Molecular and Quantum Acoustics vol.

27, (2006) 207

PIEZOELECTRIC PROPERTIES OF X/65/35 PLZT CERAMICS

DEPENDED OF THE LANTHANUM (X) IONS CONTENTS

M. Płońska, Z. Surowiak

Department of Material Science, Faculty of Computer Science and Material Science, University
of Silesia, 2 Śnieżna St., 41-200 Sosnowiec, POLAND

mplonskai@ultra.cto.us.edu.pl; surowiak@us.edu.pl

For many years the PLZT ceramics have been known as a ferroelectric material
which has various electro-optic and piezoelectric properties. The aim of this work
was to study how the lanthanum dopant (x) influences on the piezoelectric
properties of x/65/35 PLZT ceramics. All samples were sintered by the hot uniaxial
pressing method, from the sol-gel derived powders. The measurements enclose the
complex of electric parameters, such as: ε, tgδ, kp, k31, d31, SE11, g31, VR.

1. INTRODUCTION
The ferroelectric ceramics have a number of properties, which make them very useful in a
variety of applications. As an example of such materials the lanthanum – doped PZT systems,
represented also as PLZT. Solid - state nature of PLZT material is based on: the simple PbZrO3-
PbTiO3 solid solution system, the function of the lanthanum concentration as well as the Zr/Ti
ratio. Donor dopants of higher charge, like a La3+ ions, enhance domain wall mobility and result
in improved remanent polarization, coupling factors, dielectric constants, dielectric loss tangent
and increased of optical transparency of electrically “soft” PZT material [1, 2]. The result of
such doping is also attributed to the creation of vacancies (V) in the A site of perovskite crystal
structure, thus the chemical composition of PLZT is given by the formula [3]:

Pb1-xLax(Zr1-yTiy)1-x/4V0,25x O3, (1)

Creations of such vacancies ensure electric neutrality of the lead lanthanum zirconate
titanate system. The composition of PLZT is routinely represented by the notation x/(1-y)/y,
which denotes the amount of La/Zr/Ti, given in mole fractions or mole per cent.
208 Płońska M., Surowiak Z.

The goal of this study was: to obtained PLZT materials, from sol-gel derived powders by
the hot uniaxial sintering method (HUP), subjected all samples to polarization by the low
temperature method, and to study the influence of La3+ dopant on their basic dielectric and
piezoelectric properties.

2. MATERIALS AND EXPERIMENTAL PROCEDURE

Based on the PLZT phase diagram [4] to the study the chosen materials had chemical
compositions corresponding to x/65/35 ratio, with different amount of lanthanum (x), for x=0-12
mol%. The technological fabrication process of the all ceramic samples included two stages,
described in more details in previous works, i.e. [4, 5]. Firstly, a modified low temperature sol-
gel synthesis was employed to obtain PLZT nanopowders, from the organometallic precursors
of Pb(OAc)2, La(OAc)3, Zr(O-nPr)4 and Ti(O-nPr)4, in the suitable solvent – n-propyl alcohol
and stabilizing agent - acetyloacetone. The second stage involved consolidation of such
prepared powders and obtaining high density ceramics by the hot uniaxial pressing method. All
samples were received at the experimentally verified temperature, Ts = 1473 K for t = 2 h, as a
shape of discs about (10×1) mm2 of dimension. The flow chart of the preparation of PLZT bulk
ceramics is showed in Fig.1.

Fig. 1. Flow chart of the PLZT ceramics fabrication process.

After sintering each of PLZT samples were ground, polished and than stress relief
annealed at T = 873 K for t = 0.5 h. Before the dielectric and piezoelectric measurements on the
ceramics surface were deposited electrodes by the silver paste burning method. Such prepared
samples were subjected next to polarization by the low temperature method in silicone oil, with
the feeder of high voltage HEOPS-5B6. Polarized conditions were Tp = 423 K, Ep = 20 kV/cm,
t = 30 min. Piezoelectric parameters of poled samples were determined by resonance –
antiresonance method. Dielectric permittivity ε and dielectric loss tangent tgδ were measured
during the cooling cycles with Quadtech 1920 impedance meter, for the non-poled samples with
Molecular and Quantum Acoustics vol. 27, (2006) 209

temperatures T (T = Tm = TC, Tm is temperature at which ε(T) reaches its maximum – the Curie
point) [6].

