Article

pubs.acs.org/crystal

Impedance Analysis and Conduction Mechanisms of Lead Free

Potassium Sodium Niobate (KNN) Single Crystals and Polycrystals: A
Comparison Study
Muhammad Asif Rafiq,§ Maria Elisabete Costa, Alexander Tkach, and Paula Maria Vilarinho*
CICECO - Aveiro Institute of Materials, Department of Materials and Ceramic Engineering, University of Aveiro, 3810-193 Aveiro,
Portugal

ABSTRACT: Impedance spectroscopy (IS) is used to compare defects and

charge transport in (001) oriented K0.5Na0.5NbO3 (KNN) single crystals and
its polycrystalline counterpart. KNN single crystals show lower conductivity
than polycrystalline counterpart from room temperature up to 200 °C, but
above this temperature polycrystalline KNN displays lower conductivity. The
low temperature (T < 200 °C) behavior reflects the different processing
conditions of ceramics and single crystals, which account for less defects prone
to charge transport in the case of single crystals. As temperature increases (T >
200 °C) single crystals become more conductive than polycrystalline samples
in which grain boundaries act as barriers to charge transport. For even higher
temperatures, the conductivity difference between both is increased because of
the contribution of ionic conduction in single crystals. Indeed the values of
activation energy calculated to the high temperature range (T > 300 °C) were
1.60 and 0. 97 eV, confirming the charge transport because of ionic conduction
and ionized oxygen vacancies in single crystals and polycrystalline KNN, respectively. It is suggested that single crystals with low
defects content and improved electromechanical properties could be a better choice for room temperature applications, though at
high temperatures less conductive ceramics may be the choice, depending on the targeted use.

■ INTRODUCTION
The improved performance of single crystals compared with
polycrystals counterparts is well-known. The existence of
inhomogeneities in polycrystals, such as grain boundaries
(and their intrinsic defective nature) and point defects, are one
of the main reasons behind this distinctive behavior. In fact, the
performance of single-crystals relies on numerous factors
including crystal orientation, crystal cut, temperature, phase
transformations, among others; on the other hand polycrystal-
line behavior is the outcome of the complex arrangement of
these effects but damped by the intergranular regions and
inhomogeneities. This creates an intricate network of nonlinear
local effects which affects the overall material behavior.1 As a
consequence, single crystals have been preferred for some
practical applications. Piezoelectric single crystals of quartz
(SiO2), PbZn1/3Nb2/3O3−PbTiO3 (PZN−PT),
PbMg1/3Nb2/3O3−PbTiO3 (PMN−PT), LiNbO3, LiTaO3, and
BaTiO3 have been indeed chosen for applications such as
actuators, surface acoustic wave (SAW) devices, electro-optic
modulators, sonar, nondestructive testing and high perform-
ance medical transducers.2,3
Driven by the need to substitute lead based electroceramics,
potassium sodium niobate (K0.5N0.5NbO3 − KNN) is currently
considered as one of the promising lead free compositions.
KNN is a ferroelectric perovskite with a relatively high Curie
point (Tc) of ∼420 °C.4 Encouragingly, as other lead based
ferroelectric single crystals (PZN−PT, PMN−PT),2,3 KNN
crystals have shown better dielectric and nearly twice higher
electromechanical properties (d33 = 160 pC/N),5,6 as compared
to their ceramic counterparts. In one of our recent publications,
we demonstrate by piezoforce response microscopy (PFM)
that (001)-oriented KNN single crystals exhibit a long-range-
ordered domain pattern of parallel 180° domains with zigzag
90° domains.5 The absence of such a long-range ordered
domain pattern in polycrystalline KNN, probably because of
the presence of grain boundaries, seems to account for the
inferior electromechanical properties of KNN ceramics.5 But
the macroscopic electrical properties of ferroelectric materials,
such as KNN, are also affected by the charge transport behavior
and are closely related to the defects and their relationship with
the crystallographic structure, domain pattern and grain
boundaries, as well.7 Indeed, understanding the charge
transport is fundamental to control the electrical performance
of KNN ceramics.
The major defects associated with KNN, which can influence
its conductivity, are oxygen vacancies, alkaline vacancies and
space charges. These defects may pin domain walls movement,
probably leading to a decrease of its contribution to the
piezoelectric activity. Though the comparison between the
electromechanical properties of KNN single crystals and
ceramics has been reported before,5 the relationships at the
Received: November 18, 2014

