This article was downloaded by: [Texas A & M University--Kingsville]

On: 24 December 2013, At: 04:29

Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered
office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK
Ferroelectrics
Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/gfer20
A New Approach for Surface Poling of
Polyvinylidene Fluoride (PVDF)
Yung Ting
a
, Hariyanto Gunawan
a
, Chun-Wei Chiu
a
& Jain-Zhi
Zhong
a
a
Department of Mechanical Engineering , Chung Yuan Christian
University , No. 200, Chung Pei Rd., Chung , Li , 32023 , Taiwan
Published online: 23 Sep 2013.
To cite this article: Yung Ting , Hariyanto Gunawan , Chun-Wei Chiu & Jain-Zhi Zhong (2013) A New
Approach for Surface Poling of Polyvinylidene Fluoride (PVDF), Ferroelectrics, 446:1, 18-27, DOI:
10.1080/00150193.2013.820978
To link to this article: http://dx.doi.org/10.1080/00150193.2013.820978
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the
Content) contained in the publications on our platform. However, Taylor & Francis,
our agents, and our licensors make no representations or warranties whatsoever as to
the accuracy, completeness, or suitability for any purpose of the Content. Any opinions
and views expressed in this publication are the opinions and views of the authors,
and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content
should not be relied upon and should be independently verified with primary sources
of information. Taylor and Francis shall not be liable for any losses, actions, claims,
proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or
howsoever caused arising directly or indirectly in connection with, in relation to or arising
out of the use of the Content.
This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,
systematic supply, or distribution in any form to anyone is expressly forbidden. Terms &
Conditions of access and use can be found at http://www.tandfonline.com/page/terms-
and-conditions
Ferroelectrics, 446:1827, 2013
Copyright Taylor & Francis Group, LLC
ISSN: 0015-0193 print / 1563-5112 online
DOI: 10.1080/00150193.2013.820978
A New Approach for Surface Poling
of Polyvinylidene Fluoride (PVDF)
YUNG TING,

HARIYANTO GUNAWAN, CHUN-WEI CHIU,

AND JAIN-ZHI ZHONG
Department of Mechanical Engineering, Chung Yuan Christian University,
No. 200, Chung Pei Rd., Chung, Li 32023, Taiwan
PVDF has been popularly used for miscellaneous sensor and energy harvesting pur-
poses. The advantages of exible and light characteristics in particular enhance more
interest. A new approach of using ITO glass for surface poling is investigated in this
study. Instead of using metal electrode onto the PVDF surface, ITO is coated onto glass
for conducting electrode. It can provide an easy way of electrode pattern design. Also,
higher electric eld can be applied in the process of poling so that higher response is
achieved. Properties of PVDF lms are characterized by using d
31
meter to measure
the piezoelectric constant and using Fourier Transformed Infrared Spectroscopy (FTIR)
and Differential Scanning Calorimeter (DSC) to measure -crystallization. From the
experiment results, it indicates that PVDF lmmakes use of the ITOglass poling method
will gain higher output voltage and current as compared to traditional poling technique.
Comb type electrode pattern, for example, is efcient to generate higher output response
for planar polarization and is able to control the desired output voltage and current.
Using a whole piece of ITO glass for poling with pattern design can avoid from the
defect of non-uniform polarization at the corners that usually happens in using metal
electrode. Compared to the PVDF embedded in a cantilever and a pressing structure,
the latter one will gain more output response.
Keyword PVDF; ITO; surface poling
I. Introduction
In recent decades, polymer material attracts very high attention for researchers to investigate
various applications of sensor or renewable energy. Polyvinylidene uoride (PVDF) lms
is one of electroactive material that can generate electricity by using the piezoelectric direct
effect. Especially, the exibility and lightness as well as and good mechanical strength [1,
2] would be an ideal candidate. The -phase in the PVDF lms is the most useful phase
with respect to piezoelectric characteristic. Through the mechanical treatment of stretching
and polarization can provoke and change the unpoled -phase into -phase. It is known that
energy generated from PVDF lms is quite small. In the previous investigation [3], stack
and zig-zag types of PVDF were proposed to increase output power generated by PVDF
lm. It was found that stress effect along the planar direction obtains larger output than the
thickness direction. Hence, surface poling is important. Also, stretching, electrode pattern,
and poling are inuential to the performance of PVDF. Stretching PVDF lm to transform
Received November 13, 2012; in nal form February 26, 2013.

