• • 4 ,, , e '

ADVANCES IN
COLLOID AND
INTERFACE
Advances in Colloid and Interface Science SCIENCE
ELSEVIER 71-72 (1997) 183-208

Structure and functional properties of ferroelectric

polymers
Takeo Furukawa*
Department of Chemistry,Facultyof Science, Science Universityof Tokyo, 1-3 Kagurazaka,
Shinjuku, Tokyo 162,Japan

Abstract

Ferroelectric polymers represented by vinylidene fluoride copolymers with trifluoroethylene

(VDF/TrFE) have been investigated with special interest on the relationship between their
dynamical properties and structures. Copolymers containing 50-80 mol% VDF exhibit fast
polarization reversal due to the rotation of chain molecules about their axes. Annealing of
an extruded copolymer yields a highly crystalline film consisting of regularly stacked large
lamellae. The switching transient of these extruded copolymers is consistent with the
switching mechanism that progresses through a nucleation-growth process with a consider-
able waiting time (time between the generation of a nuclei and the onset of its growth) and
an accelerated growth velocity. TrFE-rich copolymers exhibit a two-step switching transient,
suggesting that polarization reversal occurs via a nonpolar state associated with the co-
polymer's antiferroelectric-like nature. Piezoelectric and pyroelectric properties were ex-
amined for their high frequency and short time characteristics. The time evolution of the
charge response induced by laser pulse irradiation consists of intrinsic pyroelectricity and
the coupling of thermal expansion and piezoelectric resonance. The intrinsic pyroelectric
response for well-annealed VDF-rich copolymers is in the sub-nanosecond range, which
promises their use as fast thermal sensors. © 1997 Elsevier Science B.V.

Keywords: Ferroelectric polymer; Vinylidene fluoride/trifluoroethylene copolymer; Polariza-

tion reversal; Piezoelectricity; Pyroelectricity; Higher order structure

*Tel.: +81 3 3260 4271; fax: +81 3 3235 2214; e-mail: tfurukaw.ch.kagu.sut.ac.jp

0001-8686/97/$32.00 © 1997 Elsever Science B.V. All rights reserved.

PllS0001-8686(97)00017-1
184 7". Furukawa /Adv. Colloid Interface ScL 71-72 (1997) 183-208

1. Introduction

Ferroelectric polymers have generated much interest in the last 15 years because
of their potential as functional materials for energy transduction and information
recording. Polyvinylidene fluoride (PVDF) was the first ferroelectrie polymer for
which a D - E (electric displacement and electric field, respectively) hysteresis loop
and a fast-switching phenomenon were demonstrated. Incorporation of trifluo-
roethylene (TrFE) into PVDF produces a random copolymer that exhibits a Curie
point, which is undetectable in pure PVDF. Early investigations into the ferroelec-
tric properties of V D F / T r F E copolymers were summarized in my review article [1].
In the early 90s, odd nylons [2] (e.g. nylon7, nylonll) were shown to undergo
ferroelectric polarization reversal in melt-quenched and uniaxially-drawn samples.
Some aromatic polyamides [3], polyureas, and polyurethanes [4] have also been
shown to be ferroelectric. These polymers exhibit D - E hysteresis behavior, but the
Curie point is yet to be observed.
Solid-state polymers are usually obtained as thin films in which the crystalline
and non-crystalline regions coexist. Most experiments on ferroelectric polymers are
done on such semicrystalline film samples. Because ferroelectric properties origi-
nate from the crystalline region, experimental data are strongly influenced by the
higher order structures, such as the degree of crystallinity, orientation, and crystal
size, in the samples. For quantitative analysis, therefore, we need samples with
well-defined higher order structure.
In this article, we examine V D F / T r F E copolymers with special emphasis on
their dynamical characteristics. For VDF-rich copolymers, we prepared samples
(using various thermal and mechanical treatments) with different higher order
structures, and measured their switching characteristics in detail. Concerning
TrFE-rich copolymers, we discovered a two-step switching phenomenon that is
characteristic of an antiferroeleetric material. Finally, we describe the dynamical
aspect of the piezoelectric and pyroelectric properties for VDF-rich copolymers.

2. Structure and basic properties of V D F / T r F E copolymers

2.1. Crystal structure

PVDF consists of a repeat unit (--CH2CF2--)that exhibits a dipole moment

/zv = 7 x 10 -30 Cm (2.1 D) associated with positively charged H-atoms and nega-
tively charged F-atoms (Fig. 1). Because such dipoles are rigidly attached to the
main chain, their orientation is subject to the conformation and packing of
molecules. If the molecule adopts an all-tram conformation and a parallel packing,
the dipoles are aligned in one direction, perpendicular to the chain axis. The
resulting crystal, called /3, possesses a large spontaneous polarization P, that is
responsible for the ferroelectrieity of PVDF. Summing up/z v over the unit volume,
we find
 T. Furukawa / Adu. Colloid Interface ScL 71-72 (1997) 183-208 185

HH

(A)

FF

(B)

c =256pm

(c)
b =491 pm: " (~ ' Ps= 130mC/m2
:
t |
! !