© XXXX American Chemical Society A DOI: 10.1021/cg5016884

Cryst. Growth Des. XXXX, XXX, XXX−XXX
Crystal Growth & Design Article

level of charge transport and point defects have not been was better than 1 °C. IS data analysis was conducted using different
established yet. However, addressing the comparison between formalisms including complex impedance Z* and complex modulus
the charge transport in KNN single crystals and ceramics may M*, which allowed access to the electrical contributions of the bulk
and grain boundaries and their associated conduction mechanisms.

■
facilitate the design of optimized KNN materials.
Complex impedance spectroscopy (IS) is a very useful
technique to (i) analyze the electrical response of materials, (ii) RESULTS AND DISCUSSION
separate bulk, grain boundary and electrode/ceramic interface The temperature dependence of ac conductivity of KNN single
contributions from the overall electrical response, (iii) identify crystals and ceramics at the frequency of 100 kHz is depicted in
conduction mechanisms, and (iv) even to characterize Figure 1. The intrinsic conductivity (σω) response is given by
ferroelectric phase transitions.8−10 IS allows to map the real
σω = σdc + Aωn (1)
and the imaginary parts (Z′ and Z″) of the impedance of a
dielectric material at various temperatures and frequencies.
Furthermore, values of the activation energy for the various
conduction mechanisms (ionic, electronic, etc.) can be
calculated, hence permitting the identification of the nature of
charge carriers and conduction phenomena.11 Despite that, IS
analysis of KNN single crystals have not been reported so far.
In the present work, a detailed and comparative investigation
of the conduction behavior of high temperature self-flux grown
KNN single crystals and conventionally prepared KNN
ceramics is conducted by IS in the frequency and temperature
ranges from 100 Hz to 1 MHz and from 30 to 480 °C,
respectively. The investigation of defects and associated
activation energies for conduction in single crystals, a grain
boundary free material, is carried out aiming to identify the role
of grain boundaries in the charge transport in KNN. The
insights gained with this analysis allow designing KNN-based
materials with optimized performance for selective uses.

