Journal of the Korean Physical Society, Vol. 62, No. 5, March 2013, pp.

794799

Eect of Li Doping on Ferroelectric and Piezoelectric Properties of

Ba0.5 Na0.5 TiO3 -BaTiO3 (BNT-BT) Thin Films

Susant Kumar Acharya and Byung Guk Ahn

Division of Advanced Materials Engineering, Hydrogen and Fuel Cell Research Center,
Chonbuk National University, Jeonju 561-756, Korea

Jung-Hwan Hyung and Sang-Kwon Lee

Basic Research Laboratory (BRL), Department of Semiconductor Science and Technology,
Chonbuk National University, Jeonju 561-756, Korea

(Received 28 January 2013)

The piezoelectric and the ferroelectric properties of x-mol% Li-doped 0.94Bi0.5 Na0.5 TiO3 -
0.06BaTiO3 (BNT-BT-Lix , x = 0, 5, 10, 15, 20) lead-free piezoelectric thin lms deposited on
Pt (111)/Ti/SiO2 /Si substrates via a metal-organic solution deposition method were investigated.
Our results show that the Li-substituted lm has a remarkable improvement in electrical properties
compared with the BNT-BT lm. We also found that the substitution was eective in decreasing
the coercive eld in the thin lms. The enhanced electromechanical properties are contributed by
both crystal structure evolution and improved microstructure. The optimal ferroelectric properties
were obtained in the lm with x = 10 providing a remanent polarization (Pr ) and a coercive eld
(Ec ) of 23.9 C/cm2 and 124 kV/cm, respectively.

PACS numbers: 77.65.Bn, 77.84.-s, 77.90.+k

Keywords: Ferroelectric, BNT-BT thin lm, Li-doped BNT-BT, Local eective piezoelectricity, Remanent
polarization
DOI: 10.3938/jkps.62.794

