Ferroelectrics

ISSN: 0015-0193 (Print) 1563-5112 (Online) Journal homepage: http://www.tandfonline.com/loi/gfer20

Dielectric and Structural Properties of PST Films

Deposited by RF Ion Sputtering on LSCO/Si
Substrates

E. Martinez , A. Fundora , O. Blanco & J. M. Siqueiros

To cite this article: E. Martinez , A. Fundora , O. Blanco & J. M. Siqueiros (2003) Dielectric and
Structural Properties of PST Films Deposited by RF Ion Sputtering on LSCO/Si Substrates,
Ferroelectrics, 293:1, 153-159, DOI: 10.1080/00150190390238351

To link to this article: http://dx.doi.org/10.1080/00150190390238351

Published online: 18 Jun 2010.

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 Ferroelectrics, 293: 153–159, 2003
Copyright  c Taylor & Francis Inc.
ISSN: 0015-0193 print / 1563-5112 online
DOI: 10.1080/00150190390238351

Dielectric and Structural Properties of PST Films

Deposited by RF Ion Sputtering
on LSCO/Si Substrates
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E. MARTINEZ,1 A. FUNDORA,2 O. BLANCO,1 and J. M. SIQUEIROS3

1 CICESE, Physics of Materials Graduate Program, Km. 107 Carr. Tijuana—Ensenada,
C.P. 22800, B.C. México
2 Facultad de Fı́sica—IMRE, Universidad de la Habana, Vedado, La Habana 10400, Cuba
3 Centro de Ciencias de la Materia Condensada, UNAM C.P. 2681, B.C., México

(Received September 4, 2002; In final form December 15, 2002)

Pb0.5 Sr0.5 TiO3 (PST) films have been obtained by RF ion sputtering on (La0.5 Sr0.5 )CoO3
substrates (LSCO). The purpose of this work is to investigate the relation between the crystalline
structure and the dielectric properties of PST films grown on LSCO electrodes. PST films
were deposited at 400◦ C in a fixed argon/oxygen (50/50) atmosphere. After deposition, PST
films were post-annealed at different temperatures. Scanning Electron Microscopy (SEM) and
X-Ray Diffraction were used for the structural studies. Crystallinity and surface morphology
revealed a strong dependence on the crystallization conditions. The dielectric properties of the
Pt/PST/LSCO/Si films were characterized through Capacitance (C) vs. Voltage (V) curves,
Polarization (P) vs. Electric Field (E) curves and Current (I) vs Voltage (V) measurements.
Leakage currents were also evaluated at each postannealing temperature.

Keywords: RF ion sputtering; Pbx Sr1−x TiO thin film; leakage current; conducting oxide

INTRODUCTION

Technological applications of ferroelectric oxides in electronic [1] and opti-

cal [2] devices have drawn attention to the study of ferroelectric thin films.
Ferroelectric oxides exhibit spontaneous electrical polarization associated to
a crystallographic phase transformation. Because of their unique properties,
ferroelectric oxides have great potential for future applications in electronic
and optical devices. Thin films are particularly important and RF ion sputter-
ing has established as an excellent technique for the deposition of perovskite
materials [3, 4] mainly because of its possibilities for scaling up, its simplic-
ity, versatility and capability for growing a wide variety of stoichiometric
oxide films in situ. The best conditions for the fabrication of PST films by
153
 154 E. MARTINEZ et al.

RF ion sputtering have not been found yet and it is one of the motivations
of this work. Additionally, many of works on ferroelectric thin films have
been focused on metallic electrode materials since they exhibit good adhe-
sion to lead based perovskite films. However, polarization fatigue has been
constantly observed and attributed to mobile oxygen vacancies and Schottky
depletion regions due to work function mismatch at the interfaces [5, 6]. If
the electrode of the ferroelectric thin films is replaced by a conducting ox-
ide, much better fatigue resistance and capacitance values can be achieved
[7, 13]. The purpose of the present work is therefore, to grow ferroelectric
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Pbx Sr1−x TiO3 thin films on LSCO/Si substrates by RF ion sputtering and to
study how the structure and properties of the films would be affected by this
kind of substrate. Some recent efforts have been directed toward growing
Pbx Sr1−x TiO3 films with other techniques [9, 10, 12, 13] in the search of
good alternative for applications.