■ EXPERIMENTAL PROCEDURE
(001)-Oriented KNN single crystals were grown using a high
temperature self-flux method. High purity K2CO3 (Merck, purity
≥99%), Na2CO3 (Chempur, ≥ 99.5%), and Nb2O5 (Chempur,
99.9%), were the starting reagents used in the present work. KNN
powders were first synthesized by a conventional solid-state reaction.
Stoichiometric amounts of the starting reagents were mixed by ball-
milling in Teflon pots in ethanol medium for 5 h using zirconia balls.
Before weighting and mixing, reagents were dried at 230 °C for 5 h.
Subsequently the mixture was calcined at 800 °C for 2 h to obtain the
perovskite phase. The perovskite formation was confirmed by x-ray
diffraction analysis. A mixture of K2CO3 and B2O3 (Merck, 95%),
selected as the flux to produce the KNN single crystals, was placed
together with KNN powder in a Pt crucible further sealed by a Pt lid.
The crucible was then inserted in a vertical furnace inside a reversed Figure 1. ac conductivity of single crystals and polycrystalline KNN at
alumina crucible to grow KNN single crystals. The complete run for 100 kHz in logarithmic scale as a function of temperature logarithm
the crystal growth was described elsewhere.5 The crystals studied in (a) and of inverse temperature (b). Three different regions are
this work were grown at a maximum temperature of 1200 °C.5 Single- identified.
crystal platelets with dimensions of about 2 × 2 × 0.02 mm3 were used
for electrical measurements.
KNN ceramics were also produced after synthesizing KNN powders
by a conventional solid-state reaction method. After the calcination
step, KNN powders were milled again for 5 h, dried, and uniaxialy where σdc stands for the dc conductivity, ω for the angular
pressed at 170 MPa into disks of 10 mm diameter and 3 mm thickness, frequency, and the exponent n lies in the range 0 < n < 1.12
which were subsequently submitted to cold isostatic pressing at 200 Near room temperature conductivity for KNN single crystals is
MPa. Sintering was carried at 1100 °C for 2 h, maintaining the pellets lower than that for polycrystalline KNN. As temperature
covered by the powders of the same composition. increases, particularly for T > 200 °C single crystals become
For the electrical characterization, the opposite faces of the ceramic more conductive than ceramics.
disks and single crystals were polished to ensure parallel surfaces and In both cases, ac conductivity follows distinct temperature
then coated with high-grade silver paint. Both type of samples, dependences on the temperature. Three different regions (I, II,
ceramics and single crystals, had very close geometrical factors GFs
and III) can be distinguished in both curves: region I from 30
(GF = electrode area/sample thickness), 0.05 and 0.06, respectively.
The electrodes were annealed at 550 °C for 20 min. Impedance to 180 °C and 205 to 300 °C for single crystals and 30 to 180
spectroscopy measurements were carried out with a computer °C and 220 to 300 °C for polycrystals; region II from 180 to
controlled precision LCR Meter (HP 4284A) under an ac voltage of 205 °C for single crystals and 180 to 220 °C for polycrystals;
1 V in the frequency range from 100 Hz to 1 MHz and temperature and region III from 300 to 400 °C for single crystals and
range from 30 to 480 °C. The accuracy of temperature measurements polycrystals, corresponding to three different slopes.
B DOI: 10.1021/cg5016884
Cryst. Growth Des. XXXX, XXX, XXX−XXX
Crystal Growth & Design
In the region I, a trend for a decrease of the conductivity with
temperature increase was observed, being stronger for
polycrystalline KNN and slighter for KNN single crystals.
Since the conductivity in semiconductors is known to be
proportional to the charge carriers concentration and their
mobilities, a slight decrease of the conductivity with temper-
ature may be related to the decrease of the charge carriers
mobility because of their scattering by phonons at constant
carriers concentration. At room temperature, these charge
carriers may be electrons or holes (missing electrons), which
carry one negative or positive unit of charge. Increase in the
electrical conductivity, observed for the KNN ceramics
annealed in the O2 atmosphere, provides evidence of hole
conduction (p-type conduction in KNN ceramic). The phonon
scattering can be described by the relation:
σ ∼ μ ∼ Tα (2)
where σ stands for the conductivity, μ for mobility, T for
absolute temperature, and α for the exponent that is a negative
number. To determine the α value, logarithm of the
conductivity is plotted in Figure 1a as a function of logarithm
of temperature. From the slope in the region I, the conductivity
of the polycrystalline KNN is proportional to T−1.61 ± 0.08 that is
between the theoretical α value of 1.5 for acoustic phonon
scattering and the value of 2.1 obtained for the scattering of
holes in semiconductors such as GaAs. For KNN single crystals,
the value of exponent α is evidently smaller than in
polycrystalline KNN, being just of −0.64 ± 0.04 that is
between the theoretical value of 0.5 for optical phonon
scattering and the value of 1.0 obtained for the scattering of
electrons in GaAs.
To clarify the conduction mechanisms responsible for the
behavior observed in regions II and III, the logarithm of the
conductivity was plotted as a function of the inverse
