG KONG POLYTECHNIC UNIVERSITY
2005
FERROELECTRIC DOMAIN STUDY BY
PIEZORESPONSE FORCE MICROSCOPY
SUBMITTED BY
ZHAO XIN
A thesis submitted in partial fulfillment of the requirements
for the Degree of Master of Philosophy in Applied Physics
AT
THE DEPARTMENT OF APPLIED PHYSICS
October 2004
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 which has been accepted for the award of any other degree or diploma,
expect where due acknowledgement has been made in the text.
___________________________ (Signed)
________ZHAO XIN__________ (Name of student)

Abstract
Abstract
Ferroelectric domains in ferroelectric materials are micro-regions with the same
oriented spontaneous polarizations. The ferroelectric domain structure and its evolution
play a very important role for many applications of ferroelectrics such as non-volatile
ferroelectric random-access-memory elements. A deep understanding of the nature of
domain structures and switching behaviors in ferroelectric materials may lead to more
applications of ferroelectrics.
Among many methods of studying ferroelectric domains, piezoresponse force
microscopy (PFM) is receiving more attention due to its relatively high resolution and
ability of in-situ domain switching. The PFM is an extended function of atomic force
microscope utilizing a conductive tip with tip radius in nanometer scale and a lock-in
amplifier, therefore nanometer-sized domain imaging and polarization switching can be
achieved through tip scanning across the sample surface with an ac and/or dc electric
field applied on the tip. In this project, ferroelectric domain evolution in Pb(Zr0.4Ti0.6)O3
(PZT40/60) film and (PbMg1/3Nb2/3O3)0.75(PbTiO3)0.25 (PMN-25PT) single crystals were
studied utilizing the PFM technique.
PZT40/60 films were deposited on Pt(111)/Ti/SiO2/Si(100) substrates by sol-gel
process followed by thermal annealing at 650°C for 5 minutes. PFM observation
revealed lamellar domain structure in the PZT40/60 grains and we attribute the lamellar
ZHAO XIN I
Abstract
domains to 90° ferroelectric domains. Polarization switching mechanism of the 90 °
domains in the PZT40/60 films under external electric fields has also been studied and it
revealed that a large area polarization switching is usually accompanied by appearance
of new direction of 90 ° domains in order to reduce the stress in the grains. By contrast,
a nanometer-sized polarization switching is believed to be accomplished by generating
180 ° switching within a single lamellar domain.
(PbMg1/3Nb2/3O3)1-x(PbTiO3)x (PMN-PT) single crystals are known as relaxor
ferroelectrics, which are different from normal ferroelectrics such as PZT films. The
relaxor ferroelectricity can be interpreted by composition non-uniformity induced polar
nanometer-sized regions (PNRs) with different Curie temperatures (Tc) and their
conversions to paraelectrics. The PMN-PT single crystals naturally have a morphotropic
phase boundary (MPB) in the range of 28~36% of PT. Ferroelectric domain structures
and their evolution in PMN-PT single crystals of 25% PT (PMN-25PT) grown by
Bridgman technique with (110)-cut and (111)-cut were studied by means of temperature
dependent PFM. It revealed that, during heating, the as-grown PMN-25PT single crystal
exhibits transition from microdomain ferroelectric phase to paraelectric phase; while
after being cooled down to room temperature the microdomain structure is rebuilt.
Nanometer-sized domains were also observed embedded in the microdomains. By
contrast, the poled (110)-cut sample exhibits transitions from macrodomain to
microdomain structures at 90 oC and from microdomain to paraelectric phase at 115 oC,
respectively. These direct observations are consistent with temperature-dependent
relative permittivity measurements.
ZHAO XIN II
Abstract
In conclusion, PFM has been implemented in the study of ferroelectric domain
structures and their evolution and some significant results have been achieved. However,
due to the limited resolution of PFM (larger than 10 nm), more detailed domain
structures are still not clear. The relatively small size of scanned area in PFM also limits
the view area of macrodomain structure. Therefore, a whole picture of domain structure
from micrometer to nanometer scale is highly desirable. In addition, PFM study of
relaxor ferroelectric phase transitions, such as from rhombohedral to tetragonal and
monoclinic structures deserves further studies.
ZHAO XIN III

Publications
Publications
1. X. Zhao, J. Y. Dai, X. G. Tang, J. Wang, H. L. W. Chan and C. L. Choy,

o
“Characterization of 90 domain structure and polarization switching in
Pb(Zr0.4Ti0.6)O3 film by piezoresponse microscope” Applied Physics A,
Published online: 20 August 2004.
2. X. Zhao, J. Y. Dai, J. Wang, H. L. W. Chan, C. L. Choy, X. M. Wan and H. S.
Luo “Domain structure and evolution in (PbMg1/3Nb2/3O3)0.75(PbTiO3)0.25 single
crystal studied by temperature-dependent piezoresponse force microscopy”
Journal of Applied Physics, Article in revision.
3. X. Zhao, J. Y. Dai, J. Wang, H. L. W. Chan and C. L. Choy, “Study of Local
Piezo-Properties for Europium Doped Lead Zirconate Titanate Thin Films by
Piezoresponse Scanning Probe Microscope,” accepted by Journal of Integrated
Ferroelectrics (16th International Symposium on Integrated Ferroelectrics (ISIF
2004) Proceedings).
ZHAO XIN IV
Acknowledgements
Acknowledgements
I would like to thank my supervisor Dr. J. Y. Dai and my co-supervisor Prof. Helen L. W.
Chan for their invaluable direction and support throughout the period of my research
work. I also thank Prof. C. L. Choy for the necessary comments and help in my
research.
I would like to thank Dr. X. G. Tang and Mr. X. M. Wan for offering me the PZT40/60
film, the PMN-25PT single crystals and all the corresponding data for these two types
of samples. Dr. Tang and Mr. Wan also gave me many comments and help about the
discussion of results.
I give my appreciation to Prof. F. G. Shin, Prof. J. M. Liu and Prof. W. B. Wu for their
comments and help.
Thanks are also given to the following people in our group, Dr. J. Wang, Mr. P. F. Lee,
Ms. H. K. Lam, Mr. S. W. Zeng and Mr. D. Y. Wang for their assistance. Thanks also
due to Mr. M. N. Yeung from the Materials Research Centre for his assistance.
I gratefully acknowledge the financial support from the Hong Kong Research Grants
Council (RGC) and the Hong Kong Polytechnic University. Finally, I would like to
thank my family and all my friends for their understanding, support and encourage.
ZHAO XIN V
Table of Contents
Table of Contents
Abstract ..............................................................................................................................I
Publications.....................................................................................................................IV
Acknowledgements.......................................................................................................... V
Table of Contents ............................................................................................................VI
List of Figures and Tables ...............................................................................................IX
Chapter 1-Introduction ..................................................................................................1
1.1 Literature Review of Ferroelectric Domain Study by Piezoresponse Force
Microscopy (PFM)........................................................................................................1
1.1.1 Brief Introduction to PFM ........................................................................1
1.1.2 Study of Domain Structure in Lead Zirconate Titanate (PZT) Films by
PFM………………………………………………………………………………...4
1.1.3 Characterization of Relaxor Ferroelectrics by PFM .................................6
1.2 Motivation of Our Research............................................................................10
1.2.1 Studies on PZT Films..............................................................................10
1.2.2 Studies on PMN-PT Single Crystals ....................................................... 11
1.3 Scopes and Outline of Thesis..........................................................................12
References...................................................................................................................14
Chapter 2-Concepts and Methodologies.....................................................................24
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Table of Contents
2.1 Ferroelectrics and Ferroelectric Domain ........................................................24
2.1.1 Introduction to Ferroelectrics..................................................................24
2.1.2 Ferroelectric Domain and Polarization Switching ..................................27
2.2 Sample Preparation for PFM Approach ..........................................................32
2.2.1 Coating Electrode....................................................................................32
2.2.2 Poling of PMN-PT Single Crystals.........................................................32
2.2.3 Polishing .................................................................................................33
2.3 Characterization Approach..............................................................................34
2.3.1 Hysteresis Characteristics .......................................................................34
2.3.2 Determination of Dielectric Property......................................................35
2.3.3 Observation of Domain Structures..........................................................36
2.3.4 Other Equipments Used in This Work ....................................................36
2.4 Detailed Description of Domain Study by PFM .............................................37
2.4.1 Imaging Mechanism................................................................................37
2.4.2 Ferroelectric Domain Switching by PFM ...............................................39
2.4.3 Demonstration of PFM Approach...........................................................40
References...................................................................................................................43
Chapter 3-Characterization of 90 ° Domain Structure and Polarization Switching in
Pb(Zr0.4Ti0.6)O3 (PZT40/60) Film by PFM..................................................................46
3.1 Experimental Approach ..................................................................................46
3.2 Results and Discussion ...................................................................................47
3.2.1 Structure ..................................................................................................47
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Table of Contents
3.2.2 Ferroelectricity ........................................................................................48
3.2.3 Nanometer Scale Characterization of Domain Structures ......................48
3.2.4 Polarization Switching Mechanism ........................................................52
Reference ....................................................................................................................58
Chapter 4-Studies of Domain Structure and Evolution in (PbMg1/3Nb2/3O3)0.75
(PbTiO3)0.25 (PMN-25PT) Single Crystals by Temperature-dependent PFM .........60
4.1 (110)-Cut PMN-25PT Single Crystal..............................................................60
4.1.1 Experimental Procedure..........................................................................60
4.1.2 Results and Discussion ...........................................................................61
4.2 (111)-Cut PMN-25PT Single Crystals ............................................................77
4.2.1 Experimental Procedure..........................................................................77
4.2.2 Results and Discussion ...........................................................................77
Reference ....................................................................................................................88
Chapter 5-Conclusions and Future Work ..................................................................91
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List of Figures and Tables
Figure 1.1 Applications of PFM.................................................................................... 2
Figure 1.2 Domain structures in (a) Pb(Zr0.2Ti0.8)O3 thin films, (b) Pb(Zr0.53Ti0.47)O3 thin
films, and (c) Pb(Zr0.4Ti0.6)O3 film .............................................................. 5
Figure 1.3 Patterns “written” on PZT films by Hong et al............................................ 5
Figure 1.4 Word and arrays made on PZT thin films by Anh and Tybell...................... 6
Figure 1.5 A typical curve of temperature dependence of relative permittivity............ 7
Figure 2.1 The crystal of BaTiO3. (a) above the Curie temperature the cell is cubic; (b)
below the Curie temperature the structure is tetragonal with Ba2+ and Ti4+
ions displaced relative to the O2- ions ........................................................ 25
Figure 2.2 Schematic diagram of 180 o and 90 o domains .......................................... 28
Figure 2.3 Typical ferroelectric hysteresis loop illustrating the coercive field Ec, the
saturation polarization Psat, and the remnant polarization Pr ..................... 29
Figure 2.4 Schematic drawing of a triangular step of a 180 o domain wall. The applied
field is parallel to the polarization on the left-hand side of the figure....... 31
Figure 2.5 Schematic drawing showing the growth of triangular-shaped nuclei on the
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steps formed by earlier nucleations............................................................ 31
Figure 2.6 Schematic diagram of the poling process .................................................. 33
Figure 2.7 A modified Sawyer-Tower circuit for the observation of ferroelectric
hysteresis loop............................................................................................ 34
Figure 2.8 Schematic diagram of the measurement of temperature dependence of
relative permittivity.................................................................................... 36
Figure 2.9 Schematic diagram of PFM imaging mechanism. ..................................... 38
Figure 2.10 Qualitative model for the piezoelectric surface movements of the
ferroelectric sample in single point contact with the PFM tip and the
cantilever movement with the surface. ...................................................... 39
Figure 2.11 Schematic diagram of polarization switching............................................ 40
Figure 2.12 The photo of PFM (Nanoscope IV, Digital Instruments, USA) we used in this
project. ....................................................................................................... 41
Figure 2.13 (a) Diagram of the “writing”, (b) piezoresponse of the written “X”, and (c)
the surface potential measurement for the “X”.......................................... 42
Figure 3.1 XRD result of PZT40/60 film on Pt/Ti/SiO2/Si substrate.......................... 47
Figure 3.2 P-E loop of PZT40/60 film on Pt/Ti/SiO2/Si substrate with (111) preferred
orientation. ................................................................................................. 48
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Figure 3.3 Topographic (a) and corresponding piezoresponse (b) images of the
PZT40/60 film............................................................................................ 49
Figure 3.4 Typical PFM images of the PZT40/60 grain topography (a); (b)
piezoresponse phase image; and (c) tip vibration density as a function of the
sample distance along the line drawn in (b); (d) cross-section TEM image of
the PZT films showing lamellar 90 ° domains with {110} atomic planes as
domain walls, the arrow points out one (110) atomic plane. ..................... 50
Figure 3.5 The surface corrugation of the PZT40/60 film: (a) and (c) the topography of
one grain and the tip vibration density along the line drawn in (a); (b) and (d)
the piezoresponse image in the grain and the tip vibration density along the
line drawn in (b).….................................................................................... 51
Figure 3.6 Piezoresponse phase image of the grain shown in Fig. 3.4 after 10 V dc
voltage poling through the bottom electrode during the tip scanning. ...... 52
Figure 3.7 Illustration of 90 ° domains’ polarization switching mechanism: (a) to (b)
shows domain switching under external electric field through domain walls’
movement; (c) to (d) shows appearance of domains extended along new
direction under external electric field. ....................................................... 54
Figure 3.8 (a) Lamellar domains in one grain; piezoresponse phase image at the moment
ZHAO XIN XI
after applying a –10 V dc voltage to the bottom electrode (b) and after 24 h
(c); (d) piezoresponse phase image after applying –18 V dc voltage, the
lamellar feature disappeared. ..................................................................... 55
Figure 3.9 (a) Topography image of one grain, the cross indicates where the tip was
fixed; piezoresponse phase image in the grain by applying dc voltage to the
bottom electrode: (b) 0 V, and (c) 10 V for 10 min. A black round speckle
appeared after being applied 10 V dc poling voltage................................. 56
Figure 3.10 Schematic diagram of the nanometer-sized polarization switching............57
Figure 4.1 Temperature dependence of hysteresis characteristics of the (110)-cut
PMN-25PT single crystal........................................................................... 62
Figure 4.2 Temperature dependence of relative permittivity (ε'~T) of (a) the as-grown
and (b) the poled (110)-cut PMN-25PT single crystals. ............................ 63
Figure 4.3 Domain structure at room temperature in (a) as-grown and (b) poled
(110)-cut PMN-25PT single crystals, and (c) a schematic diagram showing
the relation between the poling (observation) direction and polarization
directions.................................................................................................... 65
Figure 4.4 Domain size distribution of the as-grown (110)-cut PMN-25PT single crystal.
.................................................................................................................... 67
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Figure 4.5 (a) Another pieozreponse image of poled (110)-cut PMN-25PT, (b) to (e)
illustrate polarization reversal of the arrowed domain in region outlined in (a):
(b) the original piezoresponse image where “+” indicates the point where the
tip was placed; (c) the piezoresponse image after applying an upward electric
field of 6 kV/cm between the tip and bottom electrode; (d) and (e) the
piezoresponse images after scanning the indicated domain in (b) in an area of
1.5x1.5 μm2 with an upward electric field of 6 kV/cm and 8 kV/cm,
respectively. ............................................................................................... 68
Figure 4.6 Temperature-dependent piezoresponse images showing the domain evolution
of the as-grown (110)-cut PMN-25PT single crystal at (a) 25, (b) 80, (c) 110,
(d) 120, and (e) 150 oC. (f) Piezoresponse image when the sample was cooled
back to room temperature. ......................................................................... 70
Figure 4.7 Temperature dependence of (a) the domain density, (b) the average amplitude
of piezoresponse, and (c) the sum the of domain areas the of as-grown
(110)-cut PMN-25PT single crystal. .......................................................... 71
Figure 4.8 Temperature-dependent piezoresponse images of domain structure in poled
(110)-cut PMN-25PT single crystal upon heating: (a) 25; (b) 90; (c) 100; (d)
110; (e) 120; and (f) 140 oC. (g) Piezoresponse image when the sample was
ZHAO XIN XIII

