JOURNAL OF OPTOELECTRONICS AND ADVANCED MATERIALS Vol. 10, No. 7, July 2008, p.

1894 - 1897

High-voltage tunability measurements of the

BaZrxTi1-xO3 ferroelectric ceramics
F. M. TUFESCUa*, L. CURECHERIUa, A. IANCULESCUb, C. E. CIOMAGAa, L. MITOSERIUa
a
Dept. of Solid State & Theor. Phys., Al. I. Cuza University, Bv. Carol I, 11, Iasi 700506, Romania
b
Polytechnics University, 1-7 Gh. Polizu, P.O. Box 12-134, 011061 Bucharest, Romania

One of the most important nonlinear characteristic of ferroelectrics is the tunabilty, i.e. the variation of permittivity with the
applied field ε(E). The tunability properties of ceramic are rarely reported since very high voltages are needed for saturation.
However, this type of characterization for bulk material is necessary to give reference value for the films characteristics,
normally used in applications. A circuit to measure the tunability with a high accuracy was designed and realized. In the
present work, the experimental method is described. In addition, tunability data of BaZrxTi1-xO3 ceramics are shown and
discussed.

(Received April 1, 2008; accepted June 30, 2008)

Keywords: Ferroelectric, Tunability, BaTiO3-based solid solution

1. Introduction The tunability properties of ceramic are rarely

reported since very high voltages are needed for
Since the early 1970s, the ferroelectrics applied in the saturation. However, this type of characterization for bulk
automatic tunable microwave devices has been receiving material is necessary to give reference value for the films
renewed attention, and a number of practical tunable characteristics. In the present work, tunability data in some
microwave devices were enameled over the past several BZT ceramics are shown.
decades [1]. It was generally agreed that for such
application, ferroelectric should be in the paraelectric 2. Experiment
phase, since in the polar phase most ferroelectrics show
high losses. It was recently demonstrated that such 2.1 Sample preparation, structural and
viewpoint is incorrect, and low losses along with microstructural characterisaton
substantial tunability of the permittivity were observed in
the ferroelectric phase, thus concentrated again the interest For the preparation by classical solid state reaction
on the tunable ferroelectrics [1,2]. BaxSr1-xTiO3 (BST) is method high-purity raw materials as BaCO3 (Flucka), TiO2
currently the material of choice for microwave (Merck) and ZrO2 (Merck) were weighed in appropriate
applications due to its low loss and composition dependent proportions and homogenized with isopropyl alcohol in an
Curie temperature, but similar properties show other agate mortar for 1 hour. The mixture was dried and then
BaTiO3-based solid solutions like BaTi1-xSnxO3 [3]. granulated using a 4 % PVA (polyvinyl alcohol) solution
BaZrxTi1-xO3 (BZT) was not reported as tunable material, as binder agent, shaped by
but its properties recommend it as a possible candidate. uniaxial pressing at 160 MPa into pellets of 20 mm
Recently, this system became attractive from the point of diameter and ~ 3 mm thickness. The presintering thermal
view of its characteristics related to the local polar treatment was carried out in air, at 1150°C, with 3 hours
properties [4], the phase formation mechanism [5, 6] and plateau. The samples were slowly cooled, then ground,
for the dielectric/tunability properties in the view of pressed again into pellets of 10 mm diameter and 1 - 2 mm
microwave applications [7–9]. thickness and sintered in air, with a heating rate of
Tunable circuits are based on capacitors that use a 5°C/min, at 1300°C for 4 hours.
ferroelectric material as the dielectric material. Its X-ray diffraction measurements at room temperature,
dielectric constant and therefore capacitance value, can be used to investigate the purity of the perovskite phases were
adjusted by applying a DC voltage. When the value of a performed with a SHIMADZU XRD 6000 diffractometer
capacitor in a circuit is changed, the impedance and phase using Ni-filtered CuKα radiation (λ = 1.5418 Å), with a
relationships in the circuit are affected in predictable ways. scan step of 0.02° and a counting time of 1 s/step, for 2θ
These parameter changes can be exploited to yield tunable ∈(20 – 80)°.
impedance matching networks, tunable filters, phase A HITACHI S2600N scanning electron microscope
shifters, and other functions where a variable capacitor or coupled with EDX was used to analyse the ceramics
varactor diode, is used. microstructure and to check the chemical composition of
the ceramic samples.
 High-voltage tunability measurements of the BaZrxTi1-xO3 ferroelectric ceramics 1895

