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Measurement of thin film piezoelectric constants using x-ray diffraction technique

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2007 Phys. Scr. 2007 353
(http://iopscience.iop.org/1402-4896/2007/T129/078)
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IOP PUBLISHING

PHYSICA SCRIPTA

Phys. Scr. T129 (2007) 353357

doi:10.1088/0031-8949/2007/T129/078

Measurement of thin film piezoelectric

constants using x-ray diffraction
technique
Y H Yu, M O Lai and L Lu
Department of Mechanical Engineering, National University of Singapore, Singapore 117576
E-mail: yh1.yu@hotmail.com

Received 27 February 2007

Accepted for publication 21 July 2007
Published 30 November 2007
Online at stacks.iop.org/PhysScr/T129/353
Abstract
f
f
A new method to measure the piezoelectric constants of d33 and d31 of thin films using x-ray
f
diffraction (XRD) is proposed. Piezoelectric constant d33 is calculated from the measurement
of change in out-of-plane lattice spacing of the piezoelectric films while piezoelectric constant
f
d31 is obtained from the change in the slope of d versus sin2 curves before and after
applying an electric field over the film. This method improves the accuracy by directly
measuring the strains in the films induced by the externally applied electric field instead of the
surface displacement that could easily be interfered with by environment/vibration and
surface morphology of the thin films.
PACS numbers: 79.20.Ds, 77.84.Dy, 77.84.s, 78.70.Ck
(Some figures in this article are in colour only in the electronic version.)

1. Introduction
Piezoelectric ceramics have been widely used in sensors,
actuators and other devices [1, 2]. Due to the development
of miniatures in MEMS and NEMS technologies, the high
performance of piezoelectric thin films has recently been
intensively studied [15].
Since all piezoelectric thin films are grown on much
thicker substrates, deformations on piezoelectric thin films
are several orders of magnitude smaller than those of
their counterpart bulk materials. Therefore, measurement
techniques for physical characters of bulk piezoelectric
ceramics may not be adequate for thin films. For bulk
piezoelectric ceramics, the most commonly used methods
are based on the principle of dynamic characteristics such
as resonance and anti-resonance, and static methods. These
techniques are difficult to implement in thin films owing to
substrate constraint and extremely small deformation in films
which may not be detected using the conventional techniques.
Therefore, it is necessary to develop new techniques to
measure these physical properties of thin films.
After the first report on the measurement of piezoelectric
constants of thin films in 1990 [6], a great deal of research has
0031-8949/07/129353+05$30.00

been carried out in the field of characterization of piezoelectric

films. Generally, the measurement techniques can be divided
into two categories. One is to use the direct piezoelectric effect
where the electric charge is collected as an external force is
applied. Another approach adopts the converse piezoelectric
effect where mechanical response is measured as an external
electric field is applied. The former includes normal loading
method [7], pneumatic loading method (PLM) [8, 9], wafer
flexure [10], embedded beam method [11] and acoustoelectric
probe [12]. The latter includes atomic force microscopy
(AFM)/scanning tunnelling microscopy (STM) [13] and
interferometer method [14, 15]. The normal loading method
can only measure d33 . However, roughness of its contact
tip affects the homogeneity of the applied stress; and it can
produce a significant bending effect which would generate a
great amount of charge through the transverse piezoelectric
effect [16]. Although the PLM overcomes the difficulties in
loading non-uniformity, bending effect and loading direction,
the friction between the O-ring and the sample surface could
introduce remnant in-plane stress to the film and thus result in
measurement error [8].
The wafer flexure method can only measure d31 . It makes
use of the charge generated when a uniform pressure acts

2007 The Royal Swedish Academy of Sciences

Printed in the UK

353

Y H Yu et al

Function
generator

2.1. Strain measurement using XRD

X3

For randomly oriented polycrystalline or isotropic materials,

a general equation for measuring strain field using the XRD
technique can be described by equation (1) [17].

g(hkl)
Gold
PZT

X1

Bottom
electrode

Gold
X2

Substrate

Figure 1. Schematic set-up for piezoelectric constant measurement.

