ISSN 10637834, Physics of the Solid State, 2012, Vol. 54, No. 8, pp. 1602–1605. © Pleiades Publishing, Ltd.

, 2012.
Original Russian Text © O.M. Golitsyna, S.N. Drozhdin, 2012, published in Fizika Tverdogo Tela, 2012, Vol. 54, No. 8, pp. 1503–1506.

FERROELECTRICITY

Dielectric Properties of Film Materials

Based on Polyethylene Terephthalate and Polycarbonate
with Ferroelectric Inclusions
O. M. Golitsyna* and S. N. Drozhdin
Voronezh State University, Universitetskaya pl. 1, Voronezh, 394006 Russia
* email: golitsynaom@yandex.ru
Received January 30, 2012

Abstract—The dielectric properties of film materials based on polyethylene terephthalate and polycarbonate
with inclusions of triglycine sulfate (TGS) and TGS with admixture of L, αalanine (ATGS) have been stud
ied. An increase in the temperature of the phase transition in these materials as compared to in bulk TGS and
ATGS has been revealed.
DOI: 10.1134/S1063783412080124

1. INTRODUCTION carbonate (PC) with ferroelectric inclusions, which

According to the results of modern research [1], the
efficiency of working elements of pyro and piezoelec
tric detectors can be increased by development of
working elements based on nanostructured ferroelec
tric composite materials.
An attractive matrix basis for ferroelectric inclu
sions are films of porous aluminum (Al2O3) and silicon
(SiO2) oxides with a regular hexagonal morphology of
pores [2–4]. The precipitation of a ferroelectric in an
ordered array of pores makes it possible to obtain
materials distinguished by the presence of micro and
nanodimensional singlephase ferroelectric domains
uniformly distributed with a given density. The tech
nology for production of materials based on Al and Si
oxides with inclusions of triglycine sulfate (TGS),
(NH2CH2COOH)3 · H2SO4, is comparatively simple,
because TGS is easily incorporated into porous matri
ces of different topologies and geometries from the
aqueous solution [5–7]. However, the research in fer
roelectric nanostructures based on porous Al and Si
oxides has shown the importance of water for them,
which is capable of filling the pores of the initial matri
ces of Al2O3 and SiO2, being structured in them and
adsorbed by the surface of these films due to their high
hydrophily and, thus, of noticeably changing the
parameters characterizing the physical properties of
the considered structures [7, 8]. Therefore, develop
ment of sensors based on ferroelectric composite
nanostructures combining the technological simplic
ity of fabrication and stable pyro and piezoelectric
activity with increased hydrophoby is an urgent prob
lem of modern research.
This problem can be solved using film materials
based on polyethylene terephthalate (PET) and poly
are the subject of the present work.
2. SAMPLE PREPARATION
AND EXPERIMENTAL TECHNIQUE
PET is a thermoplastic polymer and a good dielec
tric possessing a high mechanical strength and distin
guished by a low hygroscopy [9, 10]. The glass transi
tion temperature of amorphous PET considered in
this work is Tg = 67°C.
PC is a thermoplastic amorphous polymer material
possessing a high hardness and strength combined
with a very high resistance to impact action. It is dis
tinguished by insignificant water absorption, high
electrical resistivity, and insignificant dielectric loss in
a wide frequency range [9, 10]. The glass transition
temperature of this material is Tg = 150°C.
Through holes in films of materials were produced
by bombardment with xenon ions (PET) and argon
ions (PC) in a nuclear accelerator (Dubna, Russia).
Observation of PET and PC film surfaces on a JEOL
JSM 6510 electron microscope has shown that the
formed through holes (through pores) are randomly
distributed (Fig. 1a). The pore sizes in PET and PC
films were ~5500 and ~370 nm, respectively. The pore
density n in PET film was ~(4.5–4.9) × 105 cm–2 and
that in PC film, ~2 × 106 cm–2.
The fillers were TGS and TGS with admixture of L,
αalanine (10 wt % αalanine in a solution): ATGS.
The structure and properties of bulk TGS crystals with
a model ferroelectric phase transition of the second
order at a temperature TC = 322 K have been studied
well and widely represented in scientific literature
[11]. The phase transition temperature of the ATGS