cooled back to the room temperature......................................................... 73
Figure 4.9 Temperature dependence of domain structures in the outlined region of Fig.
4.8 upon heating: (a) 25, (b) 90;, (c) 100, (d) 110, (e) 120, and (f) 140 oC.75
of piezoresponse and (c) the sum of the domain areas for the domain
structures shown in Fig. 4.9. ...................................................................... 76
Figure 4.11 Temperature dependence of hysteresis characteristics of the (111)-cut
PMN-25PT single crystals. ........................................................................ 78
Figure 4.12 Temperature dependence of relative permittivity (ε'~T) of (a) as-grown and
(b) poled (111)-cut PMN-25PT single crystals upon heating at frequencies of
100 Hz, 1 kHz 10 kHz................................................................................ 79
Figure 4.13 piezoresponse image of domain structures of the as-grown (111)-cut
PMN-25PT single crystal obtained at room temperature. ......................... 80
Figure 4.14 Domain size distribution of the as-grown (111)-cut PMN-25PT single crystal
corresponding to Fig. 4.13. ........................................................................ 81
Figure 4.15 Nanometer polarization switching at the same place in one grain by the dc
electric fields of (a) 4 kV/cm and (b) –4 kV/cm applied through bottom
electrode subsequently. .............................................................................. 81
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Figure 4.16 Temperature-dependent piezoresponse images of domain structure showing
domain evolution of the as-grown (111)-cut PMN-25PT at (a) 25, (b) 80, (c)
110, (d) 115, and (e) 150 oC. (f) The piezoresponse image when the sample
was cooled back to room temperature. ...................................................... 83
of piezoresponse and (c) the sum of the domain areas of the as grown
(111)-cut PMN-25PT.................................................................................. 84
Figure 4.18 Temperature-dependent piezoresponse images of domain structure showing
domain evolution of poled (111)-cut PMN-25PT single crystal: (a) 25, (b) 60,
(c) 80, (d) 100, and (e) 130 oC. (f) The piezoresponse image when the sample
was cooled back to room temperature. ...................................................... 85
Table 1 SPM techniques for ferroelectric imaging ................................................... 2
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Chapter 1 Intrtoduction
Chapter 1
Introduction
1.1 Literature Review of Ferroelectric Domain Study by
Piezoresponse Force Microscopy (PFM)
1.1.1 Brief Introduction to PFM
Since the invention of scanning probe microscopies (SPMs), more and more
applications have been reported because SPMs offer series of advantages such as high
[1-10]
resolution and low environment requirements, and so forth. The use of high-
resolution SPMs, in conjunction with conventional electrical measurements, to achieve
unique insight into the real physical processes that occur in ferroelectrics was first
reported by Saurenbach and Terris in 1990, who observed domain walls in the
ferroelectric-ferroelastic material Gd2(MoO4)3 (GMO) by detecting static polarization

[11]
surface charges. This is a sensitive and nondestructive measurement for
ferroelectrics. Following this, a lot of work on both the imaging and controlling of
ferroelectric materials by SPMs has been reported, and a series of techniques have been
[12-63]
introduced for the study of ferroelectrics using SPMs. Table 1 summarizes some
of the most common SPM imaging techniques used to characterize ferroelectric
materials and briefly presents the information obtained.
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Table 1 SPM techniques for ferroelectric imaging [10]
Technique Measure signal Relation to ferroelectric properties
Electrostatic force Electrostatic force gradient , Characterize electrostatic stray fields above
microscopy (EFM);
effective surface potential ferroelectric surface induced by surface
Scanning surface
polarization charge. Sensitive only to out-of-
potential microscopy
(SSPM) plane polarization component
Piezoresponse force Vertical and lateral surface Characterizes piezoelectric properties of the
microscopy (PFM)
displacement induced by tip surface. Vertical and lateral components of
bias signal are related to out-of-plane and in-plane
polarization components
Scanning capacitance Voltage derivative of tip- Based on polarization-induced hysteresis in

microscopy (SCM)
surface capacitance tip-surface capacitance. Only out-of-plane
polarization component can be determined
Near-field scanning Near-field optical properties Optical indicatrix of the surface reflects
optical microscopy
of the surface polarization induced anisotropy. Both in-plane
(NSOM)
and out-of-plane polarization components can
be determined
Friction force Friction forces Characterizes effects of polarization charge on

microscopy (FFM)
surface friction
Scanning non-linear Non-linear dielectric Both in-plane and out-of-plane polarization

dielectric microscopy
permittivity components can be measured
(SNDM)
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Among all of the techniques presented in Table 1, the PFM has been most
widely used, due to its ease of implementation, relatively high resolution, and
sensitivity to topography and state of the surface. Since ferroelectric domains can be
modulated to vibrate under an external electric field by applying a field between the tip
and the bottom electrode, the PFM has been used for imaging static domain structures
in thin films, single crystals, and polycrystalline materials. In addition, PFM can also be
used in the selective poling of specified regions on a surface, in studies of the thermal
evolution of domain structures, quantitative measurements of thermal phenomena, and
local hysteresis measurements. [19-63] It is not an exaggeration to say that PFM is rapidly
Fig. 1.1 Applications of PFM.
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becoming one of the primary tools in ferroelectrics research that has been routinely used
[10]
to obtain high-resolution (~10 nm) domain imaging. The information that can be
obtained by PFM is summarized in Fig. 1.1. In this project, PFM is the main technique
we have employed to study the ferroelectric domain structures.
1.1.2 Study of Domain Structure in Lead Zirconate Titanate (PZT) Films by
PFM
PZT is a well-known and widely used ferroelectric material because of its large
potential in applications in piezoelectric, pyroelectric, and non-volatile random access
memory devices. [64-66] Playing a key role in all of the above mentioned applications, the
characterization and modification of ferroelectric domains in PZT have attracted a great
deal of interest. [27-63]
In recent years, many high-resolution domain structures have been observed in a
variety of PZT films by directly placing the PFM tip in contact with the PZT film
[27-63]
surfaces, and the resolution can reach a nanometer scale. Figure 1.2 shows some
typical domain structures in different PZT films obtained by PFM. By keeping the tip
in-situ, the local hysteresis characteristics corresponding to the domains at the location
of the tip has also been obtained as an additional technique for PFM (as shown in Fig.
1.1). [38, 44, 62] Recently Hong et al mentioned that the cantilever-sample interaction may
overlap the tip-sample interaction, which can affect the hysteresis information of
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a b c
Fig. 1.2 Domain structures in (a) Pb(Zr0.2Ti0.8)O3 thin films, (b)
Pb(Zr0.53Ti0.47)O3 thin films, and (c) Pb(Zr0.4Ti0.6)O3 film. [38, 44, 62]
domains. The use of high-aspect ratio tip and large area screening electrode was
[28]
proposed to avoid this effect. However, it should be noted that although the large
area electrode can prevent the undesired signals, a topographic signal is also unavailable
for studying the relationship between the topography of sample and the domain
structure. With a large top electrode, the PFM tip can only detect the surface topography
of the electrode. In our work, the samples were without large area electrodes, and in the
domain studies the PFM tip was in direct contact with the surface of the sample.
Due to the large potential of PZT films in memory device applications, the
manipulating of the domains of PZT films and their dynamics, fatigue and loss of
retention have become one of the most attractive areas of research. Hong, Tybell, and
Ahn have achieved the “writing” of patters such as words, lines, and dot arrays on PZT
films, and some of these patterns are shown in Figs. 1.3 and 1.4. [31, 40, 61]
Fig. 1.3 Patterns “written” on PZT films by Hong et al. [ 61] P P
ZHAO XIN 5
Fig. 1.4 Word and array made on PZT thin films by Anh and Tybell. [31, 40]
1.1.3 Characterization of Relaxor Ferroelectrics by PFM
I. (1-x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 (PMN-PT) Single Crystals
Single crystal of PMN-PT, a relaxor-based complex perovskite ferroelectrics, has the
main features of strong dispersion of dielectric permittivity exhibiting of a very broad
maximum as a function of temperature, the absence of macroscopic spontaneous
polarization, and structural symmetry breaking under zero-field-cooling. Figure 1.5
shows a typical curve presenting a PMN-PT single crystal’s temperature dependence of
relative permittivity, where a significant broad peak and the dispersion can be clearly
revealed. [23] A PMN-PT single crystal provides superior piezoelectric properties and is
considered one of the best piezoelectric materials in the new-generation of transducers,
sensors, and actuators. In recent years, an increasing number of studies on PMN-PT
single crystals focusing on aspects such as phase transition, domain structure and
behavior under electric fields have been reported. [67-87]
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40000 100 Hz
Tm
1k Hz
35000 10k Hz
30000
ε' 25000
20000
15000
10000
5000
0
20 40 60 80 100 120 140 160 180 200 220 240
o
Temperature ( C)
Fig. 1.5 A typical curve of temperature dependence of relative permittivity. [23]
II. Microdomain-Macrodomain Transition
A microdomain-macrodomain transition in relaxor ferroelectrics was first proposed by

[87-91]
Yao et al. and proved by Yin using TEM. The microdomain-macrodomain
transition has now also been used to explain the domain evolution in PMN-PT single
crystals. The PMN-PT single crystals have a morphotropic phase boundary (MPB) in
the range of 28~36% of PT. When PT% > 36%, the PMN-PT single crystals behave as
normal ferroelectrics, where only macrodomains with sizes of hundreds of microns
exists. On the other hand, when PT% < 28%, only rhombohedral microdomains exist in
the single crystals; while if poled by an external electric field, these microdomains can
[67-69]
be transformed to macrodomains. The relaxor characteristics of poled PMN-PT
can be revealed by two temperatures Td and Tm, where Td is the transition temperature
from the macrodomain to the microdomain and Tm represents the phase change
temperature from the ferroelectric to paraelectric phases.[67-69, 88, 89]
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It should be noted that there are no exact definitions of the sizes of microdomain
and macrodomain; however, the microdomain and macrodomain are distinguished by
significant difference in dimension. The macrodomain is believed to be several
hundreds microns in size and can even be seen by the human eye, while the
microdomain is ranged from several microns to nanometer scale. Recently, Kholkin and
co-researchers reported domain structures of nanometer-size in PMN-20PT single
crystal and in PZN-4.5PT single crystals, another well-known relaxor ferroelectrics. [24,
25]
III. Polar Nanometer-sized Region (PNR)
It is generally accepted that the properties of relaxors are closely related to the
structures of the relaxors, which are quite different from normal ferroelectrics. PNR was
thus proposed to explain relaxor phenomena. For example, relaxors have broad
dielectric peaks, because the ferroelectric to paraelectric phase transition temperature of
each PNR is different. It is claimed that PNRs with a short-range order exist in
temperatures ranging from far above to below Tm, and agglomerate to form
[81, 82, 92-94]
microdomains upon cooling from the paraelectric phase. However,
information about PNRs and their dynamics was obtained in indirect ways such as
through x-ray and neutron diffractions, while information from direct observations has
not been obtained and the evolution of PNRs under different conditions is unclear. [81, 94]
Very recently, Shvartsman and Kholkin reported a complex polar structure, which
reflects two mutually dependent processes—the appearance of the ferroelectric state at
ZHAO XIN 8
room temperature and the existence of PNRs in a large temperature range. However, the
measured distribution of the size of the nanodomain is essentially wider than that
expected for PNRs. [25]
IV. Observation of Domain Evolution in PMN-PT Single Crystals
Because of its important role in the relaxor phenomenon, the evolution of domain
structures in relaxor ferroelectrics under different temperatures and electric fields have
attracted a great deal of interest in recent years. In early studies, the results were mainly
obtained from indirect information such as temperature dependence of relative

[67-71, 76, 79-83]
permittivity or high-energy x-ray diffraction and neutron diffraction.
Optical methods were commonly used to visualize domain structures. Tu studied the
evolution of domain structures in PMN-PT single crystals under zero-field-heating
(ZFH) and field-cooling-zero-field-heating (FC-ZFH) using a polarized microscope. [72-