I. INTRODUCTION However, it is known that this thin lm is dicult to

Piezoelectric thin lms for use in microelectromechan-
ical systems (MEMS), micro actuators, and transducers
have been extensively studied [13]. Among these appli-
cations, the most widely used materials are lead-based
thin lms, such as Pb(Zrx Ti1x )O3 (PZT), because of
their superior ferroelectric and piezoelectric properties.
However, there is signicant interest in developing piezo-
electric lead-free thin lms owing to environmental is-
sues. The search for alternative piezoelectric thin lms
has been focused on alkali niobates, modied bismuth
titanates, bismuth ferrites and other systems with mor-
photropic phase boundaries (MPBs) [46].
Among various lead-free piezoelectric thin lms, the
(Bi0.5 Na0.5 )TiO3 -BaTiO3 (BNT-BT) system is most at-
tractive due to its excellent ferroelectric and piezoelec-
tric properties. The (Bi0.5 Na0.5 )TiO3 -BaTiO3 (BNT-
BT) system exists as the MPB between the rhombohe-
dral phase (BNT) and the tetragonal (BT)phase [711].
E-mail: bkahn@chonbuk.ac.kr
E-mail: sangkwonlee@cau.ac.kr; Fax: +82-63-270-3585
Present Address: Department of physics, Chung-Ang University,
Seoul 156-756, Korea
-794-
pole adequately because of its large coercive eld, which
limits its industrial applications. Many recent studies
have reported that Li-substituted BNT-based ceramics
such as BNT-BLT [12], BNLT-BT [13], BNT-BT-BLT
[14], BNT-BKT-BLT [15], BNT-BKT-BLT-BT [16], and
BNKBT+ x-mol% Li2 CO3 [17] were remarkably eec-
tive in decreasing the coercive eld of these ferroelec-
tric ceramics. Moreover, the piezoelectric and the elec-
trochemical properties of these ceramics were also en-
hanced with Li substitution. To date, however, little
attention has been paid to the impact of Li doping on
BNT-based thin lms [18]. Thus, it is important to un-
derstand the eect of Li modications on the crystallo-
graphic, microstructural and electrochemical properties
of BNT-BT thin lms.
In this work, x-mol% Li-doped 0.94Bi0.5 Na0.5 TiO3 -
0.06BaTiO3 (BNT-BT-Lix , x = 0, 5, 10, 15, 20) thin
lms were deposited on Pt/Ti/SiO2 /Si substrates via a
metal-organic solution deposition. The eects of Li dop-
ing on the phase, microstructure and electrical properties
of the prepared BNT-BT-Lix thin lms were systemati-
cally investigated. Our results demonstrated that an op-
timized Li substitution at x =10 led to a noticeable im-
provement in the ferroelectric and the piezoelectric prop-
Eect of Li Doping on Ferroelectric and Piezoelectric Properties
erties of the BNT-BT-based lms. We conclude that the
enhanced electromechanical properties are contributed
by both crystal structure evolution and improved mi-
crostructure.
II. EXPERIMENTAL DETAILS
To prepare the BNT-BT-Lix precursor solution, we
rst made BNT-Lix and BT solutions separately and
then mixed them together in stoichiometric ratios. Bar-
ium acetate (Ba(CH3 COO)2 ), bismuth nitrate (Bi-
(NO3 )3 5H2 O), sodium acetate (NaOOCCH3 ), lithium
nitrate (LiNO3 ) and titanium isopropoxide (Ti[OCH-
(CH3 )2 ]4 ) were utilized as starting materials while
acetyl acetone, isopropyl alcohol, distilled water, and
acetic acid were used as solvents. Diethanolamine (HN-
(CH2 CH2 OH)2 ) was chosen for use as a ligand. The de-
tailed solution preparation method has been described
elsewhere [19]. In short, stock solutions were spin-coated
onto Pt/Ti/SiO2 /Si(100) substrates at a spin rate of
4500 rpm for 30 s by using a commercial photoresist spin-
ner. After each coating step, the gel lms were dried at
170 C for 10 min and pyrolyzed at 450 C for 10 min on
a hot plate. The amorphous lms were then crystallized
at a temperature of 700 C by rapid thermal anneal-
ing (RTA) under an O2 atmosphere with a soak time of
5 min. All processes including deposition, drying, pyrol-
ysis, and post-crystallization were repeated several times
to obtain a proper lm thickness.
The phase structures of the lms were characterized
by using X-ray diraction (XRD, D/MAX-111A, Rigaku
Corporation, Japan) with Cu K radiation. Atomic force
microscopy (AFM, NanoScope IIIa, Digital Instruments,
USA) was performed to evaluate both the surface mi-
crostructure and the roughness of the lms. The elec-
trical properties of the BNT-BT-Lix thin lms were
evaluated using a capacitor structure of Au/BNT-BT-
Lix /Pt, where Au electrodes with a radius of 200 m
were prepared on top of the surface through a shadow
mask by using an e-beam deposition technique under
vacuum. Polarization-electric-eld (P-E) hysteresis loops
were obtained using a TF Analyzer 2000 system (aix-
ACCT, Aachen, Germany). A precision LCR meter (HP
4284A, USA) was used to analyze the dielectric proper-
ties of the thin lms. The leakage currents though the
Au/BNT-BT-Lix /Pt capacitor were measured using a
programmable electrometer (Keithley 6517A, USA) at
room temperature. The piezoelectric properties of the
thin lms were obtained by using piezoforce microscopy
(PFM, Digital Instruments, NanoScope IV, USA) incor-
porating a lock-in amplifying technique.
III. RESULTS AND DISCUSSION
Figure 1 shows the XRD patterns of BNT-BT-Lix thin
lms annealed at 700 C by using RTA in an O2 atmo-
Susant Kumar Acharya et al. -795-
Fig. 1. (Color online) XRD patterns of BNT-BT-Lix thin
lms with dierent Li contents.
sphere for 5 min. The lms can be seen to be polycrys-
talline with no preferred orientations. No obvious change
in the crystal orientation due to the Li substitution is ob-
served. It can also be observed from the XRD images of
the thin lms that Li substitution up to 10 mol% achieves
a single perovskite phase, suggesting that Li+ diuses
into the BNT lattice to form a solid solution. However,
a secondary pyrochlore phase was detected for x = 15,
indicating that the solubility of Li in the BNT-BT lat-
tice had been exceeded [17]. The ionic radius of Li+ for
a 12-fold coordination (Li+ = 1.41 A) [20] is close to
the ionic radius of Na+ (1.39 A) [21]. Accordingly, the
radius-matching eect shows that Li+ ions eectively re-
place Na+ ions in BNT-BT-Lix for value of x up to 10.
On the other hand, for the BNT-BT-Lix (x = 15) thin
lms, excess Li+ cations enter the six-fold coordinated
B sites of the perovskite structure [17]. The substitution
of the six-fold coordinated Li+ with the larger radius of
0.76 A for the smaller radius Ti4+ (0.61 A) generates ad-
ditional oxygen vacancies because of its having a lower
valence than that of Ti4+ [21]. The as-deposited amor-
phous BNT-BT was shown to transform to the perovskite
phase through the formation of an intermediate oxygen-
decient A2 B2 O7x pyrochlore phase during a conven-
tional annealing process [22]. An increase in the Li con-
centration leads to an increase in the oxygen deciency
and tends to stabilize part of the immediate pyrochlore
phase.
Figures 2(a) (d) show the microstructure evolution
of the BNT-BT-Lix thin lms with Li content via AFM
observations. From the AFM results, elongated or rect-
angular grains can be found in the 5% and the 10% Li-
doped BNT-BT thin lms. With increasing Li content,
the grain length in the BNT-BT-Lix thin lms increased
to x = 10, but further Li doping reduced the grain size,
-796- Journal of the Korean Physical Society, Vol. 62, No. 5, March 2013