on a wafer surface [10]. The drawback is reliance on the

mathematical models which require explicit knowledge of
dimensions of the substrate, supporting house, locations of
the test capacitors, Youngs modulus and Poissons ratio
of the substrate and piezoelectric film.
In general, the AFM/STM technique detects local
vibration induced by an ac signal applied between the
conductive tip of the scanning force microscope and the
bottom electrode of the sample. Since the radius of the tip
apex is in the range of tens of nanometres, the measured
piezoelectric response is grain dependent. For some grains,
the contribution from d15 may be significant and the measured
response from out-of-plane of a piezoelectric thin film could
be substantially different from the effective value along the
poling direction [15].
The laser interferometer [14, 15] has been used to
measure the dynamic displacement at the surface of thin films.
A single beam laser interferometer has difficulty in separating
the bending and the movement of the substrate from the
thickness change of a piezoelectric film induced by an
electrical field [14]. Therefore, double-beam interferometers
have been employed to suppress the bending and the
movement of the substrate. Since the thickness change is
as small as sub-ngstrom, the measurement is very sensitive
to noise such as thermal drift of the sample, fluctuation
in refractivity of air in the optical path, and electrical
and mechanical instabilities. Thus such a technique usually
requires a very stable environment [15].
In this study, a new method using an x-ray diffraction
(XRD) technique is proposed to measure both d33 and d31 of
a piezoelectric film. Because it directly measures the strains
induced by an electric field, environmental instability on
surface displacement can be avoided.

2. Principle of measurement technique

Strains in a piezoelectric film induced by electric field can be
measured by XRD. The experimental set-up is schematically
shown in figure 1. A function generator is connected to the top
and bottom electrodes of the piezoelectric thin film capacitor.
An x-ray diffractometer is used to measure the 15 changes
within the piezoelectric thin film induced by the applied
electric field.
354

0
(S33
) = S33 + (S11 cos2 + S12 sin 2
+ S22 sin2 S33 ) sin2
+ (S23 sin + S13 cos ) sin 2,

(1)

where is the angle between the diffraction vector g(hkl)

and the specimen surface normal, is the angle between the
0
measurement direction and the coordination axis X 1 , (S33
)
is the strain in the direction defined by Euler angles and
, S11 , S12 , S22 , S33 , S23 and S13 are the components of
strain tensor, d, is the measured lattice plane spacing of the
diffraction plane (hkl), and d0 is the unstrained lattice plane
spacing of the diffraction plane (hkl).
For thin films with equi-biaxial stress state where S12 =
S13 = S23 = 0, and S11 = S22 , equation (1) can be simplified
to be:
0
(S33
) = (d d0 )/d0 = S33 + (S11 S33 ) sin2 .

(2)

2.2. Measurement of strain induced by electricity

There generally exists an equi-biaxial residual stress/strain
field in piezoelectric films [18]. XRD measures the total strain
in the films and that includes the residual strains and the
electricity induced strains. Therefore, equation (2) should be
rewritten to include electric field induced strains:
Ei
Ei
Ei
Ei
d
= (S11
S33
)d0 sin2 + S33
d0 + d0 ,

(2a)

where the superscript E i denotes the electric field along the

Ei
Ei
i-axis in the film (i = 1, 2 and 3). S11
and S33
are in-plane and
out-of-plane strains of the piezoelectric films.
When = 0, equation (2a) becomes
Ei
Ei
d,0
= S33
d0 + d0 = I Ei

or

Ei
S33
= I Ei /d0 1.

(3)
(3a)

Taking the differential of equation (2a) with respect to sin2 ,

it follows that

Ei
Ei
Ei
d,
= (S11
S33
(4)
)d0 = G Ei .
(sin2 )
Combining equations (3a) and (4), it can be shown that
Ei
= (G Ei + I Ei )/d0 1,
S11

(4a)

where I E i and G E i are respectively intercept and slope of the

Ei
d,
sin2 curve.
Assume that the total strain in the film after applying
electric field is smaller than the elastic limit of the film,
so that the residual strain in the film does not change. The
strains induced by the electric field are the differences in the
strain fields before and after applying the electric field (E i = 0
and E i = E 3 respectively). From equations (3a) and (4a), the
strains induced by electric field can be obtained as
E3
0
1S11 = (S11
S11
) = (G E3 G 0 + I E3 I 0 )/d0 ,
E3
0
1S33 = (S33
S33
) = (I E3 I 0 )/d0 ,

(5)
(6)

Measurement of thin film piezoelectric constants using x-ray diffraction technique

where 1S11 and 1S33 are the in-plane and out-of-plane strains
of the piezoelectric film induced by the external electric field.
I 0 and G 0 are respectively the intercept and the slope of the
0
d,
sin2 curve without external electric field. Similarly,
E3
I and G E 3 are respectively the intercept and the slope of
E3
the d,
sin2 curve after applying the external electric field.
2.3. Piezoelectric constants
In general, when an external electric field is applied to a
piezoelectric material, a strain field will be produced, which
can be expressed in tensor form as follows [2]:
1Skl = 6dikl E i ,

(7)

where 1Skl is the strain tensor induced by the electric field, E i

is the electric field and dikl is the piezoelectric constant tensor.
When an electric field E 3 is applied, as shown in figure 1, it
will cause
f
E3
E3
1S11
= 1S22
= d31 E 3 ,
(7a)
f

E3
1S33
= d33 E 3 .

