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A critical review: the impact of electrical poling

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on the longitudinal piezoelectric strain coefficient

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Cite this: Mater. Adv., 2022,

3, 8886
Sanskruti Smaranika Dani,a Alekhika Tripathy,a Nagamalleswara Rao Alluri,bc
Saravanakumar Balasubramaniama and Ananthakumar Ramadoss *ad

Piezoelectric materials play an essential role in the advancement of micro- and nanoelectronics
equipment. The piezoelectric properties of the materials rely upon the degree of polarization that results
from the poling mechanism. The present study put forward the improvement of piezoelectric
performance by optimizing the poling parameters in piezoelectric materials. Microstructural optimization
of flexible piezoelectric-based material is one possible technique to improve the electrical responses of
the piezoelectric nanogenerator. In particular, the correlation between the poling conditions and the
longitudinal figure of merit (d33) of various materials (lead-based, lead-free and polymers and their
composites) provides an effective analysis to supplement the available literature. This report examines
the latest research progress in different poling techniques and their consequences for achieving the
Received 19th May 2022, required beta-phase of a polyvinylidene fluoride (PVDF) film with a higher electrical output. Finally, novel
Accepted 2nd September 2022 poling techniques, the current challenges, and prospects are highlighted and critically discussed,
DOI: 10.1039/d2ma00559j currently which is relatively untouched research field for the scientific community. We believe that this
review affords systematic guidelines for poling techniques that can significantly contribute to
rsc.li/materials-advances subsequent piezoelectric nanogenerator (PENG) research.

a
Laboratory for Advanced Research in Polymeric Materials (LARPM), School for Advanced Research in Petrochemicals (SARP), Central Institute of Petrochemicals
Engineering & Technology (CIPET), Patia, Bhubaneswar-751024, Odisha, India. E-mail: [email protected]; Fax: +91-674-2740463; Tel: +91-674-2740173
b
Materials Research and Technology Department, Luxembourg Institute of Science and Technology, 41 rue du Brill, L-4422 Belvaux, Luxembourg
c
Inter-Institutional Research Group Uni.lu-LIST on Ferroic Materials, 41 rue du Brill, L-4422 Belvaux, Luxembourg
d
School for Advanced Research in Polymers: Advanced Research School for Technology & Product Simulation, Central Institute of Petrochemicals Engineering & Technology,
Guindy, Chennai-600032, India

Sanskruti Smaranika Dani received Alekhika Tripathy received her

her MSc Degree in Physics from MSc Degree in Physics from North
Veer Surendra Sai University of Orissa University. She is currently
Technology, Burla. She is a a PhD scholar at the Laboratory for
research scholar at the Laboratory Advanced Research in Polymeric
for Advanced Research in Polymeric Materials (LARPM), Central Insti-
Materials (LARPM), Central Insti- tute of Petrochemicals Engineer-
tute of Petrochemicals Engineer- ing and Technology (CIPET),
ing and Technology (CIPET), Bhubaneswar, Odisha, India. She
Bhubaneswar, Odisha, India. She is enrolled as a PhD candidate in
has worked as a project assistant the Department of Physics, Utkal
at the Institute of Physics, University, Bhubaneswar, Odisha,
Sanskruti Smaranika Dani Bhubaneswar. Her research Alekhika Tripathy India. She has worked as a project
interests include the synthesis of assistant at the Institute of Physics,
lead-free ceramic nanoparticles and composites for piezoelectric Bhubaneswar. Her research interests include the synthesis of lead-free
energy-harvesting applications. ceramic nanoparticles and composites for piezoelectric and
flexoelectric energy-harvesting applications. Her research interests
also lie in the broad areas of energy-storage devices (supercapacitors).

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1. Introduction poling parameters7,8 is one of the most beneficial and reason-

able methods from a practical application perspective. Crystal-
With the growing utilization of high-performance piezoelectric line phase of material with noncentrosymmetric property,
materials, researchers are continuously trying to improve poling procedures are thought to be strongly related to the
device activity in a variety of ways such as changing the piezo- piezoelectric, ferroelectric effects. Moreover, enhancement of
electric properties,1,2 adjusting the device configuration,3 and the piezoelectric properties, primarily the longitudinal piezo-
utilizing electrical networks for energy storage and harves- electric strain coefficient (d33), by adjusting the poling para-
ting.4,5 In addition, scientists have continued to improve the meters is a vast area of interest.9,10 Perovskite single crystals
piezoelectric performance by modifying the chemical configu- (piezoelectric/ferroelectric) have no polarization tendency until
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ration, crystallographic direction, and domain engineering.6 the domain alignment is switched through the poling technique.
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Not withstanding all of the techniques, optimization of the The influence of ferroelectric poling on the material response is
initially explored to investigate the d33 rate of soft lead zirconate
titanate (PZT), via optimizing the poling conditions.
The most feasible way to achieve stable polarization is to
Nagamalleswara Rao Alluri is a minimize exposure of the polar dielectric near to the curie
Research and Technology Asso- temperature (Tc), poled greater than the coercive field. For few
ciate in the Ferroic Materials compositions (PLZT, (Bi0.5Na0.5)TiO3-BaTiO3, P4bm phase), the
for Transducers Group, Nano- poling field below the coercive field.11,12,29 This is because
materials & Nanotechnology excessive poling (strong field) for a long duration tends to
Unit, Materials Research and over-pole the sample. This may cause electrical breakdown
Technology Department (MRT) and physical imperfections like cracks and pores in the speci-
at Luxembourg Institute of men, resulting in loss of the electrical characteristics. Mechan-
Science and Technology (LIST). ical stress and electric fields facilitate the ferroelastic and
He worked as an Academic ferroelectric transition, respectively, which successfully pole
Research Professor, Postdoctoral the systems at low electric fields with minimal built-in offset
Researcher, NMSL laboratory, polarisation for electromechanical poling.13 Long-term poling
Nagamalleswara Rao Alluri Jeju National University (JNU), can result in a biased electric field and offset polarisation in
South Korea. He received his samples, owing to the entrapment of mobile charge carriers
PhD from the School of Applied Energy Systems, Mechanical across the grains and at grain–grain interfaces.14
Engineering, JNU, Korea. He is a recipient of the BK21+ To generate piezoelectric behaviour in piezoelectric materials,
Education Minister Award and the Sponsored Research Project the poling procedure is very important.15 In a normal situation,
(as a PI) from the Korean government. His research interests the piezoelectric material is formed of tiny electric dipoles with
include the the growth of piezoelectric and ferroelectric thin random arrangements, resulting in a total dipole moment of zero.
films, nanogenerators and self-powered sensors. By applying mechanical pressure, structural deformation occurs,