Corresponding Author. E-mail: yung@cycu.edu.tw

18
D
o
w
n
l
o
a
d
e
d

b
y

[
T
e
x
a
s

A

&

M

U
n
i
v
e
r
s
i
t
y
-
-
K
i
n
g
s
v
i
l
l
e
]

a
t

0
4
:
2
9

2
4

D
e
c
e
m
b
e
r

2
0
1
3

New Approach for Surface Poling of PVDF 19
-phase into -phase has been studied in [46]. It shows that stretching of PVDF lm
with ratio greater than 3 would obtain more -crystallinity of PVDF lm and satisfy for
the later poling. Besides stretching, poling process is signicant for increasing the content
of -phase. Quite a few of poling methods have been investigated [710]. Traditional
poling technique makes use of metal plate to apply electric eld in the environment of
gradient increasing temperature. However, high electric eld is limited due to occurrence
of ashover or arcing. Corona is another polarization method induced by inhomogeneous
strain coupled with distribution of space charge in the lm [8]. A monoenergetic electron
beam was used to irradiate the surface and form space-charge on PVDF lm for poling
purpose. With partial penetration electrons, non-uniform polarization in the sample would
likely happen [11]. Photo-thermal and photo-induced poling are other methods that generate
dipole orientation periodically. A drawback is the thermal stability problem would disturb
the dipole orientation and cause non-uniform dipole orientation across the lm thickness
[12, 13]. Although the above several methods allow high electric eld, small area of poling
is the crucial disadvantage. In this article, ITO glass was used as conductor to transmit high
electric eld to reorient dipole of PVDF lm at room temperature.
Considering the direction of polarization, poling acting perpendicular to lm surface
as depicted in Figure 1 is called the thickness polarization and parallel to lm surface as
depicted in Figure 2 is called the planar polarization. Thickness polarization is widely used
for transducer or sensor. However, capacitance is small due to small thickness of lm [14].
Also, smaller lm thickness would decrease polarization effect and inuence crystallinity
[15, 16]. Conversely, planar polarization usually associated with pattern design will gain
higher capacitance by increasing electrode length. As illustrated in Figure 2, the interdigital
electrode (IDE) pattern is widely used to build sensors such as strain gage, surface acoustic
wave, structural health monitoring, or for energy harvesting applications. Surface poling
is used for planar polarization to obtain high sensitivity of IDE [17]. However, in IDE
pattern, length, width and number of nger are determinant factors. The polarization is
Figure 1. Thickness polarization.
D
o
w
n
l
o
a
d
e
d

b
y

[
T
e
x
a
s

A

&

M

U
n
i
v
e
r
s
i
t
y
-
-
K
i
n
g
s
v
i
l
l
e
]