temperature, as shown in Figure 1b, and the values of the
activation energy for conduction (σac) were calculated assuming
Arrhenius behavior:
⎛ E ⎞
σac = σ0⎜ − a ⎟
⎝ kBT ⎠ (3)
where σ0 stands for the pre-exponential term, kB for Bolzmann
constant, T for absolute temperature, and Ea for the activation
energy of conduction.
In region II, a ferroelectric phase transition occurs
(orthorhombic/monoclinic to tetragonal), responding for the
observed discontinuities in both curves. In this temperature
range the calculated activation energy values of 0.52 and 0.49
eV for KNN single crystals and polycrystals, respectively, are
close to the values reported for other perovskites near the phase
transition, as for example Pb(Fe1/2Nb1/2)O3 ceramics.13 It is
well-known that a conduction hole together with its self-
induced polarization in polar materials may form quasiparticle
known as polarons. Hence, in region II, the formation of small
polarons induced by the hole-phonon interaction enhanced by
structural deformations may be indicated by the activation
energy values of about 0.5 eV.13
In region III, the calculated activation energies are 1.60 and
0.97 eV for KNN single crystals and polycrystalline samples,
respectively. In ferroelectric perovskites, activation energies
lying between (0.4−1.2 eV) have been associated to charge
transport by oxygen defects, namely to the motion of the
ionized oxygen vacancies,13,14 which are considered as the most
C DOI: 10.1021/cg5016884
Article
mobile ionic species in perovskites.14,15 Regarding the electrical
conduction in single crystals, it is here suggested that alkaline
ions may be the charge carriers accounting for ionic conduction
taking place in this high temperature regime with an activation
energy value of 1.60 eV, which is larger than 1.2 eV, related to
oxygen vacancies. Ionic conduction has been reported for La
doped PbTiO3 (1.17−1.48 eV)16 and PZN−PT crystals (∼1.3
eV)7,17 as well.
The ac conductivity analysis allowed us to identify the
possible conduction mechanisms, and their variation with the
temperature, but did not specify the contributions from
different regions of the ceramic microstructure such as those
related to the bulk (grain interior) and/or grain boundaries.
Such material insight is very important to understand the
microstructure impact on the ceramic electrical properties.
Besides affecting the electrical transport response, defects are
also known to affect grain growth and, consequently, the
ceramic microstructure and the ferroelectric domain patterns,
which are responsible for the ferroelectric and piezoelectric
response of these materials, as KNN. Therefore, impedance
spectroscopy was used to further exploit the responsible
phenomena for the resistivity increase in KNN single crystals as
compared to the polycrystalline counterpart.
Figure 2a and b depicts the frequency dependence of the
imaginary part of both complex impedance Z* and complex
modulus M*, that is, Z″ and M″, for KNN single crystals at
high temperatures (320−480 °C). The maxima of Z″ and M″
occurred at the same frequency, which indicates that an
electrical circuit model comprising one resistance (R) and one
capacitance (C) connected in parallel is well suited to describe
these spectra. R and C in the equivalent electrical circuit
represent the electrical contribution of the bulk of the single
crystal (bulk effect). A similar behavior has been reported for
lead based single crystals of PZN-9PT,17,18 PZN-4.5PT,7 and
LiTaO3.9 On the other hand, the polycrystalline KNN
counterpart displays, in the same temperature range, Z″ and
M″ maxima at different frequencies, thus indicating that in this
case, two RC (resistance in parallel to a capacitance) modules
connected in series are required to describe properly the
impedance data of polycrystalline KNN. Accordingly, an
equivalent electric circuit comprising a series of two RC
circuits (R parallel to C) was used to model the impedance
experimental data and assisted by Zview software (version 3.2c,
Scribner Associates, Inc.). The two RC modules represent two
different electrical contributions, which were assigned to
different regions of the polycrystalline material, that is, the
bulk (grain interior with resistance, Rb; capacitance, Cb) and the
grain boundary (with resistance, Rgb; capacitance, Cgb). The
values of the resistance (R) and capacitance (C) extracted from
the electrical model, are presented in Table 1 and Table 2 for
single crystals and polycrystalline KNN, respectively. Resistance
for both KNN single crystals and polycrystals decreased with
increase in the temperature.
For any RC electrical module assigned to a specific region,
the product of R and C defines a time constant (τ) that is a
signature of the electrical contribution of that particular region,
that is, grain interior (bulk). So, it is important to analyze and
compare the time constant to better understand materials
behavior. Time constant (τ) can be furthermore expressed as τ
= ε0εrρ, where, ε0, εr, and ρ stand for the vacuum dielectric
permittivity, the relative dielectric permittivity and the electrical
resistivity of the material region modeled by RC, respectively.
Therefore, τ is unaffected by the geometrical details of the
Cryst. Growth Des. XXXX, XXX, XXX−XXX
Crystal Growth & Design Article