75]
However, limited by the resolution, the optical method is appropriate only for
observing domains of a size in the order of microns, and is focused on the compositions
with a PT% of close to 35%, which exhibit micron-sized domain structures at room
temperature. [73, 74, 78]
After the PFM was successfully applied to the study of ferroelectric materials in
the nanometer scale, the situation improved a great deal. Several studies on the direct
observation of domain structures in relaxor ferroelectrics have been reported, with the
[24-26]
resolution approaching the scale of nanometers. Nevertheless, the attempts have
ZHAO XIN 9
not been enough to achieve an understanding of relaxor ferroelectrics such as the
domain evolution under varied temperatures after poling at room temperature and the
microdomain-macrodomain transition induced by varying the temperature. Since
observing domain structures in relaxors by PFM has proven to be the most efficient
method in terms of resolution and the advantages in varying temperatures and electric
fields, studying PMN-PT domain structures by PFM under various conditions should
offer great potential.
1.2 Motivation of Our Research
1.2.1 Studies on PZT Films
Even though a fairly clear picture has been obtained, a detailed understanding of the
domain structure and the switching mechanism of PZT films is still limited, and some
discrepancies can still be found in recent reports on aspects such as the structural
o o
characterizations and domain dynamics of both 90 domains and 180 domains in
o
different PZT films. Ganpule et al have reported the study of 180 polarization
o
switching and backswitching of 90 domains in PbZr0.2Ti0.8O3 films, and have
[44]
concluded that the nucleation occurred at the grain boundaries. This switching
mechanism was also proposed by Gruverman in 1997. [37] On the other hand, Fu and co-
workers argued in their work reported in 2003 that the grain boundary is not the
essential factor in the backswitching, as they found nucleation in the middle of a grain
[50]
in Pb(Zr0.3Ti0.7)O3 thin films. In the same year, a step structure appearing in the
process of polarization switching in Pb(Zr0.4Ti0.6)O3 thin films was also reported by
ZHAO XIN 10
[63]
Zeng. Till now, the mechanism of domain polarization switching is still not well
understood, and more work on the subject still needs to be carried out and new insights
are expected in the near future.
1.2.2 Studies on PMN-PT Single Crystals
As a ferroelectric material, there are many requirements relating to the characterization
of PMN-PT single crystals so that they can be better applied. Some studies on the
temperature dependence of the relative permittivity and so forth of PMN-PT single
crystals with different compositions have been reported. However, there have been only
a few reports involving direct observations of microdomain structures and their
evolutions. Very recently, Shvartsman and Kholkin reported the results of as-grown
[25]
PMN-20PT microdomain observed by using a PFM under increasing temperatures.
However, direct observations on the evolution from the macrodomain to the
microdomain in poled PMN-PT have not yet been reported, and more details are still
required on the phase transitions of domain structures in various compositions of PT.
ZHAO XIN 11
1.3 Scopes and Outline of Thesis
Corresponding to the questions and prospects mentioned above, our work focused on
the following points:
• Characterization of domain structure and polarization switching in
Pb(Zr0.4Ti0.6)O3 (PZT40/60) film by PFM;
• Studies of domain structure and evolution in (PbMg1/3Nb2/3)0.75(PbTiO3)0.25
(PMN-25PT) single crystals by temperature-dependent PFM.
In Chapter 2, what will be firstly introduced are some basic definitions and
theories about the ferroelectrics and ferroelectric domains, which have a significant
relationship with the work we carried out. Following the concepts are the main
methodologies used in the experiments and the sample preparations before
measurements.
The following two chapters, Chapter 3 and Chapter 4, are the work we carried
out on the studies of domains in the PZT40/60 film and the PMN-25PT single crystals.
The reason of choosing PZT40/60 film for the domain studies is that 90 o domains are
supposed to exist in it and the domain shapes and polarization switching mechanism are
interesting to be figured out. On the other hand, there are large grains with size of
microns on the surface of the sol-gel deposited PZT40/60 film, thus it is easy to study
the domain structure in one single grain. As described in Chapter 3, a lamellar-shaped
domain structure was revealed in the PZT40/60 film by PFM and the domains were
o
attributed to be 90 domains. Different results of polarization switching by nano-area
ZHAO XIN 12
poling and large-area poling present different polarization switching mechanisms.
Chapter 4 contains the studies of domains in PMN-25PT single crystals,
including dielectric properties, ferroelectric properties and domain evolution of as-
grown and poled (110)-cut and (111)-cut PMN-25PT single crystals. The 25% PT is far
away from the morphotropic phase boundary (MPB), and it is believed that only
rhombohedral microdomains exist in the PMN-25PT single crystals, however, these
microdomains can be transferred to macrodomains by external electric field. Upon
heating, a transition of macrodomain-microdomain-paraelectric phase is proposed to
occur in the poled PMN-25PT single crystals. Statistical analyses were also carried out
to study the temperature dependence of domain density, average piezoresponse
amplitude and domain sizes. The results obtained in experiments of microdomain-
macrodomain transition are found to agree well with the theory.
Conclusions obtained from above studies are summarized in Chapter 5, and
prospects of future research are also proposed.
ZHAO XIN 13
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ZHAO XIN 22
Matter 3, 8159 (1991).

93. S. Wakimoto, C. Stock, R. J. Birgeneau, Z. –G. Ye, W. Chen, W. J. L. Buyers, P.
M. Gehring and G. Shirane, “Ferroelectric ordering in the relaxor
Pb(Mg1/3Nb2/3)O3 as evidence by low-temperature phonon anomalies”, Phys.
Rev. B 65, 172105 (2002).
94. B. Dkhil, J. M. Kiat, G. Calvarin, G. Baldinozzi, S. B. Vakhrushev and E. Suard,
“Local and long range order in the relaxor-ferroelectric compounds
PbMg1/3Nb2/3O3 and PbMg0.3Nb0.6Ti0.1O3”, Phys. Rev. B 65, 024104 (2001).
ZHAO XIN 23
Chapter 2 Concepts and Methodologies
Chapter 2
Concepts and Methodologies
2.1 Ferroelectrics and Ferroelectric Domain
2.1.1 Introduction to Ferroelectrics
I. General View of Ferroelectrics
It has been over 80 years since the phenomenon now known as ferroelectricity was first
[1-4]
recognized in Rochelle salt by Valasek in 1920. From 1935 to 1938, the first series
of ferroelectric crystals KH2PO4 (KDP) and (NH4)H2PO4 (ADP) were produced in

[5, 6]
Zurich. All the discovered ferroelectrics at that time were found to have hydrogen
bond before ferroelectric activity in BaTiO3 was reported in 1945, whose crystal
structure of the prototype was cubic centrosymmetric pervoskite with very high
symmetry and only five atoms per unit cell.[7] Following the discovery of BaTiO3, is the
discovery of ferroelectric activity in KNbO3, KTaO3, LiNbO3, LiTaO3, PbTiO3 and
Pb(ZrxTi1-x)O3, etc., which are now perhaps the largest single class of all
ferroelectrics—the oxygen octahedral ferroelectrics made up from basic BO6 building
blocks, and become the main industrial product in piezoelectric ceramic materials. [8-14]
Till now there have been thousands of materials reported to be ferroelectrics.
Ferroelectric materials, especially polycrystalline ceramics, are very promising
ZHAO XIN 24
for a variety of applications such as high permittivity capacitors, ferroelectric memories,
pyroelectric sensors, piezoelectric/electro-strictive transducers, electro-optical devices
and positive temperature coefficient (PTC) thermistors. Some of them have been used
in a large number of simple devices. [1, 15, 16]
II. Spontaneous Polarization
A crystal exhibiting spontaneous polarization can be visualized to be composed of
negative and positive ions, at which the free energy of the crystal is a minimum, and the
[1, 15, 16]
center of positive charge does not coincide with the center of negative charge.
For example, Figure 2.1 shows the crystal structure of BaTiO3. Above the Curie
temperature of 120 oC, the crystal structure is cubic, with Ba2+ ions at the cube corners,
O2- ions at the face centers and Ti4+ ion at the body center, as shown in Fig. 2.1 (a).
Fig. 2.1 The crystal of BaTiO3. (a) above the Curie temperature the cell is cubic; (b) below the Curie
temperature the structure is tetragonal with Ba2+ and Ti4+ ions displaced relative to the O2- ions.[15]
ZHAO XIN 25
Below the Curie temperature, the structure is slightly deformed, with Ba2+ and Ti4+ ions
displaced relative to the O2- ions, thereby creating a dipole, as shown in Fig. 2.1 (b).
Thus we may visualize each pair of positive and negative ions as an electric dipole, and
the spontaneous polarization is due to an assembly of these dipoles. Although a crystal
with polar axes exhibits piezoelectric effect, it does not necessarily to have a
spontaneous polarization vector, because the net result of electric dipoles along all polar
axes may be equal to zero.
III. Ferroelectric and Phase Transition
A crystal is said to be ferroelectric when it has two or more orientation states, i.e.,
spontaneous polarization, in the absence of an electric field and these states can be
[1, 15, 16]
shifted from one to another by an external electric field. In every state, the
spontaneous polarization is stable at null electric field.
When the temperature decreases through the Curie temperature (Tc), a
ferroelectric crystal undergoes a structural phase transition from a paraelectric phase to
a ferroelectric phase. When the temperature is above Tc the crystal does not exhibit
ferroelectricity, and the lattice symmetry in the paraelectric phase is always higher than
that of the lattice symmetry in the ferroelectric phase.
ZHAO XIN 26
2.1.2 Ferroelectric Domain and Polarization Switching
I. Ferroelectric Domain
When a ferroelectric crystal is cooled down from a paraelectric phase to a ferroelectric
phase in the absence of applied fields, there are at least two equivalent directions along
which the spontaneous polarization may occur. In order to minimize the free energy,
different regions of the crystal polarize in each of these directions, and each region of
uniform polarization being referred to as domain. The boundaries separating domains
are referred to as domain walls. [1, 15, 16]
The final domain configuration of ferroelectrics is obtained by minimizing the
total free energy of the crystal including the energy associated with the crystal surfaces
and domain walls, which can be written as: [1]
D2 D4
G1 = G10 + ∫ (α +γ )dV + WE + WW . (2.1)
2 4
In the above equation, G10 is the elastic Gibbs free energy corresponding to the
polarization P = 0; α and γ are temperature dependent coefficients; D is the electric
displacement; V presents the volume of crystal; WE is the depolarization energy caused
by surface charges tending to depolarize; Ww is called domain wall energy, which can be
re-written as:
WW = Wdip + W x , (2.2)
where Wdip is the dipolar energy, and Wx is the elastic energy. Therefore, Eq. (2.1) can
be changed into:
ZHAO XIN 27
D2 D4
G1 − G10 = ∫ (α +γ )dV + WE + Wdip + W x , (2.3)
2 4
where the depolarizing energy WE and the elastic energy Wx play the important role in
domain formation. During the ferroelectric phase transition, if the depolarizing energy is
the dominant energy, in order to lower it, 180 o domains will be formed in a ferroelectric
o
crystal. However, if the elastic energy plays a dominating role, 90 domains can be
obtained to minimize the elastic energy. Figure 2.2 shows the schematic diagram of 180
o
and 90 o domains, respectively.
Fig. 2.2 Schematic diagram of 180 o and 90 o domains
II. Hysteresis Characteristics
An important characteristics of ferroelectrics is the ferroelectric hysteresis loop, i.e., the
polarization P is a double-valued function of the applied electric field E. A hysteresis
loop can be observed by means of a varying E applied on the ferroelectric sample.
Figure 2.3 shows a typical hysteresis loop presenting the relationship between the
polarization and the electric field, which can also be named as the P-E loop.
Suggested by the hysteresis loop, a ferroelectrics behaves linearly at low fields
and very high fields. While at the so-called coercive field Ec, polarization reversal
ZHAO XIN 28
occurs giving a large non-linearity. Corresponding to the opposite orientations of the
spontaneous polarization, the saturated electric displacement extrapolated to zero field
has two equal values, which equals to saturation polarization Psat in a perfect crystal. As
the field strength decreases from the polarization saturation point, the polarizations will
generally decrease but does not return to zero, when the field is reduced to zero. Some
of the polarizations remain aligned in the positive direction and the crystal exhibits a
remnant polarization Pr.
Psat
Fig. 2.3 Typical ferroelectric hysteresis loop illustrating the coercive