Saravanakumar Balasubramaniam Ananthakumar Ramadoss is a

is working as a Jr. Scientist at Scientist (Jr) at the Advanced
the Laboratory for Advanced Research School for Technology
Research in Polymeric Materials & Product Simulation (ARSTPS),
(LARPM), Central Institute Central Institute of Petrochemical
of Petrochemicals Engineering Engineering and Technology
and Technology (CIPET), (CIPET), Chennai, India. He
Bhubaneswar, Odisha, India. He received his PhD degree in
received his doctoral degree in Mechanical Engineering from
Energy Harvesting using Piezo- Jeju National University, South
electric and Triboelectric Nano- Korea. He was a Scientist (Jr) at
generators from Jeju National CIPET: SARP-LARPM, Bhubanes-
Saravanakumar University, South Korea. His Ananthakumar Ramadoss war, Alexander Von Humboldt
Balasubramaniam research interests include the Postdoctoral Fellow at the
development of new materials University of Konstanz, Germany, a Postdoctoral fellow at the
and fabrication techniques for energy-harvesting applications and KAIST, Korea, and a Research Fellow at the CSIR-CECRI, India.
the development of new types of self-powered devices. Similarly, he His research interests mainly focus on developing nanostructured
is working in energy-storage devices such as supercapacitors, and materials and their applications in supercapacitors, nano-
batteries in the aspects of electrode material development and generators, self-powered systems, thin films, corrosion protection
electrolytes for aqueous-based devices. and bio-implant applications.

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and the material will exhibit very little polarization and thus longitudinal piezoelectric strain coefficients for polycrystalline
minimal piezoelectric output. For a better performance of the materials based on theoretical models were 407, 320, and
piezoelectric material-based devices, dipoles need to be aligned 697 pC N1, respectively.25–28 However, the experimental values
in a particular field direction. The process of inducing dipoles of the longitudinal coefficient are greater than those of the
to align in a specific direction is recognized as the poling theoretical model.29 In general, the d33 value is double that of
process. Domain switching or polarization is achieved using the d31 value; therefore, in d33 mode the device generates a
different poling techniques, mainly through the application of higher performance. On the other hand, electrode distance
a strong electric field, such as in direct-current electrical poling constraints limit the output voltage of the device in d31 mode.
(DC poling), alternating-current poling (AC poling), or corona- Contrary to this, in d33 mode, the sample displays an inferior
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discharge methods.16,17 During the poling process, domain capacitance, and the voltage output may be regulated by
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alignment takes place in the field direction, resulting in a huge modifying the electrode arrangement. Whereas the higher
net polarisation and the capture of mobile free charge carriers shear strain coefficient value is observed but quite typical to
(oxygen vacancies). This results in a more stable structure with achieve it.30,31 Abundant research has been carried out based
fewer local heterogeneities. At the end of the poling process, on fabrication and configuration procedures for device perfor-
cations may serve as defect centres for the reduction of trapped mance in the d33 mode.32,33 In particular, for the commercial
free charge carriers, which contributes to a well-saturated poling process, there is a primary concern with d33 in the view
polarization–electric field (P–E) loop. The optimal poling para- of the device performance.23 A comprehensive examination of
meters of various piezoelectric materials are thoroughly inves- the impact of the poling parameters on the d33 values could
tigated by the researchers across the globe and used as a enable the more accurate adjustment of d33 and other poling-
powerful, essential tool for enlightening the intrinsic piezo- influenced features.
electric behaviour of material.18 For instance, a higher d33 value This review covers the importance of the poling process and
of B630 pC N1 is obtained in barium zirconium titanate– the theory behind it, as well as different kinds of poling
barium calcium titanate (0.5Ba(Zr0.2Ti0.8)O3–0.5(Ba0.7Ca0.3)- technique, discusses the various factors that affect the poling
TiO3) ceramics via optimizing the poling-condition states like process, analyses the variation of d33 values for both PZT-based
the poling field and temperature.7 In addition, the d33 value of and lead-free barium titanate (BT), bismuth sodium titanate
potassium sodium niobate–lithium niobate (0.93(K0.5Na0.5)- (BNT), and potassium sodium niobate (KNN) based piezo-
NbO3–0.07LiNbO3) ceramics was improved from 210 to electric materials, polymers and composites for the poling
274 pC N1 through the selection of a preferable poling process, and the increased values of d33 due to different poling
temperature8 (nearer to the phase-transition temperature). conditions, which in turn improve the yield of piezoelectric
By summarizing the above facts and theory, it can be resolved nanogenerators (PENGs). The purpose of this study is to gain a
that targeting the optimum poling conditions is the most deeper comprehension of the poling process and its impact
successful approach for enhancing the piezoelectricity. on the electrical properties for creating superior engineered
The fundamental mechanism of piezoelectricity is the trans- materials. The electromechanical behaviour of the material
formation of mechanical strain into electrical energy which is dramatically changes in accordance with the poling circum-
interconnected through piezoelectric strain coefficients. The stances. These findings put forward new ways of developing
effectiveness and efficiency of piezoelectric-material-based materials and technologies that have a greater capacity, perfor-
devices are largely dependent on the different piezoelectric mance, and lower deterioration due to electrical fields and
strain coefficients: d15, d31, and d33, which are the shear, mechanical stress. The possible microstructural roots of this
transverse, and longitudinal piezoelectric strain coefficients, type of behaviour are also examined.
respectively. The majority of investigations have found that the
mechanism of action for piezoelectric materials is the trans-
verse (d31) mode.19–21 In contrast to the transverse mode, other 2. Piezoelectricity and polarization
piezoelectric strain coefficients such as the shear (d15) and process
longitudinal (d33) coefficients have been investigated to
improve the output performance. A detailed study has been Piezoelectricity was initially revealed by the Curie brothers,
performed by Caliò et al.22 to observe the influence of these Jacques and Pierre, in the year 1880, by experimenting on
three operating modes on the device performance basis. It has natural crystal-like quartz.34 The prefix ‘piezo’ is taken from
been proved that the poling direction in d33 and d31 is the same, Greek name ‘piezein’, which means to press, so piezoelectricity
but the strain is generated in two separate directions. On the is the process of generating electric charge via the application
other hand, in d15, the poling process can be performed across of pressure onto such materials. A non-centrosymmetric mate-
the length of the element. Due to this variation in the piezo- rial has no points of inversion, and this is the main require-
electric stain coefficient values, noticeable changes are observed ment of a piezoelectric material. So, the phenomenon of the
in the output values during application.23,24 Based on the piezoelectric effect is shown only by non-centrosymmetric
functionality of these three modes (d31, d33 and d15) a compara- materials. These materials have an outstanding beauty because
tive study has been carried out by the researchers.23 Kiran et al. of their inherent properties of electric polarization, which occur
found that the maximum values of the shear, transverse, and via the application of applied stress, and, simultaneously, they

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 Inorganic nanoparticles–polymer composites, such as

polyimides–PZT, cellulose–BaTiO3, polyvinylidene fluoride–zinc
oxide (PVDF–ZnO), etc.