Fig. 1. Molecular (A), chain (B), and crystal(C) structures of PVDF.

Ps = 2l~v/abc = 130 mCm -2 (1)

where a, b, and c are the lattice constants whose values are 858 pm, 491 pm, and
256 pm, respectively.
It is known that PVDF has several crystalline polymorphs. Melt-crystallization
yields a nonpolar a-phase consisting of TGTG' molecules packed in an antiparaUel
manner. The ferroelectric /3-phase is obtained by uniaxial-drawing of a-PVDF.
The introduction of a small amount of TrFE into PVDF causes direct crystalliza-
tion into the /3-phase from the melt. Because the F-atom is slightly larger than the
H-atom, in the copolymer the trans bond is favored over the gauche bond due to
sterical hindrance occurring in the latter. Of special interest are the copolymers
containing 50-80 tool% VDF because they exhibit a Curie point that is absent in
pure PVDF. They also show a marked increase in crystallinity as a result of
annealing at a temperature between the Curie point and the melting point. We
can, therefore, prepare copolymer samples dhat have a variety of higher order
structures.
186 T. Furukawa /Adv. Colloid Interface ScL 71-72 (1997) 183-208

2.2. Curie transition

Fig. 2 shows the temperature variation of the permittivity e' of a 75/25 mol%
copolymer of VDF and TrFE. The rapid increase in e' near 12°C (dielectric
anomaly) upon heating is attributed to the onset of cooperative dipolar motions,
leading to a ferroelectric-to-paraelectric transition. Melting at higher temperature
causes e' to decrease due to loss of cooperativity. Upon cooling, e' first increases
and then decreases due to reverse transitions, i.e. crystallization and a paraelectric-
to-ferroelectric transition. Transition temperatures upon heating are higher than
those upon cooling (130°C and 80°C, respectively), thus meaning that these
transitions are first-order.
Fig. 3 shows the phase diagram for a V D F / T r F E copolymer where the melting
point Tm the crystallization point Tcr, and the Curie point T~ upon heating are
plotted against composition. These temperatures were determined by using a
differential scanning calorimeter (DSC) at a heating and cooling rate of 10°C/rain.
The melting point is a minimum at a composition of 80/20 tool%. As the VDF
content decreases, Tm increases gradually to 200°C at PTrFE. It also increases with
increasing VDF content above 80 mol%. The Tm of a-PVDF is 175°C. The Tcr
depends upon composition in a similar manner and is located about 25°C below
rm.
The T~ of an equimolar copolymer is located near 65°C (Fig. 3). As the VDF
content increases, T~ upon heating increases to coincide with Tm at 80 tool%. This

50

40 _

30 _
Cooling/

20
oo ~ o
_.,o- • o

10 ~ • o
Heating

0 I I I I I I I
40 60 80 100 120 140 160

Temperature ('C)
Fig. 2. Dielectrictemperaturespectra for a VDF(75)/TrFE(25)copolymer.:
 T. Furukawa /Ado. Colloid Interface ScL 71-72 (1997) 183-208 187

200( Molten Phase

(

150

100 _ ~. Paraelectric Phase Tc

ID
so, " ~ i
I
I
!

Anti-ferroelectric
/
0
Phase ? / Forroe/ectric P h a s e
/

-50 - J

I /D'I I I
0 20 40 60 80 1O0
PTrFE VDF content (mol%) PVDF

Fig. 3. Phase diagram for a V D F / T r F E copolymer (O: melting point; 0 : crystallization point; zx : Curie
point on heating; • : Curie point on cooling, [] : ferroelectric-to-antiferroelectric transition point).

implies that melting begins prior to completion of the ferroelectric-to-paraelectric

transition. On the other hand, the Curie point disappears in the DSC thermogram
when TrFE becomes a major component (> 50 mol%). However, a dielectric
anomaly still exists around 50-60°C (triangles with dot) which smoothly connects
with Tc of VDF-rich copolymers. Therefore, the region between the circles and
triangles in Fig. 3 corresponds to the paraeleetrie or paraeleetric-like phase.
VDF-rieh copolymers are in a ferroelectric phase below the Curie point (Fig. 3).
On the other hand, TrFE-rieh eopolymers exhibit a double hysteresis loop in the
temperature range surrounded by the dashed lines in Fig. 3. The enclosed region
could be attributed to an antiferroelectric or an antiferroeleetrie-like phase as will
be discussed in section 4.2.