a
t

0
4
:
2
9

2
4

D
e
c
e
m
b
e
r

2
0
1
3

20 Yung Ting et al.
Figure 2. Planar polarization.
inhomogeneous in magnitude and direction in the area of electrode nger especially since
dipole is not reorient during poling process.
Generally, IDE pattern is deposited onto piezoelectric material. However, deposition
of electrode onto polymer substrate is difcult due to limitation in high temperature pro-
cessing of polymer lm. Therefore, poor conductivity of electrode on the exible substrate
will cause voltage drop during polarization [18]. Instead, ITO layer is deposited on the
glass, which is used as substrate. Thus, good conductivity between ITO layer and glass is
obtained.
In addition to the material design, structure of PVDF lm is also inuential to the
performance. Two fundamental types, the cantilever and pressing structures are used for
comparison.
II. Design of Electrode
In this article, the popular comb type electrode pattern is designed as shown in Figure 2.
ITO glass poling technique is proposed in order to enhance piezoelectric charge constant
and obtain higher output voltage. In traditional poling method, metal electrode is coated
onto the surface of PVDF lm. Limited applied electric eld is allowable for ashover and
arcing will occur when high electric eld is applied. Moreover, the difference of thermal
expansion between the electrode and polymer, and the gas as well as moisture absorption
of polymer induces degradation of conductivity and adhesion will cause voltage drop
during polarization. Different from the traditional poling method, ITO is deposited onto a
soda lime oat glass, which is used as conductor to transmit electric eld. The sandwich
structure constructed with ITO glassPVDF lmbare glass is carried out poling process
at room temperature as shown in Figure 3. In particular, pattern design is usually seen for
better output electricity and sensitivity. For instance, using the comb type pattern of metal
electrode for poling, non-uniform and inhomogeneous poling effect will happen at the
corners [19]. Using ITO glass poling method allows higher electric eld applied in poling
is able to solve this problem.
D
o
w
n
l
o
a
d
e
d

b
y

[
T
e
x
a
s

A

&

M

U
n
i
v
e
r
s
i
t
y
-
-
K
i
n
g
s
v
i
l
l
e
]

a
t

0
4
:
2
9

2
4

D
e
c
e
m
b
e
r

2
0
1
3

New Approach for Surface Poling of PVDF 21
Figure 3. Poling with electrode pattern on the sandwich structure.
III. Experiment
A. Poling
PVDF lm with thickness of 120 m is stretched with ratio R = 6 at constant temperature
80

C. ITOlayer of thickness 150 nmwith comb pattern using magnetron sputtering method
is coated onto a soda lime oat glass of 1.1 mm. Equal width w and gap g of electrode
pattern is depicted in Figure 4.
Electric eld of 700 kv/cm is applied to the sandwich structure illustrated in Figure 3
for 15 minutes. Same size of PVDF sample employed by traditional method is selected as
an example for comparison with the one made by ITO glass poling method.
B. Characterization
The content of -phase of PVDF sample is investigated by Differential scanning calorimeter
(DSC) and Fourier Transformed Infrared Spectroscopy (FTIR). DSCmodel of Perkin-Elmer
DSC7 is operated at heating rate of 10

C/min. Temperature is set in the range of 50200

C
for the melting heat enthalpy. Perkin-Elmer FTIR Spectrum One is set in with wavenumber
in the range of 4501600 cm
1
with average of 32 scans and resolution of 4 cm
1
.
Figure 4. Comb pattern of ITO glass.
D
o
w
n
l
o
a
d
e
d

b
y

[
T
e
x
a
s

A

&

M

U
n
i
v
e
r
s
i
t
y
-
-
K
i
n
g
s
v
i
l
l
e
]

a
t

0
4
:
2
9

2
4

D
e
c
e
m
b
e
r

2
0
1
3

22 Yung Ting et al.
Degree of crystallinity is calculated using differential scanning calorimeter (DSC).
Degree of crystallinity can be calculated by [20].
X =
H
f
H

f
(1)
where X is degree of crystallinity, H
f
is the fusion enthalpy of the sample PVDF and
H

f
is fusion enthalpy with 100% crystallinity, which is 102.5 J/g given in [21].
Fraction of -phase crystals F() in each sample is calculated by [6, 22]:
F () =
A

(k

/k

)A

+A

, (2)
where A

and A

is determined by absorption bands for - and -phases, respectively, and

can be estimated by
A
,
= C.K
,
.X
,
.t, (3)
where C is monomer concentration, and subscripts refer to the crystalline phases. K is
the absorption coefcient at the respective wave number, and X is degree of crystallinity
dened in eq.(1), t is thickness of PVDF lm [22].
C. Electric Response
Piezoelectric charge constant d
31
of PVDF is characterized by d
31
meter (KCF PM-3500).
PVDF sample is bonded by two pieces of polyethylene HDPE plastic. The generally used
cantilever and pressing structures as presented in Figures 5 and 6 are chosen for testing.
Corresponding to different point force applied to PVDF sample, output voltage and current
response is measured using Keithley Electrometer model of 617.
Figure 5. PVDF embedded in a pressing structure.
D
o
w
n
l
o
a
d
e
d