3. Effect of poling and piezoelectric

strain coefficients
Piezoelectric polycrystalline materials have anisotropic pro-
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perties, so their electromechanical properties differ along the

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Fig. 1 Direct and reverse piezoelectric effect. direction of excitation. These materials are composed of tiny
crystallites, and each crystallite again consists of microscopic
regions that have dipole orientations in the same direction,
can also generate an induced strain via the application of an
called ‘domains’, and they are typically created to reduce the
electric field, which is known as reverse piezoelectricity.35
system’s free energy. A domain wall is a boundary between two
Direct piezoelectricity is used in sensing devices, whereas the
domains. But each domain in the crystallite has different
reverse piezoelectric effect can be employed in actuators. Fig. 1
arrangements of dipoles from each other. So, the overall effect
shows the mechanisms of the direct and reverse piezoelectric
of randomly oriented dipoles cancels out, and the material is
effects.
depolarized. For polarization of a material, it is therefore
These two effects (the direct and reverse piezoelectric effects)
important to arrange the dipoles more or less in a particular
are expressed in terms of two equations as given below:36
path. This is achieved via the poling procedure, and the track
Si = SEijTj + dkiEk (1) along which all the dipoles are aligned is known as the poling
direction. For initiation of the poling process for any piezo-
electric material, a higher electric field is essential along with a
Di = eTikEk + dijTj (2) suitable temperature for alignment of the randomly oriented
dipoles that creates permanent polarization. Fig. 2A shows the
In eqn (1) and (2), the subscripts i, j, and k36 denote the randomly oriented dipoles before poling, the aligned dipoles
three-dimensional magnitudes. T and S are the tensors of stress after poling and the nearly aligned dipoles after the field has
and strain, respectively, that are generated by electromechani- been removed. Once the material is polarized, it cannot be
cal effects. E and D represent the applied electric field and the depolarized until a reverse field is applied. After the poling
electric displacement vector, respectively. The parameter d is process, the dipoles are nearly aligned. At zero field, most of the
the piezoelectric strain coefficient; SE is the elastic compliance dipoles conserve their aligned configuration, so the material is
estimate at a fixed electric field (E) and eT is the dielectric permanently polarized, and this state of a nearly aligned
constant or relative permittivity.36 The coefficients of piezo- process is called remanent polarization (Pr).37 Fig. 2B describes
electricity are represented with double subscripts (for example, the P–E hysteresis loop due to the polarization of ferroelectric
d33), where the 1st subscript denotes the produced charge or the materials. It has been observed that a lower value of remanent
electrical field of the supplied voltage, and the 2nd subscript polarization demands an improved energy-storage capacity.38
denotes the strain/mechanical stress direction. During the polarization process of a material, deformation
Ferroelectrics belong to a subclass of piezoelectric materials takes place permanently and the deformation (elongation or
that display spontaneous polarization because of their inherent compression) depends on the poling direction. Mechanical
non-centrosymmetric configuration. Permanent electric dipoles stress (tension or compression) is responsible for the change
are responsible for spontaneous polarization in ferroelectric in dipole positions in the piezoelectric materials that leads to
materials. These materials are included in the class of polar generation of positive (+ve) and negative (ve) surface charges
piezoelectrics, for example, PVDF, polarized PZT, polyvinylidene across the top or bottom of the material. Fig. 2C explains the
fluoride-trifluoroethylene (P(VDF-TrFE)), barium titanate (BaTiO3), direct and converse piezoelectric effect. If stress is applied
etc. Thus, all ferroelectrics are piezoelectric, although the reverse along the poling-voltage direction, compression occurs and
is incorrect. the sample becomes broader (towards the diameter) creating
Some examples of piezoelectric materials are provided here: a voltage of equal polarity to that of the poling voltage
 Naturally available piezoelectric materials are cellulose, (Fig. 2C(a)). On the other hand, elongation along the poling-
human bone, tendon, collagen, etc. voltage direction generates an opposite polarity voltage com-
 Naturally occurring piezoelectric crystals are Rochelle’s pared with the poling voltage (Fig. 2C(b)). This is the direct
salt (NaKC4H4O64H2O), topaz, quartz (SiO2), etc. piezoelectric effect, which converts mechanical stress into
 Ceramics, such as potassium niobate (KNbO3), BaTiO3, electrical energy, and the device can be used as a sensor.40
PZT, bismuth ferrite (BiFeO3), etc. The sample extends lengthwise and shrinks towards its
 Polymers, such as cellulose and derivatives, polylactic acid diameter if the applied voltage direction is along its poling
(PLA), and PVDF. direction (Fig. 2C(c)). On the other hand, if an opposite polarity

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Fig. 2 (A) Domain alignment mechanisms before, during, and after the poling process; reproduced with consent from ref. 39. Copyright 2021, Springer
Nature. (B) Polarisation–electric field hysteresis curve, and (C) piezoelectric material work as a sensor and actuator in various fields.

voltage is applied in the poling direction, then the material will material, can be denoted by the maximal stress or strain:36
be deformed, becoming shorter and wider (Fig. 2C(d)). When
1 1 T2
the device is exposed to an alternating voltage, then expansion W ¼ ST V ¼ V: (3)
2 2Y
and compression take place in the material periodically with
reference to the applied voltage frequency. In this mode the In eqn (3), V is the volume, Y is the Young’s modulus, and S and
piezoelectric specimen acts as an actuator,41 i.e., the electrical T are strain and stress tensors, respectively. The applied stress
energy is transferred into mechanical energy. Thus, the amount on the piezoelectric material produces electrical energy (Ep) as
of voltage or stress produced in a sensor or actuator device is given by36
directly proportional to the intrinsic properties of the piezo- 1 1dss 2 S2 2
electric material and the direction of the applied force/voltage EP ¼ DEV ¼ Y V: (4)
2 2 e
during the poling process. The initial polarisation will be
In eqn (4) E and D are vectors of the electric and displacement
damaged if too high a voltage is applied in the depoling
fields, respectively. Again, the electromechanical coupling fac-
direction (partially or fully depolarized). Alternatively, the elec-
tor (k (eqn (5))) (the efficiency of energy conversion) that is given
tric dipoles could be partially or entirely flipped 1801, triggering
using eqn (3) and (4) is
the specimen to depole in the opposite direction. The coercive
field is the highest depoling field that a material is able to Ep dss 2
k2 ¼ ¼Y : (5)
endure before depolarization. W e
Under operational conditions, piezoelectric materials are
For energy-harvesting applications, the piezoelectric mate-
adjusted in such a manner that anyone piezoelectric coefficient
rial will be chosen in such a manner that the material exhibits
(d15/d31/d33) will dominate the yield of the device. As mentioned
the highest d33 constant, which will impart the maximum
in the Introduction, the d33 mode (stress and voltage act in the
energy-conversion efficiency.
‘3’ direction) is practically more favourable compared with
other modes d31 and d15, indicating that the poling orientation
is always in the 3 direction. Materials that are easily distorted to 4. Poling and ferroelectric hysteresis
create greater strains and have substantial electromechanical loop
coupling coefficients are ideal for energy-harvesting applications.
Furthermore, energy-harvesting devices based on human mechan- Ferroelectric domain-wall switching via the poling process is
ical movement require low-frequency operation conditions the most important phenomenon in ferroelectrics, which
(B1 Hz), like breathing, walking or other body movements. occurs because of the application of an electric field E.42,43
In this process, the elastic energy (W), which is conserved in the This domain-wall switching is responsible for the formation of

