Home

Search

Collections

Journals

About

Contact us

My IOPscience

Micro and nanofilms of poly(vinylidene fluoride) with controlled thickness, morphology and
electroactive crystalline phase for sensor and actuator applications

This content has been downloaded from IOPscience. Please scroll down to see the full text.
2011 Smart Mater. Struct. 20 087002
(http://iopscience.iop.org/0964-1726/20/8/087002)
View the table of contents for this issue, or go to the journal homepage for more

Download details:
IP Address: 203.199.213.66
This content was downloaded on 27/11/2014 at 12:42

Please note that terms and conditions apply.

IOP PUBLISHING

SMART MATERIALS AND STRUCTURES

Smart Mater. Struct. 20 (2011) 087002 (4pp)

doi:10.1088/0964-1726/20/8/087002

TECHNICAL NOTE

Micro and nanofilms of poly(vinylidene

fluoride) with controlled thickness,
morphology and electroactive crystalline
phase for sensor and actuator applications
V F Cardoso1 , G Minas1 , C M Costa2 , C J Tavares2 and
S Lanceros-Mendez2
1
Department of Industrial Electronics, University of Minho, Campus de Azurem,
P-4800-058 Guimaraes, Portugal
2
Center/Department of Physics, University of Minho, Campus de Gualtar, P-4710-057 Braga,
Portugal

E-mail: lanceros@fisica.uminho.pt

Received 16 February 2011, in final form 24 May 2011

Published 22 July 2011
Online at stacks.iop.org/SMS/20/087002
Abstract
Poly(vinylidene fluoride), PVDF, thin films have been processed by spin-coating with
controlled thickness, morphology and crystalline phases. The influence of the polymer/solvent
mass ratio of the solution, the rotational speed of the spin-coater and the temperature of
crystallization of the films on the properties of the material has been investigated. It is shown
that high-quality films with controlled thicknesses from 300 nm to 4.5 m and with a controlled
amount of electroactive crystalline phases can be obtained in a single deposition step, which
allows tailoring the material characteristics for specific applications.
(Some figures in this article are in colour only in the electronic version)

films over large areas with high structural uniformity on the

desired substrates [11]. Few studies have been conducted to
obtain PVDF films by spin-coating with the primary goal of
obtaining good surface quality of the films with a high phase content [9, 10, 12]. In fact, the development of sensors
and actuators requires obtaining high-quality films with flat
and smooth surfaces and uniformity in terms of thickness
and electroactive phase. However, there is a considerable
controversy with respect to the obtained phase content, mainly
due to the fact that the complete processing conditions
(solvents, temperature, humidity, etc) are often not mentioned.
This paper describes how the parameters involved in the
processing of PVDF by spin-coating influence the properties
of the films. In this way, sensors and actuators based on PVDF
can be manufactured with controlled thickness, morphology
and electroactive phase content, so that the material can be
designed for specific applications.

1. Introduction
Poly(vinylidene fluoride), PVDF, is one of the most suitable
materials for advanced applications due to its exceptional
electroactive properties among polymer systems. It shows
an excellent combination of processability, mechanical and
chemical resistance, and low mechanical and acoustic
impedance [1, 2]. These properties are at the origin of
various applications, especially in the fields of sensors and
actuators [3, 4]. PVDF can exist in four crystalline phases
( , , and ). The phase is the one that exhibits the
best ferroelectric and piezoelectric properties and a variety
of methods like mechanical stretching [5], application of an
electrical field [6] or incorporation of some additives [7, 8]
have been used to obtain this crystalline phase. The use of
spin-coating has been reported for obtaining thin films of PVDF [9, 10]. This technique allows the fabrication of thin
0964-1726/11/087002+04$33.00

2011 IOP Publishing Ltd Printed in the UK & the USA

Smart Mater. Struct. 20 (2011) 087002

Technical Note

Figure 1. SEM micrographs of the PVDF films (a) without post-thermal annealing; with post-thermal annealing at: (b) 30 C, (c) 50 C,
(d) 70 C, (e) 80 C; and (f) transmittance spectra of the films.

suitable for piezoelectric sensors and actuators. For that,

a solution with 20 wt% PVDF was deposited by spincoating (angular velocity, acceleration and time of 1000 rpm,
750 rpm s1 and 30 s, respectively) and then dried at different
temperatures between 20 C (room temperature) and 80 C
using a hot plate (Prazitherm PZ23-2). It is noticeable that
the difference in porosity between the samples dried at room
temperature (figure 1(a)) and those dried at higher temperatures
(figures 1(b)(e)), which is reflected in a substantial difference
in the optical transparency (figure 1(f)). At room temperature,
the evaporation rate of DMF is slower, yielding the formation
of pores [13] and films with transmittance below 20%
across the visible range. This porous structure hampers the
deposition of conducting electrodes, hinders the poling process
and the electroactive response of the material, and prevents
applications in which transparency of the material is required.
A thermal annealing between 30 and 80 C promptly after
the deposition increases the rate of solvent evaporation [13]
avoiding the formation of pores, leading to films with a smooth
and flat surface and with a transmittance higher than 70%
across the visible range. It is also to notice the thickness
difference between porous (figure 1(a)) and nonporous films
(figure 1(b)): 9 m and 4.5 m, respectively. Annealing the
samples between 30 and 80 C does not lead to any further
variation in film thickness. On the other hand, by annealing
at 80 C or higher temperatures, the non-electroactive phase