3. RESULTS AND DISCUSSIONS

Dielectric measurements exhibited the influence of lanthanum dopant on the dielectric
parameters of the x/65/35 PLZT system. Figure 2 shows, that already with the small amount of
lanthanum dopping ε growth to the value of εm2= 28955 for 2/65/35 PLZT, while for PZT
65/35, without dopant, εm1 = 27299. Further increase of La3+ content reduced the maximum of
dielectric constant peak (Curie point) and displaced them to the low temperature, make their
more diffuse. The maximum of loss tangent overlap with maximum of the dielectric
permittivity, and increased with the increase of La content. Observed characteristics are typical
for the relaxor materials, exhibiting diffuse phase transitions.
The influence of lanthanum amounts on Curie point - εm and Tm is shown in Fig.3.

Fig.2. Temperature dependence of the Fig. 3. Influence of amount of lanthanum dopant

dielectric permittivity ε and loss tangent on Curie point, for x/65/35 PLZT with x = 0 – 12
3+
tg for x/65/35 PLZT compositions with La at. %.
x= 0–12 La3+ at.%.

Figure 4 illustrates the effect of the poling process on the PZT 65/35 samples. In the
unpoled ceramics (Fig.4a) each grain contains a number of domains, and the net polarization is
zero. After poling, as can be seen in Fig.4b, the domains are oriented with net polarization along
the direction of applied field. Such effect confirmed that material is piezoelectrically active.
210 Płońska M., Surowiak Z.

Fig. 4. SEM morphologies of the chemically etched fracture surface of: (a) unpoled PZT 65/35
ceramic; (b) poled PZT 65/35 ceramic.

Fig. 5. The influence of La3+ dopant on piezoelectric parametersx/65/35 PLZT.

Basing on the measured data’s the important piezoelectric parameters were calculated. A
summary of parameters of some selected PLZT compositions is given in table. As can also be
seen in Fig.5, the influence on each of piezoelectric factors with lanthanum amount was
observed. The acoustic velocity - VR decreases, when the elastic susceptibility - SE11 increases
with the growth of applied dopant (x = 0-9 La at.%). In case of the electromechanical coupling
coefficient -kp, the cross electromechanical coupling coefficient - k31, and the piezoelectric
modulus - d31, all values increase to the
Molecular and Quantum Acoustics vol. 27, (2006) 211

Table. The piezoelectric parameters of some selected PLZT compositions.

PLZT VR ×103 g31×10-3 k31 kp d31×10-11 SE11×10-11
x/65/35 [m/s] [Vm/N] [C/N] [m2/N]
0/65/35 2,356 12,08 0,23 0,41 4,45 1,02
2/65/35 2,147 10,49 0,24 0,46 6,91 1,27
6/65/35 2,096 8,05 0,29 0,53 14,39 1,31
8/65/35 1,934 8,8 0,14 0,33 4,12 11,77
9/65/35 1,344 6,12 0,06 0.23 2,43 39,46

4. CONCLUSIONS
As a donor dopant, La3+ makes PLZT x/65/35 electrically “soft” materials. Results have
shown that a growth of x in x/65/35 compositions exhibited diffuse phase transition in
temperature dependence of ε and tg  Also the piezoelectric properties were considerably
depended on the lanthanum contents, and for the PLZT compositions above the 9 at.% La the
polarized state were not achieved.

REFERENCES

1. Galassi C., Roncari E. Capiani, Costa A., NATO ASI Series 3: High Technology, Kluwer
Academic Publishers 76 (2000), p 87.
2. Xu Y., Ferroelectric materials and their applications, North-Holland, New York, 1991.
3. Haertling, G.H., Ferroelectrics 75 (1987), p 25
4. Płońska M., Czekaj D., Plewa J., Surowiak Z., Ceramics 71 (2002), p 424
5. Płońska M., Czekaj D., Surowiak Z., Material Science Poland 21,4 (2003), p 431.
6. Surowiak Z., Czekaj D., Molecular and Quantum Acoustics 24 (2003), p 183.