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Fig. 3 (A) Polarization process of ferroelectric materials: (a) schematic of the polarization–electric field (P–E) hysteresis loop; and (b) and (c) represent
the ferroelectric strain–electric field (S–E) butterfly hysteresis loop of the Pb(Zr0.45Ti0.55)O3 film; reproduced with the permission from.46 Copyright, 2005
Elsevier. (B) S–E butterfly loop of PZT (PbZr1xTixO3) thin films for different doping concentrations x = 0.47, 0.49, and 0.50 with different plane
orientations: (a) PZT47 (100), PZT49(100), PZT50(100), (b) PZT47(110), PZT47(100), Pt (111), and (c) PZT47 (110); reproduced with permission from ref. 47.
Copyright 2017, AIP publisher.

the ferroelectric hysteresis loop shown in Fig. 3A(a). In ferro- In contrast to the P–E loop, domain switching by polariza-
electric materials when a small amount of AC electric field is tion leads to the strain–electric field (S–E) hysteresis loop,
applied, the polarization (P) rises in proportion to E as per the which is also known as the butterfly loop due to its butterfly-
relation Pi = wijEj, which corresponds to the AB section of the like configuration. This S–E loop is mainly created because of
loop. In this section, E is not strong enough for the increment the converse piezo effect, domain switching, and domain-wall
of the AB part. A further increase in E forces a switch of the movement. Fig. 3A(b, c) represents the symmetric diagram of
domains in the applied E direction, and as a result a sharp the S–E butterfly loop. In the S–E loop at point A, the induced
increase in polarization occurs (BC segment). Finally, at strain is zero when the applied electric field is zero. By applying
point C, all domains are aligned and the ferroelectric reverts a strong E along the spontaneous polarization direction, the
to a linear dielectric, as represented by the segment CD. When material expands due to the generation of stress and traces the
the field is weakened, some of the domains are switched back, strain path ABC as per the equation:44,45
but some polarization still exists in the absence of E (PR, i.e.,
Sjk = dijkEi (6)
the remanent polarization region). In order to regain the
depolarization state, a reverse E is needed (point F). For zero- where dijk and Sjk are the piezoelectric strain coefficient and the
polarization, E must be reversed at point F. An additional rise of strain–field, respectively. At point C, maximum expansion
the reverse E leads to a new arrangement of the dipoles, leading occurs (parallel to Ps) after which the E tends to decrease and
to the saturation region (point G). To complete the cycle, E has the strain curve follows the same path but in a reverse direction
to be reversed and diminished. The coercive electric field, from C to A. After reaching point A, the strain becomes zero
abbreviated as Ec, is the field required to achieve a zero- again. E deviates its path and is no longer parallel to Ps. With an
polarization state. For most ferroelectric ceramics and crystals, increase in E of opposite polarity (the negative direction), the
the magnitude of Ec is in the range of 10–100 kV cm1. For an material continues to contract at point A in accordance with
ideal hysteresis loop (P–E), both the positive–negative coercive eqn (6). The E is strong enough at point D to switch the
field and the remanent polarization must be identical. polarization direction, and after completion of this switching

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mechanism at point E, the strain again becomes positive. and bottom metal electrodes on piezoelectric material. Alter-
A further increment of E in the negative direction increases natively, the piezoelectric sample is mechanically sandwiched
the strain up to point F, and then returns to point A because a between the top and bottom copper (or aluminium) foil/tape
decrement in E takes place in relation to eqn (6). Polarization electrodes or brush coating of conductive silver paste on
reversal and an abrupt variation of the strain occurs at point G. top and bottom of piezoelectric sample. A very close contact
Ideally, this repetition process gives rise to a beautiful butterfly between the electrodes and the piezoelectric material is needed
linear strain–electric field (S–E) loop, suggesting that the strain to enhance the polarization of the diploes. For thermal
is completely piezoelectric in nature excluding the D and G excitation, the material should be heated using a hot plate.
switching points. From this S–E butterfly loop, we can easily Temperature is the primary factor in the poling process, and a
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obtain the piezoelectric strain coefficient ‘d’ using eqn (6), preferable temperature will be very effective for enhancing
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which is thermodynamically similar for both direct and con- the piezoelectric strain coefficient (d33). Electrode poling is
verse piezoelectric effects. In fact, the S–E butterfly loop is commonly carried out using an isolating medium, such as a
much more complex, as illustrated for a PZT thin film46 in silicone oil bath/inert atmosphere, to insulate the material
Fig. 3A(c) and 3B(a–c). from excessive electric discharge, which also helps to maintain
Cornelius et al. explained the polarization response of the a constant temperature. So, the initial step is to immerse
P–E hysteresis loop, and the S–E butterfly loop of self-poled PZT the electrodes in the oil bath and gradually increase the
thin films deposited on Pt/TiO2/SiO2/Si substrates.47 d33 was temperature near to the Curie point of the material as specified;
obtained from the butterfly curves as shown in Fig. 3(B). It was this is because above the Curie temperature the activity of the
observed that the effective piezoelectric strain coefficient material will be degraded (d33 value decreases). Furthermore,
(d33,eff) varied with the substrate used for the same field the DC voltage is gradually increased until the electric field
(E = 119 kV cm1). For the positive field E+ = 119 kV cm1, (5–1000 kV cm1)48,51–53 across the sample matches the indi-
the values of d33 are 137, 180, and 140 pm V1, and for the cated saturation polarisation values. This voltage is maintained
negative field (119 kV cm1) the d33 values are 164, 189, and for a brief time period. The sample is then cooled to room
223 pm V1 along the100 direction for the PZT (PbZr1xTixO3) temperature slowly under a constant E, and the high voltage
composition (x = 0.47, 0.49, and 0.50), respectively. source is finally turned off. Subsequently, the d33 value of the
poled sample is analysed using a piezometer. Fig. 4(a) shows
the DC electrode poling technique of the sample.
5. Poling techniques
There are different methods of poling, such as (i) DC electrode 5.2. Corona discharge poling
poling, (ii) corona discharge poling, and (iii) AC electrode The traditional DC technique for poling piezoelectric samples
poling. The most used poling processes are DC electrode poling has several drawbacks. In this procedure, the electrodes must
and corona discharge poling, and AC electrode poling has been be coated on the top and bottom portion of the specimen, and
introduced recently. In the following section, we elaborately poling is applicable for tiny samples. Corona poling requires
discuss each poling process, its merits and its demerits. metallization on a single side of the piezoelectric material and
does not need a further vacuum environment. However, the
5.1. DC electrode poling corona discharge uses the breakdown of dry air or an inert
Electrode poling48 is a direct current poling method. It is gas48,51,54 to polarise the piezoelectric material, which means
a relatively simple method and is older than other methods that it is far more complicated than electrode poling. Localized
(such as corona poling and AC poling). Electrospinning49 or breakdown occurs at frail points, such as pinholes, which short-
sputtering deposition50 methods are used to deposit the top circuits the electrodes, preventing additional polarization.