field Ec, the saturation polarization Psat, and the remnant polarization
Pr. [15]
ZHAO XIN 29
III. Polarization Switching
As revealed from the P-E loop, the polarization can be reversed, at least partially, with
an applied electric field. This is a primary feature distinguishing ferroelectrics from
other paraelectrics. Till now, there has been a great deal of experimental and theoretical
works on both direct microscopic observations of domains during switching and
electrical measurements on bulk crystals in order to understand the mechanism of
polarization reversal and domain dynamics. [17-22] Based on experimental data, it is now
generally believed that polarization reversal can be accomplished either by the growth
of existing domains parallel to the applied field, by domain-wall motion, or by the
nucleation and growth of new domains. One approach to reveal the domain nucleation
and domain-wall motion by taking the 180 o domains as example is briefly described as
follows. [1]
The ferroelectric domain can grow either along the polar direction or by
sideways motion of 180 o domain walls, and it appears that for most ferroelectrics with
the polar axis normal to plate-shaped crystal, sideways motion of 180 o domain walls is
preferred to forward motion. However, as recognized very early, a domain wall is
generally only a few lattice spacings thick, and therefore the energy required to move
the wall through one lattice spacing should be comparable to the wall energy itself.
However, based on experimental data, the energy gained from the external electric field
to move the wall is much smaller than the wall energy, thus the entire domain wall
movement in the polarization switching process is unlikely. Therefore, the only model
that can explain the sideway wall motion is the nucleation and two-dimensional growth
ZHAO XIN 30
of reversed step-like domains on existing 180 o domains.
The total energy change upon nucleation of a domain can be written as:
ΔW = WW + WE − D ⋅ EV , (2.4)
where the first two terms, Ww and WE, are the wall energy and depolarization energy,
respectively, of the nucleus, and the third term, D·EV, is the electrostatic energy of the
nucleus of volume V in the applied field. The polarization D and local field E within the
nucleus are assumed to be uniform.
From the energy considerations, in which ∆W should be as small as possible, the
most favorable shape of the nucleus formed on an existing wall where it intersects the
crystal surface is the triangular shape as shown in Fig. 2.4. The requirement that the
Fig. 2.4 Schematic drawing of a triangular step of a Fig. 2.5 Schematic drawing showing the
o
180 domain wall. The applied field is parallel to growth of triangular-shaped nuclei on the
[1]
the polarization on the left-hand side of the figure. steps formed by earlier nucleations. [1]
ZHAO XIN 31
nucleus shall grow gives rise to a critical size of the nucleus determined by the a and l
and the thickness c is taken as one lattice constant in the low-field regime. Constant
nuclei can grow on the growing steps of earlier nucleus as shown in Fig. 2.5.
2.2 Sample Preparation for PFM Approach
2.2.1 Coating Electrode
Dot electrodes with diameters of 0.1 mm were coated on the PZT film for the hysteresis
loop measurement and wire-bonded for local piezoelectric properties study via PFM.
PMN-PT single crystals were coated with electrodes on both sides for the poling
process and the measurements of temperature dependence of relative permittivity. All
materials of the electrodes were selected as Au/Cr for better conductivity and adhesion
and the electrodes were coated via magnetron sputtering.
2.2.2 Poling of PMN-PT Single Crystals
The schematic diagram of the dc-poling system, where the PMN-PT single crystal was
placed, is shown in Fig. 2.6. Based on our experience, poling can be well achieved at a
temperature of 30~40 oC below the Tm, and the samples were usually placed in silicone
oil for heating.
ZHAO XIN 32
Fig. 2.6 Schematic diagram of the poling process.
2.2.3 Polishing
Although the surface roughness requirement for PFM is low, high-quality surface is
favorable for the contact between PFM tip and sample. On the other hand, the PFM
works by applying a voltage on the sample, and thus the thicker the sample, the larger
the electric field needed. The original PMN-PT single crystals were simply cut into
small plates by a diamond cutter, which could not offer the suitable surface quality and
thickness for PFM. The desired thickness and surface flatness were achieved by
mechanical polishing.
ZHAO XIN 33
2.3 Characterization Approach
2.3.1 Hysteresis Characteristics
The hysteresis characteristics of the ferroelectric samples is described by the loop of
polarization versus electric field (P-E loop), which is a basic property of the
ferroelectrics as introduced in §2.1. The P-E loop can provide much information
relating to the ferroelectric domains such as the selection of the magnitude of
modulating ac voltage and the dc switching voltage. In this project, the P-E loop was
[1, 15]
measured via a Sawyer-Tower circuit, as shown in Fig. 2.7. Before measurement,
the sample should be coated with electrodes on both sides. In the measurements of PZT
films, the voltage was rather low in order to avoid breakdown; while a high voltage was
needed in the measurements of PMN-PT single crystals due to the large thickness
Fig. 2.7 A modified Sawyer-Tower circuit for the observation of

ferroelectric hysteresis loop
ZHAO XIN 34
(about 500 μm). In order to characterize the relaxor ferroelectric property of the PMN-
PT single crystals, the PMN-PT single crystals were immersed in silicone oil for the P-E
loop measurements.
2.3.2 Determination of Dielectric Property
Ferroelectric materials are polar dielectrics. For most applications of ferroelectric
materials, the relative permittivity and dielectric loss are important practical parameters,
and studies of the dielectric properties provide a great deal of information for
understanding the molecular structure and the mechanism of electric polarization in the
ferroelectric materials. [1, 15]
As presented in Chapter 1, the PMN-PT single crystal selected in this project is a
relaxor ferroelectric whose relaxor characteristics can be revealed by the curve of
relative permittivity versus temperature (ε′-T). Therefore, the ε′-T curve is a necessary
complementary information to the PFM observation. Figure 2.8 is the schematic
diagram of the experimental setup for ε′-T curve measurements.
ZHAO XIN 35
Fig. 2.8 Schematic diagram of the measurement of temperature dependence

of relative permittivity.
2.3.3 Observation of domain structures
A number of techniques have now been developed for revealing domain structures. The
usefulness of each of these techniques varies from one material to another: (a)
birefringence induced by a mechanical stress or an electric field, which is then observed
by a polarizing microscope; (b) chemically etched samples observed by scanning
electron microscopy; (c) X-ray; (d) powder pattern method (such as sulfur powder
carrying negative charges, lead oxide red powder carrying positive charges, and carbon
powder carrying positive charges); (e) scanning probe microscopy (details of this
method will be introduced in the latter section).
2.3.4 Other Equipments Used in This Work
In order to characterize the sample structure, x-ray diffraction (XRD) and transmission
electron microscope (TEM) are also used in the experiment.
ZHAO XIN 36
2.4 Detailed Description of Domain Study by PFM
2.4.1 Imaging Mechanism
PFM is a modified AFM equipped with a conductive tip and a lock-in amplifier,
working on the detection of the local electromechanical vibration of the ferroelectric
sample caused by an external ac voltage in tip/sample/bottom electrode configuration.

[17, 18 23]
Schematic diagram of the PFM imaging mechanism is shown in Fig. 2.9. In the
experiment, the conductive tip is brought into contact with the sample surface and acts
as a movable top electrode while scanning across sample surface. The ac voltage,
Vcosωt, can be applied through either the bottom electrode or the probing tip and
provides an electric field on the sample, which causes the sample to vibrate with the
same frequency ω due to the piezoelectric effect.
By changing optical signals detected from the tip deflection into electrical
signals through the photo-detector, the first harmonic vibration signal can be obtained.
This first harmonic signal, Acos(ωt+φ), together with a reference signal, Vcosωt, will
be combined in the lock-in amplifier and form a signal of Acos(ωt+φ)×Vcosωt
=VA[cos(2ωt+φ)+ cosφ]/2. The combined signal contains both high frequency and dc
1
components. After passing through low-pass filters, only the dc component VA cos ϕ
2
containing A and φ remains, where φ is the phase of the electromechanical response of
the sample, and A is the piezoresponse amplitude. A and φ reveal the local
piezoresponse activity of the sample. By imaging A and φ over an area, one can obtain
ZHAO XIN 37
the domain image.
Fig. 2.9 Schematic diagram of PFM imaging mechanism.
ZHAO XIN 38
According to the above description, a domain model with out-of-plane and in-
plane polarizations inside is shown in Fig. 2.10. The electric field applied perpendicular
to the sample surface can cause the domain with out-of-plane polarizations to expand or
shrink in the out-of-plane direction; while the surface tilt for the in-plane domain. The
movement of the PFM tip in contact with the sample surface following the surface
movement causes the cantilever to twist and deflect corresponding to the in-plane and
out-of-plane domains, respectively. These movements can be detected by the PFM as
the first harmonic signal Acos(ω t+ϕ). Figure 2.10 shows the cantilever movement in
contacting with the sample surface. It should be noted that due to the limitation of
equipments, in this project only out-of-plane domain movement was detected and the
domain imaging was based on this detected signal.
Fig. 2.10 Qualitative model for the piezoelectric surface movements of

the ferroelectric sample in single point contact with the PFM tip and the
cantilever movement with the surface.
2.4.2 Ferroelectric Domain Switching by PFM
In the polarization switching process, the conductive tip is in contact with the sample
surface like a movable top electrode, and a dc voltage is applied through either the
ZHAO XIN 39
bottom electrode or the tip thus producing a dc electric field in the sample, which can
[17, 18, 24-28]
cause the spontaneous polarization reversal along the field direction. In this
work, a dc voltage was applied through the bottom electrode while the conductive tip
was grounded (Fig. 2.11).
Fig. 2.11 Schematic diagram of polarization switching.
2.4.3 Demonstration of PFM Approach
Figure 2.12 shows a photo of the PFM (Nanoscope IV, Digital Instruments, USA) we
used in this project. To demonstrate its working mechanism, an “X”-shaped pattern
shown in Fig. 2.13 (a) was “written” on a pulsed laser deposited PZT thin film with a
thickness of about 250 nm. In the “writing” process, a dc voltage was applied through
the bottom electrode, while the PFM tip was grounded. The magnitudes of the dc
voltage are +25 V and –25 V for the 45 o and 135 o lines, respectively.
Figure 2.13 (b) shows the piezoresponse image of the written “X”, where the
black and white contrasts in the image clearly present the “X”. The black and white
contrasts correspond to the upward and downward polarizations, respectively. This was
proved by a surface potential measurement as shown in Fig. 2.13 (c). The surface
potential analysis is carried out to detect the surface charges on the sample surface,
ZHAO XIN 40
where positive charges correspond to white contrast, and negative charges appear black
in the surface potential image. The upward polarization in the sample induces positive
charges and the downward polarization induces negative charges on the sample surface.
From the “writing” test, the PFM has been proved to have the capability to
correctly image domain structures in ferroelectric films and cause polarization
switching by a dc voltage.
Fig. 2.12 The photo of PFM (Nanoscope IV, Digital Instruments, USA) we used in
this project.
ZHAO XIN 41
1 μm
Fig. 2.13 (a) Diagram of the “writing”, (b) piezoresponse of the written
“X”, and (c) the surface potential measurement for the “X”.
ZHAO XIN 42
References
1. M. E. Lines and A. M. Glass, “Principles and applications of ferroelectrics and

related materials, Oxford, 1977.
2. J. Valasek, “Piezo-electric and allied phenomena in Rochelle salt”, Phys. Rev. 17,
475 (1921).
3. J. Valasek, “Piezo-electric activity of Rochelle salt under various conditions”,
Phys. Rev. 19, 478 (1922).
4. J. Valasek, “Properties of Rochelle salt related to the piezo-electric effect”, Phys.
Rev. 20, 639 (1922).
5. G. Busch and P. Scherrer, “A new seignettoelectric substance”,
Naturwissenschaften 23, 737 (1935).
6. G. Busch, “New dielectrics of the Rochelle salt type”, Helv. Phys. Acta. 11, 269
(1938).
7. B. M. Wul and I. M. Goldman, “Dielectric constant of titanates of the metals of
the second group,” Dokl. Akad. Nauk USSR, 46, 154 (1945) (in Russian); C. R.
(Dokl.) Acad. Scl. USSR, 46, 139 (1945).
8. B. T. Matthias, “Dielectric properties of sodium and potassium niobates”, Phys.
Rev. 82, 727 (1951).
9. B. T. Matthias, “Ferro-electric properties of WO3”, Phys. Rev. 76, 430 (1949).
10. B. T. Matthias, “New ferroelectric crystals”, Phys. Rev. 75, 1771 (1949).
11. B. T. Matthias and J. P. Remeika, “Ferroelectricity in ammonium sulfate”, Phys.
Rev. 103, 262 (1956).
12. G. Shirane, S. Hoshino and K. Suzuki, “X-ray study of the phase transition in
lead titanate”, Phys. Rev. 80, 1105 (1950).
13. G. Shirane, E. Sawaguchi and A. Takeda, “On the phase transition in lead
zirconate”, Phys. Rev. 80, 485 (1950).
14. B. Jaffe, R. S. Roth and S. Marzullo, “Piezoelectric properties of lead zirconate
titanate solid-solution ceramics”, J. Appl. Phys. 25, 809, (1954).
15. Y. H. Xu, “Ferroelectric materials and their application”, North-Holland, 1991.
16. K. Uchino, “Ferroelectric devices”, Marcel Dekker, Inc., 2000.
ZHAO XIN 43
17. M. Alexe and A. Gruverman, “Nanoscale characterization of ferroelectric

materials—scanning probe microscopy approach”, Springer, 2004.
18. A. Gruverman, O. Auciello and H. Tokumoto, “Imaging and control of domain
structures in ferroelectric thin films via scanning force microscopy”, Annu. Rev.
Mater. Sci. 28, 101 (1998).
19. A. Gruverman, O. Auciello, R. Ramesh and H. Tokumoto, “Scanning force
microscopy of domain structure in ferroelectric thin films: imaging and control”,
Nanotechnology 8, 3491 (1997).
20. C. S. Ganpule, V. Nagarajan, H. Li, A. S. Ogale, D. E. Steinhauer, S. Aggarwal,
E. Williams and R. Ramesh, “Role of 90 o domains in lead zirconate titanate thin
films”, Appl. Phys. Lett. 77, 292 (2000).
21. D. Fu, K. Suzuki, K. Kato and H. Suzuki, “Dynamics of nanoscale polarization
backswitching in tetragonal lead zirconate titanate thin film”, Appl. Phys. Lett.
82, 2130 (2003).
22. H. R. Zeng, G. R. Li, Q. R. Yin and Z. K. Xu, “Nanoscale domain switching
mechanism in Pb(Zr,Ti)O3 Thin Film”, Appl. Phys. A 76, 401 (2003).
23. S. Hong, J. Woo, H. Shin, J. U. Jeon, Y. E. Pak, E. L. Colla, N. Setter, E. Kim
and K. No, “Principle of ferroelectric domain imaging using atomic force
microscope”, J. Appl. Phys. 89, 1377 (2001).
24. H. Bluhm, A. Wadas, R. Wiesendanger, A. Roshko, J. A. Aust and D. Nam,
“Imaging of domain-inverted gratings in LiNbO3 by electrostatic force
25. T. Hidaka, T. maruyama, M. Saitoh, N. Mikoshiba, M. Shimizu, T. Shiosaki, L.
A. Wills, R. Hiskes, S. A. Dicarolis, and J. Amano, “Formation and observation
of 50 nm poalrizaed domains in PbZr1-xTixO3 thin film using scanning probe
microscope”, Appl. Phys. Lett. 68, 2358 (1996).
26. C. H. Ahn, T. Tybell, L. Antognazza, K. Char, R. H. Hammond, R. Beasley,
Fischer and J. –M. Ttriscone, “Local, nonvolatile electronic writing of epitaxial
Pb(Zr0.52Ti0.48)O3/SrRuO3 heterostructures”, Science 276, 1100 (1997).
27. E. L. Colla, S. Hong, D. V. Taylor, A. K. Tagantsev, N. Setter and K. No, “Direct
ZHAO XIN 44
observation of region by region suppression of the switchable polarization

(fatigue) in Pb(Ti, Zr)O3 thin film capacitors with Pt electrodes” Appl. Phys.
Lett. 72, 2763 (1998).
28. S. Hong, E. L. Colla, E. Kim, D. V. Taylor, A. K. Tagantsev, P. Muralt, K. No
and N. Setter, “High resolution study of domain nucleation and growth during
polarization switching in Pb(Zr,Ti)O3 ferroelectric thin film capacitors”, J. Appl.
Phys. 86, 607 (1999).
ZHAO XIN 45
Chapter 3 90 o Domain in PZT40/60 Film
Chapter 3
Characterization of 90 ° Domain Structure and

