The local piezoelectric activity of thin polymer films observed by scanning tunneling

microscopy
H. Birk, J. GlatzReichenbach, Li Jie, E. Schreck, and K. Dransfeld
Citation: Journal of Vacuum Science & Technology B 9, 1162 (1991); doi: 10.1116/1.585238
View online: http://dx.doi.org/10.1116/1.585238
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The local piezoelectric activity of thin polymer films observed by scanning

tunneling microscopy
H. Birk, J. Glatz-Reichenbach, Li-Jie, E. Schreck, and K. Dransfeld
Fakultiitfiir Physik, Universitat Konstanz, D-7750 Konstanz, Federal Republic ofGermany

(Received 24 July 1990; accepted 26 October 1990)

Here we present first measurements of the local piezoelectric activity of thin vinylidene fluoridetrifluoroethylene (VDF-TrFE) copolymer films with a spatial resolution of about 10 nm. The
average value of the piezoelectric constant d 33 is - 0.03 nm/V varying typically by about 20%
across a distance of 10 nm depending on the poling state of the film.

I. INTRODUCTION
The copolymers ofvinyIidene fluoride and trifluoroethylene
(VDF-TrFE) are scmicrystalline materials. After poling,
these piezoelectric and ferroelectric copolymers are used for
various technical applications as thin films or thicker foils. I
Their structure was investigated, e.g., by x-ray difi'raction,2
synchrotron radiation,3 scanning and transmission electron
microscopy,46 and nuclear magnetic resonance studies. 7
The microstructural analysis for these semicrystal1ine materials has been interpreted in terms of lamellar crystallites H
embedded in an amorphous matrix. The size of the crystallites seems to depend on the thickness of the film,4 decreasing for thinner films also in the lateral dimension. The degree
of crystallinity of the copolymer films depends for a given
VDF-TrFE composition on the special annealing treatment
varying between 30% and 90%.6,9
In the past the piezoelectric properties of these copolymer
films have mostly been explained by assuming that the ferroelectric crystallites are responsible for the piezoelectricity
of the films. 10, II But up to now the piezoelectrical effect has
been studied only on macroscopic samples over regions of at
least 1 mm. Here we present a first measurement of the local
piezoelectric activity of thin (VDF-TrFE) copolymer films
on a scale of the crystalline domains, by using the scanning
tunneling microscope (STM). Employing this method in a
simple experimental setup we were able to measure the local
piezoactivity of the films with a resolution of about 10--20
nm.
By the STM we measured quantitatively the vibrational
amplitude of the surface under the influence of an applied ac
voltage. Thus we can monitor the local piezoelectric activity
depending both on the lateral position and on the application
of a high dc electrical field during the previous poling process.

entire electrode area. The optically observed variation of the

thickness was less than 30 nm over a lateral distance of 5
mm. Subsequently the samples were annealed up to 145C
for 2 h in order to enhance their crystallinity. As the last step,
after cooling down again, a 20 nm gold electrode was deposited on the top of the copolymer film forming a condenser
together with the bottom aluminum electrode. The gold film
was evaporated at liquid-nitrogen temperature in order to
produce a more homogeneous gold film surface.
The geometry of the polymer film, with the two electrodes
and the tip of the STM is shown in Fig, 1. Between the
grounded top electrode and the bottom electrode both a dc
voltage could be applied for the poling process or an ac voltage for driving the film piezoelectrically.

III. THE LOCAL MEASUREMENT OF THE

PIEZOELECTRIC ACTIVITY
The STM is a powerful instrument to measure the topography of a surface on an atomic scale by using the tunneling
current as a sensor for the distance between tip and surface.
Even small motions of the top electrode perpendicular to the
surface-amounting only to a fraction of an angstrom-can

PiezoPositioner''''.......
TunneliC\g-TiP~"

Ld. L --,.
-20nm

II. SAMPLE PREPARATION

On well cleaned fiat glass plates structured aluminum
electrodes were evaporated, having a thickness of about 300
nm and an area of about 2 mm 2 Thereafter a small amount
of the (VDF-TrFE) copolymer solution containing 60
mol % VDF, dissolved in ethyl-methyl-ketone, was applied
to the substrate and-by using the spin coating techniquewe produced copolymer films having a thickness of about 1
11m, The film thickness as measured by an interference microscope turned out to be surprisingly uniform across the
1162

J. Vac. Sci. Techno!. B 9 (2), Mar/Apr 1991

1. Exp<'rimcntal setup for measuring the local piezoelectric activity

using a scanning tunneling microscope: The polymer film (thickness about
0.9 11m) is sandwiched between an AI-bottom electrode and a gold film
(thickness 20 nm) as a top electrode. The tip of a tunneling microscope is
located just ahove the gold electrode. (VI = feedback voltage, U, = bias
voltage, [md I, ~.. tunneling current.) The feedback loop controls the z position of the tip. (The x-yscan is not shown here). The voltage Up can he used
to pole the copolymer film or to switch its polarization into the reverse
direction and U d drives the film piezoelectrically,
FIG,