Fig. 4 Poling techniques: (a) Direct-current electrode poling process. (b) Corona discharge poling process. (c) Alternating-current electrode poling
process.

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This process has been used to manufacture large-area film technique are not well understood. Many scientists have
samples with great success.55 In the corona poling process, proposed theories about the principles of ACP. Chang et al.
charges from the corona point (a needle) will be dispersed over proposed that the monoclinic phase (MP) accounts for the
the bare part of the sample surface (which is not covered by better piezoelectric performance.62 Luo et al. employed domain
the electrode) producing an electric field between the sample enlargement theory to analyse the domain structure alteration
surfaces. An electrostatic kilovoltmeter55 or a comparison process.63 Qiu et al. proposed a novel theory in which the
method56 can be used to assess the sample’s surface potential. piezoelectric performance is improved by polar nano regions
There is no short-circuiting of the sample in the weaker regions (PNRs) or a localized configuration.64 He et al. later examined
because there are no electrodes. As a result, it is a more the Pb[(Mg1/3Nb2/3)0.52(Yb1/2Nb1/2)0.15Ti0.33]O3 (PMN-PYbN-PT)
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improved technique. The corona discharge approach could be structure and concluded that an extremely organized domain
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used to pole large-area samples and integrate them into a configuration is responsible for the excellent piezoelectricity.65
continuous process for industrial production. According to Qiu et al., the improvement in the piezoelectric
Unlike electrode poling, the corona poling process is an capability is connected to the decline of the 711 domain wall.66
indirect method of poling. Fig. 4(b) illustrates the corona Luo et al. investigated the effect of high-temperature ACP on
discharge process. In corona poling, a pin-point conduction PIMN-0.30PT single crystals (prepared using the continuous-
pointer (a needle) is exposed with a higher voltage B8–20 kV, feeding Bridgman (CF BM) process with different temperatures
ionizing the gas molecules near the tip. A metallic grid that is and poling fields ranging from 70 to 130 1C and 2 to
operated at a lower voltage of 0.2–3 kV and is present just below 6 kVrms cm1) and observed exceptional higher d33 values of
the needle is responsible for controlling the accelerated ionized 7000 pC N1 (29% greater than with DC poling) along with
particles that move towards the piezoelectric material. The higher free dielectric permittivity (e33T/e0) and coupling factor
number of dropped charges on the material surface is con- (k33) values under the optimized poling conditions of 90 1C at
trolled via the grid location and the applied voltage through 4 kVrms cm1, respectively.67 Recently, Su et al. made a com-
control of the supplied E. An electrode covers the bottom parative study of square- and sine-waveform ACP of (001)
surface of the material, which is in touch with a hot substrate oriented PMN-28 PT single crystals at 80 1C and at high voltage
(hot plate) to supply heat for controlling the poling process.57 (5 kVrms cm1) to solve the problem of spurious-mode vibra-
For all materials, the poling temperature should not exceed tions (SMV) and to obtain the optimized poling conditions for
300 1C for both methods (electrode poling and corona discharge). enhanced piezoelectricity and restoration of the altered elec-
trical impedance spectrum that was realized due to the ACP
5.3. Alternating current poling (ACP) process in single crystals.68 The majority of ACP investigations
Yamashita et al.58,59,74,75 recently developed an ACP approach, are based on relaxor PT materials with a lower value of Ec, such
demonstrating a cost-effective and time-saving domain- as lead magnesium niobate–lead titanate-based materials
engineering scheme that attracted the scientific community. (PMN–PT and PIN–PMN–PT), with little attention given to
Because of its excellent efficiency, minimal cost, and time relaxor PT crystals with higher Tc and Ec characteristics.
savings, ACP technology is becoming increasingly popular. In addition to the above poling techniques (DC electro
The dielectric and piezoelectric characteristics of ferroelectric poling, corona discharge and ACP) discussed earlier, polariza-
crystals are thought to be intimately connected to the ferro- tion may be achieved using alternative methods,69 for example,
electric phase and the poling direction.60 As a result, the effect other processes such as electron beam poling,70 mechanical
of ACP may also be related to the poling direction and crystal drawing,71 electrospinning,72 and additive manufacturing.73
symmetry. Furthermore, the improvement of piezoelectric char- However, these are not effective on a large scale and for all piezo-
acteristics after ACP is attributed to the change in domain electric materials.74,75 Liu et al. describe different poling methods
arrangement. The impact of the domain-wall motion is typically for the scalable manufacturing of the highly efficient electroactive
regarded as an external contribution, which is unknown. PVDF polymer74,76 as well as their merits and downsides.
AC poling is similar to DC electrode poling, with the only
difference being that in DC poling a high direct voltage is
applied, and in ACP a high alternating voltage is applied. ACP 6. Factors affecting the poling process
also leads to full polarization of the sample.61 Like the DC
electrode poling method, the sample is placed between the Domains arise for lowering the electrostatic energy of the
electrodes inside an oil bath and a very high alternating voltage depoling field when a piezoelectric material transforms from
is supplied. After poling, the material is cooled, and d33 and the para- to the ferro-electric state.45,77,78 Domain aligning
another required parameter measurement are performed. occurs in polycrystalline ceramics through applying a high
In Fig. 4(c), a schematic of the AC electrode poling technique DC field (the poling field strength) that must be higher79 than
of the active material is represented. Ec for a particular temperature range (the poling temperature).
It has been claimed that ACP is a far more appropriate Higher temperatures accelerate the domain movement, result-
method than DC poling. ACP has resulted in the enhanced ing in the realignment of spontaneous polarisation within every
piezoelectric activity of PMN–PT crystals and increased d33 grain, leading to a net polarization in the same poled direction.
values of up to 40%.59 However, the processes of the ACP As a result, one of the most essential variables in increasing the