Polarization Switching in Pb(Zr0.4Ti0.6)O3 (PZT40/60)
Film by PFM
3.1 Experimental Approach
A sol-gel process was used to prepare the ferroelectric Pb(Zr0.4Ti0.6)O3 (PZT40/60) film.
[1]
The coating solution of PZT was deposited onto Pt (111)/Ti/SiO2/Si (100) substrate
by spin coating at 3000 rpm for 30 sec. After each spin-coating process, the film was
heat-treated at 320 °C for about 10 min in air ambient using a hot plate. These steps
were repeated for six times until the desired thickness of 300 nm was reached. The PZT
film on Pt/Ti/SiO2/Si substrate was then annealed at 650 °C for 5 min by rapid thermal
annealing in oxygen ambient.
The structure of the PZT40/60 film was characterized by XRD. In order to
measure the ferroelectric property of the film, gold top electrodes with a diameter of 0.1
mm were coated on the surface of the film. The P-E loop was measured via the Radiant
Technologies RT66 ferroelectric instrument. The domain structure was characterized by
PFM (Nanoscope IV, Digital Instruments) by the imaging of piezoresponse in the region
without top electrode. The PFM was operated in the piezoresponse mode and equipped
with a Pt/Ir-coated tip whose radius was less than 25 nm and force constant was 2.8
ZHAO XIN 46
N/m. During imaging, an ac voltage with a Vp-p of 4.0 V at 16.5 kHz was applied to the
bottom electrode. In order to know the structure in more details, TEM was also
performed to study the cross-section of the PZT40/60 film.
3.2 Results and Discussion
3.2.1 Structure
As illustrated by the XRD result (Fig. 3.1), the PZT40/60 film possesses a single
perovskite phase. The fact that the intensity of the (111) diffraction peak is much higher
than that of other diffraction peaks suggests that the film has a (111) preferred
orientation.
Pt(111)
(111)
Intensity (CPS)
(100)
(200)
Si(200)
20 30 40 50 60
2θ(deg)
Fig. 3.1 XRD result of PZT40/60 film on Pt/Ti/SiO2/Si substrate.
ZHAO XIN 47
3.2.2 Ferroelectricity
Figure 3.2 shows a typical P-E loop of the PZT40/60 film, where well-defined
ferroelectric hysteresis characteristics with a remnant polarization (Pr) of 19 μC/cm2 and
a coercive field (Ec) of 133 kV/cm can be obtained.
40
30
20
Polarization (μC/cm )
2
10
-10
-20
-30
-40
-400 -300 -200 -100 0 100 200 300 400
Electric field (kV/cm)
Fig. 3.2 P-E loop of PZT40/60 film on Pt/Ti/SiO2/Si substrate with (111) preferred orientation.
3.2.3 Nanometer Scale Characterization of Domain Structures
Figure 3.3 shows the PFM topographic and piezoresponse images of the PZT40/60 film.
The topographic image of the film reveals a polycrystalline structure consisting of
faceted grains with an average size of 1 μm. In the corresponding piezoresponse image,
lamellar-shaped regions with bright and dark contrast can be clearly observed in the
grains, suggesting a lamellar ferroelectric structure in the grains. It can also be seen that
the domains are usually restricted inside the grains and cannot cross the grain
boundaries.
ZHAO XIN 48
a b
1 μm
Fig. 3.3 Topographic (a) and corresponding piezoresponse (b) images of the
PZT40/60 film.
A detailed domain structure in a single grain (Fig. 3.4 (a)) is shown in Fig. 3.4
(b), where a lamellar domain structure with distances between two strips ranging from
20 to 25 nm can be seen. Similar lamellar domains in PbTiO3 film were reported earlier
and were attributed to 90 ° domains by Loppacher and co-workers. [2] According to Hu

[3] [4-8]
and Chen’s simulation and the Speck-Streiffer-Pompe-Romanov domain model ,
we believe that the lamellar domains observed in the PZT40/60 grains are 90 º domains.
In the tip vibration density analysis (Fig. 3.4 (c)) of the lamellar domains as a function
of sample distance along the dotted line drawn in Fig. 3.4 (b), the peak-to-peak value of
the piezoresponse phase difference is about 160 º, which is close to 180 °. This suggests
the separation of the 90 º domains’ piezoresponse component is in a direction normal to

[9]
the film. In fact, our TEM observation revealed that the lamellar domain boundaries
are in the {110} atomic planes, thus verifying that the ferroelectric domains are 90 °
domains (see Fig. 3.4 (d)).
ZHAO XIN 49
According to the Speck-Streiffer-Pompe-Romanov domain model, the domain
walls exert a strain component normal to the film surface because of defects
accumulated in the boundaries between adjacent domains, and this strain results in a
[10]
surface corrugation. Our experimental results agree well with this domain model as
shown in Fig 3.5, from which an obvious surface corrugation can be observed. The
cross-section analysis revealed that, the heights of the corrugation peaks are in the range
of 0.5~1.5 nm, and the distance between each pair of two peaks is about 80 nm, which
are fairly close to those determined from the cross-section analysis of the domain
structures.
Fig. 3.4 Typical PFM images of the PZT40/60 grain topography (a); (b)
piezoresponse phase image; and (c) tip vibration density as a function of the
sample distance along the line drawn in (b); (d) cross-section TEM image of the
PZT films showing lamellar 90 ° domains with {110} atomic planes as domain
walls, the arrow points out one (110) atomic plane.
ZHAO XIN 50
a b
250 nm
c d
Fig. 3.5 The surface corrugation of the PZT40/60 film: (a) and (c) the topography of
one grain and the tip vibration density along the line drawn in (a); (b) and (d) the
piezoresponse image in the grain and the tip vibration density along the line drawn in
(b).
ZHAO XIN 51
3.2.4 Polarization Switching Mechanism
To study the switching process of lamellar 90 ° domains under external electric field, a
dc voltage was applied to the bottom electrode during the tip scanning across the sample
surface. Figure 3.6 shows the piezoresponse image of the same grain after being poled
by a 10 V dc voltage applied to the bottom electrode. Compared to Fig. 3.4 (b), one can
see the change of the domain structure, indicating a polarization switching inside the
particular grain. In addition, besides the lamellar domains extending along the direction
the same as that in Fig. 3.4 (b), some new lamellar domains with a bending angle of
about 120 ° appeared on the poled grain. The appearance of the new lamellar 90 °
domains during polarization switching under external electric field is believed to
minimize the stress induced in the grain. It is also interesting to notice that the
Fig. 3.6 Piezoresponse phase image of the grain shown in Fig. 3.4 after 10
V dc voltage poling through the bottom electrode during the tip scanning.
ZHAO XIN 52
piezoresponse image shown in Fig. 3.6 illustrates crystal defects in the grain as outlined
by the dotted line. The irregular shape and discontinuity of lamellar domains in this
outlined area suggest that it may correspond to crystal defect other than domain
boundaries. The misalignment of the lamellar domains as indicated by arrows is due to
the defect pinning, and similar pinning effect in polarization switching was reported
earlier by Lupascu and Rabe. [11]
In order to understand this switching mechanism, we may consider the
tetragonal PZT structure as pseudo-cubic. Such a structure contains six equivalent
twinning planes: (110), (101), (011), ( 1 10), ( 1 01), (0 1 1), and each of the twinning
planes can act as 90 ° domain wall. For a grain with only one domain wall system
among the six, if a polarization switching is accomplished through the movement of the
90 ° domain walls, it will induce large shear stress in the grain along one direction.
However, if new 90 ° domain wall systems with different twinning planes are generated
and help to finish the polarization switching, the stress can be evenly distributed. These
two switching processes are illustrated in Fig. 3.7, where (a) to (b) indicate the
polarization switching through the domain walls movement, while (c) shows that there
is only one twinning plane as 90 ° domain walls, and in (d), another extending direction
of 90 ° domains appear under the external electric field.
Based on the understanding of this mechanism, we propose that, if we call the
regions possessing different domain walls corresponding to the six different twinning
planes in the pseudo-cubic structure as “domain”, the lamellar 90° domains can be
ZHAO XIN 53
referred to as “subdomain”. Both the “domain” and “subdomain” walls are moveable
during the polarization switching, and minimized strain energy may be achieved due to
the walls’ movement.
a b
c d
Fig. 3.7 Illustration of 90 ° domains’ polarization switching mechanism: (a) to
(b) shows domain switching under external electric field through domain walls’
movement; (c) to (d) shows appearance of domains extended along new
direction under external electric field.
Figure 3.8 illustrates polarization switching and retention in another area of the
film where similar lamellar domain structure can be seen in the original piezoresponse
image (Fig. 3.8 (a)). After switched by a –10 V dc voltage added to the bottom electrode
during scanning, the lamellar domain structure (Fig. 3.8 (b)) has almost the same
change as the former grain shown in Fig. 3.6. However, the observation after about 24 h
showed that the lamellar domain structure has switched back to their original state (Fig.
ZHAO XIN 54
3.8 (c)). A further poling by –18 V dc voltage almost completely switched the domains,
and the lamellar feature disappeared (Fig. 3.8 (d)).
Fig. 3.8 (a) Lamellar domains in one grain; piezoresponse phase image at the
moment after applying a –10 V dc voltage to the bottom electrode (b) and
after 24 h (c); (d) piezoresponse phase image after applying –18 V dc voltage,
the lamellar feature disappeared.
In order to investigate how the lamellar domain structure is modified by an external
electric field, polarization switching in a nanometer-sized single point has also been
demonstrated. After applying a 10 V dc voltage to the bottom electrode for 10 minutes
while fixing the tip on the surface of a grain as indicated by a cross shown in Figs. 3.9
(a) and (b), a black speckle with a diameter of about 300 nm appeared in the
piezoresponse image (Fig. 3.9 (c)). The appearance of the round-shaped speckle
ZHAO XIN 55
suggests a different switching mechanism compared to a large area switching, which
can be realized through 90 ° domain walls movement or generating new 90 ° domains,
as shown in Figs. 3.6 and 3.8. The polarization switching inside a slab with neighbor 90
° domains can be a 180 ° or 90 ° switching. For a 90 o switching (arrow 1 in Fig. 3.10),
polarizations in the switched region will be consistent with the neighbor domains, but
two twisted interfaces will be generated in the same slab. This 90 ° switching causes
lattice strain and is not favorable from the viewpoint of strain energy. In contrast, a 180
° switching, where the polarization is reversed to the opposite direction (arrow 2, Fig.
3.10), does not cause additional strain, but “tail-to-tail” or “head-to-head” 90 ° domains
will be formed with the neighbor domains. This switching is favorable in the viewpoint
of strain energy but not the electrical field since space charges will be built. However, if
a round-shaped area is switched (what we observed), where the interface area with the
neighbor 90 ° domains is minimum, it will be favorable from both the strain energy and
o
electrical energy viewpoints. Therefore, we conclude that a 180 switching is most
likely happened during the nanometer sized polarization switching.
Fig. 3.9 (a) Topography image of one grain, the cross indicates where the tip was fixed;
piezoresponse phase image in the grain by applying dc voltage to the bottom electrode:
(b) 0 V, and (c) 10 V for 10 min. A black round speckle appeared after being applied 10
V dc poling voltage.
ZHAO XIN 56
2 1
Fig. 3.10 Schematic diagram of the nanometer-sized polarization switching.
In summary, we carried out PFM to characterize the domain structure in the sol-
gel deposited PZT40/60 film. Lamellar domains were observed and we attributed those
domains to 90 ° domains. Polarization switching mechanism has been studied by
applying a dc bias to the film. It was found that polarization switching in a large area
was accompanied by the appearance of new directions for the 90 ° domains in order that
the strain energy can be reduced. In contrast, for a small area with nanometer size, 180 °
switching are believed to occur during polarization switching.
ZHAO XIN 57
Reference
1. X. G. Tang, H. L. W. Chan, A. L. Ding and Q. R. Yin, “Processing effects on the

microstructure and ferroelectric properties of Pb(Zr,Ti)O3 thin films prepared by
sol–gel process”, Surf. Coat. Technol. 161, 169 (2003).
2. C. Loppacher, F. Schlaphof, S. Schneider, U. Zerweck, S. Grafström, L. M. Eng,
A. Roelofs and R. Waser, “Lamellar ferroelectric domains in PbTiO3 grains
imaged and manipulated by AFM”, Surf. Sci. 532-535, 483 (2003).
o
3. H. L. Hu and L. Q. Chen, “Computer simulation of 90 domain formation in
two-dimensions”, Mater. Sci. Eng. A 238, 182 (1997).
4. A. E. Romanov, A. Vojta, W. Pompe, M. J. Lefevre and J. S. Speck, “Domain
patterns in (111) oriented tetragonal ferroelectric films”, Phys. Stat. Sol. (a) 172,
225 (1999).
5. J. S. Speck and W. Pompe, “Domain configurations due to multiple misfit
relaxation mechanisms in epitaxial ferroelectric thin films. I. Theory”, J. Appl.
Phys. 76, 466 (1994).
6. J. S. Speck, A. C. Daykin, A. Seifert, A. E. Romanov and W. Pompe, “Domain
configurations due to multiple misfit relaxation mechanisms in epitaxial
ferroelectric thin films. 111. Interfacial defects and domain misorientations”, J.
Appl. Phys. 78, 1696 (1995).
7. A. E. Romanov, W. Pompe and J. S. Speck, “Theory of microstructure and
mechanics of the ... a1/ a2/ a1/ a2 ... domain pattern in epitaxial ferroelectric and
ferroelastic films”, J. Appl. Phys. 79, 4037 (1996).
8. A. E. Romanov, M. J. Lefevre, J. S. Speck, W. Pompe, S. K. Streiffer and C. M.
Foste, “Domain pattern formation in epitaxial rhombohedral ferroelectric films.
II. Interfacial defects and energetics”, J. Appl. Phys. 83, 2754 (1998).
9. S. C. Harnagea, A. Pignolet, M. Alexe and D. Hesse, “Piezoresponse scanning
force microscopy: what quantitative information can we really get out of
piezoresponse measurements on ferroelectric thin films”, Integr. Ferroelectrics
44, 113 (2002).
10. C. E. Zybill, H. Boubekeur, P, Radojkovic M. Schwartzkopff, E. Hartmann, F.
ZHAO XIN 58
Koch, G. Groos, B. Rezek, R. Bruchhaus and W. Wersing, “Direct observation of

single domains in poled (111) PZT (PbZr0.25Ti0.75O3) films”, Surf. Sci. 440, 221
(1999).
11. D. C. Lupascu and U. Rabe, “Cyclic cluster growth in ferroelectric perovskites”,
Phys. Rev. Lett. 89, 187601 (2002).
ZHAO XIN 59
Chapter 4 Domain evolution in PMN-PT Single Crystals
Chapter 4
Studies of Domain Structure and Evolution in