2.3. Polarization reoersal

In the ferroelectric phase, VDF-rich copolymers incorporated with PVDF exhibit

188 T. Furukawa /Adv. ColloM Interface ScL 71-72 (1997) 183-208

a typical D - E hysteresis loop as demonstrated in Fig. 4 for a VDF(65)/TrFE(35)

copolymer at 20°C with an eleetric field E applied in a sinusoidal form at 1 Hz. In
the low field regime ( < 30 MV/m), the D - E relation is nearly linear. As E is
increased, hysteresis starts to appear. In the high field regime (> 60 MV/m), we
obtain a square hysteresis loop that is independent of the amplitude of E. The
intersect of the loop with the abscissa defines the coercive field E c which is ca. 50
MV/m. The intersect with the ordinate gives the remanent polarization Pr ca. 80
m C / m 2, which depends upon not only composition but also higher order structures
of the sample.
Fig. 5 shows the compositional variation of Pr in which the data plotted are the
largest experimental values obtained so far. Also plotted (dashed line) is the value
of the spontaneous polarization calculated assuming a rigid dipole. Pr reaches a
maximum at a VDF content of 80 tool% and decreases gradually as VDF decreases
to 50 tool%. This gradual decrease is attributed to a decrease in the average dipole
moment because the dipole moment of a TrFE unit is one-half that of a VDF unit.
As the VDF content falls below 50 mol%, Pr decreases rapidly due to a loss of
ferroelectricity. The further decrease in P~ in the 80-100 mol% range is at-
tributable to a decrease in crystallinity. The observed P~ of PVDF is ca. 65
m C / m z, which is one-half that predicted by using spontaneous polarization (dashed
line), ca. 130 m C / m 2.

100

50

E
o =

-50 -

-100 -

I I I I
-100 -50 0 50 100

E (MY/m)

Fig. 4. D - E hysteresis loops for a VDF(65)/TrFE(35) copolymer at 20°C.

 T. Furukawa / Ado. Colloid Interface ScL 71-72 (1997) 183-208 189

140
o

120

100 calculated

E 80'
E
~,_ 6 0

40 .. / observed

20

0 I I I I
n 20 40 60 80 1O0
PTrFE PVDF
VDF content (mol%)
Fig. 5. Composition dependence of observed and predicted the remanent polarization Pr for VDF/TrFE
copolymers.

3. Switching characteristics of VDF-rich copolymers

3.1. Ferroelectric switching measurement

Ferroelectric polarization reversal is commonly examined by means of a D - E

hysteresis measurement in which a sinusoidal electricfield E is applied to a sample
and the resultingelectricdisplacement D is then measured. A n alternativemethod
is a switching measurement, which uses a step-wise E and measures D as a
function of time t.
Fig. 6 shows a block diagram of the apparatus developed for the fcrroclectric
switching measurement. A high step-voltage up to 3.5 kV is applied to a sample
through a switch,which is a silicone-controUed rectifier(SCR). The rise time of the
applied voltage is ca 1 ~s. For fast (nanosecond) measurements at lower voltages
(< 500 V), the S C R is replaced by a mercury rclay.Thc response from the sample
is detected by a capacitor or a resistor in terms of charge or current, respectively,
and is stored in transient memory.
Representative results are shown in Fig. 7 where log D is plotted against log t.
Here, D R represents the result obtained by applying E in the direction opposite
the existing polarization. Any sharp change in D indicates polarization reversal
190 T. Furukawa /Adv. Colloid Interface Sci. 71-72 (1997) 183-208

MICRO L
COMPUTER
"l
TRANS'
NTI
MEMORY
SYSTEM I"
t.oG I
TIMER I
1' I'/

SWITCH
HIGH _L_ r
VOLTAGE
SOURCE

Fig. 6. Experimental set-up for ferroelectric switching measurement.

occurring as a result of dipole reorientation. If E is applied in the direction of Pr

the resulting electric displacement D F exhibits only a gradual increase because
most dipoles are already aligned parallel to the field direction. Such directionality
confirms that the material of interest is ferroelectric. Both D R and D F contain
contributions from the dielectric response and the dc conduction. By subtracting
D F from D R, we obtain the response that arises mostly from ferroelectric polariza-
tion reversal.
Fig. 8 shows the switching characteristics of a VDF(78)/TrFE(22) sample pre-
pared by rapid cooling from the melt to room temperature (melt-quenched)
followed by annealing at 145°C for 1 h. The increment of D corresponds to the
amount of reversed polarization equal to double the remanent polarization (i.e.
2P r) which is independent of the strength of E. The position of the O D / O l o g t peak
defines the switching time r~, which decreases as E is increased.
Fig. 9 shows a plot of log z~ versus the reciprocal of E. The straight line
indicates an exponential relationship between ~-~ and E:

r s = ~'~o e x p ( E a / E ) (2)

where E a is the activation field and r,0 is the switching time at an infinite field,
which were determined to be 0.8 G V / m and 10 ns, respectively.