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Fig. 5 (A) Variation of the d33 value along with the electromechanical coupling factor (kp) with respect to the (a) poling field, (b) poling temperature, and
(c) poling time at 25 1C, respectively; reprinted with permission from ref. 29. Copyright 2015, Springer. (B) Fluctuation of the d33 value along with the
planar (kp) and thickness (kt) electromechanical coupling factor of KNLN6 ceramics with respect to the (a) poling field, (b) poling temperature, and
(c) poling time; reproduced with permission from ref. 83. Copyright 2007 Elsevier.

piezoelectric characteristics is the poling process (poling d33 and kp values nearly equal to 670 pC N1 and 60% were
conditions). achieved. Fig. 5(A and B) represent the various investigations
The degree of alignment of the dipoles depends on several performed on longitudinal piezoelectric coefficients based on
factors in the poling process, such as the uniformity and value of the poling conditions.
the applied temperature, the field strength, the dimensions of the Recently a significant contribution was made by Tao et al.
materials, the time duration and consistency of the applied electric through comparing the poling conditions and d33 values of
field as well as its frequency,61,80 the manufacturing procedure, the PVDF films fabricated via the fused filament fabrication (FFF)
filler content or doping concentration, the porosity and the of commercial PVDF film. It was observed that the optimized
percentage of impurities.57,81 During the poling process, mechan- poling conditions, stretching ratio (R), and d33 values of the
ical stress also has an impact on the domain-wall movement.57,82 FFF PVDF film were 30 V mm1, 80 1C and 30 min, 4, and
Among the above-mentioned numerous factors, the applied field 7.29 pC N1, respectively, which are lower compared with the
strength, operating temperature and poling time are the most commercial PVDF film d33 value of 28 pC N1. The enhanced
effective parameters that will affect the piezoelectric strain coeffi- performance of the commercial PVDF film is due to its higher
cient value. So, the primary focus is on these three parameters, poling field (50 V mm1) and stretching ratio (R 4 4). However,
which will affect the d33 value and device application based on its the printed PVDF film has B10–100 times higher d33 and
performance. Some examples are discussed below. Fb (65%) values, in contrast to previously specified PVDF
Kumar et al.29 investigated the optimum poling conditions reports.85–87 Different practical applications, such as pressure
and their influence on d33 and the electromechanical coupling sensors, frequency detectors and wind energy harvesting, were
factor (kp) of mechanically synthesized lead–lanthanum–zirco- also demonstrated using the printed PVDF film.88 Fig. 6 illus-
nate–titanate (PLZT 8/60/40) ceramics. This work helped to trates the optimization of the poling conditions and stretching
discover the maximum d33 of 750 pC N1, using the optimized ratios through a comparison of the FFF-method-fabricated
poling conditions of an electric field of 45 kV cm1, with a PVDF film and a commercial hot-pressed PVDF film.
poling temperature (of 75–125 1C) for 30 min. Du et al.83 Tao et al. studied the strong dependency of the poling
synthesized the lead-free ceramic KNN and examined the temperature on heavy-metal-doped KNNS-B(RE)NH ceramics
impact of the poling conditions on its properties. The experi- and also reported better piezoelectric properties (d33 = 420–
mental results showed that d33 and kp increased with the poling 440 pC N1) in a broad poling-temperature range of 35–120 1C.
field, temperature, and poling period, where the optimized The fabricated device was poled using both DC and AC poling
values for pure KNN are 40 kV cm1, 140 1C, and 20–25 min, conditions of B30–120 1C, 3–4 kV cm1 and 10 min, and the
respectively. Chandrakala et al.84 studied the optimized the domain behaviour was also investigated by varying the poling
poling parameters of the synthesized lead-free CeO2-doped temperature (Tp = 35–120 1C) and field (2–8 V) with an optimized
barium calcium zirconate titanate (BCZT–0.08 wt% CeO2) sys- heavy metal Dy content (x = 0–0.25). It was observed that with
tem to obtain an improved piezoelectric outcome. Under these x = 0.25, Tp = 55–80 1C and a field of 4 V, complete domain
tuned conditions (50 1C, 3Ec, and 30 min), respective maximum orientation occurs.89 Fig. 7 demonstrates the dependence of domain

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Fig. 6 (a)–(c) Variation of d33 for printed PVDF and commercial PVDF with poling conditions (poling voltage, poling time, and poling temperature);
(d) FTIR spectra of printed PVDF films with different stretching ratios (R = 1, 2, 3, and 4); (e) Fb and d33 values of PVDF films before printing (filament) and
after poling the printed PVDF films (R = 1, 2, 3, and 4) and; (f) stretch ratios and comparison of printed and commercial PVDF film Fb values before and
after poling; reproduced from ref. 88 with permission from the Royal Society of Chemistry.

orientation and Tp, as well as the variation of the piezoelectric demonstrate strong piezoelectricity. PZT was first reported
properties with the heavy metal content and poling conditions. around 1952 by scientists of the Tokyo Institute of Technology.
Although a variety of compounds, including lead-based and PZT materials outperform previously identified metal oxide-based
lead-free compounds,92–95 have been investigated, more research is piezo-materials such as BaTiO3 in terms of their operating tem-
still required, notably in terms of the poling effect, its circum- perature and sensitivity. In contrast to metal oxide-based barium
stances, and property optimization, to contest lead-based materials. titanate, PbZr0.52Ti0.48O3 has a higher operational temperature
and sensitivity, making it one of the most commonly utilized
piezoelectric materials in the world. PZT and lead titanate (PT)
7. Poling influence on lead-based are ceramics that are used extensively in sensor and transducer
ceramics, lead-free ceramics, polymers applications because their characteristics can be modified
and composite materials through doping with various dopant.96–103,108 Most of the
commercial products produced by PZT ceramics consist of a
7.1. Lead-based piezoelectric materials solid solution of PbTiO3/PbZrO3 compositions. In the doping
PZT is an inorganic material with the formula Pb[ZrxTi1x]O3 process, a modest quantity of dopant is added to the piezo-
(0 r x r 1). It belongs to the perovskite family (ABO3), which electric ceramic to modify its characteristics. The substitution

