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Enhancement of crystallographic and electrical properties in 0.9Pb(Mg1/3Nb2/3)O3-

0.1PbTiO3 thin films grown on Pb(Zr,Ti)O3-buffered platinized silicon substrates by sol-gel

process

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2010 IOP Conf. Ser.: Mater. Sci. Eng. 8 012002

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Symposium G, E-MRS 2009 Spring Meeting IOP Publishing
IOP Conf. Series: Materials Science and Engineering 8 (2010) 012002 doi:10.1088/1757-899X/8/1/012002

Enhancement of crystallographic and electrical properties in


0.9Pb(Mg1/3Nb2/3)O3-0.1PbTiO3 thin films grown on
Pb(Zr,Ti)O3-buffered platinized silicon substrates by sol-gel
process

X H Zhu, G Le Rhun, E Defaÿ1 and M Aïd


CEA, LETI, MINATEC, 17 Rue des Martyrs, F38054 Grenoble, France

E-mail: edefay@cea.fr

Abstract. We present here a comparative study of sol-gel-derived 0.9Pb(Mg1/3Nb2/3)O3-


0.1PbTiO3 (PMNT) thin films about 120 nm in thickness that were, respectively, deposited
directly on a platinized Si substrate and on a Pb(Zr,Ti)O3 (PZT)-buffered one, but were both
annealed at 750 °C in ambient air. It was found that the PZT buffer layer plays an important
role in the enhancement of crystallographic and electrical properties of PMNT thin films. The
PMNT film grown on PZT-buffered platinized Si substrate showed a nearly pure perovskite
structure, while the film without buffer layer contained a big amount of pyrochlore phase.
Also, the PZT buffer layer changed the preferred orientation of PMNT thin films from (111) to
mainly (110) orientation, and helped to improve the films' densification and microstructural
evolution. Coherent with what was observed comparatively in structural characterization,
enhanced dielectric and leakage current characteristics were observed in the film with buffer
layer. For the PMNT film grown directly on Pt-coated Si substrate, the dielectric permittivity is
as low as 570, whereas the value is enhanced to 1200 for the PMNT film with PZT buffer
layer. Moreover, the leakage current density of PMNT thin films is reduced remarkably,
roughly 4-5 orders of magnitude lower, by introducing the PZT buffer layer.

1. Introduction
Lead magnesium niobate titanate [(1-x)Pb(Mg1/3Nb2/3)O3-xPbTiO3, abbreviated as PMNT] has
attracted considerable interest in recent years because of its exciting dielectric and electromechanical
properties [1-3]. In particular, the composition with x=0.1, i.e., 0.9Pb(Mg1/3Nb2/3)O3-0.1PbTiO3,
displays the dielectric maximum near room temperature, offering great potential for applications in
high-value integrated capacitors. However, the growth of pure perovskite PMNT thin films is known
to be quite difficult due to the relatively poor thermodynamic stability relative to the pyrochlore phase
and due to the compositional complexity along with the high volatility of lead element [4]. A good
approach to overcome this problem is to introduce an effective buffer or seed layer, such as TiO2 [5],
PbO [6], LaNiO3 [7], La0.5Sr0.5CoO3 [8], BaTiO3 [9], bilayered Pb(Zr0.2Ti0.8)O3/PbOx [10], etc.
In this work, we report on the fabrication of PMNT thin films on Pt/TiO2/SiO2/Si substrates with
and without a Pb(Zr0.52Ti0.48)O3 (PZT) buffer layer. The effect of PZT buffer layer on the structural and
electrical properties of PMNT thin films is investigated.