0734-211X/91/021162-04$Ol.00

Co) 1991 American Vacuum SOCiety

1162

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1163

Blrk et al.: local piezoelectric activity of thin polymer films

thus be detected. In our case we apply a periodic driving

voltage Ud (of about 10 V and a frequency of20 Hz) via the
top and bottom electrodes to the poled copolymer film. In
this way surface vibrations having an amplitude of about 0.3
urn are induced jfthe copolymer film is locally piezoelectric.
As is well known I2 the tunneling current It depends exponentially on the tunneling gap d,

I,-exp[ -- (2Ifl)/irn!'d],
with m being the electronic mass and the effective work
function of gold, which for our experimental condition is in
the range of 100 meV. I )

IV. THE CONSTANT-CURRENT MODE OF THE STM

For a quantitative measurement of the local piezoclectrical effect we used the STM in the "constant current" mode:
To stimulate the piezoelectric motion ofthe copolymer film
we applied a slowly varying (20 :Hz) triangular driving voltage Ud to the film electrodes as shown in Fig. 2.
The tunneling current is kept constant by a feedback loop
and thus the tunneling tip accurately follows the motion of
the top electrode. By measuring the magnitude of the feedback signal with a lock-in amplifier, we could observe directly the vibrational amplitude perpendicular to the sample surface (z direction in Fig. 2) and thus determine the local value
ofthe piezoelectric constant d 3 ,. In our experiments, we obtained an average value of about 0.03 nm/V on a poled copolymer film in good agreement with macroscopic observations on thicker films of nearly the same copolymer
material. 10
In these experiments we took special care to electrostatically screen the tip from the ac driving field Ud If the shielding by the thin top electrode would not be complete a displacement current to the tip-being proportional to
(d Ud I dt) -could in principle be added to the tunnel current
and thus disturb the measurement. In our experiments we
used such a low frequency (20 Hz) that no "pick-up" signal
was observed.

1163

v. THE INFLUENCE OF HIGH ELECTRICAL FIELDS

ON THE SURFACE MOTION DURING
PIEZOELECTRIC STIMULATION OF THE
COPOLYMER FILM
If we superimpose (in addition to the driving voltage U d
at 20 Hz) a poling voltage Up of a lower frequency (typically
10 mHz) to the copolymer film, we can follow the timedependent variation of its local piezoactivity. The value of
the piezoelectric constant d u is a function of the poling voltage and its saturation is reached for an applied field of 90
MV1m (see Fig. 3). The coercive field turned out to be 50
MV 1m for our 0.85 /-lm thin copolymer films, which is about
10 MV 1m higher than reported for films which are several
/-lm thick. 14 For a sudden application of small poling voltages (of approximately 35 MV1m), the corresponding
change of the piezoelectric activity needs several seconds to
build up which we can clearly see as a time dependence of the
hysteresis loop (such as shown by the inner curve in Fig. 3)
where the poling voltage varies with a frequency of 10 mHz.
If, however, the poling field amplitude is high (Up> 100
MV1m) the local switching time is faster than 1 ms. 9
Additionally, we saw a shift of the whole hysteresis loop
parallel to the positive vertical axis particularly for a film
thickness below 1 pm and for an applied poling field well
above the coercive field of 50 MV1m. At present, this phenomenon is not yet understood.
VI. PIEZOELECTRICAL IMAGING

Subsequently we moved the tip at constant tunneling current in a one-dimensional scan across the sample over a lateral distance of 180 nm at a speed of 0.2 nm/s while the driving
voltage Uel was applied. The vibrational amplitude was measured locally with the lock-in technique. Simultaneously we
monitored the topology of the gold covered copolymer film
(see Fig. 4). We found no clear correlation between the am-

1.50,

:' :::1
t~ 0,"1
~

-0.50

t
r

~ 4;~ I

iZ~_/11

.,/17

~-~-,I..~-'B

1E -1.00 1_

I
I
I

1.50-~--------~---
-----.~
120
80
40
0
40
80
120
poling field [MV/m]

101

Ibl

FIG. 2. The piezoelectric surface motion of a (60-40) VDF-TrFE copolymer film as measured by the STM in the constant current moue. The slowly
varying triangular driving voltage U" (lower trace) and the feedback voltage VI (upper trace, typically 40 m V) afe plotted as a function of time for
(a) positive and for (b) negative poling. The absolute value of the surface
amplitude tu is derived from the calibration of the z piczopositioner. The
resulting observed local piezoelectric constant d'1 ~,- 0.03 nm/V is nearly equal for both directions of the polarization. The driving frequency was
20Hz.

