Thin Solid Films 510 (2006) 213 – 221

www.elsevier.com/locate/tsf

Residual stress development in Pb(Zr,Ti)O3/ZrO2/SiO2 stacks

for piezoelectric microactuators
E. Hong a,*, R. Smith b, S.V. Krishnaswamy b, C.B. Freidhoff b, S. Trolier-McKinstry a
a
Materials Research Institute, The Pennsylvania State University, University Park, PA 16802, USA
b
Northrop Grumman Electronics, Sensors System Sector, Baltimore, MD 21203, USA

Received 9 August 2005; received in revised form 9 December 2005; accepted 16 December 2005
Available online 31 January 2006

Abstract

The residual stress of multilayers in piezoelectric microelectromechanical systems structures influences their electromechanical properties
and performance. This paper describes the development of residual stress in 1.6 Am Pb(Zr0.52,Ti0.48)O3 (PZT)/0.3 Am ZrO2/0.5 Am SiO2 stacks
for microactuator applications. The residual stresses were characterized by wafer curvature or load-deflection measurements. PZT and zirconia
films were deposited on 4-in. (100) silicon wafers with 0.5 Am thick thermally grown SiO2 by sol – gel processes. After the final film
deposition, the obtained residual stress of PZT, ZrO2, and SiO2 were 100 – 150, 230 – 270, and 147 MPa, respectively. The average stress in
the stack was ¨ 80 MPa. These residual stresses are explained in terms of the thermal expansion mismatch between the layers and the substrate.
Load-deflection measurements were conducted to evaluate localized residual stresses using released circular diaphragms. The load-deflection
results were consistent with the average stress value from the wafer curvature measurements. It was found that more reasonable estimates of the
stack stresses could be obtained when mid-point vertical deflection data below 6 Am were used, for diaphragms 0.8 – 1.375 mm in diameter.
D 2005 Elsevier B.V. All rights reserved.

Keywords: Stress measurement; Zirconia; Lead zirconate titanate; Microelectromechanical systems (MEMS); Piezoelectric actuator