(PbMg1/3Nb2/3O3)0.75(PbTiO3)0.25 Single Crystals by
Temperature-dependent PFM
4.1 (110)-Cut PMN-25PT Single Crystal
4.1.1 Experimental Procedure
The PMN-25PT single crystal was synthesized by the modified Bridgman technique and
the major faces were cleaved as normal to the <110> direction (provided by the State
Key Laboratory of High Performance Ceramics and Superfine Microstructures,

[1-3]
Shanghai Institute of Ceramics, Chinese Academy of Science). Here, the direction
“<110>” refers to the pseudocubic axes, and here after the single crystals cut
perpendicular to this direction are called as “(110)-cut” single crystals. For
measurements of the temperature dependence of dielectric permittivity and hysteresis
loops (P-E loops), Au was coated on both sides as electrodes. In order to determine the
domain evolution in as-grown and poled single crystals, one sample was poled along the
<110> direction by an electric field of 4.5 kV/cm at 70 oC for 15 min, and of 2.25
kV/cm in the process of cooling the sample down to room temperature. Using an
impedance analyzer (HP4194A) equipped with a temperature chamber (Delta 9023), the
temperature dependence of the relative permittivity of the as-grown and poled single
ZHAO XIN 60
crystals were measured at temperatures of 40 to 240 oC at frequencies of 100, 1k, and
10k Hz. The temperature dependence of the hysteresis characteristics of the PMN-25PT
single crystal in the (110)-cut were measured using a Sawyer-Tower circuit at the
temperature from room temperature (denoted as 25 oC) to 140 oC, which is much higher
than the Tm.
For the PFM characterization of domain structure, the as-grown and poled
samples were mechanically polished to a thickness of about 15 μm and a PFM
(Nanoscope IV, Digital Instruments) utilizing a conductive tip coated with Pt was
carried out. In the experiments, the tip was electrically grounded, while a modulating
voltage of 6 V (peak-to-peak) with 11 kHz was applied on the bottom electrode, through
which the dc voltage was also applied in the operation of polarization switching.
4.1.2 Results and Discussion
I. Ferroelectric Properties
The P-E loops obtained at different temperatures are shown in Fig. 4.1. The remnant
polarization (Pr) at room temperature (25 oC) is measured to be 32.0 μC/cm2, which is
very close to the value of the saturation polarization. The coercive field (Ec) is also
determined to be 2.6 kV/cm from the P-E loop at room temperature. When the
temperature rises to 90 oC, the saturation polarization decreases by 31% to a value of 22
μC/cm2, while Pr decreases by 53% to 15 μC/cm2. As the temperature rises, the Pr
decreases much faster than the saturation polarization, and at 140 oC the Pr is almost
ZHAO XIN 61
zero. It should be noted that when the temperature is raised to 140 oC, which is well
above the Tm, the hysteresis characteristics can still be identified from the P-E loop.
40 40
o
o
25 C 90 C
30 30
20
20
2
10 10
0 0
-10 -10
-20 -20
-30 -30
-40 -40
-6 -4 -2 0 2 4 6 -6 -4 -2 0 2 4 6
40 40
o o
100 C 110 C
30 30
2
20 20
10 10
0 0
-10 -10
-20 -20
-30 -30
-40 -40
-6 -4 -2 0 2 4 6 -6 -4 -2 0 2 4 6
40 40
o o
120 C 140 C
30 30
2
20 20
10 10
0 0
-10 -10
-20 -20
-30 -30
-40 -40
-6 -4 -2 0 2 4 6 -6 -4 -2 0 2 4 6
Electric field (kV/cm) Electric field (kV/cm)
Fig. 4.1 Temperature dependence of hysteresis characteristics of the (110)-cut PMN-25PT

single crystal.
ZHAO XIN 62
This suggests that the microdomains can still exist at temperatures much higher than Tm
in the PMN-25PT single crystals. The features of a large Pr, the slow decrease of
saturation polarization and non-zero Pr at high temperatures, are characteristics of
relaxor ferroelectrics and have also been observed by Zhao et al. An explanation for
these features in terms of a microdomain-macrodomain transition has been given. [4-6]
II. Dielectric Properties
The temperature-dependent relative permittivities (ε′~T) of the as-grown and poled
PMN-25PT single crystals are shown in Fig. 4.2. Relaxor ferroelectricity is apparent as
illustrated in Figs. 4.2 (a) and (b), where the Tm is determined to be 115 oC.
Corresponding to the empirical equation:
Tm = 5 x − 10 , (4.1)
where x presents composition of PT, the single crystal can be confirmed to be PMN-
[7, 8]
25PT. Figure 4.2 (b) also reveals a transition temperature at Td = 90 oC, where the
dispersion feature for different frequencies at T > Td suggests a macrodomain-to-
microdomain transition in the poled sample. [4-6] In contrast, there is only a small
4 4 Tm 100 Hz
4.0x10 100 Hz 2.0x10 Td
a Tm 1k Hz b 1k Hz
4
3.5x10 10k Hz 10k Hz
4 4
3.0x10 1.5x10
4
2.5x10
ε'
4 4
2.0x10 1.0x10
ε'
4
1.5x10
4 3
1.0x10 5.0x10
3
5.0x10
0.0 0.0
40 60 80 100 120 140 160 180 200 220 40 60 80 100 120 140 160 180 200 220
o o
Temperature ( C) Temperature ( C)
Fig. 4.2 Temperature dependence of relative permittivity (ε'~T) of (a) the as-
grown and (b) the poled (110)-cut PMN-25PT single crystals.
ZHAO XIN 63
shoulder at 90 oC for the as-grown sample, indicating that the microdomain structure is
dominant. The curves of tanδ corresponding to both the as-grown and the poled samples
were also measured at the same frequencies for the relative permittivity measurements.
The values of the tanδ are less than 10-3, suggesting that the dielectric loss of the crystal
is very low.
III. Domain Structure and Polarization Switching
Figure 4.3 shows the piezoresponse images of the as-grown and poled (110)-cut PMN-
25PT single crystals at room temperature. It can be seen from Fig. 4.3 (a) that speckle-
shaped domains, with sizes varying from a few micrometers to smaller than 100 nm, are
the dominant domains in the as-grown single crystal at room temperature. A similar
domain structure has been reported recently. The nanometer-sized domains are usually
referred to as nanodomains and their coalition results in micro-sized domains that are
referred to as microdomains. [9]
In contrast to the speckle-shaped domains in the as-grown sample, stripe-like
domains are found to exist in the poled single crystal as shown in Fig. 4.3 (b). The
widths of the stripes vary from several to 10 µm, which are much larger than the
diameter of the speckle-like microdomains in the as-grown sample. It is apparent that,
in the poled sample, microdomains have been transformed to macrodomains due to the
[4]
application of an external electric field. Based on the experimental condition, the
regions with “black” contrast in Fig. 4.3 (b) correspond to the macrodomains formed by
ZHAO XIN 64
the poling process, and the “white” contrast regions are believed to be the domains that
have not been successfully poled or the domains that have been depolarized. The stripe
5 µm
15 µm
c [001]
[ 1 1 1]
[0 1 1]
[1 1 1]
[010]
[100]
Fig. 4.3 Domain structure at room temperature in (a) as-grown and

(b) poled (110)-cut PMN-25PT single crystals, and (c) a schematic
diagram showing the relation between the poling (observation)
direction and polarization directions.
ZHAO XIN 65
shape of the domains is consistent with the reported optical observations of the
macrodomains. [3] PMN-25PT crystal has a rhombohedral structure at room temperature,
and thus have eight possible <111> polarization directions. Under an electric field along
the pseudo-cubic <110> direction, the polarization should occur along the two <111>
closest to the <110> direction (Fig. 4.3 (c)). Therefore, the observed domain contrast is
the projections of the stripe-shaped domains on the {110} planes.
Corresponding to Fig. 4.3 (a), the domain size distribution of the as-grown
(110)-cut PMN-25PT single crystal is shown in Fig. 4.4, from which an exponential
relationship between the domain number and the domain size can be revealed. It should
be noted that the domain areas are measured by the DI analyzing software (Nanoscope
IV, the Digital Instruments, USA) in two dimensions. It is believed that the white and
black areas have the same distribution and we counted white areas in the domain images
in our work. Based on Lehnen and Shvartsman’s results for Sr0.61-xCexBa0.39Nb2O6
(SBN61: Ce) and PMN-20PT single crystals, the relaxor properties have been well
described using random-field Ising model (RFIM). In the case of 2-D RFIM, the
domain size distribution follows a power law with an exponential cutoff as follows:
Sd
N d ( S d ) ~ S d−δ exp(− ) , (4.2)
S0
where Nd is the number of domains of the size of Sd, and S0 is the upper cutoff of the
[9-11]
domain size. The experimentally observed domain sizes in our sample can also fit
well with Eq. (4.2), and the best fit yields the value of exponent δ as being 2.41 and S0
as being 1.30 μm2.
ZHAO XIN 66
300
280
260
240
220
Number of domains
200
180
160
140
120
100
80
60
40
20
0
0.1 1 10
2
Domain Areas (μm )
Fig. 4.4 Domain size distribution of the as-grown (110)-cut

PMN-25PT single crystal.
Polarization switching at room temperature was also performed and the “white”
domains can be in-situ poled by an external dc electric voltage applied on the PFM tip.
Another domain image is shown in Fig. 4.5 (a). It can be seen that besides the stripe-
like domains, there are some speckle-shaped domains with micron size, which are
believed to be the domains that have not been successfully poled or those that have been
depolarized. The domain indicated by the arrow in the outlined region in Fig. 4.5 (a) is
the one we used for the polarization switching, and a “+” on the domain indicates the
point where the tip was placed (Fig. 4.5 (b)). An upward dc electric field of 6 kV/cm
was applied between the tip and bottom electrode, and a black speckle in the domain
appeared after 3 min’s poling (Fig. 4.5 (c)). The polarization switching was also
demonstrated through a scan of this domain area, which was 1.5x1.5 μm2 in size. After a
scan of several minutes, the size of the domain decreased (Fig. 4.5 (d)). After a further
scan using an increased electric field of 8 kV/cm, the domain was completely switched,
as shown in Fig. 4.5 (e).
ZHAO XIN 67
2 μm
b c
d e
1 μm
Fig. 4.5 (a) Another piezoresponse image of poled (110)-cut PMN-25PT, (b) to (e) illustrate
polarization reversal of the arrowed domain in region outlined in (a): (b) the original
piezoresponse image where “+” indicates the point where the tip was placed; (c) the
piezoresponse image after applying an upward electric field of 6 kV/cm between the tip and
bottom electrode; (d) and (e) the piezoresponse images after scanning the indicated domain in (b)
in an area of 1.5x1.5 μm2 with an upward electric field of 6 kV/cm and 8 kV/cm, respectively.
ZHAO XIN 68
IV. Domain Evolution at Various Temperatures
Figure 4.6 shows piezoresponse images of the as-grown sample at different
temperatures. During heating, it can be seen that the contrast between the oppositely
polarized domains decreases and the boundaries of the domains become rougher (Fig.
4.6 (b)-(d)), while there is little change in the shape and number of domains. Some
microdomains can still be seen when the temperature is above the transition temperature,
Tm. At 150 oC, however, most of the domains disappear (Fig. 4.6 (e)). When the
temperature was decreased to room temperature, the microdomain structure appears
again, as shown in Fig. 4.6 (f). This domain structure evolution is consistent with the
temperature-dependent relative permittivity measurement as shown in Fig. 4.2 (a).
The temperature dependence of the domain density, average piezoresponse
amplitude, and sum of the domain areas are shown in Fig. 4.7. As mentioned before, all
the data were obtained by counting the white area using the DI analyzing software. It
can be seen from Fig. 4.7 that the sum of the domain areas and the domain density
changed very little at lower temperatures. However, when the sample is heated to a
temperature near the transition temperature, Tm, both the domain density and the sum of
the domain areas decrease quickly but they do not become zero even when the
temperature is well above Tm. The residual domains are believed to be those that contain
polar nanometer-sized regions (PNRs) which can exist at temperatures well above Tm. [9,
12-16]
On the other hand, the average piezoresponse amplitude has a similar change as
the Pr, which decreases continuously to a value close to zero. The non-zero amplitude at
high temperature reveals that polarization persists in a broad temperature range due to
ZHAO XIN 69
the existence of PNRs.
a b
c d
e f
2 μm
Fig. 4.6 Temperature-dependent piezoresponse images showing the domain evolution of
the as-grown (110)-cut PMN-25PT single crystal at (a) 25, (b) 80, (c) 110, (d) 120, and
(e) 150 oC. (f) Piezoresponse image when the sample was cooled back to room
temperature.
ZHAO XIN 70
4.0
a
3.5
Density (10 N/m )