3. 2. Effect o f annealing on structure and switching characteristics

To examine structure-property relationship with respect to ferroelectric polariza-

tion reversal, we prepared two kinds of samples; melt-quenched and extruded
(extruded from the melt). In the melt-quenched sample, there is no preferred
orientation of molecules, whereas in the extruded sample, molecules are well-ori-
 T. Furukawa / Adv. Colloid Interface ScL 71-72 (1997) 183-208 191

0.0

-0.5

,l,,~, f EDR/
o
'-pr ~ ' | ''~; E
-2.0
-2.5

-3.0 I I I I
-3 -2 -1 0 1 2
log t (s)
Fig. 7. Time evolutionof the electric displacement D inducedby a stepped electricfield E applied in
the directionopposite(D R) to the remanent polarization P~ and in the same direction(Dr).

ented. Both samples were subjected to annealing at elevated temperatures to

increase crystallinity.
Fig. 10 shows the effect of annealing on the switching characteristics of an
extruded VDF(78)/TrFE(22) copolymer. The as-extruded sample exhibits essen-
tially no polarization reversal. As the sample is annealed at a temperature just
above the Curie point (128°C), polarization reversal starts to appear. Annealing at
higher temperatures causes further increase in the amount of reversed polarization
as well as sharpening of the a D / a l o g t peak. The field dependence of zs is basically
the same as that seen in an unoriented sample (Fig. 9).
We examined the structure of these two samples (melt-quenched and extruded)
before and after annealing by using a scanning electron microscope (SEM). Figs.
l l A - 1 1 C show SEM images of the fractured surface parallel to the extrusion
direction (vertical) and to the film thickness (horizontal). The as-extruded sample
(llA) exhibits vertical striation associated with oriented chain molecules. Anneal-
ing at 128°C gives rise to horizontal stripes (liB), suggesting a formation of
crystalline lamellae. As the annealing temperature is increased to 145°C, extremely
large lamellae 100 nm thick and 1/zm wide are stacked in a parallel manner along
the extrusion direction (llC). The SEM image of the fractured surface perpendicu-
lar to the extrusion direction (liD) provides a better view of these stacked
lamellae.
Comparing the results from the switching measurements (Fig. 10) and the SEM
measurements (Fig. 11), we find that annealing causes a rapid increase in crys-
192 T. Furukawa /Adv. Colloid Interface Sci. 71-72 (1997) 183-208

0.15

E 0.10
o
v

0.05

0.0q
-5 -4 -3 -2 -1 0 1
10g t (S)

0.20 L 100 90

E 0.15

o
0.10
"o

0.05

0.00 1 I
-5 -4 -3 -2 -1 0 1
log t (s)
Fig. 8. Switching characteristics of melt-quenched and annealed VDF(78)/TrFE(22) copolymers at
20°C.

tallinity, leading to a marked increase in the amount of reversed polarization. The

extremely sharp OD/Ologt peak of a well annealed sample would be due to very
large lamellae.
The melt-quenched samples have similar structural changes due to annealing,
i.e. a marked increase in crystallinity and in the growth of large lamellae, as
 T, Furukawa / Adv. Colloid Interface Sci. 71-72 (1997) 183-208 193

0-

- 2 --
o

-6--

I , I, l I
5 10 15 20 25 30

lIE (m/GV)
Fig. 9. Switching time ~'s versus the reciprocal of the applied electric field E for a VDF(78)/TrFE(22)
copolymer.

revealed by SEM measurements (analogous to Fig. C but wihout preferred orienta-

tion). Switching characteristics also show a significant increase in Pr as well as a
sharpening of the OD/Ologt peak as shown in Fig. 10 for a well-annealed sample.
Fig. 12 shows a comparison of the switching transients of well-annealed samples
of melt-quenched and extruded copolymers. The amount of reversed polarization
of the melt-quenched sample is 20% larger than that of the extruded. From a
structural viewpoint, polarization reversal of V D F / T r F E copolymers occurs as a
result of the rotation of chain molecules about their axes. Therefore, molecules
oriented in the thickness direction (i.e. E direction) do not contribute to polariza-
tion reversal. Quantitatively, molecules oriented with angle 0 with respect to the
thickness direction contribute to Pr as a coefficient sin 0. Assuming that molecules
are randomly oriented in a melt-quenched sample, the expected Pr is ~r/4 that of a
completely oriented sample, for samples with the same crystallinity. Thus, the
difference in Pr for the extruded and melt-quenched samples is due to molecular
orientation, which confirms that chain rotation is responsible for polarization
reversal in V D F / T r F E copolymers.
Another important difference between the two samples is the shape of the
switching transient. The extruded sample undergoes a very sharp change in D,
whereas the melt-quenched sample exhibits a rather gradual change (Fig. 12). The
time evolution of the switching transient reflects how polarization reversal pro-
194 T. Furukawa /Adv. Colloid Interface ScL 71-72 (1997) 183-208

0.25

0.20 annealed at 145"C

0.15 137"C
E
0
v

c~ 0.10 128"C

0.05 as-extruded

0.00
-4 -3 -2 -1 0
log t (s)

