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On the question of the critical end point

in the (1 − x)PbMg1/3Nb2/3O3-xPbTiO3
relaxor ferroelectric single crystals based
on acoustic emission data studies
Evgeniy Dul’kin, Antoni Kania and Michael Roth
EPL, 133 (2021) 67001

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 March 2021
EPL, 133 (2021) 67001 www.epljournal.org
doi: 10.1209/0295-5075/133/67001

On the question of the critical end point

in the (1 − x)PbMg1/3Nb2/3O3-xPbTiO3 relaxor ferroelectric
single crystals based on acoustic emission data studies

Evgeniy Dul’kin1 , Antoni Kania2 and Michael Roth1

1
Department of Applied Physics, The Hebrew University of Jerusalem - Jerusalem 91904, Israel
2
A. Chelkowski Institute of Physics, University of Silesia in Katowice - 41-500 Chorzow, Poland

received 7 January 2021; accepted in final form 25 February 2021

published online 11 May 2021
PACS 77.80.Jk – Relaxor ferroelectrics
PACS 77.80.B- – Phase transitions and Curie point
PACS 43.40.Le – Techniques for nondestructive evaluation and monitoring, acoustic emission

Abstract – (1 − x)PbMg1/3 Nb2/3 O3 -xPbTiO3 , [100]-oriented relaxor ferroelectric crystals were

studied by means of dielectric and acoustic emission methods in a temperature range up to 200 ◦ C
and under a dc bias electric field up to 1.2 kV/cm. The monoclinic-tetragonal and tetragonal-
cubic ferroelectric phase transitions were successfully detected by both experimental methods.
The bias electric field dependence of the temperature of a dielectric constant maximum, related to
tetragonal-cubic phase transitions, exhibits a V-shape effect with a threshold field of 0.5 kV/cm.
In contrast, the bias electric field dependence of the temperature of a monoclinic-tetragonal phase
transition exhibits no V-shape effect but points out a tricritical point at 0.7 kV/cm. These results
have not confirmed the existence of the critical end point in the crystals under studies.

c 2021 EPLA
Copyright 

Introduction. – After being discovered in 1954 by
Smolenskii and co-workers, Pb-based PbB′1−x B′′x O3 per-
ovskite relaxor ferroelectrics (RFEs) have been the ob-
jects of scrupulous and intensive studies. In contrast
to ordered ferroelectrics (FEs), they are characterized
by fundamental intrinsic chemical disorder in the B-sites
ions of different valence, which is responsible for their
unique physical properties and, consequently, extremely
wide range of applications [1]. Such a chemical disorder
is known to be a reason to give rise to quenched random
electric fields [2], which in turn is a reason of nucleation
of polar nanoregions (PNRs) [3]. It is well documented
that in the case of canonical RFEs the PNRs nucleate be-
low the high-lying Burns temperature, start to grow below
intermediate temperature, provide a huge, smeared and
frequency-dependent maximum of the dielectric constant,
ε, at temperature Tm [4–6], and freeze below a glass tem-
perature, Tg [6], into a mesoscopic dipolar glass ground
state [7], as the temperature decreases. While, in the
case of non-canonical RFEs with FEs doping, the freez-
ing temperature is replaced by the Curie temperature, Tc ,
of a spontaneous FE phase transition, as the temperature
decreases [1,6].
During the last decade two effects, resulting from the
application of a bias electric field, E, to RFEs, have been
revealed.
The first effect consists in the non-trivial behavior of
Tm in dependence on E and is called the V-shape effect,
i.e., initially the Tm remains constant or slightly increases,
then decreases and attains the minimum (turning point)
at some small threshold field, Eth , and then increases as
happens in normal FEs with a 2nd-order phase transi-
tion, as E is enhanced [8]. The V-shape effect is observed
in PbMg1/3 Nb2/3 O3 -xPbTiO3 (PMN-xPT) single crystals
with different orientations [8–10], and is concluded to be
the result of the competition between both the random
fields and E when affecting the PNRs [8].
The second effect consists in the existence of a critical
end point (CEP) of liquid-vapor type, where a piezomod-
ulus reaches the maximum, above which the supercriti-
cal behavior starts. It differs from the tricritical point
(TCP), in which a line of 1st-order phase transition meets
a line of 2nd-order one in the E -T phase diagram of the
PMN-0.295PT [111]-oriented crystals [11]. An existence
of such the CEP is explained due to the coincidence of
both low-temperature rhombohedral phase and direction