2
12
3.0
2.5
2.0
1.2
b
1.0
Amplitude (mV)
0.8
0.6
0.4
25
c
ΣDomain Area (μm )
2
20
15
10
20 40 60 80 100 120 140 160

o
Temperature ( C)
Fig. 4.7 Temperature dependence of (a) the domain density, (b) the average amplitude of
piezoresponse, and (c) the sum of the domain areas of as-grown (110)-cut PMN-25PT
single crystal.
Figure 4.8 shows the evolution of the temperature-dependent domain structure
in the poled (110)-cut PMN-25PT single crystal, where (a)-(f) correspond to the domain
images at 25, 90, 100, 110, 120 and 140 oC upon heating, respectively. All of the images
were obtained in almost the same region. It should be noted that the temperature-
dependent domain observation corresponding to Fig. 4.3 (b) was not successful. The
result shown in Fig. 4.8 is the image of another region that does not show very uniform
stripe-like microdomains. It can be seen from Fig. 4.8 (a) that at room temperature the
ZHAO XIN 71
domain walls are smooth and the contrast is sharp. In the temperature range from room
temperature to 90 oC, there is no significant change in the size and shape of the domains.
However, when the temperature reaches 90 oC, the sizes of the “white” speckles and
stripes increase, and some new speckles appear. At 100 oC, as shown in Fig. 4.8 (c),
more “white” speckles with size of less than 100 nm appear, and one can see that the
sizes of the speckles and stripes keep on increasing. When the temperature reaches 110
o
C, it is also apparent that the contrast of the stripe-like domain becomes weaker, and
some stripe-shaped domains disappear; while the size of the newly appeared speckle-
shaped domains increased to several hundred nanometers (Fig. 4.8 (d)). The domain
structure continues to change as the temperature increases. When the temperature
surpasses Tm, reaching 120 oC, the contrast of the piezoresponse image becomes much
weaker and the domain walls become rather blurred (Fig. 4.8 (e)). At a temperature of
140 oC, which is well above the Tm, no obvious domain structure can be identified in the
piezoresponse image (Fig. 4.8 (f)), where a gray contrast dominates the image, except
for a few “black” and “white” dots that may correspond to the normal ferroelectric
domains of PbTiO3 or to defective pinned domains. When the sample was cooled down
to room temperature, no stripe-shaped macrodomain could be seen from the
piezoresponse image, except for some speckle-liked domains with sizes smaller than 1
μm (Fig. 4.8 (g)). It can be concluded that without an external field no macrodomain
can form in the cooling.
ZHAO XIN 72
a b
c d
e f
g Fig. 4.8 Temperature-dependent

piezoresponse images of domain
structures in poled (110)-cut
PMN-25PT single crystal upon
heating: (a) 25; (b) 90; (c) 100;
(d) 110; (e) 120; and (f) 140 oC.
(g) Piezoresponse image when
5 μm
the sample was cooled back to
the room temperature.
ZHAO XIN 73
In order to understand the detail of the newly appearing domains, Fig. 4.9 shows
the evolution of the domains in the region outlined in Fig. 4.8 (a). Analyses of the
temperature dependence of the domain density, the average piezoresponse amplitude
and the sum of the domain areas in this region were illustrated in Fig. 4.10. There are a
few points related to the Figs. 4.9 and 4.10 that need to be noted. First, a domain wall
expansion during heating is apparent for the “white” domains shown in Figs. 4.9 (a) to
(c). This can be understood by the fact that the depolarization field in the poled crystal
will back-switch the poled area and new domains tend to nucleate at the domain walls
due to the relatively low domain wall energy. However, the piezoresponse does not
increase, although the domain wall expands during heating. Second, in contrast to those
in the as-grown sample, both the domain density and the sum of the domain areas in the
poled sample increase near Tm, corresponding to the newly appeared “white” dots in Fig.
4.9 (b). The white dots are indications of the transition from macrodomain to
microdomain structures. The microdomains that possess a relatively low Tc will be
back-switched first and result in the appearance of the “white” dots. Third, when the
temperature is higher than Tm, PMN-25PT changes to a paraelectric phase; therefore, no
obvious domain contrast can be observed as shown in Fig. 4.9 (f). It is also worth noting
that, the white dot that has been in-situ poled by the PFM tip (the circled area in Figs.
4.9 (a) to (e)), as illustrated in Fig. 4.5, appeared again when the temperature increased
and grew in size until the temperature was higher than Tm. The reason that this domain
is difficult to pole during the sample poling but can easily be switched back after in-situ
poling remains unclear. However, the local random fields due to the built-in charge
disorder in PMN-type relaxors may be one of the main reasons. [9]
ZHAO XIN 74
a b
c d
e f
1 µm
Fig. 4.9 Temperature dependence of domain structures in the outlined region of

Fig. 4.8 upon heating: (a) 25, (b) 90, (c) 100, (d) 110, (e) 120, and (f) 140 oC.
ZHAO XIN 75
35
30
Density (10 N/m )

2
25
12
20
15
10
5
1.6
1.4
Amplitude (mV)
1.2
1.0
0.8
0.6
18
16
2
14
12
10
8
6
4
2
20 40 60 80 100 120 140
o
Temperature ( C)
Fig. 4.10 Temperature dependence of (a) the domain density, (b) the average
amplitude of piezoresponse and (c) the sum of the domain areas for the domain
structures shown in Fig. 4. 9.
ZHAO XIN 76
4.2 (111)-Cut PMN-25PT Single Crystals
4.2.1 Experimental Procedure
The (111)-cut PMN-25PT single crystal samples were prepared by the same method as
was used with the (110)-cut PMN-25PT single crystals. Here, (111) refers to the
pseudocubic atomic planes perpendicular to the direction of <111>. In order to
investigate the dielectric properties, ferroelectric properties and domain evolution of the
sample, the same experimental procedure as in the study of (110)-cut PMN-25PT single
crystals was carried out. It should be noted that the poling carried out on the (111)-cut
sample was along the <111> direction.
4.2.2 Results and Discussion
I. Ferroelectric Properties
Figure 4.11 shows the P-E loops of the as-grown (111)-cut PMN-25PT single crystal
obtained at different temperatures, where shapes and tendencies similar to the (110)-cut
PMN-25PT single crystal can be seen. It should be noted that the value of Pr for the
(111)-cut PMN-25PT is higher than that for the (110)-cut PMN-25PT, which can be
understood by the fact that <111> is the direction of the spontaneous polarization. On
the other hand, the value of Ec of the (111)-cut is also higher than that of the (110)-cut
sample, which may lead to difficulty in poling along the <111> direction compared to
the <110> direction.
ZHAO XIN 77
40 40
O O
25 C 90 C
30 30
2
20 20
10
10
0
0
-10
-10
-20
-20
-30
-30
-40
-40
-8 -6 -4 -2 0 2 4 6 8 -8 -6 -4 -2 0 2 4 6 8
40 40
O O
100 C 110 C
30 30
2
20 20
10 10
0 0
-10 -10
-20 -20
-30 -30
-40 -40
-8 -6 -4 -2 0 2 4 6 8 -8 -6 -4 -2 0 2 4 6 8
40 40
O O
120 C 140 C
30 30
2
20 20
10 10
0 0
-10 -10
-20 -20
-30 -30
-40 -40
-8 -6 -4 -2 0 2 4 6 8 -8 -6 -4 -2 0 2 4 6 8
Electric field (kV/cm) Electric field (kV/cm)
Fig. 4.11 Temperature dependence of hysteresis characteristics of the (111)-cut

PMN-25PT single crystals.
ZHAO XIN 78
II. Dielectric Properties
The temperature-dependent relative permittivities (ε′~T) of the as-grown and poled
(111)-cut PMN-25PT single crystals are shown in Figs. 4.12 (a) and (b), respectively.
Similar to the (110)-cut PMN-25PT single crystal, relaxor ferroelectricity can be clearly
seen for the (111)-cut PMN-25PT single crystal, where the Tm can also be determined to
be 115 oC. However, as revealed from the ε′~T curve of the poled sample, at a
temperature of about 90 oC, where the dispersion appears, there is only a shoulder;
while it has been shown that there is an obvious peak at that temperature for the (110)-
cut sample. The absence of an obvious transition peak at 90 oC suggests unsuccessful
poling and the formation of macrodomains. Accordingly, the domain evolution in the
poled (111)-cut PMN-25PT single crystal will not be as obvious as that occurred in the
(110)-cut sample. This will be discussed in following sections. The dielectric loss was
also measured and the values are less than 10-3.
4
3.0x10
Tm 3.5x10
4
100 Hz
a b Tm 100 Hz
1 kHz
4
3.0x10
4
1 kHz
2.5x10 10 kHz
4
10 kHz
2.5x10
4
2.0x10 Td
4
2.0x10
ε'
4
ε'
1.5x10
4
1.5x10
4
1.0x10 4
1.0x10
3
5.0x10 5.0x10
3
0.0 0.0
40 60 80 100 120 140 160 180 200 220 40 60 80 100 120 140 160 180 200 220
o o
Temperature ( C) Temperature ( C)
Fig. 4.12 Temperature dependence of relative permittivity (ε'~T) of (a) as-

grown and (b) poled (111)-cut PMN-25PT single crystals upon heating at
frequencies of 100 Hz, 1 kHz 10 kHz.
ZHAO XIN 79
III. Domain Structures and Polarization Switching
Figure 4.13 shows the domain structure in the as-grown (111)-cut PMN-25PT single
crystal at room temperature, in which the dominant domain shape is also speckle-like.
However, in the same area, the domains in the (111)-cut sample seem to be smaller in
number than those in the (110)-cut sample. By analyzing the domain size distribution
(Fig. 4.14), the domains in the (111)-cut PMN-25PT single crystal also follow Eq. (4.2)
and the values of exponent δ and S0 were simulated to be 1.89 and 0.64 μm2.
5 μm
Fig. 4.13 Piezoresponse image of domain structure of the as-grown (111)-cut PMN-25PT single
crystal obtained at room temperature.
ZHAO XIN 80
50
40
Number of domains
30
20
10
0.1 1 10
2
Domain Areas (μm )
Fig. 4.14 Domain size distribution of the as-grown (111)-cut PMN-25PT

single crystal corresponding to Fig. 4.13.
In the in-situ polarization switching process, the grounded PFM tip was placed
in the speckle-shaped domain shown in Fig. 4.15 (a), while an upward dc electric field
of 4 kV/cm was applied on the sample. A black speckle appeared in the domain after 1
min of poling. When a negative electric field was applied at the same place for 1 min,
a b
1 μm
Fig. 4.15 Nanometer polarization switching at the same place in one grain by the dc electric
fields of (a) 4 kV/cm and (b) –4 kV/cm applied through bottom electrode subsequently.
ZHAO XIN 81
however, the black speckle almost disappeared as shown in Fig. 4.15 (b). This is a
demonstration of localized poling and backswitching.
IV. Domain Evolution at Various Temperatures
Figures 4.16 (a)-(e) illustrate the domain evolution upon heating from room temperature
to 150 oC in the as-grown (111)-cut PMN-25PT single crystal. Similar to that in the as-
grown (110)-cut PMN-25PT single crystal, the shape and density of the domains show
little change below Tm (Figs. 4.16 (a)-(c)), except that the piezoresponse contrast
becomes weaker. When the temperature exceeds Tm (Fig. 4.16 (d)), some domains
disappear; and when the temperature reaches 150 oC, only a few domains can be seen
from the piezoresponse image (Fig. 4.16 (e)). Figure 4.16 (f) is the piezoresponse image
of the corresponding region after being cooled back to room temperature. It can be
observed that the domains appear again with different shapes compared to those in Fig.
4.16 (a) due to the random field during the cooling process.
The temperature dependence of the domain density, the average piezoresponse
amplitude and the sum of the domain areas for the as-grown (111)-cut PMN-25PT
single crystal are also analyzed as shown in Fig. 4.17, where similar tendencies as those
of the as-grown (110)-cut sample are revealed. The temperature dependence of the
domain density and the sum of the domain areas revealed that the domain density in the
(111)-cut sample decreases faster than that in the (110)-cut sample. It can also be seen
that the domain sizes in the (111)-cut sample are larger than that in the (110)-cut
ZHAO XIN 82
a b
c d
e f
5 μm
Fig. 4.16 Temperature-dependent piezoresponse images of domain structure showing

domain evolution of the as-grown (111)-cut PMN-25PT at (a) 25, (b) 80, (c) 110, (d)
115, and (e) 150 oC. (f) The piezoresponse image when the sample was cooled back to
room temperature.
ZHAO XIN 83
30
25
Density (N/m )
20
2
15
10
5
4.0
3.5
3.0
Amplitude (mV)
2.5
2.0
1.5
1.0
0.5
100
90
2
80
70
60
50
40
20 40 60 80 100 120 140
o
Temperature ( C)
Fig. 4.17 Temperature dependence of (a) the domain density, (b) the average
amplitude of piezoresponse and (c) the sum of the domain areas of the as grown
(111)-cut PMN-25PT.
sample. Therefore, it may be concluded that more microdomains or PNRs exist in the
(110)-cut single crystal than the (111)-cut single crystal in a broad range of temperature,
even well above the Tm; i.e. along the <110> direction, the PMN-25PT single crystal
exhibits better relaxor characteristics than the <111> direction.
The domain evolution in the poled (111)-cut PMN-25PT single crystal is shown
in Fig. 4.18. At room temperature, only microdomains are observed, and the domain
structures are in disorder. When the sample is heated from room temperature to over Tm,
ZHAO XIN 84
a b
c d
e f
5 µm
Fig. 4.18 Temperature-dependent of piezoresponse images of domain structure

showing domain evolution of poled (111)-cut PMN-25PT single crystal: (a) 25, (b)
60, (c) 80, (d) 100, and (e) 130 oC. (f) The piezoresponse image when the sample
was cooled back to room temperature.
ZHAO XIN 85
no new domain appears. This is different from the case for the poled (110)-cut PMN-
25PT single crystal. Above Tm, the microdomains disappear. Domain structures appear
again when the temperature is decreased to room temperature as shown in Fig. 4.18 (f),
where the domain structures are still in a disordered condition. The poled (111)-cut
PMN-25PT single crystal does not behave in the same way as the poled (110)-cut PMN-
25PT single crystal. This may be understood by following the conclusion of Zhao et al.
that although <111> is the spontaneous polarization direction, along <111> direction,
the crystal exhibits relatively poor piezoelectric properties compared to the <110> and
[4-6]
<100> directions. Evidence for this is that the piezoelectric coefficient (d33) of the
poled (111)-cut PMN-25PT single crystal is 70~80 pC/N, which is much smaller than
that of the poled (110)-cut PMN-25PT single crystal, which is 600~700 pC/N.
Explanations of this phenomenon that have been proposed are polarization rotation and
engineered domains. [17-22]
In summary, ferroelectric domain structures and evolution in as-grown and poled
PMN-25PT single crystals have been studied by means of temperature-dependent PFM.
The results revealed that for the (110)-cut PMN-25PT, the poled sample presents stripe-
shaped macrodomains at room temperature. These macrodomains were found to
undergo a transition to microdomains and, finally, to undergo a paraelectric phase
transition upon being heated to the transition temperature from room temperature. By
contrast, the as-grown sample shows only the presence of microdomains. These direct
observations provide evidence of the domain structure and evolution predicted by
temperature-dependent relative permittivity measurement. The studies on the orientation
ZHAO XIN 86
dependence of the dielectric and piezoelectric properties showed that along the
spontaneous polarization direction, (111)-cut PMN-25PT single crystal possesses
relatively poor piezoelectric properties and that no macrodomain successfully forms
during the unsuccessful poling process.
ZHAO XIN 87
Reference
1. Z. Yin, H. Luo, P. Wang and G. Xu, “Growth, characterization of relaxor