0.8

0.6 annealed at 145°C

o
v

*" 0.4 137"C

0

0.2 - 128"C

0.0 ' '~ ~ as-extruded

-z -3 -2 -1 0
log t (s)
Fig. 10. Switching characteristics of extruded and annealed VDF(78)/TrFE(22) copolymers at 20°C.

gresses after the application of the step-wise electric field. The switching process in
crystalline lamellae would be affected by their orientation with respect to this
applied field. Because the extruded copolymer consists of well-aligned lamellae, the
observed switching transient may represent that of each lamella. On the other
 T. Furukawa /Ado. Colloid Interface ScL 71-72 (1997) 183-208 195

: 4J

~ i~

,, (, ., i
(A) (B)

(C) (D) 5oonm

Fig. ll. SEM images of the fractured surface of a VDF(78)/TrFE(22) film (A) as-extruded, (B)
annealed at 128°C, and (C, D) annealed at 145°C.

hand, the switching transient of the melt-quenched sample is subject to an

'orientation average', which results in a much broader spectrum of the transient. In
the following, we analyze the switching transient of extruded copolymers.

3.3. Anal, sis of switching transient

It is generally accepted that polarization reversal in a ferroelectric is based on a

nucleation-growth mechanism [5]. When an electric field is applied, polarization
reversal starts with the generation of the nuclei of reversed domains, followed by
nuclei growth that is seen as domain-wall motions. For single crystal ferroelectrics
such as BaTiO 3, such domain-wall motions can be observed by using an optical
microscope. This mechanism is consistent with the observed coercive field being
much lower than phenomenologieal prediction.
Assuming random nucleation, the number of generated nuclei at time t is

N = N 0 ( 1 - e -R') (3)
196 T. Furukawa /Adv. Colloid Interface ScL 71-72 (1997) 183-208

0.25

0.20 extruded

0.15
E

c~ 0.10

0.05

0.00 I f I I I
-4 -3 -2 -1 0
log t (s)
Fig. 12. Comparison of the shape of switching transient for melt-quenched and as-extruded
VDF(78)/TrFE(22) copolymers.

where R is the nucleation probability and N O is the total number of available

nucleation sites. If the generated nuclei grow m-dimensionally at a velocity o, the
total volume of all reversed domains V (extended volume) is given by
-d d N

where F is a shape factor. As growth proceeds further, ingestion of nucleation sites

occurs. Growing domains then coalesce. Taking ingestion and coalescence into
consideration, the actual reversed polarization P given by Avrami [5] is

P = 2Psi1 - e -g ] (5)
where Ps is the spontaneous polarization. Fig. 13 shows a schematic of the
nucleation-growth process for the ease of two-dimensional growth.
Substituting Eqs. (3) and (4) into Eq. (5) and then integrating, we obtain an
analytical expression for P, which can then be simplified as

P = 2P~[1 - e - ( t / r s ) ' ] (6)

Here, the exponent n is related to the growth dimension m. When the growth
velocity v is small (t :~ l / R ) , polarization reversal occurs after most nucleation
sites are activated. For this case, n = m results [5]. On the other hand, if v is very
large (t < l / R ) , polarization reversal is completed as soon as a small amount of
nuclei are generated, thus yielding n = m + 1 [5].
 T. Furukawa / Adv. Colloid Interface Sci. 71-72 (1997) 183-208 197

@
0
ole
(A) (B) (C)
Generated Growth Coalescence
Nuclei Sites of Sites of Sites
Fig. 13. Schematic of the nucleation-growth mechanism for ferroelectric polarization reversal.

The value of n determines the shape of the switching transient curve in terms of
the sharpness of the aD/alogt peak, as represented in Fig. 14 for observed and
predicted (using Eq. [6]) peaks for the melt-quenched and extruded copolymers.
The corresponding n value of the extruded copolymer is larger than 5, which
requires an unrealistic growth dimension of 4 to 5. The observed transient also
shows departure from the predicted transient when t < ~-s/10.
To explain such a large n value and to reproduce the switching transient over
the entire range of t, we introduce three assumptions into our analysis: (a) v is not
constant but has an acceleration a; (b) generated nuclei must wait a time Tw
before they start to grow; and (c) generated nuclei have a certain initial volume
before growth. Incorporating these assumptions, the extended volume is expressed
as

6
• Extruded n =6
o Melt-Quenched ~ / ~
i
Calculated 3 ~ ' ~
4
0

-0.6 -0.4 -0.2 0.0 0.2 0.4

Iogt/~:s

Fig. 14. Comparison of observed aD/alogt peak with that predicted from an exponential function.
198 T. Furukawa /Adv. Colloid Interface Sci. 71-72 (1997) 183-208

O,

I IIIIII

, n=5.3

. i,,/" ,; a,v, ro,~. I

-3=
-5 -4 -3 -2 -

log t (s)
Fig. 15. Observed and fitted switching transients for extruded and well-annealed V D F / T r F E co-
polymers.