67001-p1
Evgeniy Dul’kin et al.
of E, resulting in the merging the low-temperature rhom-
bohedral and the high-temperature cubic phases with-
out a boundary in the [111]-oriented crystals, whereas
in crystals of another orientations several intermediate
boundaries are shown to exist and the CEP would not
be expected to observe [12]. While the CEP is observed
only in pure PMN, the [111]-oriented crystals [12,13], no
CEP is observed in both [110]- and [100]-oriented ones
in the vicinity of the turning points of Tm and the TCP
is not attained [14]. However, later it is shown that the
CEP (referred to as CP) presumably exists in the vicin-
ity of the turning point of Tm in PMN-x PT (x = 0.00,
0.06, 0.13, and 0.24), [100]-oriented crystals [15], based
on the observation of a piezomodulus maximum similar
to that observed in PMN-0.295PT, [111]-oriented crys-
tals [11,12]. This assumption is then discussed based
on the observation of a pyroelectric current maximum in
PMN-0.2PT, [100]-oriented crystals, pointing out the CEP
(referred to as CP) in the vicinity of the turning point of
Tm , where a Widom-like line presumably begins instead
of the 2nd-order FE transition [16]. It is worth stress-
ing that no word concerning the existence of the TCP in
PMN-x PT, [100]-oriented crystals is said.
Along with both piezoelectric and pyroelectric data the
CEP is detected using an acoustic emission technique (AE)
in PMN-0.3PT, [001]-oriented crystals [10]. A justifica-
tion for the application of AE to detect the CEP is caused
by an approximately proportional correspondence between
the strains and its count rate values [17–19]. It is worth
noting that all the CEPs, determined in PMN-x PT crys-
tals by a maximum of piezomodulus [15], pyrocurrent [16],
and AE [10], are localized around the turning point of Tm .
Over the past decade AE has proven itself to be a very re-
liable method to detect all the phase transitions and char-
acteristic points [20–22], as well as their behaviors under
a bias electric field in some Pb-based RFEs [10,22].
Based on our experience of detecting the phase transi-
tions and characteristic points in RFEs we have applied an
AE method to study the 0.70PMN–0.30PT, [100]-oriented
crystals.
Experiment. – Single crystals of 0.70PMN-
0.30PT, [100]-oriented, were grown by the flux method.
The PbO–Pb3 O4 –B2 O3 system was used as the sol-
vent [23,24]. The AE technique is described in great
detail elsewhere [10]. A crystal plate with gold contacts is
pasted with a silver epoxy to the polished side of a fused
silica acoustic rod waveguide. A PZT-19 disk piezoelectric
sensor is attached to the rear end of the waveguide. The
sensor is electrically coupled to a 500 kHz band-pass low
noise variable (up to 40 dB) preamplifier connected to a
detector-amplifier (40 dB). A chromel-alumel thermocou-
ple junction is glued to the waveguide near the crystal.
The higher part of the acoustic waveguide with the pasted
sample is mounted in a resistance element tube furnace.
The dielectric data are measured using a HP4263A LCR
meter wired to the sample. The thermocouple, amplifier,
67001-p2
Fig. 1: Plot of both the real part of a dielectric constant, ε′ ,
and the AE count rate, Ṅ , in dependence on temperature, T,
in the absence of applied bias field, E (filled signs —heating;
empty signs —cooling).
and LCR meter outputs are interfaced with a PC for cou-
pled readout. The measurement of both real part ε′ of
the dielectric constant and the AE count rate Ṅ (s−1 ) are
performed with the frequency of 100 Hz in the tempera-
ture range 100–300 ◦C with a rate of about 1–3 ◦ C/min.
When measuring the AE count rate Ṅ under a bias elec-
tric field, a high voltage supply is wired to the crystal and
the data are recorded by a fixed steps of 0.1 kV/cm and
up to 1.2 kV/cm of the applied bias field, E, during the
thermal cycling.
Before each cycle the crystals are annealed at tempera-
ture of 200 ◦C for 15 min and then measurements of both
dielectric and AE data during cooling and heating under
bias electric field, E (field heating after field cooling regime
(FHaFC)), are performed.
Results and discussion. – Figure 1 presents both real
part of the dielectric constant, ε′ , and the AE count rate,
Ṅ , data in dependence on temperature, T, and in the
absence of applied bias field, E. The dielectric constant
exhibits two anomalies: low temperature, corresponding
to the monoclinic-tetragonal phase transition, Tmt ; and
high temperature, corresponding to the tetragonal-cubic
phase transition, Ttc , in Tm , similar to that observed in
PMN-0.33PT, [001]-oriented crystals [10]. The latter ex-
hibits a smeared maximum with ε′ ≈ 5.2 · 104 on cooling
and a smeared maximum with ε′ ≈ 4.6 · 104 on heating.