1. Introduction actuators consisting of a PZT layer sandwiched between top

Ferroelectric thin films have been widely incorporated into
microelectromechanical systems for microactuators and
microsensors [1,2]. Especially, lead zirconate titanate
[Pb(ZrxTi1x )O3] (PZT) films near the morphotropic phase
boundary (x ¨ 0.5) are often used due to their excellent
piezoelectric properties. PZT films have been deposited by
pulsed laser deposition, metalorganic chemical vapor deposi-
tion, sputtering, and chemical solution deposition routes
among others [3,4]. In this work, chemical solution deposition
was utilized.
For microactuator applications, unimorph structures with
one piezoelectric and one passive layer are commonly adapted
to amplify displacements. To date, micromachined cantilever-
type actuators using the d31 or d33 piezoelectric constant have
been fabricated. Kueppers et al. [5] fabricated PZT micro-
* Corresponding author. Tel.: +1 814 865 9931.
E-mail address: exh187@psu.edu (E. Hong).
0040-6090/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2005.12.300
and bottom electrodes and polysilicon. For 390 Am long
cantilevers, maximum tip deflections of 20 Am were obtained
at an applied voltage of 10 V. In contrast, Zhang et al. [6] used
the d33 piezoelectric constant of PZT to drive their cantilevers.
They deposited PZT on silicon nitride and the structures were
driven using interdigitated (IDT) electrodes. The 280 Am long
cantilevers generated tip deflections of 30 Am at 100 V.
Micromachined switches using the d33 coefficient allow the
transmission lines to be formed directly beneath the cantilevers
[7]. In clamped structures such as diaphragms and bridges,
piezoelectric unimorphs using IDT electrodes are preferable
since the piezoelectric layer expands between the IDT fingers,
resulting in deflections exceeding the structure thicknesses [8].
Several researchers have investigated residual stress in PZT
films, focusing on changes in ferroelectric properties due to the
stress. Tuttle et al. [9] reported that PZT films deposited on
sapphire developed compressive stresses and exhibited higher
remanent polarization than those deposited on silicon wafers,
which were in tension. It is believed that the stress conditions at
the Curie temperature determine the domain configuration of
214 E. Hong et al. / Thin Solid Films 510 (2006) 213 – 221
the ferroelectric and consequently influences the ferroelectric
properties. In addition, reduction in the residual stresses by
mechanical or annealing processes yielded measurable changes
in the dielectric, ferroelectric and piezoelectric properties of
PZT films [10 – 12].
In piezoelectric microelectromechanical systems applica-
tions, the stresses of the PZT and other structural layers influence
the mechanical and structural properties as well as electric
properties of PZT films. In particular, the stresses in cantilevers
should be balanced to obtain flat structures. If not, the structures
are severely bent upward or downward [6], making it impossible
to fabricate functional microdevices. In clamped structures such
as diaphragm and bridges, the residual stress influences the
resonance frequencies and response to external stimuli such as
differential pressures [8]. Thus, to design microactuators and
microsensors using PZT films, knowledge of the residual stress
of the PZT and structural layers is essential.
The present work investigates stress development in PZT/
ZrO2/SiO2 stacks for fabricating diaphragm-type microactua-
tors driven by IDT electrodes for micropumps and optical
switches [13]. A thermally grown SiO2 layer, which has
compressive stress, was used both as a passive layer and to
reduce the average stress of the structures. The silicon oxide
was grown in steam (by wet oxidation). The zirconia layer
prevented chemical reaction between PZT and the underlying
SiO2 or silicon. The thickness and process condition was
optimized to enable subsequent deposit of crack free PZT
films. PZT and zirconia films were deposited by sol – gel
processes on 4-in. silicon (100) wafers with a thermally grown
oxide. Changes in the residual stress of each layer in the stacks
were characterized by wafer curvature measurements. The
average stress of the stacks was confirmed by load-deflection
measurements after circular diaphragms of the stacks were