Fig. 2. (Color online) AFM micrographs of BNT-BT-Lix

thin lms with dierent Li contents: (a) x = 5, (b) x = 10,
(c) x = 15, and (d) x = 20.

and the shape of the grains became spherical, with more

pores being found on this surface. The root-mean-square
(rms) roughness values for the 5, 10, 15, 20% Li-doped
samples were determined to be 3, 3.6, 6.6, and 6.8 nm,
respectively, indicating that the grain growth increased
the lm roughness with increasing Li content from 0 to 10
mol%. In addition, when the Li content exceed 10 mol%,
the appearance of pinholes resulted in a further increase
in the rms of 6.6 nm. The microstructural evaluation
of the Li-doped Bi0.92 Na0.92 Ba0.06 Sr0.02 TiO3 system re-
ported by Lin and Kwok [23] showed a similar trend with
the grain size decreasing signicantly when the Li doping
was increased from 5 to 15%. The grain growth with in-
creasing Li content (x > 10) can also be explained by the
fact that Li addition in BNT-BT-Lix may decrease the
sintering temperature. Thus, both bulk and lm materi-
als with a higher Li content may grow more suciently
and show larger grain sizes when the sintering or an-
nealing temperature is xed. However, for Li contents
x > 10, the appearance of pores can be attributed to
relatively enhanced volatilization. The suppressed grain
growth may result from the enhanced volatilization and
possible formation of a second phase.
To characterize the ferroelectric properties of the Li-
doped BNT-BT thin lms, we performed polarization-
electric eld (P-E) measurements by using a metal-
ferroelectric-metal conguration. Figure 3(a) shows well-
dened saturated P-E hysteresis loops for all the lms at
1 kHz. The variations of remanent polarization (Pr ) and
coercive eld (Ec ) values with x are shown in Figure
3(b). With increasing atomic fraction to x = 10, the Pr
Fig. 3. (Color online) (a) Polarization-electric eld (P-
E) hysteresis loops for BNT-BT-Lix thin lms with various
Li-doping concentrations and (b) remanent polarization (Pr )
and coercive eld (Ec ) values of BNT-BT-Lix thin lms as
functions of Li content.
slightly increases and then decreases quickly with fur-
ther increasing Li content. At x = 10, the Pr reaches
the maximum value of 23.8 C/cm2 while the Ec lin-
early decreases with increasing Li content. Again, the
partial substitution of Na+ by Li+ eectively decreases
the coercive eld, but maintains the high Pr in the P-E
hysteresis loop. This allows ecient poling of the thin
lms, resulting in a signicant enhancement of their fer-
roelectric properties. Our results correspond well with
previously published reports on Li-doped bulk BNT-BT
ceramics [13,14]. The change in Pr with Li amount can be
assigned to the multisite occupation behavior of the Li+
cations in the perovskite structure and the generation of
Eect of Li Doping on Ferroelectric and Piezoelectric Properties Susant Kumar Acharya et al. -797-