EXPERIMENTAL PROCEDURE

Conventional ceramic preparation processes were used to prepare the

(Pb0.5 Sr0.5 )TiO3 target for this investigation. High-purity PbO 99.9%, SrCO3
99.5% and TiO2 99.5% oxide powders were used as raw materials. Pow-
ders of proper compositions were weighed, mixed and milled for 4 h. The
powders were calcined at 700◦ C for 1 h in air and milled powders were
granulated. Pellets were formed by pressing the granulated powders at a
pressure of 5 ton/cm2 . The pellets were then sintered for 5 h at 1300◦ C.
During the sintering stage, the specimens of lead containing materials were
completely covered with powders of the same composition, to prevent pos-
sible loss of PbO. LSCO substrates were obtained by DC sputtering from
a stoichiometric target (La0.5 Sr0.5 )CoO3 with a 80/20(Ar:O) mixture at a
pressure of 6 mT at 650◦ C. In this study, PST thin films were prepared by
RF ion sputtering. Deposit conditions are specified in Table I. To determine
the growth orientation and degree of crystallinity of the PST films, X-ray
diffraction (XRD) studies using a Philips X’pert XRD diffractometer were
performed. The surface morphology of the PST films was examined with a
JSM-5300 scanning electron microscope by JEOL. The dielectric properties
of the PST50 films were measured by with a RT66A ferroelectric tester. In
order to measure the electrical properties, Pt upper electrodes of 0.3 mm in
diameter were prepared using a shadow mask in a DC sputtering system.
Capacitance-Voltage (C-V) and leakage current (I-V) characteristics were
also measured with an RT66A tester By Radiant Technologies Inc. for all
postannealing temperatures.
 DIELECTRIC AND STRUCTURAL PROPERTIES OF PST FILMS 155

TABLE I Deposition conditions for (Pb0.5 Sr0.5 )TiO3 films

Target (Pb0.5 Sr0.5 )TiO3

Working gas (Ar/O) 50%/50%
Gas pressure 6 mTorr
Rf power 200 W
Substrate-target distance 3 cm
Substrate temperature 400◦ C
Post-annealing temperatures 550, 600, 650◦ C
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RESULTS AND DISCUSSION

The deposit conditions to grow (Pb0.5 Sr0.5 )TiO3 films on LSCO/Si(111)

substrates are shown in Table I.

A. Crystallization and Morphological Properties

As deposited PST films at 400◦ C did not show crystallinity. After deposi-
tion, PST films were subsequently postannealed at 550, 600 and 650◦ C for
10 minutes. Their crystal structures were examined by XRD as shown in
Fig. 1. The crystallization of PST films occurred at 650◦ C. A polycrystalline
phase with reflections in the (110), (111), and (211) directions was formed.
The surface morphology of PST thin films obtained by SEM for various
postannealing temperatures is shown in Fig. 2. Clearly, the surface of the
PST film is smooth, dense, and uniform without cracking and voids at 550◦ C

Figure 1. XRD profile of PST50 films deposited on LSCO/Si(111) at three different

post-annealing temperatures.
 156 E. MARTINEZ et al.
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Figure 2. Surface morphology of PST films grown on LSCO/Si(111) at (a) 550◦ C,

(b) 600◦ C, and (c) 650◦ C.

and 600◦ C. The grains were formed at 650◦ C where the crystallization is
evident. Notably, the surface morphology at 650◦ C was very rough. Also,
the grain size increased for higher post-annealing temperatures, as shown
in Fig. 2. This result is consistent with that of previously reported PST thin
films deposited by the liquid-source misted chemical method [13].