fabricated by micromachining techniques.
2. Experimental procedure
2.1. Zirconia film preparation
Zirconia is a chemically stable material, which has a high
melting point (> 2370 -C) [14]. ZrO2 buffer layers have
previously been shown to prevent reaction between PZT and
SiO2 [15]. The zirconia solution was prepared using 2-
methoxyethanol (2-MOE) as the solvent. The precursor was
zirconium n-propoxide (Aldrich Chemical Co., Milwaukee,
WI). Initially, zirconium n-propoxide was added to 2-MOE in a
flask inside a glove box. The mixture was then reacted at 110 -C
for 2 h in a dry argon ambient in a rotary evaporator. After
reaction, the solution was distilled at 115 -C under vacuum to
remove by-products. The solution was modified with 23 vol.%
acetic acid and 7 vol.% acetylacetonate at room temperature. It
was found that this improves the quality of the film and makes it
possible to deposit particle-free, smooth and uniform films on 4-
in. wafers. Acetic acid and acetylacetonate are chelating agents;
they reduce the tendency of the alkoxide compounds to
hydrolyze during deposition [16]. However, solutions with this
modification do not have a shelf life of more than one day. It
seems that an esterification reaction between acetic acid and
2-MOE, liberating water, causes precursor precipitation [17].
For this reason, the solution was modified just before being
used. The final concentration of the zirconia solution was
0.4 M. Either thermally oxidized silicon (0.5 Am SiO2/Si) or
silicon wafers were used for zirconia film deposition. The
silicon oxide was grown on (100) Si wafers in steam at
1000 -C. Zirconia solution was then dispensed onto the wafers
using a syringe with a 0.1-Am filter. The wafers were spun at
3000 rpm for 30 s using a photoresist spinner (HeadWay
Research, Inc., Garland, TX). The spin-coated layer was
pyrolyzed by a two-step process (300 -C, 60 s, then 450 -C
for 60 s) to remove organic compounds. The layer was then
crystallized at 700 -C for 60 s in a Heat-pulse 610 rapid thermal
processing unit (AG Associates, Sunnyvale, CA). Each layer
was ¨ 70 nm thick. To get the desired thickness, the process was
repeated. Finally, the zirconia layers were annealed in air in a
conventional box furnace at 700 -C for 2 h.
2.2. Lead zirconate titanate film preparation
PZT (with a Zr/Ti ratio of 52:48) solution was prepared
using 2-MOE as the solvent. Details of the processing can be
found elsewhere [18]. Lead acetate trihydrate, zirconium n-
propoxide, and titanium iso-propoxide (Aldrich Chemical Co.,
Milwaukee, WI) were used as precursors. Initially, lead acetate
trihydrate was dissolved in 2-MOE in a rotary evaporator flask
in a dry argon ambient at 115 -C. After it was completely
dissolved, the solution was distilled under vacuum to a white
powder. At the same time, a mixture of zirconium n-propoxide
and titanium iso-propoxide was prepared in the glove box. The
mixture was stirred for 10 min at room temperature and added
to the flask containing the dehydrated Pb-precursor. The mixture
was reacted for 3 h at 115 -C under a dry argon ambient, then
distilled under vacuum to remove by-products until half of the
solution remained. 22 vol.% acetylacetone, 5 vol.% acetic acid,
and additional 2-MOE were added to modify the solution. The
concentration of the solution was 0.75 M with 20 mol% excess
lead content. PZT films were deposited on zirconia passivated
silicon wafers. For PZT deposition, a lower spin-coating speed
of 1500 rpm was used to obtain thicker layers per coating. The
same heat treatments as the zirconia processing (excepting the
final 2 h annealing) were conducted. Each layer was ¨ 0.2 Am
thick. To get the desired thickness, the spin coating and thermal
processes were repeated.
2.3. Film characterization
The microstructure and orientation of the zirconia and PZT
films were determined using a scanning electron microscope
(S-3500N, Hitachi Ltd., Tokyo, Japan) and a Scintag X-ray
diffractometer (Scintag, Inc., Sunnyvale, CA). Ni-filtered Cu
Ka radiation was used and X-ray diffraction data were
collected between 20- and 60- 2h at a rate of 2-/min. The
zirconia layer and PZT film thickness were determined from
SEM cross-sectional images or by a surface profiler (Alpha
Step 500, Tencor, Inc., San Jose, CA).
 E. Hong et al. / Thin Solid Films 510 (2006) 213 – 221 215