oxygen vacancies [17]. For BNT-BT-Li10, a small num-

ber of Li+ cations compensated for the A-site deciencies
due to the volatilization of A-site cations during the an-
nealing process, which may contribute to the increased
Pr . Above this doping level, oxygen vacancies are cre-
ated for ionic charge compensation. The higher concen-
tration of oxygen vacancies in the lm makes the pin-
ning eect stronger and the ferroelectric domain switch-
ing under an electric eld lower, resulting in a decrease
in the Pr [16]. It should be noted that the Pr values for
the BNT-BT-Lix lms are lower than those of the bulk
BNT-BT whereas the Ec values are considerably higher.
Similar results have been reported for doped BNT thin
lms [8,10], which is attributed to the clamping eect
[9].
The dielectric measurements for the BNT-NT-Lix thin
lms were carried out with a 200 mV sine wave at a fre-
quency of 100 kHz. The results indicate that the dielec-
tric permittivity at zero electric eld was signicantly
enhanced from 543 (undoped) to 571 (Li10) by Li
doping. A similar enhancement in dielectric properties
can be found in Li-doped BNT-based ceramics [1315].
The applied voltage dependence of the leakage current
density (J-V) for the BNT-BT-Lix thin lms was also
determined at room temperature. It was found that the
BNT-BT-Lix lms with Li doping exhibit a lower leakage
current then the BNT-BT lm up to a Li doping level of
10%, and then increase. The BNT-BT-Lix thin lm with
10 mol% exhibited the lowest leakage current density of
1.9 106 A/cm2 at 100 kV/cm. Several factors af-
fect the current-eld characteristics of ferroelectric thin
lms, including the intrinsic Li-doping eect: the dier-
ent grain structures among the Li-doped thin lms, and
the eects from vacancies [24]. First, due to the volatili-
ties of bismuth and sodium during heat treatment, some
intrinsic oxygen vacancies appear and produce electrons
according to the following equation:

