Ferroelectrics

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

Fabrication and Characterization of Pb-Rich

Lead Strontium Titanate Films by RF Magnetron
Sputtering

T. Fujii , T. Tanaka , M. Ishikawa & M. Adachi

To cite this article: T. Fujii , T. Tanaka , M. Ishikawa & M. Adachi (2006) Fabrication and
Characterization of Pb-Rich Lead Strontium Titanate Films by RF Magnetron Sputtering,
Ferroelectrics, 335:1, 119-125, DOI: 10.1080/00150190600689662

To link to this article: http://dx.doi.org/10.1080/00150190600689662

Published online: 10 Oct 2011.

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 Ferroelectrics, 335:119–125, 2006
Copyright © Taylor & Francis Group, LLC
ISSN: 0015-0193 print / 1563-5112 online
DOI: 10.1080/00150190600689662

Fabrication and Characterization of Pb-Rich Lead

Strontium Titanate Films by RF
Magnetron Sputtering

T. FUJII,∗ T. TANAKA, M. ISHIKAWA, AND M. ADACHI

Downloaded by [Amity University], [gaurav gupta] at 23:23 23 September 2015

Department of Electronics and Informatics, Toyama Prefectural University,

Kosugi-machi Toyama 939-0398, Japan

Lead strontium titanate (PST) films were fabricated by RF magnetron sputtering. Pb-
rich PST films on Ir(111)/SiO2 /Si and Pt(111)/Ti/SiO2 /Si substrates showed perovskite
structure. Dielectric loss of the PST film on Pt(111)/Ti/SiO2 /Si substrate showed smaller
value compared to that on Ir(111)/SiO2 /Si substrate. This results might be originated
from the grain size and surface roughness of the PST films; PST films fabricated on
Pt(111)/Ti/SiO2 /Si substrate showed small grain and smooth surface. Ir electrode is
advantageous to reduction of fatigue properties in Pb(Zr,Ti)O3 ferroelectric random
access memory, however, Pt/Ti bottom electrode is favorable in case of PST films because
of a small lattice mismatch between metal and PST films.

Keywords Lead strontium titanate; RF magnetron sputtering; dielectric property

Introduction
Ferroelectric thin films such as lead-based perovskite structures have been actively studied
as one of the promising materials for ferroelectric random access memories (FeRAMs) and
other piezoelectric devices. Lead strontium titanate [(Pb,Sr)TiO3 , PST] is a solid solution
of lead titanate and strontium titanate with a perovskite structure. Curie temperature of
the PST changes from −230◦ C to 490◦ C with increasing the Pb/Sr ratio. Therefore, using
PST films, many electronic devices could be expected. Sr-rich PST ceramics has been re-
ported as a tunable material for microwave devices at room temperature due to its large
electric field-dependent dielectric constant [1, 2]. Another work of Sr-rich PST ceramics
has been focused on its large breakdown field, and possibility of high-energy-density ca-
pacitors was found [3]. The authors have been studied Pb-rich PST films by RF magnetron
sputtering [4–6] and sol-gel technique [7]. PST film prepared by RF magnetron sputtering
on SrTiO3 (100) substrate showed remanant polarization of 30 µC/cm2 [5]. In this study,
Pb-rich PST films were fabricated by RF magnetron sputtering on Si based substrate using
PST ceramics target. PST films fabricated on Ir(111)/SiO2 /Si and Pt(111)/Ti/SiO2 /Si sub-
strates showed perovskite structure. Dielectric loss of the PST film on Pt(111)/Ti/SiO2 /Si
substrate showed smaller value compared to that on Ir(111)/SiO2 /Si substrate. This results

Paper originally presented at IMF-11, Iguassu Falls, Brazil, September 5–9, 2005; received for
publication January 26, 2006.
∗
Corresponding author. E-mail: tadashi@pu-toyama.ac.jp
[703]/119
 120/[704] T. Fujii et al.

might be originated from the grain size and surface roughness of the PST films; PST films
fabricated on Pt(111)/Ti/SiO2 /Si substrate showed small grain and smooth surface.