Figure 2. XRD diffractogram of PZT on Ni substrate.

(7b)

Therefore, from equations (5) to (7) the piezoelectric

f
f
constants d31 and d33 can be expressed as follows:
f

E3
E3
d31 = 1S11
/E 3 = 1S11
t/V = (G E G 0 + I E I 0 )t/(V d0 ),
(8)
and
f
E3
d33 = 1S33
/E 3 = (I E I 0 )t/(V d0 ),
(9)

where t is the thickness of the piezoelectric thin film and V is

the electrical potential difference applied to the top electrode
and the bottom electrode. Since the unstrained lattice spacing
0
d0 of the films is often unknown, d,0
can be used to replace d0
without producing significant error (generally less than 0.1%).

3. Experimental
PZT(52/48)/TiN heterostructural thin films were deposited
on a nickel alloy substrate by pulsed laser deposition (PLD). A
Lambda Physik KrF excimer laser beam (wavelength 248 nm,
pulse width 25 ns, repetition rate 10 Hz) with an incidence
angle of about 45 was employed. The laser ablation was
carried out at a laser fluence of 12 J cm2 . The films were
deposited at the optimized substrate temperature of 600 C.
The oxygen partial pressure was 300 m Torr when depositing
PZT while the chamber was kept in vacuum when depositing
TiN. The substrate was held parallel to the rotating target at a
distance of 40 mm. Top gold electrodes of 3 mm in diameter
were deposited on to the piezoelectric thin film surface by
sputtering with a shallow mask for piezoelectric constant
measurement.
A Philips XPert MPD x-ray diffractometer with a
chromium (Cr) anode was used to measure the piezoelectric
constants. The x-ray incident spot size of 1.5 mm diameter
was adopted. A mini probe was built to supply electric field to
the ferroelectric/piezoelectric specimens on Eulerier sample
stage. A microscope was used to locate the x-ray spot at the
centre of the top electrodes on the specimens. An arbitrary
function generator (Tektronix, AFG310) was used to apply

Figure 3. SEM image of cross section of the PZT/TiN/Ni

multilayer structures.

the electric field over the top and bottom electrodes of the
piezoelectric film capacitor. Cross-sectional microstructures
of the films were examined using field-emission scanning
electron microscopy (FE-SEM, Hitachi S4100).

4. Results and discussion

At typical 2 diffractograph of the PZT/TiN/Ni multilayer
structures is shown in figure 2. A number of diffraction
peaks from multiple planes of PZT was observed while the
(100) plane showed some extent of preferred orientation.
To minimize the error during strain measurement, the (310)
plane of the PZT was selected for strain measurement after
considering both x-ray intensity and diffraction angle.
A cross-sectional image of the PZT/TiN/Ni multilayer
structures is shown in figure 3. Columnar grain structure of the
PZT film grown on Ni substrate with very thin barrier layer of
TiN is observed. The thickness of the PZT film was measured
to be about 2.1 m.
The peak positions of the (310) plane of the PZT film at
different tilt angles were evaluated in step sizes of 0.02 .
The measurement time at each step was 10 s. d versus
sin2 curves of the film before and after applying an external
electric field are shown in figure 4. Linear d sin2 curves
can be observed for the capacitor both with and without
application of the electric field.
355

Y H Yu et al
1.2955
0V

1.2950

5V

1.2945
d (A)

R 2 = 0.9749

1.2940
1.2935
1.2930
R 2 = 0.9949

1.2925
1.2920
0

0.1

0.2

0.3

0.4

0.5

0.6

sin2

Figure 4. d versus sin2 curves of PZT film before and after

applying electric field.

