Integrated Ferroelectrics

An International Journal

ISSN: 1058-4587 (Print) 1607-8489 (Online) Journal homepage: http://www.tandfonline.com/loi/ginf20

THE CRYSTALLINE AND DOMAIN PROPERTIES OF

PLT THIN FILMS FABRICATED BY RF SPUTTERING

JIAGANG WU , XIAOWU YUAN , DINGUAN XIAO , HONG LIU , ZHAHUI PU ,

JILIANG ZHU & JINGUO ZHU

To cite this article: JIAGANG WU , XIAOWU YUAN , DINGUAN XIAO , HONG LIU , ZHAHUI PU ,
JILIANG ZHU & JINGUO ZHU (2006) THE CRYSTALLINE AND DOMAIN PROPERTIES OF PLT
THIN FILMS FABRICATED BY RF SPUTTERING, Integrated Ferroelectrics, 79:1, 219-226, DOI:
10.1080/10584580600659860

To link to this article: http://dx.doi.org/10.1080/10584580600659860

Published online: 12 Oct 2011.

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 Integrated Ferroelectrics, 79: 219–226, 2006
Copyright © Taylor & Francis Group, LLC
ISSN 1058-4587 print / 1607-8489 online
DOI: 10.1080/10584580600659860

The Crystalline and Domain Properties of PLT Thin

Films Fabricated by RF Sputtering

Jiagang Wu, Xiaowu Yuan, Dinguan Xiao, Hong Liu, Zhahui Pu,
Jiliang Zhu, and Jinguo Zhu∗
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Department of Materials Science, Sichuan University, Chengdu 610064, China

ABSTRACT

The PLT thin films were prepared on the various substrates by RF magnetron sputtering
with using PLT ceramic targets. The X-ray diffraction (XRD) and piezoresponse force
microscopy (PFM) were used for determining the crystalline and domain properties of
the PLT films. The experiment results show that the pure perovskite structure was formed
in the PLT thin films under the optimum deposition condition. The crystalline properties
of PLT ferroelectric thin films were dependence of the experimental air pressure, the
ratio of O2 and Ar2 , annealing temperature and so on. PFM images showed that the
180◦ domain was the main domain structure of PLT thin films. The higher annealing
temperature could help to form larger domain in the PLT thin films.

Keywords: PLT; RF magnetron sputtering; PFM

1. INTRODUCTION

Ferroelectric thin films have recently attracted great interest as new dielectric
materials for ferroelectric random-access memories (FeRAM), micro-electro-
mechanical systems (MEMs), pyroelectric detectors and array, and nonlinear
optical devices [1–3]. As film fabrication technologies, sputtering, metalorganic
chemical vapor deposition (MOCVD), metalorganic decomposition (MOD) and
sol-gel methods can be enumerated. The sputtering technique has advantages
over the other methods from the viewpoint of industrialization because it has
good step coverage, high deposition rate and compatibility with semiconductor
processor as well as being an economical process. In the case of the growth
of oxide thin films by sputtering, it has been reported that the bombardment

Received April 17, 2005; in final form January 23, 2006.

∗
Corresponding author. E-mail: nic0400@scu.edu.cn

[1629]/219
 220/[1630] J. Wu et al.

of energetic oxygen atoms and/or ions results in resputtering and deteriorates

the quality of growing of thin films. Hayashi et al. [5] reported that the growth
rate linearly increases with increasing input RF power density. Kushida and
Takeuchi [6], Toorii et al. [7] reported that the composition of PbTiO3 , PZT thin
films changes with sputtering gas pressure, respectively. (Pb1−x Lax )Ti1−x/4 O3
(PLT) has an excellent pyroelectric, dielectric and ferroelectric properties and
can be used in many applications such as pyroelectric detectors and nonlin-
ear optical devices [8–10]. In this paper, the PLT thin films were deposited on
various substrates by RF magnetron sputtering. The dependence of the crys-
talline and domain properties of PLT thin films on the preparing conditions was
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investigated systematically.