B. Electrical Properties
Capacitance measurements were evaluated using an RT66A analyzer with a
maximum voltage (Vmax ) of 3 volt. The capacitance-voltage curves for PST
films (1100 nm thick) grown on LSCO/Si substrates annealed at 550,600 and
650◦ C for 10 min are shown in Fig. 3a. Capacitance values were obtained
sweeping from a maximum positive voltage to a negative voltage and back in
each case. The maximum capacitance values were at about zero voltage and
increase with postannealing temperature which improves crystallinity and
 DIELECTRIC AND STRUCTURAL PROPERTIES OF PST FILMS 157
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Figure 3. (a) Capacitance-Voltage curves of PST films post-annealed at 550, 600

and 650◦ C deposited on LSCO/Si(111) measured at room temperature. (b) Applied
voltage dependence of capacitance at two different temperatures of measurement of
PST films annealed at 650◦ C.

the capacitive properties of the films. It is important to notice the symmetric

shift of the C-V curves with respect to zero voltage as they are taken from
positive to negative or from negative to positive voltage. This behavior is
possibly be related to the presence of an internally bias field generated by the
difference in work functions of the LSCO and Pt of the electrodes [11, 14, 15]
and the PST film. Hysteresis in the capacitance values appears as voltage
is swept up and down resulting from the different values of the interface
capacitance produced by a Schottky barrier that is different for each electrode
(top and bottom). Similar results were obtained for SrTiO3 films grown on
LSCO [11]. For all films, the magnitude of capacitance turns out to be lower
when going from negative to positive than from positive to negative voltage.
PST films post-annealed at 650◦ C which showed the best crystallinitity and
good capacitive properties were measured at different temperatures and the
increase in capacitance as the measurement temperature was raised was
evident (Fig. 3b).
The current-voltage (I-V) characteristics of the PST thin film annealed at
550,600 and 650 for 10 minutes are shown in Fig. 4a. The leakage current
 158 E. MARTINEZ et al.
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Figure 4. (a) Leakage current density vs. Applied Voltage for films annealed at 550,
600 and 650◦ C (b) P-V relation of the Pt/PST/LSCO/Si(111) capacitor measured at
room temperature with a maximum voltage Vmax = 3 volts.

density of the PST thin film was measured applying a DC voltage in the
sample and measuring the current through the film considering the upper
electrode area. It is observed that current density increases with the increase
in voltage but without reaching electrical breakdown. Leakage density cur-
rents diminish with increasing post-annealing temperature, as was the also
case with capacitance. A maximum of 3 volts was used to study the P-V
behavior at room temperature. Low polarization values were found for the
PST films on LSCO/Si from the ferroelectric P-V curve shown in Fig. 4b.

CONCLUSIONS

Polycristalline PST films have been successfully grown on LSCO/Si(111)

substrates by RF ion sputtering. XRD and SEM studies show the PST thin
films to have low crystallinity and smooth surface for 550 and 600◦ C post-
annealing temperatures. At 650◦ C PST films were well crystallized and a
granular microstructure is evident. PST thin films showed, from electrical
measurements, high dielectric constant and good insulating properties that
are improved as the post-annealing temperature is increased, as was also the
case for C-V and I-V measurements. Low polarization values were found for
 DIELECTRIC AND STRUCTURAL PROPERTIES OF PST FILMS 159

the PST films on LSCO/Si (Fig. 4b) when compared with results obtained
by other authors using different techniques [10–12]. However, this result is
important because there are no other reports for PST films grown by RF ion
sputtering.

ACKNOWLEDGMENTS

This work was partially sponsored by CoNaCyT Proj. No. 33586-E and
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DGAPA-UNAM Proj. No. IN104000. We thank, V. Garcı́a, P. Casillas,

I. Gradilla, E. Aparicio, for their technical help and valuable suggestions.

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