Pressure Transducer

Needle Valve

Specimen Vacuum Pump

Vacuum Chuck
Lever Valve

Fig. 1. Load-deflection experimental set-up.

2.4. Fabrication of circular diaphragms
For load-deflection measurements, circular diaphragms
which had a PZT/ZrO2/SiO2 stack were fabricated using
deep reactive ion etching (DRIE). The stack was prepared by
depositing the thin film stack on silicon wafers with a 0.5-Am
thick SiO2 layer. Cr/Au (150 Å:1500 Å) was formed on top
of the stacks by evaporation to provide good reflective planes
for interferometric measurements. The thicknesses of PZT/
ZrO2 were ¨ 1.6 Am and 0.3 Am, respectively. The diaphragm
diameters were in the range of 0.8 – 1.375 mm. The
diaphragms were then released by removing the silicon under
the stacks from the back of the wafers using DRIE. The
wafers were clamped electrostatically and the backside was
cooled by helium gas.
2.5. Wafer curvature measurement
At the wafer level, the residual stress of a film on a substrate
was evaluated by Stoney’s equation [19]. By monitoring the
change in curvature of a wafer before and after deposition of a
thin film, the film stress was obtained.
The substrates used were 4-in. silicon (100) wafers (biaxial
modulus = 181 GPa [20]). The thicknesses of the wafers were in
the range of 510 – 570 Am. The curvatures of the wafers were
measured using a thin film stress measurement system (FLX-
2320, Tencor, Inc., San Jose, CA). Zirconia and PZT films
were sequentially deposited on either 4-in. silicon or silicon
with 0.5 Am thermal SiO2 on both sides. The curvature was
subsequently measured. To obtain the initial stress of the
thermal oxide, the silicon oxide on the backside of the wafers
was stripped using buffered oxide etchant, with the front side
of the wafer covered with photoresist. The time delay between
the deposition and the measurement was usually about 30 min.
2.6. Load-deflection measurement
The diaphragm load-deflection measurement involves the
simultaneous application of a uniformly distributed pressure
load to either surface of a thin film diaphragm and measure-
ment of the out-of-plane deflection [21,22]. Fig. 1 shows the
measurement set-up. A vacuum chuck with a suitable window
and vacuum channel was machined from a solid aluminum
block. A lever valve was used to subject the device to the
vacuum created by a rotary vacuum pump. A needle valve was
then used to regulate the applied vacuum level by controlled
flow of air back into the system. A MKS Baratron Type 127
pressure transducer was connected to a MKS PDR-1-1C power
supply and digital readout to monitor the pressure inside the
chuck. The midpoint displacement measurement was con-
ducted using a Wyko interferometer (Veeco, Tuscon, AZ).
While the wafer curvature measurement evaluates the
residual stress of a film at the wafer-level, this method can
evaluate the residual stress in each diaphragm across the wafer.
The load-deflection relationship of an edge clamped circular
diaphragm, assuming that the deflection is small compared to
its radius, is expressed by Eq. (1) [23,21].
8t E 4tr0
P¼ d3 þ 2 d ð1Þ
3r4 1  m r
where P is the differential pressure, t is the diaphragm
thickness, r is the radius of the diaphragm, d is the out-of-
plane displacement, E is the Young’s modulus, m is the
Poisson’s ratio, and r 0 is the residual stress.

diaphragm

reflective plane 500 μm

Fig. 2. Top surface of diaphragms released by DRIE.

216 E. Hong et al. / Thin Solid Films 510 (2006) 213 – 221

(a) By measuring deflections of diaphragms at the mid-point as

1000 a function of differential pressure and fitting the data to Eq. (1),
900 the Young’s modulus and residual stress were estimated using

Monoclinic
Tetragonal
800 known geometric parameters (Fig. 2).
Intensity (arb. units)

700

Si
3. Results and discussions
600 700oC, 2 hrs anneal
500 3.1. Structural characterization
400
It is difficult to deposit crack-free PZT films directly on
Tetragonal

300 silicon or silicon with thermally grown oxide due to Pb-

200 diffusion and formation of a lead silicate glass. In this study,
PZT films were deposited on silicon wafers with thermal
100 700oC RTA
oxide (or bare silicon wafers) and zirconia layers of thickness
0 ranging from 70 nm to 0.3 Am. As a barrier layer, zirconia
20 30 40 50 60
should be kept as thin as possible to minimize its influence on
2 θ (o)
the micromachined structures. It was found that the minimum
(b) thickness of zirconia films needed was greater than 0.2 Am
800
and the film had to be annealed at 700 -C in air for more than
700 2 h to enable growth of crack free PZT films up to a thickness of
3.0 Am. It was found that PZT films cracked whenever they were
600 deposited on ZrO2 less than 0.2 Am thick, independent of
Intensity (arb. units)

500
whether or not the ZrO2 was pre-annealed at 700 -C for 2 h. The
X-ray diffraction patterns from the cracked films showed a broad
400 peak (2h = 30-) at the position for the pyrochlore phase.
PZT(100)

PZT(110)

PZT(111)
PZT(200)

PZT(210)

PZT(211)

Fig. 3 shows X-ray patterns for zirconia and PZT films. The
300
zirconia films were deposited on a silicon wafer with 0.5 Am
200 thick SiO2. The X-ray pattern showed a weak tetragonal ZrO2
peak, indicating poor crystallinity. After annealing at 700 -C
100 for 2 h, a monoclinic phase was developed. The PZT films on
the zirconia were pure perovskite phase without any pyrochlore
0
20 30 40 50 60 as observed by the X-ray patterns. A SEM micrograph of the
2θ( ) o cross-section of the wafer shows a sharp interface between the
zirconia and PZT layers. There was no visible sign of reaction
Fig. 3. X-ray diffraction patterns of (a) zirconia film and (b) PZT film on ZrO2. between SiO2, ZrO2 or PZT, indicating that zirconia acted as an
effective buffer layer. Both films exhibited columnar structures.
The PZT films showed good uniformity (less than 3% variation
across a 4-in. wafer).