1602
 DIELECTRIC PROPERTIES OF FILM MATERIALS
50 μm
(а)
10 μm
(b)
Fig. 1. Morphology of (a) the surface of PET after bom
bardment with xenon ions and (b) the surface of PET with
ferroelectric inclusions observed by scanning electron
microscopy on a JEOL JSM 6510 microscope.
crystal is displaced by 1–3 K (depending on the L, α
alanine content in the solution) toward higher temper
atures as compared to of bulk TGS [12]. The ferroelec
tric was incorporated into the pores of PET and PC
films from oversaturated solution of TGS (ATGS) salt
at the constant temperature T = 55°C. To that end, at
the temperature T = 55°C, a reduced pressure p = 0.5
atm was created under the film, which provided pre
cipitation of the ferroelectric material into the matri
ces of PET and PC films. TGS and ATGS microcrys
tals formed in this case on the surface outside pores
were removed by fine polishing of the samples. After
that, the samples were annealed at a temperature of
100°C for 3 h in order to reduce the possible influence
of structured water on the studied processes. Elec
trodes, whose thickness did not exceed 50 nm, were
applied by vacuum evaporation of silver onto both sur
faces of the samples. Silver was applied onto the upper
surface of each sample through a mask, which had the
form of a round hole with a diameter d = 4 mm. The
lower surface of samples was covered with silver com
pletely.
PHYSICS OF THE SOLID STATE Vol. 54 No. 8
1603
35
34
33
C, pF
32
31 2 4
3
30
29 1
20 30 40 50 60 70 80 90 100
T, °C
Fig. 2. Temperature dependences of the capacitance C of
the PET sample with inclusions: (1) heating; (2) cooling;
(3) 3 months later, heating; and (4) 3 months later, cooling.
The presence of ferroelectric inclusions in pores
was controlled by means of a JEOL JSM 6510 micro
scope (Fig. 1b). The fraction of pores filled with ferro
electric for PC film was ~50%; for PET samples it was
higher and reached ~70%. The capacitance C and
conductance G were measured by a BM 484 Tesla
bridge at a frequency of 1.592 kHz with the measuring
voltage amplitude U0 = 0.3 V. During the studies, in
the intervals between measurements, the samples were
stored in air at room temperature.
3. EXPERIMENTAL RESULTS
Figure 2 shows the temperature dependences of the
capacitance C for a PET + TGS sample in the heat
ing–cooling mode (curves 1 and 2). The observed
maxima of these dependences are found at the tem
perature of ~51°C, which exceeds the phase transition
temperature TC in bulk TGS. After three months, the
curves C(T) exhibit stability and preserve the positions
of maxima and the absolute values of C (Fig. 1, curves
3 and 4) in contrast, e.g., to nanocomposite materials
of porous Al and Si oxides with TGS inclusions [7].
Such an anomalous dependence C(T) with a maxi
mum at T ~ 51°C was also found in PC + TGS sam
ples (Fig. 3, curves 1 and 2). Moreover, the stable posi
tion of the curves C(T) for PC + TGS materials is also
preserved for a long time.
Figure 4 shows the temperature dependences of the
conductance G for the same samples, which qualita
tively repeat the dependences C(T) in Figs. 2 and 3. It
is worth noting that the considered dependences G(T)
do not change with time. The same behavior of the
dependence C(T) and G(T) for the materials under
study makes it possible to present only the depen
dences C(T).
For PET + ATGS and PC + ATGS samples, a dis
placement of the maxima of dependences C(T)
2012
1604 GOLITSYNA, DROZHDIN

0.022
37.0

36.5 1
1 0.018
36.0
2
C, pF

G, µS
35.5 0.014
2
35.0

34.5 0.010

34.0
0.006
20 30 40 50 60 70 20 30 40 50 60 70
T, °C T, °C

Fig. 3. Temperature dependences of the capacitance C of Fig. 4. Dependences G(T) for a freshly prepared PC sam
the PC sample with inclusions: (1) heating and (2) cooling. ple with TGS inclusions: (1) heating and (2) cooling.

3
35
4
34
4.5
33 2
C, pF

4.0 1
C, pF

32 1
2 3
31 3.5
4
30
3.0
20 30 40 50 60 70 20 30 40 50 60 70 80 90
T, °C T, °C
Fig. 5. Dependences C(T) for freshly prepared (1, 2) PET +
ATGS and (3, 4) PC + ATGS samples: (1, 3) heating and Fig. 6. Dependences C(T) for freshly prepared (1, 2) PET
(2, 4) cooling. and (3, 4) PC samples: (1, 3) heating and (2, 4) cooling.

(Fig. 5) and G(T) is observed toward higher tempera
tures as compared to the ATGS bulk crystal.
In nanoscale composite materials with ferroelectric
inclusions, there are some factors that increase the
phase transition temperature TC as compared to in
massive ferroelectric. The most probable reason of
extending the ferroelectric phase may be the electro
static interaction of ferroelectric inclusions [13]. The
phase transition temperature can also be increased as
a result of the interaction of ferroelectric inclusions
with double electric layers emerging on the interface
between phases [14]. We may assume that the shift of
the maxima of the dependences C(T) (G(T)) may be
related to the interaction of ferroelectric TGS (and
ATGS) inclusions with one another and with double
electric layers on the interface between phases in the
pores of PET and PC.
The curves C(T) obtained on thermocycling
(Fig. 2, curves 1 and 2; Fig. 3, curves 1 and 2; and
Fig. 5, curves 1–2, 3–4 ) do not coincide in the entire
temperature interval. The observed hysteresis is stable
in time: for example, 3 months since the time of prep
aration of the composite materials, the temperature
hysteresis is preserved (Fig. 2, curves 3 and 4). Such
behavior of the dependences C(T) may be related to
the nature of the initial polymer materials, which was
observed earlier in polyvinylidene fluoride–trifluoro
ethylene copolymer [15]. Indeed, the dependences
C(T) for PET and PC polymer materials without fer
roelectric inclusions, shown in Fig. 6, indicate the

PHYSICS OF THE SOLID STATE Vol. 54 No. 8 2012

 DIELECTRIC PROPERTIES OF FILM MATERIALS
presence of hysteresis phenomena in the initial matri
ces.
4. CONCLUSIONS
Thus, the precipitation of TGS and ATGS into
pores made by bombardment of PET and PC with
xenon and argon ions leads to stable capacitance C and
conductance G of such structures, whereas the same
characteristics of composite materials based on porous
films of AL and Si oxides with ferroelectric inclusions
change with time. The comparatively high values of C
and G and stability of the dependences C(T) and G(T)
with time make it possible to consider the PET +
TGS(ATGS) and PC + TGS(ATGS) materials as
promising working elements for a wide range of pyro
and piezoconverters.
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Translated by E. Chernokozhin
2012