b
y

[
T
e
x
a
s

A

&

M

U
n
i
v
e
r
s
i
t
y
-
-
K
i
n
g
s
v
i
l
l
e
]

a
t

0
4
:
2
9

2
4

D
e
c
e
m
b
e
r

2
0
1
3

New Approach for Surface Poling of PVDF 23
Figure 6. PVDF embedded in a cantilever structure.
IV. Result and Discussion
A. Material Properties
DSC curve of PVDF sample is shown in Figure 7. As seen, the crystallization endothermic
peak is higher while using ITO poling method. It results from higher electric eld can be
applied that will create more dipole orientation. Enthalpy of PVDF sample is estimated
about 43.25 J/g and 46.87 J/g for traditional and ITO poling methods respectively by
measuring the effective area of each peak in Figure 7. With the measured fusion enthalpy,
degree of crystallinity of PVDF sample is calculated as 0.42 and 0.45 for traditional and
ITO poling methods respectively by using eq. (1).
The -phase crystallinity was also conrmed by FTIRspectra as shown in Figure 8. It is
seen that the absorption peaks occur at 782 cm
1
for -phase and 862 cm
1
for -phase. The
absorption coefcient K

and K

for the -phase and -phase are 6.110

4
and 7.710
4
cm
2
/
Figure 7. DSC curve of traditional and ITO poling.
D
o
w
n
l
o
a
d
e
d

b
y

[
T
e
x
a
s

A

&

M

U
n
i
v
e
r
s
i
t
y
-
-
K
i
n
g
s
v
i
l
l
e
]

a
t

0
4
:
2
9

2
4

D
e
c
e
m
b
e
r

2
0
1
3

24 Yung Ting et al.
Figure 8. FTIR spectra of traditional and ITO poling.
mole respectively, and the monomer concentration is 0.0305 mole/cm
3
[6]. As seen in
Figure 8, the intensity of is higher for ITO than traditional poling method. By using eq.
(2)(3), the -phase fraction F() after stretching process is calculated about 78.6% and
84.9% for the conditions of traditional and ITO poling methods respectively.
In traditional poling method, smaller piezoelectric charge coefcient d
31
and lower
output response is obtained. When higher electric eld is applied in traditional poling
method, ashover and arcing is arisen so as to disturb and prevent polarization process
[23]. Besides that, deposition of metal electrode onto thin-lm type of polymer in high-
temperature processing and difference of thermal expansion as well as gas and moisture
absorption would lead to poor conductivity and adhesion; thus, it will cause voltage drop
Figure 9. d
31
vs applied voltage (Color gure available online).
D
o
w
n
l
o
a
d
e
d

b
y

[
T
e
x
a
s

A

&

M

U
n
i
v
e
r
s
i
t
y
-
-
K
i
n
g
s
v
i
l
l
e
]

a
t

0
4
:
2
9

2
4

D
e
c
e
m
b
e
r

2
0
1
3

New Approach for Surface Poling of PVDF 25
Figure 10. Traditional vs ITO poling for a cantilever structure (Color gure available online).
during polarization. In ITO poling method, ITO layer is used as an electrode and deposited
on soda lime oat glass, which preserves good conductivity. Voltage drop during poling
can thus be minimized efciently. As seen in Figure 9, higher electric eld up to 700 kv/cm
can be applied while using ITO. Piezoelectric charge coefcient d
31
of PVDF sample
is measured as 28 pC/N and 16 pC/N for ITO poling and traditional poling methods
respectively. As compared to traditional poling method, piezoelectric charge coefcient
d
31
and fraction of -phase are greater mainly due to the more effective dipole orientation
when applying high electric eld.
B. Electricity Generation
Figures 10 and 11 show the voltage and current response of PVDF lm constructed as a
cantilever and a pressing structure by using the ITO and traditional poling methods.
Figure 11. Traditional vs ITO poling for a pressing structure (Color gure available online).
D
o
w
n
l
o
a
d
e
d