150
Horizontal
100 Vertical 1.6 μm PZT
1.2 μm PZT
50 0.8 μm PZT
0.4 μm PZT
Residual Stress (MPa)

0
0.2 μm PZT
-50
-100
-150
0.3 μm ZrO2
-200 Annealed at 700oC for 2 hrs
-250
-300 0.5 μm SiO2
-350
0 1 2 3 4 5 6 7 8 9
Layers (#)
Fig. 4. Residual stress of multilayer films on 4-in. SiO2/Si wafers. Horizontal and vertical refer to a scan line parallel to the primary flat of the wafer and that
perpendicular to the flat, respectively.
 E. Hong et al. / Thin Solid Films 510 (2006) 213 – 221 217

300
Horizontal
250 Vertical
0.2 μm PZT
200 0.4 μm PZT

Residual Stress (MPa)

150
0.8 μm PZT
1.2 μm PZT
1.6 μm PZT
100
0.3 μm ZrO2
50

0
Annealed at 700oC for 2 hrs
-50

-100
0 1 2 3 4 5 6 7 8
Layers (#)
Fig. 5. Residual stress of multilayer films on 4-in. Si wafers. Horizontal and vertical refer to a scan line parallel to the primary flat of the wafer and that perpendicular
to the flat, respectively.

3.2. Wafer curvature measurement
Fig. 4 shows the stress development in 1.6 Am PZT/0.3 Am
ZrO2/0.5 Am SiO2 stacks. The stress of the initial thermal oxide
layer varies from  300 to  310 MPa (compressive).
Deposition of a 0.3 Am zirconia film increases the total stress
to  180 MPa. Annealing the wafer at 700 -C for 2 h results in
a total stress of  200 MPa. The first layer of PZT increases the
total stress to 0 MPa. The total stress of the stack was 80 MPa.
To determine the effect of annealing on the thermal oxide, the
experiment was repeated with an additional annealing step at
700 -C for 2 h; it resulted in reduction of the stress of the thermal
oxide by 13%. The final stress of the stack was ¨ 90 MPa. Thus,
by using an additional annealing step for the thermal oxide, the
final stress of the stack could be controlled. However, this
complicates interpretation of the stress in the PZT and ZrO2
layers because there may be simultaneous stress changes in the
SiO2 during the heat treatment steps.
To eliminate the effect of stress changes due to the thermal
oxide, the same film stacks were produced directly on Si wafers.
Fig. 5 shows the evolution of residual stress with film thickness.
The stress of the as-deposited zirconia film was ¨ 80 MPa and
the annealing process drops the stress to  40 MPa. The
deposition of the first PZT layer increased the total stress to
210 MPa. With the subsequent deposition of PZT layers, the
total stress approached 100 MPa.
From the total stress, the stress of each layer can be
calculated by Eq. (2).
Xn
rt t t ¼ ri ti ð2Þ
i¼1
where r t and t t are the total stress and thickness of the stack
and r i and t i are the stress and thickness of each layer. n is the
number of the layers.
Fig. 6 shows the calculated stress of each individual layer
using Eq. (2). It is known that the residual stress in a sol –gel

800
Horizontal
700 Vertical
600
0.2 μm PZT
Residual Stress (MPa)

500

400

300

200 0.4 μm PZT

0.8 μm PZT
1.2 μm PZT
100 1.6 μm PZT
0.3 μm ZrO2
0
Annealed at 700oC for 2 hrs
-100
0 1 2 3 4 5 6 7 8
Layers (#)
Fig. 6. Apparent residual stress of multilayer films on 4-in. silicon wafers with an additional annealing step. Horizontal and vertical refer to a scan line parallel to the
primary flat of the wafer and that perpendicular to the flat, respectively.
218 E. Hong et al. / Thin Solid Films 510 (2006) 213 – 221