! dM~
V= J~[tJ"~" J F(½a(t-t w - s ) z + v ( t - t w - s ) +r2)mds (7)
o~ dt]s

Fig. 15 shows the results of fitting the observed transient for the extruded and
annealed copolymer with this expression. We find that the observed transient is
well reproduced. The a and 7", account for the sharp rise in D with time t. The
radius of the nuclei r 0 contributes to the initial gradual increase in D. In practice,
the even-order nonlinear permittivity also contributes to the initial gradual in-
crease in D as we previously reported [6].
We have succeeded in reproducing the observed very sharp switching transient
of extruded and annealed samples of copolymers by introducing a variety of
factors, such as a and Tw. Because such samples consist of regularly-stacked large
lamellae, we believe that the observed sharp switching transient represents the
events occurring in respective crystalline lamellae. Much broader switching tran-
sients in unoriented copolymers can be interpreted by taking into consideration the
averaging effect arising from orientation distribution.

4. Switching characteristics of TrFE-rich copolymers

4.1. Double hysteresis and two-step switching charactens"acs

As stated earlier, the amount of reversed polarization rapidly decreases as the
VDF content is decreased to below 50 mol%. Although there remains a dielectric
 T. Furukawa /Ado. Colloid Interface Sci. 71-72 (1997) 183-208 199

anomaly, the ferroelectric-to-paraelectrie transition in such samples is undetectable

by DSC measurements. In this section, we look at the loss of ferroelectricity in
TrFE-rich copolymers.
Fig. 16 shows the D - E relation for uniaxially-drawn and annealed V D F / T r F E
copolymers with compositions 65/35, 47/53, and 37/63 mol%. The square hys-
teresis loop that is characteristic of VDF-rich copolymers is transformed into a
double hysteresis loop as TrFE becomes a major component (> 50 mol%). Double
hysteresis suggests that polarization reversal progresses through a nonpolar state.
The VDF(47)/TrFE(53) copolymer experiences the nonpolar state just after the
applied field is reversed, whereas the 37/63 copolymer drops to the nonpolar state
at zero field.
Fig. 17 shows D - E hysteresis measurements at various temperatures for the
VDF(47)/TrFE(53) copolymer. As the temperature is decreased to -40°C, double
hysteresis is lost and transforms into a regular single loop. This implies that the
polar phase is more stable than the nonpolar phase below -40°C.
The ferroelectric switching measurements for the VDF(47)/TrFE(53) copolymer
in Fig. 18 show a two-step switching transient, thus confirming that polarization
reversal progresses through a nonpolar state in the time domain. The dependence
of the time constant on field strength is stronger for the polarization change from

100

S ~'~'~65/35

50

E
O 0
v
E

-50 -

-100 I I
-100 -50 0 50 100

E (MY/m)
Fig. 16. D - E hysteresis loops for VDF(65)/TrFE(35), 47/53, and 37/63 copolymers at room tempera-
ture.
200 T. Furukawa /Adv. Colloid Interface ScL 71-72 (1997) 183-208

60

c0OC
40

20

7.
_E
o 0
E
v

-20 - "'-....40oC
-40 -

25°C
-60 -
I I I I
-150 -100 -50 0 50 100 150
E (MY/m)

Fig. 17. D - E hysteresis loops for a VDF(47)/TrFE(53) copolymer at 25, 0, - 10 and -40°C.

negative to zero than that from zero to positive. These two time constants are
unified when the E reaches 90 M V / m . Fig. 19 shows plots of these two time
constants versus the 1/17, obtained at various temperatures. As the temperature is
decreased to -40°C, we obtain a single switching process in accord with the
regular square hysteresis loop at the same temperature.

4.2. Possibility of anti-ferroelectricity

There are two possibilities that give rise to a double hysteresis loop or a two-step
switching phenomenon. One is that the ferroelectric undergoes a first-order
transition. Near the Curie point, both the ferroeleetric and paraeleetric phases are
at an energy minimum for such a ferroelcctric. Just above the Curie point, the
external field induces a paraelectric-to-ferroelectric transition, resulting in a dou-
ble hysteresis loop. The other possibility is that the material in concern is the
antfferroelectric consisting of two sublattices that have spontaneous polarizations
opposite in direction. The application of an external field causes polarization
reversal of one of the sublattices, thus inducing a transition to the ferroelectric
phase.
Here we have shown that TrFE-rich copolymers exhibit a double hysteresis loop
as well as a two-step switching phenomenon. One question that arises is whether
the copolymer is an antiferroelectric or a first-order ferroelcctric. It is known that
the ferroelectric transition of VDF-rich copolymers is first-order as revealed by
 T. Furukawa /Adv. Colloid Interface ScL 71-72 (1997) 183-208 201