Experimental
An RF (13.56 MHz) magnetron sputtering equipment was used to fabricate PST films and
also electrode metal films of Ir, Ti and Pt. PST thin films with perovskite structure were
prepared on Ir(111)/SiO2 /Si and Pt(111)/Ti(101)/SiO2 /Si substrates. SiO2 layer was fab-
ricated by thermal oxidation of Si(100) wafers in H2 O atmosphere for 1 h at 900◦ C. The
metal films for lower electrode were prepared by the RF sputtering in Ar atmosphere of
5–8 mTorr; 60 nm of Ir layer was sputtered for 3 min at 550◦ C, 100 nm of Ti layer was sput-
tered for 8 min at 540◦ C, and 100 nm of Pt layer on Ti film was sputtered for 3 min at 550◦ C.
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PST target used in this study was made from high purity PbO, SrCO3 , and TiO2 powders with
the ratio of Pb/Sr = 60/40 and Ti/(Pb+Sr) = 1. Those composition would show ferroelectric
property at room temperature. Calcination and Sintering conditions were 850◦ C for 1 h and
at 1100◦ C for 1 h. Small amount of PbO pellets (12 mm-diameter and 2 mm-thickness) and
pure titanium metal chips (5 mm × 5 mm and 1 mm-thickness) were also used on the PST
target to adjust Pb and Ti compositions of PST films. PbO pellets was calcined at 700◦ C for
1 h. Typical sputtering conditions of PST films are shown in Table 1. The reason why we
used two kind of bottom electrode metal is that most of PST films on Ir bottom electrode
did not show high resistivity. We could not measure dielectric properties of the PST films
on Ir(111)/SiO2 /Si substrate only a few samples, then in this study Pt(111)/Ti(101)/SiO2 /Si
substrate was also used, which is generally used in ferroelectric films.
The crystal structure and crystallographic orientations of PST films were examined by
the X-ray diffraction (XRD). Surface morphology of PST films was observed by scanning
electron microscopy (SEM). An energy dispersive X-ray spectrometer (EDX) was used
to determine the ratio of Pb/(Pb+Sr) and Ti/(Pb+Sr) in PST films. The capacitance and
dielectric loss of the films were measured by using the YHP4192A LF impedance analyzer.

Results and Discussions

Structure and Composition of PST Films

XRD patterns of the PST films are shown in Figs. 1 and 2. In case of Fig. 1, (111)-oriented
perovskite PST film was obtained on Ir/SiO2 /Si substrate. Using Pt/Ti/SiO2 /Si substrate,
PST film exhibits perovskite structure with several diffraction peaks as shown in Fig. 2.

Table 1
Typical sputtering conditions of PST thin films

Substrate Ir(111)/SiO2 /Si or

Pt(111)/Ti(101)/SiO2 /Si
Target PST 60/40 Ceramics
Substrate Temperature 630–650◦ C
Input RF Power 100 W
Gas Pressure 5–8 mTorr
Gas Flow Rate Ar 10 sccm
Film Thickness 200–400 nm
 Fabrication and Characterization of PST Films [705]/121
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Figure 1. XRD pattern of PST film on Ir/SiO2 /Si substrate.

Table 2 shows Pb and Ti composition of PST films determined by EDX. PST films
fabricated on both Ir/SiO2 /Si and Pt/Ti/SiO2 /Si substrate show near stochiometric value
of Pb/(Pb + Sr) and Ti/(Pb + Sr) ratio. To fabricate stoichiometric PST films, further
optimization of the amount of PbO pellets and Ti chips will be needed.

Dielectric Properties
Temperature dependence of dielectric constant and dielectric loss were measured. Mea-
suring signal oscillation level was 0.05 V and frequency was 100 kHz. Top Pt electrode

Figure 2. XRD pattern of PST film on Pt/Ti/SiO2 /Si substrate.

 122/[706] T. Fujii et al.

Table 2
Pb and Ti composition of PST films

Substrate Pb/(Pb+Sr) Ti/(Pb+Sr)

on Ir/SiO2 /Si 0.56 0.98
on Pt/Ti/SiO2 /Si 0.60 0.91
(PST Target) 0.60 1.00

(1 mm φ) was fabricated on PST/metal/SiO2 /Si by DC sputtering at room temperature.

