Journal of the Korean Physical Society, Vol. 51, No. 2, August 2007, pp.

719722

The Ferroelectricity and Electrical Properties of P(VDF-TrFE)

Copolymer Film
Dong-Won Kim, Gwang-Geun Lee and Byung-Eun Park
Department of Electrical and Computer Engineering, University of Seoul, Seoul 130-743
(Received 9 November 2006)
Poly(vinylidene fluoride-trifluoroethylene)(P(VDF-TrFE)) copolymer thin films with a molar ratio of 75/25 have been studied to investigate their ferroelectricity. P(VDF-TrFE) solutions of 3,
7 and 10 wt% were fabricated on Si(100) substrates by using a spin-coating method. In order to
achieve crystallization, we annealed the deposited films at 150 C for one and half hours without
any addional treatments, such as a heat-treatment, poling, or mechanical drawing. The thicknesses
of the deposited films were 60, 170 and 400 nm for the 3, 7 and 10 wt% solutions, respectively.
Hysteretic characteristics were observed in the capacitance-voltage (C-V) curves for Au/P(VDFTrFE)/Si diodes and may be considered to be due to the ferroelectric nature of the P(VDF-TrFE)
films. The memory window width was measured at a low voltage below 1 V for a film coated with
a 3 wt% solution. The memory window widths in this metal-ferroelectric-semiconductor (MFS)
fabricated with 3, 7 and 10 wt% P(VDF-TrFE) solutions were about 1.2, 2.7 and 3.6 V for a bias
sweep from 5 V to 5 V, respectively.
PACS numbers: 77.84.Jd
Keywords: Poly(vinylidene fluoride-trifluoroethylene), P(VDF-TrFE), Ferroelectric polymer, Memory window

tributed to form the copolymer and are crystallized into

a single crystalline phase analogous to the phase PVDF
[6]. In the copolymer of VDF and TrFE, the molar content of VDF controls the spontaneous polarization value.
P(VDF-TrFE) with VDF of a 70 80 % exhibits high
polarization while the crystal structure and crystallinity
are decided by the content of TrFE [7,8].
Recently, there have been many studies on
ferroelectric-gate field-effect transistors (FeFETs)
for nonvolatile memory devices [9]. A direct deposition
of ferroelectrics on a Si substrate causes inter-diffusion
of constituents. As a consequence, a metal-ferroelectricinsulator-semiconductor (MFIS) structure with a buffer
layer has been proposed [10]. On the other hand,
because the P(VDF-TrFE) film is deposited at room
temperature, such an inter-diffusion does not matter. In
this research, we deposited P(VDF-TrFE) thin films on
silicon substrates and studied the ferroelectricity of the
films by observing the capacitance-voltage (C-V) characteristics. The surfaces of the films were also observed
by using a scanning electron microscope (SEM).

I. INTRODUCTION
Since H. Kawai discovered the strong piezoelectricity in poly(vinylidene fluoride) (P(VDF)) in 1969,
PVDF and its copolymer, poly(vinylidene fluoridetrifluoroethylene) (P(VDF-TrFE)), have been intensively studied for a wide range of applications, including
nonvolatile memory in organic electronic devices, owing
to their ferroelectricity, piezoelectricity and pyroelectricity [1,2]. PVDF has been reported to be crystallized variously into four types of crystalline phase (, , and
). All types, except the phase, form a polar phase.
The spontaneous polarization of the and the phases
was reported to be nearly half that of the phase, and
the phase can be converted into the phase by mechanical drawing or annealing under high pressure after
high temperature annealing [3, 4]. On the other hand,
P(VDF-TrFE) can easily form the phase without an
additional process by adding a small amount of TrFE.
The copolymer exhibits much higher crystallinity than
PVDF does. P(VDF-TrFE) can be directly crystallized
into the phase by heat treatment at a temperature
between the Curie transition temperature (Tc ) and the
melting temperature (Tm ) [5]. Yagi et al. reported that
the size of the hydrogen atom is similar to that of fluorine; for that reason, VDF and TrFE are randomly dis E-mail:

II. EXPERIMENT
The P(VDF-TrFE) copolymer powder with VDF 75
% and TrFE 25 % was dissolved in a dimethylformide
(DMF) solvent. At the same time, three kinds of so-

pbe@uos.ac.kr; Fax: +82-2-2249-6802

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Journal of the Korean Physical Society, Vol. 51, No. 2, August 2007

Fig. 1. (a) C-V characteristics for Au/P(VDF-TrFE)/Si diodes with a 3 wt% P(VDF-TrFE) film at 1 MHz and (b) Memory
window width calculated from the C-V curves with respect to the applied voltage.

lutions were prepared with concentrations of 3, 7 and

10 wt%. P-type Si(100) wafers were used as substrates.
After cleaning by using a standard process (acetone,
methanol and de-ionized water), We dipped the substrates in a dilute HF solution to remove surface oxide.
The thin films were deposited by using a spin-coating
method. The deposited films were annealed on a hotplate at 150 C for one and half hours because the melting and the Curie transition temperature were 150 C
and 120 C, respectively. The thicknesses of the deposited films were about 60, 170 and 400 nm for 3, 7 and
10 wt%, respectively. The MFS structure of Au/P(VDFTrFE)/p-Si was used to measure the ferroelectric properties. The top electrode with a diameter of 200 um
was vacuum-evaporated. A topography image was obtained by using a scanning electron microscope (SEM).
The capacitance-voltage (C-V) characteristics were measured by using a HP4280A C-V plotter.