+i iit 0"06F

°070;
f 0.00
-5 -4 -3 -2 -1 0

Iogt(s)

0.10 !
8O
E 0 •08
O
E 0.06
7 ~ 60 50
o0 ) 0.04
¢~
0.02
0.00
-5 -4 -3 -2 -1 0
Iogt(s)
Fig. 18. Switching characteristics of a VDF(47)/TrFE(53) copolymer at 25°C.

thermal hysteresis of the transition behavior. However, no clear indication of

double hysteresis has been reported so far. As the VDF content is decreased to
equimolar composition, thermal hysteresis is lost and the transition becomes
second-order.
As the transition of TrFE-rich copolymers is second order, we expect that the
two-step switching arises from their antiferroelectric or antiferroelectric-like na-
ture. Fig. 20 shows a schematic of the structural change during polarization
reversal for TrFE-rich copolymers of VDF. Structure A describes the paraelectric
phase in which molecules adopt a random conformation, resulting in disordered
202 T. Furukawa /Adv. Colloid Interface ScL 71-72 (1997) 183-208

0-

-1 -

69
v

"2~
o

i
"3

"4

o 25 °C
-5
I I I I
5 10 15 20 25 30

1/E (m/GV)
Fig. 19. Switching time r s against I/E for the two-step switching transient of a VDF(47)/TrFE(53)
copolymer at various temperatures.

dipole orientation. Structure C expresses the antiferroelectric phase consisting of

all-tram molecules packed in an ant/parallel manner. An alternative structure, B,
assumes a random packing of all-tram molecules. To answer which structural
change is occurring, we must determine the crystal structure of TrFE-rich copo-
lymers at temperatures where the two-step switching is observed.

5. Piezoelectric and pyroelectric properties

As far as application is concerned, ferroelectric polymers have received much

attention as soft transducer materials because of the polymers" piezoelectric and
pyroelectric properties [7]. This section describes our recent work on the dynamical
aspect of these properties, particularly in the high frequency or the short time
ranges.
The piezoelectric constant dq and the pyroelectric constants Pi are defined as
 T. Furukawa /Adv. Colloid Interface ScL 71-72 (1997) 183-208 203

+P -p

Nonpolar P=O
Fig. 20. Structural changes during the two-step switching transient for TrFE-rich copolymers.

dq = -~J/e Pi t OT /e (i = 1 - 3 , j = 1-6) (7)

where D is the electrical displacement, E is the electric field, X is the stress, and
T is temperature.
The uniaxially-drawn and poled V D F / T r F E film has a C=v symmetry. Therefore,
the matrix form of d u and Pi are

0 0 0 0 dis 0
dij = 0 0 0 d24 0 0 (8)
d31 d32 d33 0 0 0

(9)

Here, 1 refers to the draw direction, 3 to the poling direction, and 2 is orthogonal
to both 1 and 3. For undrawn samples, d31 = d32 and d15 = d24. The values of
204 T. Furukawa /Adv. Colloid Interface ScL 71-72 (1997) 183-208

nonzero components are not a material constant but depend upon the remanent
polarization Pr imparted by poling. For a VDF(65)/TrFE(78) copolymer, we obtain
a good linear relationship with respect to d31/s~l and P3 as demonstrated in Fig.
21. Pr depends upon the higher order structure of the sample and its maximum
value is limited to the spontaneous polarization of the crystalline regions.

5.1. Piezoelectric resonance

The piezoelectric constant at high frequencies is measured by using a resonance

method. Fig. 22 shows the dielectric spectra for a V D F / T r F E copolymer over a
broad frequency range at room temperature. The spectra show two kinds of
resonance [8] superimposed on a broad dielectric relaxation. The resonance near
400 kHz is assigned to the length extension (LE) mode vibration and that around
40 MHz and its odd order harmonics are attributed to the thickness extension (TE)
mode vibration. Here the sample used for the measurement was 20 /zm thick, 10
mm long, and 5 mm thick. Sample deformations associated with LE mode and TE
mode resonances are depicted in the figure. In the former the length extension is
acompanied by thickness and width contractions, whereas the thickness extension
occurs without length and width contractions in the latter.

120 60

100 - 50

80 - 40

- 30
3
v
7~
- 20

20 - 10

0 I
0 20 40 60 80 100
Pr (me/m2)
Fig. 21. Dependence of the piezoelectric constant dal/sll and the pyroelectric constant P3 on the
remanent polarization Pr for a VDF(65)/TrFE(35) copolymer.
 T. Furukawa /Adv. Colloid Interface ScL 71-72 (1997) 183-208 205

lo[ x
8~ M o d e
TE Mode
61- ~. . . . . . . . . . . . . . . . . .
X

0
4 5 6 7 8 9
Iogf (Hz)

4 TE Mode
i
~. . . . . . . . .
!
.,=
3- LE Mode
%
2 ::~:~

0 " t I "
4 5 6 7 8 9
Iogf (Hz)
Fig. 22. Frequency spectra of the complex permittivity E* = e - is" containing piezoelectric resonance
for a V D F / T r F E copolymer.