2. Experimental details
PVDF in powder form (Solef 1010, Solvay) was dissolved in
N,N -dimethylformamide (DMF) (Aldrich, analytical grade)
using a magnetic stirrer. Heating at 30 C was used in
the first 15 min of the mixture to help dissolving and
preventing agglomerates. Then, PVDF films were deposited
by spin-coating (Laurell WS-6505-6NPP/A1/AR2) on highly
polished glass substrates. Room temperature and humidity
were 20 C and 50%, respectively. The morphology of
the films was studied using a scanning electron microscope
(SEM) NanoSEM-FEI Nova 200 and their transmittance using
an optical spectrophotometer (Shimatzu UV-3101PC). Film
thickness was measured using a profilometer (Veeco Dektak
150) and a digital micrometer (Fischer Dualscope 603-478).
The crystalline phases of the films were determined by infrared
spectroscopy (FTIR Spectrum 100) with an ATR system
(FTIR-ATR) and confirmed by x-ray diffraction (XRD, Bruker
D8 Discover). Piezoelectric response was measured with a d33 meter APC YE2730A.

3. Results and discussion

The influence of thermal annealing on the morphology and
surface quality of the PVDF films was studied.
The
aim is to obtain films with a smooth and flat surface,
2

Smart Mater. Struct. 20 (2011) 087002

Technical Note

Figure 2. (a) FTIR-ATR spectra of films subjected to various

post-thermal annealings; and (b) -phase content and the
corresponding piezoelectric coefficients module of the PVDF films
as a function of the thermal annealing.

Figure 3. Film thickness (a) as a function of the angular velocity of

the spin-coater for various mass fractions of PVDF/DFM and a
thermal annealing of 30 C and (b) the corresponding -phase
content.

of the polymer is obtained, as revealed by the formation of a

ringed-spherulitic microstructure (figure 1(e)) and confirmed
by FITR (figure 2(a)). Figure 2 shows the FTIR-ATR spectra
of the films annealed at temperatures from 20 to 80 C.
Taking into consideration specific absorption bands, 763 and
839 cm1 , ascribed to the and phases, respectively,
the -phase fraction present in the films is calculated [14].
Figure 2(b) shows the -phase content of the samples and
their piezoelectric coefficients after poling by corona. A
decrease of the -phase content with increasing annealing
temperature is observed due to the increase of the solvent
evaporation rate and faster crystallization of the film, which
leads to preferential formation of the phase [15]. In this
way, smooth and flat PVDF films 4 m thick and with
-phase content from 0 to 75% can be obtained just by
varying the thermal annealing temperature. We note that 75
to 85% is the maximum amount of phase in commercial
films. Moreover, the higher the -phase content, the higher
the piezoelectric coefficient of the film [16] (figure 2(b)) and
therefore its performance in sensor and actuator applications.
The electrical poling of the PVDF films was performed by a
corona discharge at a controlled temperature inside a homemade corona chamber. The applied voltage was 10 kV at a
constant current of 15 A. The distance between the sample
and the tip was 2 cm and the poling temperature was 100 C.
The films were subjected to the corona field for 45 min and then

cooled down to room temperature with the applied electrical

field. For a thermal annealing at 30 C, a maximum value of
the piezoelectric coefficient of 21 pC N1 with a -phase
content of 75% was obtained (figure 2(b)). With increasing
annealing temperature, a continuous decrease of the -phase
content and the piezoelectric response is observed until the
thermal annealing at 80 C, in which the -phase content
disappears and the piezoelectric response becomes zero. It
is important to notice at this point that the -phase content
of the polymer increases slightly with the poling process [17]
making no significant difference on the overall piezoelectric
response for a given initial -phase content [18]. In this sense,
it is really critical in the control of the -phase content before
the poling process, as this is the main fact, together with the
poling conditions (field and temperature), that determines the
final piezoelectric response.
In addition to the piezoelectric response, it is also
important to control the thickness of the films. This was
achieved by preparing samples from PVDF/DMF solutions
with 10, 15 and 20 wt% of PVDF at spin-coating velocities
ranging from 1000 to 8000 rpm. All samples were further
subjected to a thermal annealing at 30 C to obtain the best
electroactive characteristics and the maximum transmittance.
Figure 3(a) shows that the higher the angular velocity of the
3

Smart Mater. Struct. 20 (2011) 087002

Technical Note

angular velocity of the spin-coating process and PVDF/DMF

mass ratio.