b
y

[
T
e
x
a
s

A

&

M

U
n
i
v
e
r
s
i
t
y
-
-
K
i
n
g
s
v
i
l
l
e
]

a
t

0
4
:
2
9

2
4

D
e
c
e
m
b
e
r

2
0
1
3

26 Yung Ting et al.
As seen that, voltage and current response using ITO poling method is much greater
than the traditional poling method. In comparison the cantilever structure with the pressing
structure, the latter one gains higher response. The outcome results from inhomogeneous
stress and stress concentration in one direction in the cantilever structure. However, it is
noted that greater stress effect occurs not in the thickness direction but along the planar
direction in the pressing structure. Hence, d
31
surface poling is signicant and demanding.
V. Conclusions
Developing of PVDF by using the electrode pattern and ITO poling techniques is studied
in this article. The popular comb type electrode pattern is selected as an example for planar
polarization. IR spectra using FTIR is carried out to see the absorption band of sample.
The degree of crystallinity is measured about 0.42 and 0.45 using DSC for traditional and
ITO poling method respectively. The -fraction is calculated about 78.6% and 84.9% for
traditional and ITO poling method respectively. Piezoelectric charge coefcient d
31
is 16
and 28 pC/N for traditional and ITO poling methods respectively. With these performance
indices, the conclusion can be drawn that the proposed ITO poling technique is superior
to the traditional method. Moreover, ITO glass itself has small resistance of 12 ohm/sq,
can reduce current ow, therefore it can eliminate the occurrence of ashover or arcing.
Furthermore, smooth surface of ITO glass is instrumental to complete close contact with
PVDF lm, which is inuential to poling process. For specic pattern design such as comb
type, uniform poling effect is achieved without the defect at the corners while using metal
electrode in the traditional method. With d
31
surface poling, using pressing structure will
obtain larger output response than the cantilever structure.
Acknowledgments
This research was supported by National Science Council under the grant NSC98-2221-
E-033-035-MY2, and the project of the specic research elds in the CYCU as grant
CYCU-98-CR-ME, and sponsored by Soundwide Technology Corp.
References
1. Piezolm Sensors: Technical Manual, Measurement Specialties Incorporation, pp. 1, April
(1999).
2. W. Y. Chang, T. H. Fang, S. Y. Liu, and Y. C. Lin, Phase Transformation and Thermomechanical
Characteristics of Stretched Polyvinylidene Fluoride. Mater. Sci. Eng. A. 480, 477482 (2008).
3. H. Gunawan, and Y. Ting, Experimental Investigation of Electrode Pattern Design for PVDF
Response. IEEE ASEMD., 101104 (2011).
4. R. Gregorio. Jr., Determination of The , and Crystalline Phases of Poly(vinylidene uoride)
Films Prepared at Different Conditions. J. Appl. Polym. Sci. 100, 32723279 (2006).
5. P. Sajkiewicz, A. Wasiak, and Z. Goclowski, Phase Transitions During Stretching of
Poly(vinylidene uoride). Eur Polym J. 35, 423429 (1999).
6. A. Salimi, and A. A. Youse, Conformational Changes and Phase Transformation Mechanisms
in PVDF Solution-Cast Films. J. Polym Sci Part B: Polym Phys 42, 34873495 (2004).
7. J. E. Mckinney, and G. T. Davis: Plasma Poling of Poly(vinylidene uoride): Piezo- and Pyro-
electric Response. J. Appl. Phys. 51, 16761681 (1980).
8. P. D. Southgate, Room Temperature Poling and Morphology Changes in Pyroelectric Polyvinyli-
dene Fluoride. Appl. Phys. Lett. 28, 250252 (1976).
D
o
w
n
l
o
a
d
e
d

b
y

[
T
e
x
a
s

A

&

M

U
n
i
v
e
r
s
i
t
y
-
-
K
i
n
g
s
v
i
l
l
e
]