2.2 High voltage measurements cell (HVMC) (G) with stabilized frequency is applied to the sample (P1)
by means of a separation capacitor (CS). A current
For the high measurement voltage measurements, a dependent on the ceramic sample capacity is flowing
few precautions have to be taken. A high voltage through the resistor (RM) connected to the (P2) contact;
measurements cell (HVMC) was realized (Fig. 1). The the voltage on this resistor is applied through a pass-band
ceramic sample under measurement (S) is usually a plan- filter (PBF) on a selective amplifier (SA). These two
parallel ceramic disk with diameter between 10÷20 mm blocks, strictly accorded to the frequency of the generator
and thickness in the range of (0.6÷3) mm. Ag, Au or Pt (G) realize such a signal/noise ratio favorable to correctly
electrodes (E) obtained by sputtering or deposited from measure the capacity in the conditions of ripple and noise
electrode paste, with thickness below 0.1 mm (E) are of the high-voltage generator (HT).
commonly used.

Fig. 2. Block circuit for measuring the high voltage dc-

tunability: (FG) – function generator, (HVS) – high
voltage source, (FG) – function generator, (PR) –
Fig. 1 High-voltage measurement cell: (1) – main body, protection resistor,
(2) and (3) – lids, (4) insulating support, (5) insulating (G) – generator, (CS) – separation capacitor, (P1), (P2)
cover, (6) transformer or silicon oil, (S) – sample, – ceramic sample contacts, (RM) – resistor, (PBF) –
(E) – electrodes, (H) – heating element, (TS) – pass-band filter, (SA) – selective amplifier, (VE1), (VE2)
temperature transducer, (PTFE) – polytetrafluoretilene, – electronic voltmeters, (TR) –temperature regulator (H)
(F) – terminals of the heating element. – heater, (DASM) – data aquisition system
measurements, (PC) – computer.

The ceramic sample is connected to the circuit by

means of thin Cu wires (P1) and (P2) with diameters of The voltage measured with the electronic voltmeter
around 0.5 mm. To apply a high voltage without (VE1) is in relationship with ceramic capacitance
breakdown and without causing discharge at the electrodes dependent on the high-voltage (tunability), which is
margins, the sample is embedded into a high-voltage measured by the electronic voltmeter (VE2). The
measurement cell (HVMC) containing silicon oil or temperature control in the sample chamber is ensured by
transformer oil (6). The HVMC is cylindrical and is the temperature regulator (TR) commanding a heater (H).
realized from Al and contains: the main body (1) and two A PC – controlled system connected to a data acquisition
lids, a cover one for manipulating and accessing the system of measurements (DASM) is used to command and
sample (2) and a bottom lid (3), ensuring the access on the measure: (a) the generator voltage, (b) the sample
heating element (H). Inside the main body, a temperature capacitance, (c) the temperature and its time-variation. By
transducer (TS) is introduced. On the top, the HVMC is using this circuit, the high voltage tunability ε(E)
enclosed by an insulating cover (5) put on the top of the dependences of some BaTiO3 –based ceramics were
insulating support (4). The connecting cables are insulated accurately measured. In the present paper, the data
out from the HVMC box by using polytetrafluoretilene obtained for a BaZrxTi1-xO3 ceramic are shown.
(PTFE) having a breakdown voltage over 40kV.
3. Results and discussions
2.3 Circuit for the high voltage tunability
measurements 3.1. Phase composition and microstructure

A circuit to measure the tunability was designed and The room temperature X-ray diffraction pattern
realized (Fig. 2). The high voltage source (HVS) is of the powder resulted after presintering at 1150°C/3 hours
commanded by a function generator (FG), amplified with shows the presence of a well crystallized perovskite major
a TREK 30/20A-H-CE amplifier (PE) is applied by means phase, with the BaTiO3 structure (Fig. 3(a)). A small
of a protection resistor (PR) aimed to limit the current amount of BaZrO3 was also identified as secondary phase
through the ceramic sample in case of breakdown of the at the detection limit proving that, in the first stage of the
ceramic sample. A sine wave produced by the generator thermal treatment, the two perovskite phases individually
1896 F. M. Tufescu, L. Curecheriu, A. Ianculescu, C.E. Ciomaga, L. Mitoseriu