spin-coater and the lower the viscosity of the solution, the

thinner the samples. In this way, PVDF films with a thickness
from 300 nm to 4.5 m can be obtained by adjusting the
PVDF/DMF mass ratio and the angular velocity of the spincoater. Thinner films cannot be obtained by this method as
there is a compromise between the concentration of DMF and
the evaporation rate of the solvent which in turn depends on
the angular velocity during spin-coating deposition. For larger
DMF content, the viscosity is lower and the film crystallizes in
a porous structure. Thinner films can be eventually obtained
by the incorporation of a heating system within the spincoater [9]. Thicknesses larger than 4.5 m are also difficult
to obtain by increasing the viscosity of the solution. For higher
polymer mass ratios, the dissolution of PVDF involves the
use of heating, which can affect the properties of the obtained
films [19]. Finally, the effect of the rotational velocity on the phase content and piezoelectric coefficient of the PVDF films
was studied. As referred to previously, a higher evaporation
rate favored formation of the phase. So, an increase
in the -phase content with increasing rotational velocity
and decreasing PVDF/DMF mass ratio could be expected.
However, as shown in figure 3(b), the higher the rotational
speed and the lower the PVDF/DMF mass ratio, the higher
the -phase content of the films, with -phase content up
to 100%. This can be explained by the stretching of the
polymer chains generated by the shear and elongation forces
during spin-coating deposition, which superimposes the effects
of solvent evaporation rate and promotes the - to -phase
transformation [5]. The higher the rotational speed, the larger
is the stretching effect and therefore the -phase content. No
variation of the piezoelectric response is observed with the
variation of the angular velocity of the spin-coater due to
the large electroactive phase content of all samples and their
relatively small variation with increasing angular velocity [18].

Acknowledgments
The authors want to express their thanks to the
Portuguese Foundation for Science TechnologyFCT for financial support (grant nos PTDC/BIO/70017/2006, PTDC/
CTM/69316/2006, NANO/NMed-SD/0156/2007, SFRH/BD/
44289/2008 (VFC) and SFRH/BD/68499/2010 (CMC)).

References
[1] Ueberschlag P 2001 Sensors Rev. 21 11825
[2] Sencadas V, Gregorio Filho R and Lanceros-Mendez S 2006
J. Non-Cryst. Solids 352 22269
[3] Lovinger A J 1982 Developments in Crystalline Polymers vol 1
ed D C Basset (London: Elsevier Applied Science)
[4] Nalwa H S 1995 Ferroelectric Polymers: Chemistry, Physics,
and Applications vol 1 (New York: Dekker)
[5] Sencadas V, Gregorio Filho R and Lanceros-Mendez S 2009
J. Macromol. Sci. B 48 51425
[6] Davis G T, McKinney J E, Broadhurst M G and Roth S C 1978
J. Appl. Phys. 49 49985002
[7] Martins P, Costa C M and Lanceros-Mendez S 2011 Appl.
Phys. A 103 2337
[8] Nasir M, Matsumoto H, Minagawa M, Tanioka A, Danno T and
Horibe H 2007 Polym. J. 39 6704
[9] Ramasundaram S, Yoon S, Kim K J and Lee J S 2008
Macromol. Chem. Phys. 209 251626
[10] Kang S J, Park Y J, Sung J, Jo P S, Park C, Kim K J and
Cho B O 2008 Appl. Phys. Lett. 92 012921
[11] Norrman K, Ghanbari-Siahkali A and Larsen N B 2005 Annu.
Rep. Prog. Chem. C 101 174201
[12] He X and Yao K 2006 Appl. Phys. Lett. 89 112909
[13] Magalhaes R, Duraes N, Silva J, Silva M, Sencadas V,
Botelho G, Gomez Ribelles J L and
Lanceros-Mendez S 2011 Soft Mater. 9 114
[14] Salami A and Yousefi A A 2003 Polym. Test 22 699704
[15] Chinagli D L, Gregorio R Jr, Stefanello J C, Altafim R A P,
Wirges W, Wang F and Gerhard R 2010 J. Appl. Polym. Sci.
116 78591
[16] Gomes J, Nunes J S, Sencadas V and Lanceros-Mendez S 2010
Smart Mater. Struct. 19 065010
[17] Sencadas V, Costa C M, Moreira V, Monteiro J,
Mendiratta S K, Mano J F and Lanceros-Mendez S 2005
e-Polymers 002 112
[18] Gomes J, Serrado Nunes J, Sencadas V and
Lanceros-Mendez S 2010 Smart Mater. Struct. 19 065010
[19] Benz M, Euler W B and Gregory O J 2001 Langmuir
17 23943

4. Conclusion
This paper demonstrates a simple and reproducible way to
prepare electroactive PVDF samples for sensor and actuator
applications with controlled thickness from 300 nm to 4.5 m,
electroactive phase content from 0 to 100%, d33 piezoelectric
coefficients from 0 to 21 pC N1 and optical transmittance
up to 70% in the visible range. The control of the PVDF films
has been achieved by varying thermal annealing temperature,