FIG. 3. The 11ystcresis of the piezoelectric activity for a 0.85 pm thick (6040) VDF-TrFE copolymer film: The inner curve (A) shows a hysteresis for
a poling voltage well below the saturation field strength. For higher poling
voltages outer curve (D) clearly shows the saturation ofthe surface motion.
For both curves a small driving voltage Ud (4 V amplitUde at a frequency of
20 Hz) and a variable poling voltage (up to 100 V amplitude at a frequency
of 10 mHz) arc simultaneously applied. The ae piezoelectric surface motion
(caused hy the driving voltage U,,) is plotted as a function of the poling
field. Saturation of the surface motion is reached for eleCtrical fields above
90 MV 1m. The coercive field tumed out to be of about 50 MV 1m.

J. 'lac. Sci. Techno\. B, Vol. 9, No, 2, Marl Apr 1991

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1164

Birk et af.: Local piezoelectric activity of thin polymer films

1164

r--..- - - -.-.-. - -.--, - ' ]

O-40 VDF-TrFE Copolymer

850 nm
~ film thickness:--------------

----

.-;;;::

~120

5>

.s

60

-~---

~ 30

IreversaL of the

lscan direction

II'

~ O~============-='=-~I=-=-=-="=--='~
2,0

1.5

'"E

'">

ill

g;

OS

00

l'E::H
'"

1.0
0.5
00 i===;;=============P=====i
1.0

iil

0.5

600

1200

&0

.8
't 30

.g

- direction
r---

8.

~can

Ol

90

.2

Ireversal of the

-;: 90

<5

.~

,_-.1.--,

120

600

1200

1800

loteral scanning distance

[Al

FIG. 5 Simultaneous measurcment of the topology (top) and thc piezoelectric surface motion (bottom) for an x-cut quartz (3 MHz transducer) in a
one-dimensional scan. The vertical dashed line marks the reversal of the
scan direction. Here the driving voltage U" is 150 V at a frequency of 50 Hz .
The time for the whole scan of 200 nm is 1000 s.

1800

lateral scanning distance : A1

FIG. 4. A one-dimensional sean of the topology (top) and of the piezoelectfic surface motion (middle) is shown for a 0.85 pm thick poled (l00 V for
10 s) (6~O) VDF-TrFE copolymer film as measured simultaneously.
The dashed line marks the reversal of the scan direction. The modulating
driving voltage U" is 5 V at a frequency of 20 Hz. The time needed for the
200 nrn long line scan is 1000 s. Additionally we show the piezoactivity of
the same 60--40 copolymer film in the nearly depolarized state (bottom).
The topology here is nearly the same as before and has therefore been omitted.

plitude of the surface motion and the corresponding surface

topology.
For fully poled copolymer films, the vibrational amplitude varied by about 20% of its average value across lateral
distances of about 50 nm. Interestingly, the spatial fluctuations of the vibrational amplitude became larger for weakly
poled copolymer films. For nearly depolarized samples (see
bottom curve of Fig. 4) the local deviations ofthe amplitude
from the average value became relatively stronger.
For comparison we measured also in the same experimental setup (shown in Fig. 1) the local piezoactivity of a single
crystalline x-cut quartz plate (thickness 1 mm and also covered with a 20 nm gold top electrode) which is expected to
vibrate homogeneously since our driving frequency (20 Hz)
was well below any mechanical resonance frequency of the
quartz plate. As expected the lateral deviations of the amplitude are much smaller (see Fig. 5). The remaining variation
(by about 10%) may perhaps be due to the spatial change of
the electrical resistance of the thin gold electrode. This point
needs further investigation.
With the new method presented here it is possible to detect
the local piezoactivity of gold covered poled ferroelectric
polymer films. The lateral resolution ofimaging the piezoactive regions in this way is only limited by the thickness of the
covering gold film (about 20 nm). If the thickness of the
copolymer film approaches the dimension of the crystallites,
the contrast between regions with and without piezoactivity

should become noticeable. For a more detailed study of the

piezoactivity at molecular resolution it is necessary to use a
different technique. 15

VII. CONCLUSION
Using the scanning tunneling microscope we have been
able to measure the piezoelectric constant d 33 of (VDFTrFE) copolymer films with nanometer resolution. It
turned out, that its value is not constant across a poled sample, but fluctuates laterally by up to 50% of its average value
within 50 nm depending on the poling state.
Applying a slowly variable electrical field we are able to
measure quantitatively the field induced local piezoelectric
surface motion. It shows a typical hysteresis effect with saturation behavior for electrical fields above 90 MV1m.
Thus we have shown that it is possible by using the STM to
observe with nm resolution the change of the macromolecular structure induced by an electric field.

ACKNOWLEDGMENTS
We gratefully acknowledge stimulating discussions with
S. Akari, G. von Eynatten, D. Schilling, P. Ziemann, the
valuable help of Ute Petzold with the drawings and the financial support of the Deutsche Forschungsgemeinschaft
(SFB 306)_

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J. Vac. Sci. Techno!. B, Vol. 9, No.2, Mar/Apr 1991

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Bir!< at al.: local piezoelectric activity of thin polymer films

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J. Vac. Sci. Techno!' S, Vol. 9, No.2, Marl Apr 1991

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