form from the raw materials, according to equations (1) 3.2. DC-tunability data at room temperature
and (2).
Figure 5 shows the capacitance tuning curve for a
BaCO3 + TiO2 → BaTiO3 + CO2 ↑ (1) ceramic capacitor realized with the BZT ceramic described
BaCO3 + ZrO2 → BaZrO3 + CO2 ↑ (2) before. By comparison with other literature data [1], a very
smooth ε(V) curve was found, proving the reliability of the
The rise of the thermal treatment temperature leads to present system to accurately measure the high voltage
the isomorphic integration of the BaZrO3 in the BaTiO3 tenability of ferroelectric ceramics. For this capacitor, the
crystalline lattice (eq. 3), so that after sintering at zero voltage capacitance was about 194 pF but when a
1400°C/4 hours, a single phase composition corresponding voltage of ~11kV is applied, the capacitance decreases by
to the BaTi0.9Zr0.1O3 solid solution was obtained (Fig. about one half and tends to saturate. Thus, the present
3(b)): ceramic has a rather high tunability, related to its high
density and homogeneous microstructure, which might
0.9 BaTiO3 + 0.1 BaZrO3 → BaTi0.9Zr0.1O3; (3) find some important applications.
For example, when used as an element in a resonant
circuit, a reduction in capacitance by one half corresponds
P - BaTiO3ss
* - BaZrO3 to a resonant frequency shift of 42% and similarly a 3:1
P capacitance change corresponds to a frequency shift of
x = 0,10
over 70%. An important point to remember is that the
ferroelectric capacitor has a very small leakage current,
Intensity (a.u.)

and therefore the power dissipation in the control circuit is

(a) 1150°C
(b) 1400°C virtually negligible. Phase shifters are also a
straightforward application of variable capacitance. As
P P pointed out earlier, when capacitance changes, the phase
P
P
P response of the circuit is affected. The critical parameter to
(b) P P
P P
P be varied in a phase shifter is, of course, the phase. Phase
P
(a) * P P
P shifters have important applications in base stations and
* * * P
are a critical device in the functioning of phased array
20 30 40 50 60 70 80 antennas. Phased array antennas are expected to increase
2θ (CuKα degrees) the efficiency of wireless systems by allowing signals to
be radiated only in the direction required, instead of
Fig. 3. Room temperature X ray diffraction patterns of: sending it out in all directions as is commonly done now
(a) presintered powder; (b) sintered ceramic sample.
[10].

1.0 BaZr0.10Ti0.90O3
Tunability: 1-ε(V)/ε(0)

The SEM image of the surface of the ceramic

0.9
sample obtained after sintering at 1450°C/4 hours shows a solid state
dense, homogeneous and pore-less microstructure, 0.8 sintered at Ts=1450 C
0
consisting of large grains (of ~ 50 µm), as a result of the
0.7
grain growth process induced by the higher thermal
treatment temperature. Perfect connections at the triple 0.6
junctions and well-defined grain boundaries were also
pointed out by the micrograph represented in the Fig. 4. 0.5
T=300 K
For such a dense ceramic, good tunability data have to be 0.4
obtained. 0 2 4 6 8 10 12
DC Voltage (kV)

Fig. 5. DC-tunability at room temperature obtained for a

BaZr0.10Ti0.90O3 ceramic

Further studies aimed to determine the temperature

dependence of tunability in this ceramic and its low-field
dielectric characteristics, together with efforts in modeling
the tenability data will follow.

4. Conclusions
Fig. 4. Surface SEM image of the Ba Zr0.10Ti0.90O3
ceramic sample obtained after sintering at 1450°C/4 hours. In the present work, a system to measure the high
voltage tenability characteristics of a ferroelectric ceramic
 High-voltage tunability measurements of the BaZrxTi1-xO3 ferroelectric ceramics 1897

was designed and realized. The system was tested by using [4] R. Farhi, M. El Marssi, A. Simon, J. Ravez, Eur. Phys.
a BZT ceramic with good microstructural characteristics J. B9 599 (1999).
(homogeneous microstructure, high density, pure phase). [5] K. Aliouane, A. Guehria-Laidoudi, A. Simon, Solid
Very accurate experimental tunabilities have been State Ionics 7, 1324 (2005).
obtained. A reduction of the capacitance to around a half [6] J. Bera, S.K. Rout, Mater. Lett. 59, 135 (2005)
when applying a voltage of around 11 kV was observed. [7] U. Weber, G. Greuel, U. Boettger, S. Weber, D.
Some possible applications of this nonlinear effect were Hennings, R. Waser, J. Am. Ceram. Soc. 84, 759
mentioned. (2001).
[8] Z. Yu, C. Ang, R. Guo, A.S. Bhalla, Appl. Phys. Lett.
Acknowledgements 81, 1285 (2002).
[9] Q. Feng, C.J. McConville, D.D. Edwards, J. Am.
The present work was performed in the frame of the Ceram. Soc. 88, 1455 (2005).
Romanian research grant CEEX-FEROCER (2006-2008).

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11, 73 (2003). Corresponding author: [email protected]