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Fig. 7 (A) Compositional and temperature difference of d33, kp, and er: (a) fluctuation of d33 and kp values with heavy metal content (x = 0–0.55);
(b) variation of er with composition (x = 0–0.25) and Tp= 150 to 200 1C; and (c) and (d) variation of d33 with Tp with DC (c) and AC (d) poling with x
(0–0.25). (B) (a) Dependence of d33 with Tp for KNN-based materials, (b) plots of d33 with respect to Tp for various KNN-based ceramics,90,91 and
(c) schematic of domain behaviour with poling temperature and field; reproduced with the permission from ref. 89. Copyright Wiley publications.

of dopants such as Ti4+/Zr4+ and La3+ or Bi3+ with Pb2+in PZT Prewitt et al.105 poled commercial PZT ceramics with a
ceramics leads to a decrease in the ageing effect and coercive poling field and temperature range of 0–20 kV cm1 and
fields but an increase in the piezoelectric coupling factor, 25–175 1C, respectively, for a constant poling period of 5 min
dielectric constant, and loss, respectively. These are also known using a silicone oil bath. The measured d33 value ranged from
as ‘soft ferroelectrics’ since they are generated by adding 0 to 413 pC N1, indicating a powerful correlation between d33
dopants with a higher valence. By contrast, dopants with a and the poling parameters (temperature and E values). The
low valence are used in ‘hard’ ferroelectrics. Hard ferroelectric effect of the poling time (15, 30, 45, 60 and 90 min) on the PZT
materials have a low dielectric loss and electrical resistivity, ceramic was studied by Chaipanich et al. through poling the
along with a greater coercive force, a reduced dielectric con- samples in an insulating medium at a 130 1C poling tempera-
stant, and poling is often more challenging.99,104 Fig. 8 illus- ture and a field strength of 10 kV cm1.106 The specimen that
trates the PZT-based piezoelectric nanogenerator (PENG) and was poled for 45 min showed a higher d33 (28 pC N1) com-
its diverse applications. pared with materials polarized for 15 or 90 min (16 pC N1 and

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Fig. 8 (A) Functioning of a PZT nanogenerator (NG): (a) schematic of a flexible PZT NG; (b) blue, green, and red fluorescent regions indicate the intact
nucleus, live and dead smooth muscle cells, respectively, of rat cells placed on the surface of the NG; (c) comparative study of cell growth on culture
plates and the device; and (d) and (e) incorporation of the NG into a bovine heart (d) and the respective output voltage (e); reproduced with permission
from ref. 133. Copyright 2014, National Academy of Sciences. (f) Diagrammatic representation of the implantable thin-film based i-PENG PZT; and
(g) measured voltage output of swine chest after anaesthesia; reprinted with permission from ref. 134. Copyright 2015 Springer Nature. (B) PZT-based
PENG demonstration as a biosensor to detect the activity of a human arm: (a) verification of the PENG performance using an oscilloscope; and (b) and (c)
generated voltage (b) and current (c) output developed by the bending and releasing movement; adapted with permission from ref. 135. Copyright 2020,
American Chemical Society. (C) Self-powered system using PZT-NH2 NPs based flexible PENG: (a) device layers; (b) magnified scheme represents the
particle to polymer interaction; (c) cross-sectional image of film and its particle to polymer interaction; (d) optical image of PZT-NH2 NPs based PENG
device and its flexibility; reprinted with permission from ref. 136. Copyright 2018, Royal Society of Chemistry. (D) Working of a large-area PZT thin-film
PENG prepared on a flexible substrate using a laser lift-off (LLO) method: (a) 3.5  3.5 cm PZT thin-film NG; (b) generated current signals via (i) forward
and (ii) inverse finger-bending process; (c) array of 105 blue LEDs in series during finger bending; and (d) glowing of LEDs in a dark room when the thin
film is released from the bending position; reproduced with permission from ref. 137. Copyright 2014, Wiley-VCH.

22 pC N1, respectively). Thus, 45 min was considered as the Marsilius et al. analysed two PZT samples (commercial
optimum poling time; also at this critical time (45 min), grade), i.e., the soft-doped PZT 151 ceramic with a coercive
the electromechanical coupling coefficient (kp = 19.87%) was field of 10 kV cm1,119 and the hard-doped PZT 181 ceramic
the highest. with a coercive field of 18 kV cm1.119 Prepared samples were
Shifeng et al.107 poled a composite of PZT and sulphoalu- poled using nine different procedures in the temperature range
minate cement with different PZT concentrations of 60, 70, 80 of 150–45 1C with a poling field strength of 20–30 kV cm1. The
and 85 wt%. An increase in the d33 value occurred with an highest d33 value of B517 pC N1 was shown by soft-doped PZT
increase in the poling field strength (E) for poling time of 151 compared with the hard-doped PZT 181 samples (270 pC N1).
20 min at 120 1C, but above a 40 kV cm1 electric field the Guo et al. investigated the piezoelectric and dielectric
d33 value decreased for the same poling parameters. behaviour of h001i and h011i oriented single-crystals of

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Pb(Mg1/3Nb2/3)O3–PbTiO3 near the metastable orthorhombic 7.2. Lead-free piezoelectric materials

ferroelectric phase (FE0) region and demonstrated that, using In the early 2000s, the main challenge with piezoceramics was
a poling field of 10 kV cm1, extraordinarily high d33 values the use of lead-based compounds, which needed to be replaced
of up to 2500 pC N1 can be reached, due to the irreversible with lead-free compounds. Environmental rules, such as the
polarization from the monoclinic phase space group Cm (MA) Waste Electrical and Electronic Equipment (WEEE) regulations
to space group Pm (MC).109 Bian et al. fabricated the BT-based and restrictions on some harmful toxins via the Restriction of
0.55Pb(Ni1/3Nb2/3)O3–0.15PbZrO3–0.3PbTiO3 (PNN–PZT–xBT) Hazardous Substances (RoHS) directive, prohibited the use of
highly orientated[001]C textured ceramic using a templet lead-based materials. However, due to their strong piezoelectric
grain growth method and achieved higher piezoelectric prop-
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capabilities, lead-based materials have a large commercial

erties (d33 = 1210 pC N1, d33

¼ 1773 pm V1 at 5 kV cm1) and a
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share in piezoelectric-related applications. Several research

figure of merit (g33  d33 = 21.92  1012 m2 N1) that are greater organizations have attempted to create lead-free piezoelectric
(13%, 54%, and 68%, respectively) than for the PNN–PZT compo- materials as a substitute for lead-based ceramics. Numerous
site without BT.110 lead-free ceramics have already been discovered that have
Guo et al.109 investigated two piezoelectric materials PMNT improved electromechanical characteristics. These materials,
and PZNT. Three compositions were examined as per the phase however, have the disadvantage of a weak depolarizing
transition behaviour and properties of the crystal, and the temperature, during which their piezoelectricity begins to
samples (containing distinct PT contents) were poled at differ- deteriorate. The most efficient method for producing controlled-
ent field strengths of 20–30 kV cm1 using a silicone oil textured-based lead-based piezoelectric ceramics are the tem-
insulating medium, and the d33 values investigated. It was plated grain growth (TGG) method. TGG was used to boost the
observed that d33 increased to 1550 pC N1 with a poling field piezoelectricity of textured lead-free ceramics. As demonstrated by
of 10 kV cm1, and a sharp increment of d33 2500 pC N1 Saito et al.,187,198,199 their non-toxic textured ceramic excellent
occurred with a field of 30 kV cm1. Table 1 summarizes the strain compared with marketable lead-based materials, and it
poling conditions (field strength, temperature, time, and thick- also showed high reliability at an optimized temperature range.