From equations (8) and (9), the piezoelectric constants

f
could be calculated to be d33 = 78 1012 m V1 (pC N1 )
f
12
and d33 = 278 10 m V1 . Compared to the reported
f
value of d33 of about 60130 pm V1 for (100) textured PZT
films using an interferometer [19] and 35 pm V1 of the
unpoled OMCVD PZT at MPB measured using the normal
loading method [7], this range of values agree fairly well
with the measurement result obtained in the present study
for weakly-oriented and unpoled PZT film using the XRD
technique. Since the XRD technique is a converse method in
which the electric field is applied to the piezoelectric film, the
film is poled to some extent.
It is known that the piezoelectric film is a part of the
composite filmsubstrate structure. Mechanical clamping by
the substrate, electrode as well as the surrounding inactive
film can strongly influence the piezoelectric properties of
f
f
the film [15]. Thus the measured d33 and d31 values are
the effective piezoelectric constants of the films at certain
measurement conditions. As a result of such clamping effect,
f
it turns out that d33 is always smaller than d33 and the absolute
f
value of the films e31 may be larger than that of e31 for their
counterpart bulk materials [1, 20, 21].
f
e31 of PZT films with a thickness of 13 m has
been reported to be 8 to 12 C m2 [19], which may be
f
converted to d31 of about 80 to 120 pC m1 if a Youngs
modulus of 100 GPa is used. This value seems to be lower
than that measured in this experiment. In fact, a stronger
clamping effect is imposed by not only the substrate but
also the surrounding inactive PZT film in the present study.
The published Youngs modulus values range from 37 to
400 GPa [10]. Thus, the difference in clamping conditions
and possible lower Youngs modulus of the films could have
f
contributed to the higher d31 value measured in this study.
All available methods for determination of transverse
piezoelectric constant require explicit knowledge of the elastic
modulus of the piezoelectric films. Such modulii are not
known in most cases [22] and they could be very different
f
from those of the counterpart bulk materials. Therefore e31
f
was measured instead of d31 in most cases. The newly
developed method using the XRD technique has the advantage
of directly measuring the effective transverse piezoelectric
f
constant d31 without the requirement of the elastic modulus
f
of the piezoelectric films. However, it should be noted that d31
356

could be affected by the difference in clamping conditions on

the tested capacitors.
Most of the static or quasi-static techniques using
the converse effect determine the effective piezoelectric
constants of the films through the measurement of the surface
displacement of the film or the change in thickness of
the sample (from top surface of the film to the bottom
surface of the substrate) instead of the strains in the films.
The total displacement of the top surface of the film consists
of contributions from the thickness change of not only the
film but also the substrate and the electrodes as well as
from deflection due to bending [20]. The displacement due
to bending of the substrate may be several times higher than
that of the film itself. Since the change in thickness is as small
as sub-ngstrom, the measurement for surface displacement
becomes extremely sensitive to noises such as thermal drift of
the sample, fluctuation in refractivity of air in the optical path,
and electrical and mechanical instabilities. Therefore, such a
technique usually requires a very stable environment [15]. In
addition, surface morphology and reflection could also affect
the measurement.
Some studies [22] on the effect of top electrode size on
f
the measured piezoelectric constant d33 of thin films have
been reported. Generally, it is expected that the larger the top
electrode size, the lower the measured piezoelectric constant
values of the films. Different sizes of top electrode dimensions
are used in thin film piezoelectric constant measurement. As
reported, 1.5 to 2.5 mm in diameter in PLM [8, 9], 1.5 mm in
diameter in the normal loading method [7] and 0.5 to 2 mm in
diameter for the laser interferometer [15]. In this experiment,
top electrode size of 3 mm in diameter is used. The size of
the top electrode can be significantly reduced if stronger x-ray
sources such as rotating anode and synchrotron source [23]
are adopted.
XRD is a well established method for measuring the
strain and stress within materials. Its repeatability is better
than 5% [24]. Assuming that the measurements on applied
external electric field and film thickness are not the major
contributor to measuring piezoelectric constants by XRD, the
repeatability of this technique is expected to be 5% or better.

5. Conclusions
f

1. Both d33 and d31 in piezoelectric films can be measured

f
using the XRD technique. d33 is calculated from
the change in the out-of-plane lattice spacing of the
f
piezoelectric films while d31 is obtained from the change
in the slope of the d versus sin2 curves before and
after applying an electric field over the films.
2. The present newly developed method using the XRD
technique which directly measures the strains instead of
displacement induced by an externally applied electric
field eliminates errors as a result of influence due to
environment and/or vibration.

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