The dielectric spectra observed can be described by [9]

k321 tan a )
1 + 1-k~-------~ a
E33 ffi 8~3 tan b (10)
206 T. Furukawa /Adv. Colloid Interface Sci. 71-72 (1997) 183-208

with
°'
a = 2v v ps~ (11)

and

o,t / cg
b = 2v v (12)
P

where ~o is the angular frequency, p is the density, l is length, t is thickness, s is

the elastic compliance, c is the elastic stiffness constant, and k is the electro-
mechanical coupling coefficient defined by
ag,
k32~- xE k~3= x o (13)
,g33511 833C33
Here e x is the free permittivity and e x is the clamped permittivity.
Using Eq. (10), we can reproduce the observed spectra by adjusting the constants
as best-fit parameters. In this case, we obtained k 3 = 0.27 and k31 = 0.09, which
lead to estimates of the piezoelectric constants d31 and e33 by the use of the elastic
and dielectric constants appearing in Eq. (13). We are also able to determine the
frequency spectra of the clamped permittivity e x (dashed curves in Fig. 22), which
is completely independent of piezoelectric resonance. The broad relaxation
observed has been attributed to dipolar fluctuations in the crystalline regions [10].

5.2. Pyroelectric d y n a m i c s

The dynamical characteristics of the pyroelectricity can be measured by the use

of laser pulse heating [11]. Fig. 23 shows the time evolution of the charge response
from a freely suspended VDF(75)/TrFE(25) sample after the irradiation of a 7 ns
YAG laser pulse. The time spectra consist of four processes: (a) initial fast rise
( < 10 ns); (b) TE-mode damped oscillation (10 ns-1 ~s); (c) LE-mode damped
oscillation (1 ~s-10 ms); and (d) final decrease due to thermal diffusion outward
from the sample (10 ms-10 s). The TE mode and LE mode oscillations in the
charge response occur as a result of rapid thermal expansion coupled with
piezoelectric effects.
Comparing Figs. 22 and 23 reveals that two types of mechanical vibration
contribute to dielectric and pyroelectric spectra through piezoelectric coupling.
The former was measured on the frequency domain whereas the latter on the time
domain. Therefore, Fourier transform of one of the spectra is necessary to make
comparison on the same (frequency or time) domain. Detailed analysis is now in
progress. We expect to obtain further information about the dynamics of not only
dielectric and pyroelectric properties but also piezoelectric, thermal and mechani-
cal properties of V D F / T r F E copolymers.
 T. Furukawa /Adv. Colloid Interface ScL 71-72 (1997) 183-208 207

40

LE Mode ':':~::
30-

0Q..
20-
(3

10-

0
-'0 -8 -6 -4 -2 0

Iogt (s)
Fig. 23. Time spectra of the charge response for a VDF(75)/TrFE(25) copolymer induced by laser pulse
irradiation.

Regarding the fast response, by removing the TE-mode component, we obtained

the time spectra describing fast pyroelectric dynamics. The spectra consist of two
components. The first is an initial rapid rise attributed to the intrinsic pyroelectric-
ity that appears prior to thermal expansion in parallel with an integrated laser

30

25

20

(3
10

0 I I I I I
0 50 1O0 150 200 250 300
t (ns)
Fig. 24. Fast pyroelectric response for a VDF/TrFE copolymer.
208 T. Furukawa /Adv. Colloid Interface ScL 71-72 (1997) 183-208

pulse. This property holds promises in using V D F / T r F E copolymers as very fast

pyroelectric detectors. The second component is the gradual rise (time constant of
100 ns) associated with dipolar fluctuations in accord with the dielectric relaxation
in Fig. 22.

6. Concluding remarks

Structure-property relationship has been examined for V D F / T r F E copolymers

over the entire range of composition. Annealing is a very efficient technique for
controlling higher order structures such as the degree of crystallinity and the
crystalline size of this copolymer. It was found that the crystalline size does affect
the ferroeleetric switching characteristics of VDF-rich copolymers. The melt-
quenched and annealed sample consisting of regularly packed large crystalline
lamellae exhibited unusually sharp switching transient for which quantitative
interpretation was given. The uniaxially-drawn and annealed TrFE-rich copolymers
exhibited two-step switching phenomena implying their antiferroelectric or antifer-
roeleetric-like nature. Further investigation using such well-defined samples would
lead to microscopic understanding for the V D F / T r F E eopolymers. Concerning
functional properties were presented dielectric frequency spectra and pyroeleetrie
time spectra in that piezoelectric contribution associated with mechanical reso-
nance were commonly observed. The results provided rich information about
thermo-eleetro-meehanical dynamics of V D F / T r F E eopolymers as well as key data
for fast sensor applications.

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