2. Experimental

1
To whom any correspondence should be addressed.


c 2010 IOP Publishing Ltd 1
Symposium G, E-MRS 2009 Spring Meeting IOP Publishing
IOP Conf. Series: Materials Science and Engineering 8 (2010) 012002 doi:10.1088/1757-899X/8/1/012002
0.9Pb(Mg1/3Nb2/3)O3-0.1PbTiO3 thin films were prepared using a sol-gel process. The commercial
stock solution for the films was synthesized from lead acetate trihydrate Pb(CH3CO2)2·3H2O,
magnesium acetate tetrahydrate Mg(CH3CO2)2·4H2O, niobium pentaethoxide Nb(OC2H5)5, and
titanium-tetra-iso-propoxide Ti(i-OC3H7)4. To compensate for lead loss during the annealing
treatment, 10 mol% excess lead was added to the precursor solution. PMNT thin films were first
deposited on Pt(111)/TiO2/SiO2/Si(100) substrates with and without a PZT buffer layer by spin coating
at 2000 rpm for 20 s. Then, the as-deposited films were pyrolyzed in a Jipelec furnace at 400 °C for 5
min to remove organics. Such coating and pyrolysis treatments were repeated three times to achieve a
desired thickness. Finally, the films were annealed at 750 °C in a conventional furnace in ambient air
for 20 min to improve densification and crystallization. It should be noted that the PZT buffer layer
was also derived from a similar sol-gel process and well annealed at 700 °C prior to the PMNT
deposition, having a thickness of about 30 nm.
The crystallographic structures of the PMNT thin films were analyzed by x-ray diffraction (XRD)
with a Siemens D5000 diffractometer using CuKα radiation. The surface morphology and cross-
sectional microstructure of the films were observed by using a Hitachi S-5000 scanning electron
microscope (SEM). In order to measure the dielectric and electrical properties of the films, square
platinum top electrodes of 90×90 µm2 in area and 100 nm in thickness were fabricated by sputtering
and subsequently a lift-off process. The dielectric properties of the PMNT films were measured with a
Hewlett-Packard 4275A multi-frequency LCR meter. The leakage current-voltage measurements were
performed by using an HP4140B pA meter/DC voltage source.

3. Results and discussion


Figure 1 shows XRD θ-2θ scans of the PMNT thin films grown, respectively, on a bare and a PZT-
buffered Pt/TiO2/SiO2/Si substrates. From the figure it is clear that the PZT buffer layer dramatically
improved the perovskite phase formation in the PMNT film. The film deposited on bare Pt still
exhibited strong (222) reflection of pyrochlore phase, whereas the other one grown under identical
conditions on the PZT buffer layer exhibited a nearly pure perovskite structure, without noticeable
trace of pyrochlore phase. Also interesting to note is that the PZT buffer layer changed the preferred
orientation of the PMNT thin films from (111) to mainly (110) orientation. Both the purification of
perovskite phase and the change in preferential orientation indicate that the PZT buffer layer has a
remarkable effect on the crystallographic properties of PMNT thin films.

Figure 1. XRD θ-2θ scans of the sol-gel-derived PMNT thin films grown on (a) Pt(111)/TiO2/SiO2/Si
and (b) PZT-buffered Pt(111)/TiO2/SiO2/Si.

Figure 2 shows cross-sectional SEM images of the PMNT thin films. For better comparison, two
films annealed at 700 °C have also been characterized and shown in Fig. 2. It can be seen that there

2
Symposium G, E-MRS 2009 Spring Meeting IOP Publishing
IOP Conf. Series: Materials Science and Engineering 8 (2010) 012002 doi:10.1088/1757-899X/8/1/012002

still existed a large number of pores in the 700 °C annealed film without buffer layer, as shown in Fig.
2(a); however, the 700 °C annealed film with buffer layer, as shown in Fig. 2(b), already exhibited a
fairly dense microstructure, suggesting that the PZT buffer layer helped to improve the densification
and microstructural evolution of PMNT thin films. Furthermore, for annealing at 750 °C, the film with
buffer layer looks denser and has a sharper film/electrode interface. It is noted here that the PMNT
layer thickness is determined to be about 120 nm.