III. RESULTS AND DISCUSSION

Figure 1 shows the C-V characteristics of the P(VDFTrFE)/Si structure measured at very low voltage and 1
MHz. The C-V curves were measured at a bias sweep
range from 0.2 V to 1 V. The C-V plot showed a
hysteresis loop, with a clockwise trace as indicated by
the arrows in Figure 1. This loop indicated the ferroelectric behavior of the P(VDF-TrFE) film. Figure 1
shows the hysteresis loop was not yet saturated for a
bias sweep voltage of 0.2 V whereas for a bias sweep
voltage above 0.4 V, it was setting into saturation. The
memory window width calculated from the C-V curves is
summarized in Figure 1(b). The memory window width
gradually was increased as the sweep voltage range increased from 0.2 V to 1 V. It is worth noting that
the typical saturated ferroelectric hysteresis loops were
obtained at a sweep voltage range of 0.4 V. Reece et

al. reported good ferroelectric characteristics at an operating voltage of 15 V for 170-nm-thick P(VDF-TrFE)
(75/25) copolymer thin films fabricated on 100-nm-thick
SiO2 /Si structures (i.e., MFIS) by using the LangmuirBoldgett method [11]. The reasons for a saturated ferroelectric hysteresis loop at a very low operation voltage
in our work as compared with results of Reece et al. can
be attributed to our P(VDF-TrFE) (75/25) copolymer
thin films being fabricated directly on silicon substrates
and to the thickness of the thin films (60 nm) being relatively thin. It was very encouraging result that the
hysteresis loop was saturated, and the memory window
width was about 0.2 V at a sweep range of 0.4 V. Thus,
a new possibility exists for using this film in low-voltage
memory devices operating at 0.4 V. Using the accumulation capacitance value, the relative dielectric constant
of P(VDF-TrFE) film was estimated to be about 7.
Figure 2(a) shows the C-V characteristics when the
3 wt% P(VDF-TrFE) film was measured at a relatively
high sweep range from 1 V to 5 V. The memory window width of the hysteresis loop was estimated to be 1.2
V, which is useful for device applications. At the same
time, in order to make certain of the effect of mobile ionic
charges on the hysteresis loop, we changed the scanning
speed of the bias voltage from 0.01 to 0.75 V/s in the
C-V measurement. However, the memory window width
did not change with the scanning speed range investigated. This suggests that the hysteresis characteristics
resulted because of ferroelectricity of the P(VDF-TrFE)
thin film. In the cases of the 7 and the 10 wt% P(VDFTrFE) films, the C-V characteristics are showed in Figs.
2(b) and (c). As compared with Figure 2(a), the memory window width is far wider than that of the 3 wt%.
The variations of the memory window widths for 3, 7
and 10 wt% of the P(VDF-TrFE) are illustrated in Figure 3. The memory window widths were 1.2, 2.7 and 3.6
V for 3, 7 and 10 wt% P(VDF-TrFE) thin films when
the sweep range was 5 V. The memory window width
gradually expanded, as the sweep range was increased.

The Ferroelectricity and Electrical Properties of P(VDF-TrFE) Dong-Won Kim et al.

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Fig. 2. C-V characteristics for Au/P(VDF-TrFE)/Si diodes with a (a) 3, (b) 7 and (c) 10 wt% P(VDF-TrFE) thin film
measured at 1 MHz as the voltage was swept from 1 V to 5 V.

Fig. 4. The SEM image of the 3 wt% P(VDF-TrFE) thin

film annealed at 150 C for one and half hours.
Fig. 3. Memory window width (V) versus the applied voltage (V) for the various wt% solutions.

IV. CONCLUSION

Figure 4 shows a SEM image of the 3 wt% P(VDFTrFE) thin film. As one can see from this image, surface
lamellae were observed, and chain of molecules was ordered in a crystalline lamella. It is assumed that each
chain of molecules instantaneously rotated in a crystalline lamella like a trunk of tree.

We fabricated P(VDF-TrFE) (75/25) thin films on a

p-type Si(100) substrates by using a spin-coating method
with 3, 7 and 10 wt% solution. The P(VDF-TrFE) films
were annealed at 150 C for one and half hours without
any additional process, such as a heat-treatment, poling,
or mechanical drawing. From the C-V measurements,
hysteric curves were observed, implying the ferroelec-

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Journal of the Korean Physical Society, Vol. 51, No. 2, August 2007

tric nature of P(VDF-TrFE). Particularly, the 3 wt%

P(VDF-TrFE) film showed a saturated hysteresis loop
with a memory window width of 0.2 V at a very low
sweep range of 0.4 V. We conclude from these results
that a copolymer of VDF and TrFE is one of the most
promising candidates for a ferroelectric organic copolymer. We also found that this structure is a reliable means
for achieving a low-cost, high-density, nonvolatile random access memory with a very low operating voltage.

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