Table 1. Resistance and Capacitance Extracted from the

Electric Model at Various Temperatures for KNN Single
Crystalsa
T (°C) resistance (Ω) capacitance (F)
35 5.15 × 107
3.10 × 10−11
100 4.33 × 107 6.28 × 10−11
160 3.84 × 107 5.59 × 10−11
200 6.76 × 107 1.08 × 10−10
260 3.56 × 106 1.71 × 10−10
320 3.41 × 106 7.00 × 10−10
340 3.29 × 106 7.10 × 10−10
350 2.37 × 106 7.17 × 10−10
360 1.99 × 106 7.41 × 10−10
370 1.66 × 106 7.96 × 10−10
380 1.26 × 106 8.33 × 10−10
390 8.64 × 105 9.57 × 10−10
400 3.01 × 105 2.32 × 10−10
410 8.83 × 104 4.07 × 10−9
420 4.06 × 104 3.53 × 10−9
430 2.97 × 104 3.24 × 10−9
440 2.10 × 104 3.25 × 10−9
450 1.54 × 104 3.42 × 10−9
460 1.32 × 104 3.08 × 10−9
480 9.55 × 103 2.50 × 10−9
a
A decrease in the resistance is observed with the increase in the
temperature.

Table 2. Resistance and Capacitance of Bulk (Rb, Cb) and

Grain Boundaries (Rgb, Cgb) of KNN Ceramics after Fitting
with Electric Circuita
polycrystalline KNN
Figure 2. Variation of the imaginary part of impedance (a) (Z″) versus
T (°C) Rb (Ω) Cb (F) Rgb (Ω) Cgb (F)
frequency and (b) (M″) versus frequency at various temperatures for
KNN single crystals. The variation in higher temperature region (>400 35 5.83 × 105 2.40 × 10−10 3.90 × 106 4.90 × 10−10
°C) in the frequency range 1 kHz to 100 kHz is shown in the inset. 100 1.40 × 106 2.04 × 10−10 2.49 × 107 1.35 × 10−10
The occurrence of peak maxima of Z″ and M″ versus frequency 160 1.51 × 106 3.20 × 10−10 4.10 × 107 1.27 × 10−10
indicate the presence of one phenomena, that is, bulk contribution. 200 8.28 × 105 5.17 × 10−10 1.94 × 107 2.48 × 10−10
260 7.03 × 105 1.43 × 10−10 2.29 × 106 2.40 × 10−10
325 1.64 × 105 4.47 × 10−10 1.02 × 106 1.04 × 10−9
350 1.14 × 105 5.22 × 10−10 6.45 × 105 1.42 × 10−9
material region under consideration. For each RC module of 375 1.02 × 105 5.53 × 10−10 5.78 × 105 1.54 × 10−9
the referred electrical circuit model, a time constant can be 400 5.31 × 104 1.06 × 10−9 3.08 × 105 3.02 × 10−9
calculated, that is, for the bulk of single crystals and ceramics, 425 4.67 × 104 1.95 × 10−9 2.40 × 105 4.66 × 10−9
and for the grain boundary of the ceramics. Moreover the 450 4.04 × 104 1.48 × 10−9 2.48 × 105 3.82 × 10−9
temperature dependence of such τs can be traced as shown in 480 2.87 × 104 1.23 × 10−9 3.82 × 105 1.99 × 10−9
Figure 3. At low temperature, the time constant corresponding a
to the single crystals stays close to the time constant of the A decrease in the resistance is observed with the increase in the
temperature.
ceramic grain boundaries whereas at high temperature (300−
400 °C) it approaches to the time constant of the bulk of the
polycrystals or even pass it for T > 400 °C.
Mathematically, the time constant is dependent on both,
variation of the time constant of single crystals reflects
resistance and capacitance (τ = RC). Figure 4 where bulk
predominantly the variation of its bulk resistance.
resistance and bulk capacitance of both KNN single crystals and
polycrystals are plotted against the temperature allows to Furthermore, arguments accounting for a different defect
inspect the variation of the time constant. As observed, the nature in single crystals and ceramics may elucidate the time
resistance of the bulk of KNN single crystals is higher than that constant profiles. Single crystals were prepared by a high
of the bulk of polycrystalline KNN ceramics at low temperature temperature self-flux method in a covered sealed platinum
(Figure 4a), whereas at high temperature this relationship crucible. As compared to the high temperature ceramic
becomes inverted; concerning the capacitance values, the bulk processing, this method helps to minimize defects concen-
capacitance of KNN ceramics is always higher than the bulk tration. Defective ceramics are in general prepared, because of
capacitance of KNN single crystals, being their difference nearly the volatile nature of K and Na, which results in the formation
constant in the whole temperature range (Figure 4b). These of cationic vacancies, VK′ , VNa
′ during the processing and is
results point out that under increasing temperature the described in Kroger−Vink notation as
D DOI: 10.1021/cg5016884
Cryst. Growth Des. XXXX, XXX, XXX−XXX