These data are in good agreement with those observed in
ref. [23].
The sharp pronounced bursts of AE point out the tem-
perature of Tmt ≈ 102 ◦ C in the FC regime and ≈112 ◦ C
in the FH regime, Tm ≈ 124 ◦ C in the FC regime and
≈130 ◦ C in the FH regime, i.e., AE clearly distinguishes
both these temperatures due to essentially the difference
in their count rates: Ṅ ≈ 40–64 s−1 and 20–10 s−1 , re-
spectively. The temperature hystereses of both Tmt and
Tm are equal to 10 ◦ C and 6 ◦ C, respectively, intrinsic for
1st-order phase transitions.
 On the question of the critical end point in (1 − x)PbMg1/3 Nb2/3 O3 -xPbTiO3
Fig. 2: Plot of both the monoclinic-tetragonal ferroelectric
phase transition temperature, Tmt (circle signs), and the di-
electric constant maximum temperature, Tm (square signs), in
dependence on applied bias field E (filled signs —FH regime;
empty signs —FC regime).
Figure 2 presents both Tmt and Tm , detected by means
of AE, in dependence on bias electric field, E. Tm exhibits
a clearly seen V-shape effect, characteristic for PMN-
x PT crystals [8–10]. Initially the Tm slightly increases
in the vicinity of E by approximately 0.2 kV/cm, then de-
creases. It attains the turning point at Eth ≈ 0.5 kV/cm
and then increases again, as E is enhanced. Its temper-
ature hysteresis gradually reduces, as E is enhanced, and
it practically vanishes at Eth . Note that Eth is found to
be approximately the same as that in PMN-0.33PT, [001]-
oriented crystals [10].
Besides, a main result of this paper is that Tmt does not
exhibit V-shape effect and its thermal hysteresis reduces
gradually up to Eth , but does not vanish, as is shown
in fig. 2(a), obtained by means of pyroelectric current in
ref. [16], and continues up to E ≈ 0.7 kV/cm, above which
it vanishes and the Tmt (E) dependence looks a single line,
i.e., the turning point of Tm does not coincide with the
hysteresis vanishing point. Such corrected data became
possible to obtain thanks to sharper bursts of Ṅ of AE in
contrast to smeared both dielectric [15], and pyrocurrent
curves [16]. A hysteresis vanishing point is known to occur
at a TCP, where a 1st-order phase transition line meets a
2nd-order phase transition line, and, consequently, Etcp ≈
0.7 kV/cm. This data resembles that observed in pure
PMN, [100]-oriented crystals in fig. 7(c) in ref. [14]: a
thermal hysteresis reduces at Eth ≈ 5 kV/cm (not marked
there) corresponding to a turning point of Tm , but a TCP
is not attained.
Figure 3 presents both Tm and Ṅmt , corresponding to
the FH regime, in dependence on bias electric field, E.
Ṅmt gradually increases and exhibits a smeared maxi-
mum toward the E tcp and then steeply decreases, as E
is enhanced, due to minimization of strain when occurring
a 2nd-order phase transition. This maximum of Ṅmt
67001-p3
Fig. 3: Plot of both the dielectric constant maximum temper-
ature, Tm , and the AE count rate of the monoclinic-tetragonal
ferroelectric phase transition, Ṅmt , in dependence on applied
bias field, E, in the FH regime.
means a large strain, which in turn is proportional to the
piezomodulus, d31 , maximum in the vicinity of the turn-
ing point of Tm , measured in PMN-x PT, [100]-oriented
crystals [15].
It is clearly seen that the Ṅmt (E) dependence in
fig. 3 similar to both d 31 [15], and pyroelectric coefficient
γm (E) dependence in PMN-0.2PT, [100]-oriented crys-
tals in fig. 2(b) [16]. Both d31 and γm exhibit a maxi-
mum in the vicinity of the turning point of Tm and then
steeply decrease, presumably manifesting a beginning of a
Widom-like line (the continuation of the 1st-order phase
transition line above the CEP [11,12]) [16]. On the other
hand, the γm (E) dependence in fig. 2(b) [16], is similar
that obtained in pure BaTiO3 crystals in fig. 8 of ref. [25].
γm exhibits also a maximum and then steeply decreases
toward the TCP, where a 1st-order phase transition meets
a 2nd-order one, as E is enhanced. Such similarity of
both γm (E) dependencies led us to the conclusion that
a reason of both γm and d33 decrease is the existence of
the TCP instead of the CEP in PMN-x PT, [100]-oriented
crystals [15,16], and, consequently, no CEP is believed to
exist in [100]-oriented crystals, at least.
Conclusions. – In summary, we have studied the
0.70PbMg1/3Nb2/3 O3 –0.30PbTiO3, [100]-oriented relaxor
ferroelectric single crystals by means of dielectric and
acoustic emission techniques under dc bias electric field.
Based on acoustic emission count rate data in dependence
on bias electric field we have concluded that in the studied
crystals the critical end point does not exist, whereas the
existence of the tricritical point is confirmed.
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