Table 1
The calculated residual stress from thermal mismatch
Materials a TCE Young’s Modulus (GPa) Poisson’s ratio Stress (MPa)
Si 2.6 150 0.17
PZT 2.0 – 6.7a 70 – 100 0.3
ZrO2b 8.4 160 – 205 0.27
a
a TCE,ferroelectric = 2.0 ppm/-C and a TCE,paraelectric = 6.7 ppm/-C.
b
Fully stabilized zirconia.
PZT film mainly comes from the mismatch in thermal
expansion coefficients between the film and the substrate [9]
and can be expressed by the following equation:
Ef
r¼ ðaf  as ÞDT
ð 1  mf Þ
where E f and m f are the Young’s modulus and Poisson’s ratio of
the film, a f and a s are thermal expansion coefficients of the
film and the substrate and DT is the temperature difference
between the crystallization temperature (700 -C) and room
temperature.
The calculated stresses of the films are summarized in Table 1
[24]. The values are in agreement with the measured values (Fig.
6) for films 0.4– 1.6 Am thick. However, the apparent stresses of
the zirconia and the first PZT layer are significantly different
from what is expected. This is thought to be due to changes in the
stress of the zirconia film. Zirconia films on either Si or SiO2/Si
wafers exhibited stresses of 20 – 100 MPa after the deposition.
After an annealing process at 700 -C for 2 h, the stresses of the
zirconia films became more compressive (to  40 MPa). This
stress change can be explained by the phase transformation
between the tetragonal phase and the monoclinic phase of the
zirconia films. As shown in Fig. 3, the annealing step developed
the monoclinic phase, which generates a volume expansion of
¨ 4% [14].
The ZrO2 films also showed stress relaxation as seen in Fig.
7. Stress relaxation in films can be explained by either
structural changes or adsorption of moisture into the film
through the grain boundaries [25]. For structural relaxation, as
the stress itself is the driving force, a change in the sign of the
50
40
30
Residual Stress (MPa)
stress will not occur. Thus, in zirconia films, where stress
changes with time from tensile to compressive, adsorption of
moisture in air is a reasonable mechanism for the stress change.
– Water molecules absorbed into the pores leads to compressive
100 – 144 stress in the film. In addition, it has been proposed that
835 – 1000
repulsion between the OH dipoles induces a compressive stress
component in the films when ZrO2 reacts with moisture and
hydrates [26]. Due to the stress aging of zirconia films, it is not
easy to estimate the actual stress of a zirconia layer in either
PZT/ZrO2/Si or PZT/ZrO2/SiO2/Si stacks. It is expected that
aging of buried zirconia films will be negligible because the
PZT layer blocks direct contact with moisture. As an
approximation, the stress of the zirconia film in the stack was
ð3Þ calculated assuming the stress of the first PZT layer (in Fig. 6)
to be in the range of 100 – 150 MPa. The calculated stress of the
zirconia film was 230 – 270 MPa. In addition, the best linear fit
to the data in Fig. 7 yields an initial stress value of ¨188 MPa.
These values are much smaller than those calculated in Table 1.
However, this stress value would be reasonable considering
that the zirconia film (in Fig. 3) is partially amorphous. By
replacing 1 mol% Zr with Ca, the crystallinity of the film was
improved for the same heat treatment and the residual stress
increased to ¨400– 500 MPa, approaching calculated values
(data not shown). Subtracting the total stresses of a PZT/ZrO2/
Si stack (in Fig. 5) from that of a PZT/ZrO2/SiO2/Si stack (in
Fig. 4), the stress of the thermal oxide was calculated to  145
MPa after the final film deposition. The stress change in the
thermal oxide can partly be explained by viscous flow of the
silicon oxide [27]. In addition, induced stress in the silicon
oxide by the zirconia and PZT layers during the annealing or
crystallization steps can also contribute in the stress relaxation
of the silicon oxide. The stresses of the films are summarized in
Table 2.
3.3. Load-deflection measurement
Load-deflection measurements were conducted using re-
leased circular diaphragms. As seen in Fig. 2, the DRIE process
produces a well-defined circular boundary. In this study, the
residual stress were estimated using either comparatively large
deflection data (the maximum midpoint deflections were in
range of 12.5 –25 Am) or smaller deflection data (when the
maximum midpoint deflections were in range of 4.5– 6 Am).
Large deflection test results: The deflections of diaphragms