2. EXPERIMENTAL PROCEDURE

A commercial RF-sputtering-magnetron sputtering system (JGP560C10, SKY,

China) was used for the deposition of PLT thin films. The deposition chamber
could evacuated to 6 × 10−6 Pa using a molecular pump. The deposition of thin
films was carried out at 2∼4 Pa for different time using different ratio of Ar2 and
O2 as a sputtering gas. The substrate could be heated to 700◦ C using a micro-
furnace. The PLT thin films were prepared at different substrate temperature,
and crystallized by postannealing at different temperature. The input RF power
density was about 2 W/cm2 and the DC bias voltage to the substrates was as
change from −200 V to +50 V. Table 1 shows the typical sputtering conditions
for PLT thin films.
As a sputtering target, PLT ceramic targets of 70 mm diameter and 4 mm
thickness were prepared by sintering PbO, La2 O3 and TiO2 powder (99.9%

Table 1
Typical deposition conditions for PLT thin films prepared by RF sputtering

Item Parameters

Substrate SiO2 /Si(100)

Pt/Ti/SiO2 /Si(100)
Substrate Temperature Room temperature to 400◦ C
Target PLT ceramic target (φ = 70 mm)
Substrate-target Distance 5∼7 cm
Base pressure 4 × 10−5 Pa
Working pressure 2 ∼ 4 Pa
Sputtering power density 1.5 ∼ 2.5 W/cm2
Input RF power density 1.5 ∼2.5 W/cm2
Substrate spin rate 10–20 r/minute
Depositing rate 4∼8 nm/minute
 Crystalline and Domain Properties of PLT Thin Films [1631]/221

purity). The molar ratio of Pb:La:Ti was 1.0:0.1:0.975. The excess Pb was used
to compensate the loss of Pb when targets were sintered. The substrates of this
research used were SiO2 /Si and Pt/Ti/SiO2 /Si(100), respectively. The layers of
Ti, Pt are employed as bottom electrode layers. The thickness of each layer
on (100) single crystal silicon is 640 nm (SiO2 ), 30 nm (Ti) and 300 nm (Pt),
respectively.
The crystalline properties of the deposited films were performed using an
X-ray diffractometer (DX-1000, China). The morphology and the film thick-
ness was observed by scanning electron microscopy(Hitach S–450, Japan).
The domain properties of PLT thin films were analyzed by piezoresponse force
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microscopy (SPA-300HV, Japan).

3. RESULTS AND DISCUSSION

3.1 Crystalline Phases and Lattice Parameters of PLT Thin Films

As shown in Fig. 1, the PLT thin film deposited at room temperature in working
pressure 2 Pa (Ar:O2 = 7:3) and annealed at 575◦ C in air atmosphere has better
crystalline property.
Table 2 shows the lattice parameters of PLT thin film annealed at different
temperature for 1 hour. From Table 2, it was found that the c/a ratio of PLT
thin film annealed at 575◦ C for 1 hour was 1.061, very closed to the c/a ratio of
PbTiO3 crystal (1.065). The c/a ratio of PLT was decreased with the annealing

Figure 1. The XRD patterns of the PLT thin films deposited at room temperature
(Ar:O2 = 7:3) and annealed at different temperature.
 222/[1632] J. Wu et al.

Table 2
Lattice parameters of PLT thin film annealed at different tem-
perature for 1 hour

Annealed
◦ ◦
temperature (◦ C) a (A) c (A) c/a

600 3.7761 3.8241 1.013

585 3.9550 4.1521 1.05
575 3.9138 4.1521 1.061
550 3.9321 4.1586 1.058
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temperature increasing. Because the higher substrate temperature is helpful for

the re-evaporation of the diffusion atoms on the surface of substrate, especial
for the volatile lead atoms, so that the composition of PLT would deviates the
theoretic stoichiometry and the crystalline properties of PLT films would be
deteriorated. Although the high sputtering gas pressure could minimize change
in composition and plasma damage [7], the rough surface morphology of films
and target degradation would occur when by sputtering high gas pressure. The
lower working pressure can keep the energy of sputtering atoms so that these
atoms could diffuse longer distance on the surface of substrate to form the
crystalline phase. So in this paper, the gas pressure of 2∼4 Pa was selected
as the working pressure. From Figure 2, it was found that the PLT thin films
deposited at 4 Pa working pressure had better crystalline properties.