ferroelectric PMN-PT single crystals”, Ferroelectr. 229, 207 (1999).
2. H. Luo, G. Xu, H. Xu and Z. Yin, “Growth and characterization of relaxor
ferroelectric PMNT single crystals”, Ferroelectr. 231, 97 (1999).
3. H. Luo, G. Xu, H. Xu, P. Wang and Z. Yin, “Compositional homogeneity and
electrical properties of lead magnesium niobate titanate single crystals grown by
a modified Bridgman technique”, Jnp. J. Appl. Phys. 39, 5581 (2000).
4. X. Zhao, “Dielectric piezoelectric and pyroelectric properties of relaxor-based
ferroelectric PMN-PT single crystals”, PhD thesis (2004).
5. X. Zhao, J. Wang, H. L. W. Chan, C. L. Choy and H. Luo, “Effect of bias field
on the dielectric properties of 0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3 single crystals
with different orientations”, accepted by Appl. Phys. A.
6. X. Zhao, J. Wang, Z. Peng, H. L. W. Chan, C. L. Choy and H. Luo, “Triple-like
hysteresis loop and microdomain-macrodomain transition in the relaxor-based
0.76Pb(Mg1/3Nb2/3)O3-0.24PbTiO3 single crystal”, Mater. Res. Bull. 39, 223
(2004).
7. Z. Feng, H. Luo, Y. Guo, T. He and H. Xu, “Dependence of high electric-field-
induced strain on the composition and orientation of Pb(Mg1/3Nb2/3)O3–PbTiO3
crystals”, Solid. State. Commun. 126, 347 (2003).
8. X. Wan, H. Luo, J. Wang, H. L. W. Chan and C. L. Choy, “Investigation on
optical transmission spectra of (1-x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 single crystals”,
Solid. State. Commun. 129, 401 (2004).
9. V. V. Shvartsman and A. L. Kholkin, “Domain structure of 0.8Pb(Mg1/3Nb2/3)O3-
0.2PbTiO3 studied by piezoresponse force microscopy”, Phys. Rev. B 69,
014102 (2004).
10. W. Kleeman, J. Dec, P. Lehnen, T. Woike and R. Pankrath, in Fundamental
Physics of Ferroelectrics 2000, edited by R. E. Cohen, AIP Conf. Proc. No 535
(AIP, New York, 2000), p. 26.
11. P. Lenhnen, W. Kleemenn, T. Woike and R. Pankrath, “Ferroelectric
ZHAO XIN 88
nanodomains in the uniaxial relaxor system Sr0.61-xCexBa0.39Nb2O6: Cex3+”, Phys.

Rev. B 64, 224109 (2001).
12. Z. –G. Ye, Y. Bing, J. Gao, A. A. Bokov, P. Stephens, B. Noheda and G. Shirane,
“Development of ferroelectric order in relaxor (1-x)Pb(Mg1/3Nb2/3)O3-xPbTiO3
(0 ≤ x ≤ 0.15)”, Phys. Rev. B 67, 104104 (2003).
13. T. Y. Koo, P. M. Gehring, G. Shirane, V. Kiryukhin, S. –G. Lee and S. –W.
Cheong, “Anomalous transverse acoustic phonon broadening in the relaxor
ferroelectric Pb(Mg1/3Nb2/3)0.8Ti0.2O3”, Phys. Rev. B 65, 144113 (2002).
14. N. D. Mathan, E. Husson, G. Calvarin, J. R. Gavarri, A. W. Hewat and A. Morell,
“A structural model for the relaxor PbZn1/3Nb2/3O3 at 5 K”, J. Phys.: Condens.
Matter 3, 8159 (1991).
15. S. Wakimoto, C. Stock, R. J. Birgeneau, Z. –G. Ye, W. Chen, W. J. L. Buyers, P.
M. Gehring and G. Shirane, “Ferroelectric ordering in the relaxor
Pb(Mg1/3Nb2/3)O3 as evidence by low-temperature phonon anomalies”, Phys.
Rev. B 65, 172105 (2002).
16. B. Dkhil, J. M. Kiat, G. Calvarin, G. Baldinozzi, S. B. Vakhrushev and E. Suard,
“Local and long range order in the relaxor-ferroelectric compounds
PbMg1/3Nb2/3O3 and PbMg0.3Nb0.6Ti0.1O3”, Phys. Rev. B 65, 024104 (2001).
17. S. -E. Park and T. R. Shrout, “Ultrahigh strain and piezoelectric behavior in
relaxor based ferroelectric single crystals”, J. Appl. Phys. 82, 1804 (1997).
18. D. –S. Paik, S. –E. Park, S. Wada, S. –F. Liu and T. R. Shrout, “E-field induced
phase transition in <001>-oriented rhombohedral 0.92Pb(Mg1/3Nb2/3)O3-
0.08PbTiO3 crystals”, J. Appl. Phys. 85, 1080 (1999).
19. S. Wada, S. Suzuki, T. Noma, T. Suzuki, M. Osada, M. Kakihana, S. –E. Park, L.
E. Cross and T. R. Shrout, “Enhanced piezoelectric property of barium titanate
single crystals with engineered domain configurations”, Jpn. J. Appl. Phys. 38,
5505 (1999).
20. S. –E. park, S. Wada, L. E. Cross and T. R. Shrout, “Crystallographically
engineered BaTiO3 single crystals for high-performance piezoelectrics”, J. Appl.
Phys. 86, 2746 (1999).
ZHAO XIN 89
21. H. Fu and R. E. Cohen, “Polarization rotation mechanism for ultrahigh

electromechanical response in single-crystal piezoelectrics”, Nature 403, 281
(2000).
22. Y. Guo, H. Luo, K. Chen, H. Xu, X. Zhang and Z. Yin, “Effect of composition
and poling field on the properties and ferroelectric phase-stability of
Pb(Mg1/3Nb2/3)O3-PbTiO3 crystals”, J. Appl. Phys. 92, 6134 (2002).
ZHAO XIN 90
Chapter 5 Conclusions and Future Work
Chapter 5
Conclusions and Future Work

In this project, ferroelectric domain structures and their switching mechanisms in the
PZT40/60 film and PMN-25PT single crystals have been studied by means of PFM. In
particular, temperature-dependent macrodomain to microdomain evolution in the
relaxor ferroelectric PMN-25PT single crystals has been investigated. The results can be
concluded as follows:
In the sol-gel deposited PZT40/60 film, lamellar ferroelectric domain structures
with distance between strips ranging from 20 to 25 nm were revealed by the PFM
o
observation. These lamellar domains were attributed to 90 ferroelectric domains,
o
according to reported simulation and theoretical domain models. In addition, the 90
domain structure was also evidenced by the corrugation morphology, which has been
o
thought to be a significant feature of 90 domain structure formed due to the lattice
strain, and was observed on the grain surface in our experiment. The polarization
switching experiments revealed that a large area polarization switching was realized
through formation of 90 o domains in new directions; while in contrast, 180 o switching
is more favorable for nanometer-scaled polarization switching.
The study of ferroelectric domain structures and temperature-dependent domain
evolution in the as-grown and poled (110) and (111)-cut PMN-25PT single crystals
revealed the following results:
ZHAO XIN 91
1) Both the as-grown (110)-cut and the (111)-cut PMN-25PT single crystals exhibit
speckle-shaped microdomains with domain sizes ranging from less than 100 nm to
several microns. The domain size distribution decreases exponentially as the
temperature increases. During the heating process from room temperature to
approaching Tm, there is no obvious change in the density and the sum of the areas
of the microdomains, except for a continuous decrease in the average
piezoresponse amplitude. When the temperature exceeds Tm, the microdomains
start to disappear, and when the temperature is well above Tm, only polar
nanometer-sized regions (PNRs) retain, revealing the ferroelectricity in a broad
temperature range. The speckle-shaped microdomain can be rebuilt by the random
field in the cooling process.
2) Stripe-shaped macrodomains with widths of around 20 µm were observed by the
PFM in the (110)-cut and poled PMN-25PT single crystal. These macrodomains
were found to undergo a transition to microdomains during heating to temperatures
well above 90 oC. When further heated to temperatures higher than the phase
transition temperature of 115 oC, the microdomains will finally disappear.
3) By contrast, there is no obvious peak corresponding to a microdomain-
macrodomain transition can be seen from the curve of the temperature dependence
of relative permittivity for the (111)-cut and poled PMN-25PT single crystal.
Correspondingly, there are no obvious macrodomains observed. This may be due
to the difficulty of poling or relatively poor piezoelectric property along the <111>
direction compared to the <110> direction.
ZHAO XIN 92
In this thesis, some work on the studies of domains in normal and relaxor
ferroelectrics have been carried out. More research is still needed to provide deep
understanding of the polarization switching mechanism and the velocity of the domain
wall movement. In addition, corresponding to theories of the engineered domain and the
polarization rotation, the (100)-cut PMN-25PT single crystal has the best piezoelectric
and dielectric properties. Evidence from more direct observation on the domain
evolution obtained by using a temperature-dependent PFM is required. PMN-PT single
crystals in morphotropic phase boundary (MPB) exhibit more complex piezoelectric
and dielectric properties. More direct observations and further understanding of the
domain evolution under an external electric field and different temperatures is required.
Studying the domain evolution of PMN-PT single crystals in MPB is also an interesting
future project.
ZHAO XIN 93

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FERROELECTRIC DOMAIN STUDY BY

PIEZORESPONSE FORCE MICROSCOPY

THE HONG KONG POLYTECHNIC UNIVERSITY

PIEZORESPONSE FORCE MICROSCOPY

A thesis submitted in partial fulfillment of the requirements

for the Degree of Master of Philosophy in Applied Physics

THE DEPARTMENT OF APPLIED PHYSICS

THE HONG KONG POLYTECHNIC UNIVERSITY

knowledge and belief, it reproduces no material previously published or written nor

expect where due acknowledgement has been made in the text.

________ZHAO XIN__________ (Name of student)

THE HONG KONG POLYTECHNIC UNIVERSITY

Ferroelectric domains in ferroelectric materials are micro-regions with the same

ferroelectric random-access-memory elements. A deep understanding of the nature of

Among many methods of studying ferroelectric domains, piezoresponse force

amplifier, therefore nanometer-sized domain imaging and polarization switching can be

(PZT40/60) film and (PbMg1/3Nb2/3O3)0.75(PbTiO3)0.25 (PMN-25PT) single crystals were

studied utilizing the PFM technique.

PZT40/60 films were deposited on Pt(111)/Ti/SiO2/Si(100) substrates by sol-gel

process followed by thermal annealing at 650°C for 5 minutes. PFM observation

THE HONG KONG POLYTECHNIC UNIVERSITY

domains to 90° ferroelectric domains. Polarization switching mechanism of the 90 °

revealed that a large area polarization switching is usually accompanied by appearance

a nanometer-sized polarization switching is believed to be accomplished by generating

180 ° switching within a single lamellar domain.

(PbMg1/3Nb2/3O3)1-x(PbTiO3)x (PMN-PT) single crystals are known as relaxor

relaxor ferroelectricity can be interpreted by composition non-uniformity induced polar

conversions to paraelectrics. The PMN-PT single crystals naturally have a morphotropic

and their evolution in PMN-PT single crystals of 25% PT (PMN-25PT) grown by

exhibits transition from microdomain ferroelectric phase to paraelectric phase; while

Nanometer-sized domains were also observed embedded in the microdomains. By

contrast, the poled (110)-cut sample exhibits transitions from macrodomain to

microdomain structures at 90 oC and from microdomain to paraelectric phase at 115 oC,

respectively. These direct observations are consistent with temperature-dependent

relative permittivity measurements.

THE HONG KONG POLYTECHNIC UNIVERSITY

In conclusion, PFM has been implemented in the study of ferroelectric domain

from micrometer to nanometer scale is highly desirable. In addition, PFM study of

relaxor ferroelectric phase transitions, such as from rhombohedral to tetragonal and

monoclinic structures deserves further studies.

ZHAO XIN III

THE HONG KONG POLYTECHNIC UNIVERSITY

1. X. Zhao, J. Y. Dai, X. G. Tang, J. Wang, H. L. W. Chan and C. L. Choy,

Pb(Zr0.4Ti0.6)O3 film by piezoresponse microscope” Applied Physics A,

Published online: 20 August 2004.

2. X. Zhao, J. Y. Dai, J. Wang, H. L. W. Chan, C. L. Choy, X. M. Wan and H. S.

Luo “Domain structure and evolution in (PbMg1/3Nb2/3O3)0.75(PbTiO3)0.25 single

crystal studied by temperature-dependent piezoresponse force microscopy”

Journal of Applied Physics, Article in revision.

3. X. Zhao, J. Y. Dai, J. Wang, H. L. W. Chan and C. L. Choy, “Study of Local

Piezo-Properties for Europium Doped Lead Zirconate Titanate Thin Films by

Piezoresponse Scanning Probe Microscope,” accepted by Journal of Integrated

Ferroelectrics (16th International Symposium on Integrated Ferroelectrics (ISIF

THE HONG KONG POLYTECHNIC UNIVERSITY

comments and help.

THE HONG KONG POLYTECHNIC UNIVERSITY

Table of Contents ............................................................................................................VI

List of Figures and Tables ...............................................................................................IX

Chapter 1-Introduction ..................................................................................................1

1.1 Literature Review of Ferroelectric Domain Study by Piezoresponse Force

1.1.1 Brief Introduction to PFM ........................................................................1

1.1.2 Study of Domain Structure in Lead Zirconate Titanate (PZT) Films by

ZHAO XIN__ (Name of student)