20 of different sizes (0.8 – 1.375 mm in diameter) were measured

10 at pressures up to 100 kPa. The maximum midpoint deflection
at a given pressure varied with diameter and at 80 –100 kPa
0
-10
Table 2
-20 The estimated residual stress of the films
-30 Film Initial stress (MPa)a Final stress (MPa)b
-40 SiO2 300 147
PZT 100 – 150
-50
1000 10000 100000 ZrO2 40 – 100 MPa 230 – 270c
a
Time (sec) Stress before the PZT film deposition.
b
Stress after the PZT film deposition.
c
Fig. 7. Residual stress of zirconia film as a function of time. Calculated stress assuming stress of the first PZT layer is 100 – 150 MPa.
was in the range of 12.5– 24 Am. A typical plot of differential
pressure versus the midpoint deflection for a 1.375 mm
diaphragm is shown in Fig. 8(a). To estimate the biaxial
modulus and the residual stress of the diaphragm actuator, the
curve in Fig. 8(a) was fitted to Eq. (1). The R 2 value is
0.99972, indicating a very good fit between the model and the
data. For diaphragm actuators, the Young’s modulus was
calculated using a Poisson’s ratio of 0.269 in Eq. (1). The
Poisson’s ratio was calculated using a mixing rule for
multilayer structures (Eq. (4)) [28] and the Poisson’s ratios of
the layers in the diaphragm actuators in Table 1.
1 The estimated Young’s moduli and residual stress of the
meff ¼ ðm1 t1 þ m2 t2 þ m3 t3 Þ ð4Þ
t diaphragms are summarized in Table 3. The average Young’s
where m i and t i are the Poisson’s ratio and thickness of the ith modulus was 65.9 GPa with a standard deviation of 3.3 GPa. In
layer. addition, the average residual stress was 79.1 MPa with a
standard deviation of 3.6 MPa.
Small deflection test results:
220 E. Hong et al. / Thin Solid Films 510 (2006) 213 – 221

90
Small Deflection estimates may provide a first order measure of the relative
Large Deflection contribution of the neglected bending stiffness. In Fig. 10(b), we
show the difference between the larger deflection estimate for
85 each of 5 devices, and the average small deflection estimate for 6
Residual Stress σ0 (MPa)

devices. Hence, the difference between the large and small

deflection estimates of residual stress was negligibly small for
the largest devices (1.375 mm), but was nearly 15% for the
80 smallest device (0.8 mm). Thus, we conclude that the differences
between the two estimates of residual stress almost certainly can
be attributed to neglecting the effect of strain energy due to
bending in the model. In contrast, the small deflection estimates
75
of residual stress were less variable and showed no dependence
on diameter to thickness ratio. In effect, the assumption that the
strain energy due to bending is small in comparison to that due to
in-plane stretching and residual stress starts to break down for
800 900 1000 1100 1200 1300 1400 large deflections of small devices. However, a good estimate of
Diameter d (μm)
Fig. 9. Residual stress determined from large and small load-deflections. (a)
90