Crystal Growth & Design
Figure 3. Time constant (τ, where τ = RC) of bulk of KNN single
crystals and of bulk and grain boundary of polycrystalline KNN. At low
temperature, the time constant of single crystals matches closely to the
grain boundary of polycrystalline KNN whereas at high temperature
(∼300 °C) it matches closely the bulk of polycrystalline KNN.
Figure 4. Variation of (a) resistance and (b) capacitance versus
temperature of KNN single crystals and polycrystals. With temperature
rise resistance values of KNN single crystals were significantly affected
as compared to the polycrystalline counterpart and so has a dominant
effect on time constant.
E DOI: 10.1021/cg5016884
Article
′ + 2VK′
2NaNa + 2KK + 2OO ↔ K 2O + Na 2O + 2V Na
+ 2VÖ
VK → VK′ + h•
′ + h•
VNa → V Na
(4)
where A′ stands for vacancies of K/Na, VÖ and O×O
for the
oxygen vacancy and O2− at the oxide ion site, respectively and
h• stands for free carrier holes. In addition, oxygen vacancies VÖ
may be formed during the sintering process at high temper-
atures and, subsequently oxidized during the cooling process as
1
VÖ + O2 → OO× + 2h•
2 (5)
Thus, at room temperature, a higher resistivity for KNN
single crystals as compared to its polycrystalline counterpart
should be expected, as it is indeed observed (Figure 1). As
previously mentioned, defects normally pin the domain walls
and thus result in poor ferroelectric and electromechanical
properties. So, the low amount of defects and higher resistivity,
together with the absence of grain boundaries may be the
reasons explaining the better ferroelectric and electromechan-
ical performance of KNN single crystals produced in this work
and by other researchers.5,6
■ CONCLUSIONS
Electrical behavior of self-flux grown (001) oriented
K0.5Na0.5NbO3 single crystals and polycrystalline counterparts
was assessed and compared in this work. The room
temperature resistance of KNN single crystals (5.17 × 107
Ω) is much higher than that of the polycrystalline counterpart
(5.83 × 105 Ω), but above this temperature KNN polycrystals
exhibit higher resistance. Related with the processing
conditions, it is proposed that at low temperatures the less
defective nature of single crystals with defects less predisposed
to charge transport accounts for their high resistance, while at
temperatures above 200 °C the grain boundaries of KNN
polycrystals acting as barriers to charge transport respond for
their high resistivity. Indeed the activation energy for
conduction in KNN single crystals and polycrystals at high
temperature (>300 °C), calculated to be 1.60 and 0.97 eV and
assigned to the ionic conduction and oxygen vacancies,
respectively, proves the different charge transport nature in
KNN single and polycrystals. It is suggested that for
applications at room temperature (or close to) single crystals
with low defects content offer privileged conditions for
maximizing ferroelectric and electromechanical properties and
hence should be preferred for their related applications. On the
other hand, for a high temperature regime, polycrystalline
materials because of their lower conductivity might be a better
option for electromechanical applications.
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: paula.vilarinho@ua.pt.
Present Address
§
Department of Metallurgical and Materials Engineering,
University of Engineering and Technology, Lahore, Punjab,
Pakistan.
Notes
The authors declare no competing financial interest.
Cryst. Growth Des. XXXX, XXX, XXX−XXX
Crystal Growth & Design Article

■ ACKNOWLEDGMENTS
This work was funded by FEDER through Programa
Pb(Zn1/3Nb2/3)0.91Ti0.09O3 single crystal. Cryst. Res. Technol. 2010,
45 (10), 1003−1011.

Operacional Factores de Competitividade - COMPETE and

national funds through FCT - Fundaçaõ para a Ciência e
Tecnologia within CICECO project - FCOMP-01-0124-
FEDER-037271 (FCT Ref. PEst-C/CTM/LA0011/2013).
Muhmmad Asif Rafiq and Alexander Tkach acknowledge also
FCT for the financial support (SFRH/BD/66942/2009 and
IF/00602/2013).

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temperature conduction mechanism of flux grown

F DOI: 10.1021/cg5016884
Cryst. Growth Des. XXXX, XXX, XXX−XXX