OO = VOI + 2e + 1/2OO , (1)
Fig. 4. (Color online) Local piezoresponse characteristics:
(a) amplitude and (b) eective d33 hysteresis loops of BNT-
where OO is the oxygen ion on its normal site, VOI is
the intrinsic oxygen vacancy and e is the free electron. BT, BNT-BT-Li10 and BNT-BT-Li20 thin lms measured at
As mentioned above, the substitution of Li+ cations at room temperature.
low doping levels into the A sites of the BNT-BT lattice
compensates for the oxygen vacancies, thereby decreas-
ing the leakage current. On the other hand, the excess The piezoresponse measurements were obtained by
Li+ cations at a high doping level (x > 10) occupied the keeping the PFM tip xed on the grain and apply-
B sites substituted for Ti4+ cations. The substitution ing a direct current (DC) voltage from 10 to 10 V
of Li+ at B sites (Ti4+ ) increases the oxygen vacancies, while recording the signal. Figure 4(a) displays the varia-
giving rise to an increase in leakage current. Besides, it tions of the static piezoresponse (PR) amplitude (A) for
is generally accepted that grain boundaries and void de- BNT-BT, BNT-BT-Li10, and BNT-BT-Li20 thin lms
fects in thin lms also act as a leakage current paths. As with the bias DC electric eld for thin lms at room
the Li-doping concentration is increased further above 10 temperature. For all the thin lms, typical buttery-
mol%, the grain size decreases, leading to an increase in shaped displacement-voltage loops are obtained, and the
the proportion of grain boundaries in the lm, thereby electrically-induced displacements of the lms ranged
increasing the current-path concentration. This may be from 0.7 to 0.15 under a bipolar driving force of 10 V.
the reason for the increased leakage current characteris- The nonlinear and hysteretic part in the loops indicates
tics for the lm samples with Li-doping concentrations the contribution to the strains from the movement of
above 10 mol%. the domain walls in the BNT-BT-Lix lms [24]. The ef-
-798- Journal of the Korean Physical Society, Vol. 62, No. 5, March 2013
fective d33 values were derived from d33 = A cos , as
shown in Fig. 4(b). We found that the maximum values
and remanent d33 were 51.6 and 19.9 pm/V, 57.3,
and 25 pm/V and 26.3 and 15.3 pm/V for BNT-
BT, BNT-BT-Li10, and BNT-BT-Li20 thin lms, re-
spectively. With increasing of Li-doping concentration,
the pinning center density induced by the charged carri-
ers trapped in potential wells decreases, thereby aect-
ing the mobility of the domain walls [25]. This may be
the reason for the observed increase in the piezoelectric
properties of BNT-BT-Li10. We found that the highest
d33 value was at x = 10 in the BNT-BT-Lix lms. This
value is in good agreement with that for the Li-doped
BNT-BT bulk ceramics [13, 14, 26]. When Li doping is
further increased, the eective d33 value is decreased as
in the case of the BNT-BT-Li20 thin lms because of
Li+ entering into the B sites of the perovskite structure
and forming the pyrochlore phase, as explained above.
The extrinsic contributions to piezoelectricity by pol-
ing are related to the grain size of the lm [27]. The BNT-
BT-Li10 lm showed a larger grain size than the other
compositions, which may cause a considerable change in
the piezoelectric properties. Owing to the clamping ef-
fect imposed by the substrate or the bottom electrode, a
piezoelectric thin lm usually exhibits a reduced mechan-
ical strain and, thus, a smaller piezoelectric coecient
than the bulk (152 208 pC/N) Li-doped BNT-BT
[14]. Nevertheless, the observed d33 values for the BNT-
BT-Lix lms are relatively large, showing their poten-
tial for replacing toxic piezoelectric PZT lms in future
environmentally-friendly piezoelectric devices.
IV. CONCLUSION
In summary, Li-doped BNT-BT thin lms with various
contents of Li were fabricated via a metal-organic deposi-
tion process. It has been found that the Li substitution of
the BNT-BT signicantly improves the ferroelectric and
piezoelectric properties of the BNT-BT thin lms. Both
the local eective piezoelectric d33 and the remanent po-
larization Pr increase with increasing Li content, showing
their maximum values at x = 10, and then tend to de-
crease with further increases in Li content. A relatively
high Pr of 23.9 C/cm2 was achieved in the BNT-BT-
Li10 lm under an applied electric eld of 124 kV/cm.
The leakage in the BNT-BT-Lix lms remains a chal-
lenge as it limits the Pr achievable in these lms, and
Li addition was found to have a signicant inuence on
the conducting process under a low electrical eld. The
Li-doped BNT-BT lms with a specic composition of
x = 10 exhibited a local eective piezoelectric d33 of
57.3 pm/V, which is comparable to that of PZT lms,
suggesting that BNT-BT-Lix lms have the potential to
be a good alternatives to PZT in the environmentally-
friendly piezoelectric device applications.
ACKNOWLEDGMENTS
This work was supported by the Fusion Research
Program for Green Technologies through the National
Research Foundation of Korea (NRF) funded by the
Ministry of Education, Science and Technology (Grant
no. 2010-0019097) and was also partially supported by
the Selection of Research-oriented Professor Program of
Chonbuk National University in 2010 and by the Pri-
ority Research Centers Program, and by the Basic Sci-
ence Research Program through the National Research
Foundation of Korea (NRF), funded by the Ministry of
Education, Science and Technology (2010-0019694).
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