Figures 3 and 4 show the dielectric properties of PST films on Ir/SiO2 /Si and Pt/Ti/SiO2 /Si
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substrate. Dielectric constant and dielectric loss of PST film on Ir/SiO2 /Si substrate at room
temperature are 647.3 and 0.05, respectively. That of PST film on Pt/Ti/SiO2 /Si are 801.6
and 0.04, respectively. Dielectric loss was improved all the measured temperature range in
the case of Pt/Ti/SiO2 /Si substrate.
In this study, at first we chose Ir as a bottom electrode material. Because it is well
known that Ir bottom electrode is very effective for a fatigue problem in Pb(Zr,Ti)O3 based
FeRAMs. But we could measure dielectric property only several PST samples on Ir/SiO2 /Si
substrate. So Pt/Ti electrode, which is generally used in ferroelectric devices as bottom
electrodes, was used instead of Ir electrode.
We considered this different electrical property in two films with relation to a lattice
constant of the films. Between Pb-rich PST (tetragonal, a = 0.38993–0.39050 nm) and Ir
(cubic, a = 0.38394 nm), there is ∼1.6% of lattice mismatch, however between PST and
Pt (cubic, a = 0.39240 nm) lattice mismatch is small value of ∼0.5%. From SEM images,
grain sizes of the PST film on Ir/SiO2 /Si substrate are 200–500 nm, and large roughness
exist on the films as shown in Fig. 5. Grain size of the PST film on Pt/Ti/SiO2 /Si substrate

Figure 3. Dielectric properties of PST film on Ir/SiO2 /Si substrate.

 Fabrication and Characterization of PST Films [707]/123
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Figure 4. Dielectric properties of PST film on Pt/Ti/SiO2 /Si substrate.

is less than 200 nm and the grains are uniform as shown in Fig. 6. In addition, the PST film
on Pt/Ti/SiO2 /Si substrate showed smoother surface than that on Ir/SiO2 /Si substrate. From
above result, in the case of PST/Ir/SiO2 /Si structure, probability of metal diffusion from
top electrode would be high, because of its rough surface. In the case of PST/Pt/Ti/SiO2 /Si
structure, smooth PST surface would lead to a favorable metal/PST interface, and as a result
small dielectric loss could be obtained.
In our previous research [5], PST films fabricated by RF magnetron sputtering on
Ir(100)/SrTiO3 (100) substrate exibit ferroelectric hysteresis loop, and remanant polarization

Figure 5. SEM image of PST film on Ir/SiO2 /Si substrate.

 124/[708] T. Fujii et al.
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Figure 6. SEM image of PST film on Pt/Ti/SiO2 /Si substrate.

of 30 µC/cm2 , and coercive field of 60 kV/cm were obtained. The crystalinity of above film
was examined by X-ray φ-scanning, and then the film was found almost single crystalline
PST. In this study, even if Pt/Ti/SiO2 /Si substrate was employed, we could not observe
ferroelectric hysteresis curve of PST films. It was thought that crystalinity of PST films
on Ir/SiO2 /Si or Pt/Ti/SiO2 /Si substrates might be deteriorated property rather than that
of PST films on Ir/SrTiO3 substrate, and the shift of Ti composition of PST films from
stoichiometric value (Ti/(Pb+Sr) = 1) might affect poor ferroelectric properties. To fabricate
(001)-oriented PST films is a key issue because a large remnant polarization could be
expected in PST(001) films which orientation is parallel to the spontaneous polarization.
Using SrTiO3 (100) substrate, ferroelectric PST(001) films were obtained, however to obtain
ferroelectric PST films on low cost substrate such as Si is important point for minimizing the
device prices. In this sense, an insulating buffer layer and bottom electrode metal with small
difference of thermal expansion coefficient and lattice mismatch from that of ferroelectric
films are necessary.

Summary
Pb-rich PST films were fabricated by RF magnetron sputtering. PST films fabricated on
Ir(111)/SiO2 /Si and Pt(111)/Ti/SiO2 /Si substrates showed perovskite structure. Dielectric
loss of the PST film on Pt/Ti/SiO2 /Si substrate showed smaller value compared to that
on Ir/SiO2 /Si substrate. This results might be originated from the grain size and surface
roughness of the PST films; PST films fabricated on Pt/Ti/SiO2 /Si substrate showed smaller
grain and smoother surface than that on Ir/SiO2 /Si. It is important to obtain stoichiometric
PST films for applications to ferroelectric and piezoelectric devices. To fabricate (001)-
oriented PST films is very important issue because a large remnant polarization could
be expected PST(001) film which orientation is parallel to the spontaneous polarization.
To use Si based substrate, in other words without using expensive single crystalline sub-
strate such as SrTiO3 or MgO, is also important factor for reducing the fabrication cost of
devices.
 Fabrication and Characterization of PST Films [709]/125

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