Comparison of large versus small deflection results: On

average, the residual stress determined using the full range of Residual Stress σ0 (MPa)
load-deflection data was about 8.5% lower than the value
obtained using only small deflection data. In addition, it is 85
important to note that the difference between the two methods
decreased monotonically with diameter, as illustrated by Fig. 9.
Note that a steady increase in residual stress with diameter was
predicted by fitting the large deflection data, whereas no effect of
diameter was predicted by fitting the small deflection data. Since 80
all devices tested were obtained from the same wafer and
fabricated under identical condition, there was no reason to
expect that the residual stress was a function of device diameter.
Rather, two factors were considered to have contributed to the
difference in the estimates of residual stress obtained from large 75
0 2 4 6 8 10
versus small deflection data. The first factor was the relative
magnitude of the midpoint deflection in comparison to the Deflection/Thickness Ratio
thickness. For a 0.8-mm diameter diaphragm, the maximum (b)
15
midpoint deflection was 5 times larger than the diaphragm
thickness. In comparison, the maximum midpoint deflection for
a 1.375 mm diaphragm was 10 times larger than the diaphragm
thickness. To quantify the possible effect of the displacement to
thickness ratio, the load-deflection data sequence for the largest 10
Difference (%)

diameter (1.375 mm) was terminated at various points and the

truncated data set was used to obtain estimates of the residual
stress as a function of deflection to thickness ratio, as shown in
Fig. 10(a). Referring to the Fig. 10(a), the truncated data sets for
the 1.375-mm device yielded nearly identical estimates of r 0 at 5
all levels of deflection to thickness ratio. This observation lends
credence to the idea that the deflection to thickness ratio does not
influence the estimate of residual stress obtained using large
load-deflection data and the non-linear fit.
However, the second factor was the difference in the 0
estimates of the residual stress for large versus small deflection 300 400 500 600
data for small diameter devices. In this case, the assumption that Diameter/Thickness Ratio
the bending stress could be neglected is problematic and Fig. 10. (a) Estimate of residual stress as a function of maximum deflection/
degraded the accuracy of the large deflection estimate. More- thickness ratio and (b) difference in two estimates of residual stress as a
over, the difference between the large and small deflection function of diameter/thickness ratio.
 E. Hong et al. / Thin Solid Films 510 (2006) 213 – 221
the residual stress can still be estimated using the small
deflection data. Residual stress values estimated from the load-
deflection measurement are higher by 7.5% than those from the
wafer curvature measurement. This deviation may be explained
by (1) stress contribution of Cr/Au electrode for the load-
deflection measurement and (2) the thickness reduction of the
compressive thermal oxide during the RIE process. Considering
these factors, these two measurement methods provided
reasonably consistent residual stress values.
4. Conclusions
1.6 –2.0 Am PZT and zirconia films were prepared on 4-
in. oxidized silicon wafers by sol – gel processes. Both
solutions used 2-MOE as the solvent. The zirconia acted
as a buffer layer to prevent the reaction between the PZT and
SiO2. It was found that the zirconia films should be thicker
than 0.2 Am and need to be annealed at 700 -C for more
than 2 h to deposit crack-free PZT films. The cross-section
of the wafer shows sharp interfaces between the layers,
indicating no significant reaction. The zirconia film showed
stress relaxation, which was apparently related to absorption
of water molecules into the pores. After the final film
deposition, the residual stress values of PZT, ZrO2, and SiO2
by wafer curvature measurements were 100 –150, 230 –270,
and  147 MPa, respectively. The average stress in 1.6 Am
PZT/0.3 Am ZrO2/0.5 Am SiO2 stacks was ¨ 80 MPa. In the
load-deflection measurement, more reasonable residual stres-
ses could be estimated using small deflection data. In the
large deflection case, the deviation of the calculated residual
stress might come from an increasing contribution of the
bending stress to the deflection. An effective Young’s modulus
(65.9 GPa) and a tensile residual stress (85.8 MPa) were
obtained. These two stress measurements for the piezoelectric
stacks provided reasonably consistent results.
Acknowlegement
Authors are grateful to Dr. Mark Horn and Dr. Lawrence
Pilione for their advice in stress measurements. The research
reported in this paper was performed in connection with
Cooperative Agreement number DAAD17-00-21001 with the
U.S. Army Research Laboratory.
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