3.2 SEM and AFM Observations of the PLT Thin Films

Figure 3 shows some of the AFM images of PLT thin films annealed at differ-
ent temperature for 1 hour in air atmosphere. AFM images show a crack-free
surface and large grains formation on the surface of the PLT thin films an-
nealed at different temperature for 1 hour. Table 3 shows the data analysis of
the AFM images of PLT thin films annealed at different temperature for 1 hour.
From the Table 3, it was found that the root mean square (RMS) of surface

Table 3
Data analysis of the AFM image of PLT thin film annealed at dif-
ferent temperature for 1 hour

Annealed temperature RMS (nm) Rz (nm) Grain size (nm)

575◦ C 2.543 25.0 30.7

600◦ C 3.632 30.7 35.6
625◦ C 4.094 49.4 42.4
 Crystalline and Domain Properties of PLT Thin Films [1633]/223
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Figure 2. The XRD patterns of the PLT thin films prepared at different working pressure
(Ar:O2 = 8:2).

roughness of PLT thin films annealed at 575◦ C, 600◦ C and 625◦ C for one hour
was 2.543 nm, 3.632 nm, and 4.094 nm, respectively. With the annealed tem-
perature increasing, the surface alteration Rz and the grain size of PLT thin
films were also increasing. It was caused by the exceeding growth of the grain
when PLT thin films annealed at higher temperature.
Figure 4 shows that the interface between PLT film and SiO2 /Si substrate
is rather sharp and the film thickness is about 600 nm.

Figure 3. AFM images of PLT thin films annealed at a) 575◦ C, b) 600◦ C, c) 625◦ C for
1 hour in air atmosphere.
 224/[1634] J. Wu et al.
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Figure 4. The thickness of PLT films deposited at Pt/Ti/SiO2 /Si (Ar:O2 = 8:2; 2 Pa,
substrate temperature 300◦ C, annealing temperature 600◦ C) for 2 hours.

3.3 Domain Properties of the PLT Thin Films

To investigate nanoscale domain mapping and switching, piezoresponse force

microscopy (PFM) is applied [11]. Figure 5 shows the in-plane polarization
images of the PLT thin films prepared by the different ratio of Ar and O2
annealed at 600◦ C for 60 minutes. From Fig. 5, it was found that the dense
and small domains of PLT film show 180◦ domain structure when PLT film
deposited at Ar:O2 was 8:2. However, the domain of PLT film show rather

Figure 5. The in-plane polarization images of the PLT thin films prepared by the
different ratio of Ar and O2 annealed at 600◦ C for 60 minutes a) Ar:O2 = 8:2;
b) Ar:O2 = 7:3.
 Crystalline and Domain Properties of PLT Thin Films [1635]/225
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Figure 6. The in-plane polarization images of the PLT thin films prepared by the differ-
ent ratio of Ar and O2 annealed at 700◦ C for 10 minutes a) Ar:O2 = 8 : 2; b) Ar:O2 = 7:3.

loose structure when PLT film deposited at Ar:O2 is 7:3. Maybe more oxygen
atoms could enter into the PLT films and form more oxygen defections in PLT
thin film when PLT film deposited at high oxygen partial pressure.
Figure 6 shows the in-plane polarization images of the PLT thin films
prepared by the different ratio of Ar and O2 annealed at 700◦ C for 10 minutes.
From Fig. 6, it was found that the higher annealing temperature could help to
form larger domain in the PLT thin films. However, the discontinue domain
could be attained in PLT films when the annealing time was shorter (at 700◦ C
for 10 minutes). That means the good crystallinity of PLT thin films is the base
for the domain mapping and switching.

4. CONCLUSION

The PLT thin films with pure perovskite structure were prepared on various
substrates by RF magnetron sputtering using PLT ceramic targets. The exper-
imental results show that the PLT thin films with good crystalline properties
could be fabricated by using optimum depositing conditions. The crystalline
properties of PLT ferroelectric thin films were strongly dependence of the work-
ing gas pressure, the ratio of O2 and Ar2 , annealing temperature and so on. The
higher annealing temperature could help to form larger domain in the PLT thin
films. PFM images showed that the 180◦ domain was the main domain structure
of PLT thin films. When PLT film deposited at high oxygen partial pressure,
more oxygen atoms could enter into the PLT films and form more oxygen de-
fections in PLT thin film, so that the domain of PLT thin films shows looser
structure.
 226/[1636] J. Wu et al.

ACKNOWLEDGMENTS

This work was supported by the National Key Fundamental Research Pro-
gramme and the National Science Foundation of China (NSFC).

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