a
t

0
4
:
2
9

2
4

D
e
c
e
m
b
e
r

2
0
1
3

New Approach for Surface Poling of PVDF 27
9. D. Schilling, K. Dransfeld, E. Bihler, K. Holdik, and W. Eisenmenger, Polarization Proles of
Polyvinylidene Fluoride Films Polarized by a Focused Electron Beam. J. Appl. Phys. 65, 269275
(1989).
10. S. Yilmaz, S. Bauer, and R. Gerhard-Multhaupt, Photothermal Poling of Nonlinear Optical
Polymer Films. Appl. Phys. Lett. 64, 27702772 (1994).
11. B. Gross, R. Gerhard-Multhaupt, A. Berraissoul. and G. M. Sessler, Electronbeam Poling of
Piezoelectric Polymer Electrets. J. Appl. Phys., 62, 14291432 (1987).
12. P. M. Blanchard, and G. R. Mitchell, Localized Room Temperature Photo-induced Poling of
Azo-dye-doped Polymer Films for Second-order Nonlinear Optical Phenomena. J. Phys D-Appl.
Phys. 26, 500503 (1993).
13. S. Bauer, Poled Polymers for Sensors and Photonic Applications. J. Appl. Phys. 80, 55315558
(1996).
14. N. J. Kidnes, Z. J. Homrighaus, T. O. Mason, and E. J. Garboczi, Thin Solid Films. 496, 539545
(2006).
15. G. Liu, and C. W. Nan, Thickness Dependence of Polarization in Ferroelectric Perovskite Thin
Films. J. Phys. D-Appl. Phys. 38, 584589 (2005).
16. S. Horii, S. Yokoyama, H. Nakajima, and S. Horita, Thickness Dependence of Material Properties
of Epitaxial Pb(ZrxTi1-x)O3 Films on Ir/(100) (ZrO2)1-x(Y2O3)x/(100)Si Structures. Jpn. J.
Appl. Phys. 38, 53785382 (1999).
17. Z. W. Zou, J. H. Kai, M. J. Rust, and C. H. Ahn, A Nano Interdigitated Electrodes Array On
Polymer For Disposable Impedimetric Biosensr. Workshop on Solid State Sensor, Actuator, and
Microsystems, 148151 (2006).
18. S. K. Park, J. I. Han, W. K. Kim, and M. G. Kwak, Deposition of Indiumtin-Oxide Films on
Polymer Substrates for Application in Plastic-based Flat Panel Displays. Thin Solid Films. 397,
4955 (2001).
19. C. Wang, Z. Y. wang, T. L. Ren, Y. P. Zhu, Y. Yang, X. M. Wu, H. N. Wang, H. J. Fang, and
L. T. Liu, A Micromachined Piezoelectric Ultrasonic Transducer Operating in d33 Mode Using
Square Interdigital Electrodes. IEEE Sensors J. 7, 967976 (2007).
20. X. J. Zhao, J. Cheng, S. J. Chen, J. Zhang, and X. L. Wang, Controlled Crystallization of
Poly(vinylidene uoride) Chains from Mixed Solvents Composed of Its Good Solvent and
Nonsolvent. J. Polym. Sci. B. 48, 575581 (2010).
21. W. T. Mead, A. E. Zacharidas, T.. Shimada, and R. S. Porter, Solid State Extrusion of
Poly(viny1idene uoride). 1. Ram and Hydrostatic Extrusion. Macromolecules. 12, 473478
(1979).
22. R. Gregorio Jr., and M. Cestari, Effect of Crystallization Temperature on The Crystalline Phase
Content and Morphology of Poly(vinylidene uoride). J. Polym. Sci. B-Polym. Phys. 32, 859870
(1994).
23. T. T. Wang, and H. V. Seggern, High Electric Field Poling of Electroded Poly(vinylidene uoride)
at Room Temperature. J. Appl. Phys. 54, 46024604 (1983).
D
o
w
n
l
o
a
d
e
d

b
y

[
T
e
x
a
s

A

&

M

U
n
i
v
e
r
s
i
t
y
-
-
K
i
n
g
s
v
i
l
l
e
]

a
t

0
4
:
2
9

2
4

D
e
c
e
m
b
e
r

2
0
1
3