(a) (b)

(c) (d)

Figure 2. Cross-sectional SEM micrographs of the PMNT thin films. Figures (a) and (c) correspond to
the films deposited on bare Pt but annealed at 700 °C and 750 °C, respectively, while (b) and (d) for
those deposited on the PZT buffer layer, which were also annealed at 700 °C and 750 °C, respectively.

Figure 3 shows the relative dielectric constant (εr), measured at room temperature and at a
frequency of 100 kHz, as a function of the applied dc bias voltage for the PMNT thin films without
and with buffer layer. Coherent with the buffer layer-induced improvement in structural characteristics
of PMNT thin films, their dielectric properties are greatly enhanced by using the PZT buffer layer. The
film without buffer layer possesses a rather low value of εr (~570), whereas the value is enhanced to
1200 for the PMNT film with buffer layer. Also, the dielectric permittivity can be much better tuned
by dc electric field in the film with buffer layer. It is worth mentioning that no ferroelectric-like
hysteresis was observed in the film without buffer layer, while the film with buffer layer displayed a
typical hysteretic behavior, which has been confirmed by piezoelectric measurements (not shown
here). The observed ferroelectric response in the film with buffer layer originates either in part from
the contribution of the very thin PZT buffer layer or intrinsically from the PMNT layer itself due to
film strain effect [11], though bulk 90PMN-10PT is known to be a relaxor ferroelectric with only a
slim hysteresis loop.
Figure 4 shows the variations of leakage current density (J) with the applied dc electric field (E)
for the PMNT films without and with buffer layer. As can be seen in the figure, the leakage current
increases exponentially with the increase in dc electric field for the film without buffer layer. In
contrast, the leakage current density for the film with PZT buffer layer remains low when the dc
electric field is increased, indicative of a completely different leakage mechanism. For instance, at E=-
400 kV/cm, the leakage current density of the PMNT film with buffer layer is about 5.2×10-6 A/cm2,
which is roughly 4-5 orders of magnitude lower than that of the film without buffer layer (about
1.75×10-1 A/cm2). The remarkable reduction in leakage current for the film with buffer layer is
believed to stem from the denser microstructure and the improved interfacial quality.

3
Symposium G, E-MRS 2009 Spring Meeting IOP Publishing
IOP Conf. Series: Materials Science and Engineering 8 (2010) 012002 doi:10.1088/1757-899X/8/1/012002

Figure 3. Dielectric constant as a function of Figure 4. Variations of leakage current density


the applied dc bias voltage for the PMNT with the applied dc electric field for the PMNT
thin films without and with PZT buffer layer. films without and with PZT buffer layer.

4. Conclusions
0.9Pb(Mg1/3Nb2/3)O3-0.1PbTiO3 thin films of 120 nm thickness were, respectively, deposited on a bare
platinized Si substrate and on a Pb(Zr,Ti)O3-buffered one. The PMNT film grown on PZT-buffered
substrate shows a nearly pure perovskite structure, while the film without buffer layer contains a big
amount of pyrochlore phase. Also, the use of PZT buffer layer changes the preferred orientation of
PMNT thin films from (111) to mainly (110) orientation. It is demonstrated that the PZT buffer layer
is helpful in improving the densification and microstructural evolution of PMNT thin films. Coherent
with the structural improvement, enhanced dielectric and leakage current characteristics have been
obtained in the film with buffer layer. For the PMNT film grown directly on Pt-coated Si substrate, the
dielectric permittivity is as low as 570, whereas the value is enhanced to 1200 for the PMNT film with
PZT buffer layer. Moreover, the leakage current density of PMNT thin films is reduced remarkably,
roughly 4-5 orders of magnitude lower, by introducing the PZT buffer layer. All the results obtained
indicate that the PZT buffer layer plays an important role in the enhancement of crystallographic and
electrical properties of PMNT thin films.

Acknowledgments
This work was supported by EU project "CAMELIA" under Contract No. NMP3-CT-2006-033103.

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