ness) as well as the d33 or d33 values of the poled lead-based Many textured lead-free materials, such as (Bi,Na)TiO3 (BNT)187,198
materials. On the basis of the Table 1 data, we have prepared a and (K,Na)NbO3 (KNN),199 have been produced that show
schematic graph (Fig. 9). enhanced d33 values along with a good output performance.


Table 1 Lead-based devices with d33 or d33 values with respect to their optimized poling conditions

Poling conditions
Field strength Temperature Time Thickness d33 (pC N1) or
Lead-based materials (kV cm1) (1C) (min) (mm) 
d33 (pm V1) Ref.
PZT60/40 films (100) 60 — — 0.0009 100 111
PZT-5H 25 100 — 5 677 112
PUR-PZT 10 100 30 1 246 113
PMNT and PZNT 30 RTa — — 2500 109
0.67Pb(Mg1/3Nb2/3)O3–0.33PbTiO3 (PbMgNbO3–PbTiO3) 2 100 — 0.9 41900 114
PZT and sulphoaluminate cement 40 120 20 2 16 107
PMN–38PT o1104 20 — — 0.5 1200 115
PIMNT 10 RTa 10 0.4 4500 116
PZT ceramic 10 130 45 — 28 106
PZT nanofibers 440 140 1440 0.5 — 117
PbTiO3 60 170 10 1.5 75b 118
PZT ceramic 20 25–175 5 1 413 105
PZT 151 20–30 150 — 6 517 119
PZT nanofibers 40 130 15 0.005 — 120
PZT nanowires 40 130 10 0.005 600 121, 122
PZ26 100 B100 30 1 290 122
PZT Fe 30 160 15 10 230 123
PZT Nb 30 160 15 10 470 123
Cellulose paper derived ceramics (CPDC) 20 130 — 6.5 50 124
PLZT — — — — 108 125
PYN–PZT–Mn2 40 120 40 0.8 343 126
(1x)[(Pb1ySry)(Mg1/3Nb2/3)O3]–x(Pb1ySryTiO3) (PsMN–PsT) 20 120 30 B1.5 630 127
0.15Pb(Mg1/3Nb2/3)O3–0.38PbHfO3–0.47PbTiO3 (PMN–PHPT) 20 RTa 5 — 428.3 128
PbZr0.4Ti0.6O3 10 — — — 528 129
PZT fiber 25 RTa 5 5 300b 130
0–3 PZT–PDMS Corona poling (90) 120 120 0.130–0.165 78.33 131
0.49Pb(Ni1/3Nb2/3)O3–0.51Pb(Hf0.3Ti0.7)O3 (PNN–PHT) 20 — 30 1 957 132
PNN–PZT 5 — — 0.25 1210 (1773b) 110
a b 
RT = Room temperature. Represents the d33 value.

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Fig. 9 Dependence of the d33 or d33 response of lead-based materials with poling conditions in Table 1.

Recently Panda et al. reviewed an article based on the higher d33 which will decrease the TO–T phase transition temperature; on
values of lead-free piezoceramic and composite materials (BCTZ, the other hand, it will increase the TC modestly. This specifies
BCSnT, BCHfT, and KNN), and explained the mechanism for that the doping of suitable cations or anions in a parent lattice
obtaining their higher piezoelectric properties as well as the like BaTiO3 enables temperature uniformity in piezoelectric
probable future aspects for their further enhancement.138 materials, which is a significant parameter for numerous
Fig. 10 shows some examples of the three main groups of lead- practical application points of view.158 Several research projects
free piezoelectric perovskite materials (BT, KNN, and NBT) that have documented the piezoelectric, ferroelectric, dielectric, and
are used due to health and environmental concerns. diffused phase-transition properties of barium calcium zirco-
7.2.1. Barium titanate (BT)-based materials. BaTiO3, which nate titanate (BCZT), and barium strontium titanate (BST)
has steady piezoelectric and dielectric properties, is regarded as piezoceramics.19,151,152,158–166
the most valuable lead-free ferroelectric material that has a An increment in the density of the 901 domain wall areal
perovskite ABO3 configuration.145 So, BaTiO3-based ferroelec- dimension was observed in the BaTiO3 ceramic when the
tric materials are regarded as having the most potential due to applied poling conditions were 5 kV cm1, 105 1C and 30 min,
their broad range of uses (ceramics and thin films) and have which helped to enhance the d33 value and relative dielectric
large-scale applications as transducers, actuators, sensors, and constant (er) at room temperature.167 The BZT-BCT solid
so on.146–150 Polymorphic phase transitions (PPTs) are highly solution shows higher d33 coefficient values (630 pC N1) and
necessary for achieving enhanced piezoelectric properties,151 kp values under the ideal poling conditions of 2.5 kV cm1 at
i.e., from the orthorhombic to the tetragonal phase (TO–T) and 40 1C for 20 min.168
from the rhombohedral to the orthorhombic phase (TR–O) at Previously Liu et al. achieved higher d33 values of 620 pC N1
ambient temperature to obtain phase coexistence at 300 K. The in the lead-free system BZT-xBCT system near the morpho-
substitution of Sn4+, Hf4+, and Zr4+ in place of Ti4+ in BaTiO3 logical phase boundary (MPB) region.152 Later Mayamae et al.
raises the temperature of the PPT from a lower temperature investigated the lead-free 0.9BaTiO3–(0.1  x)CaTiO3–xBaSnO3
(0 1C and 90 1C) to an ambient one.151 Improved piezoelectricity (BCT–xBS) system for actuator applications. With poling
can be attained in BaTiO3-doped materials such as (Ba,Ca)- conditions of 40 kV cm1, room temperature, and 30 min,
(Ti,Sn)O3 (BCST) and (Ba,Ca)(Ti,Zr)O3 (BCZT) via the replace- enhanced piezoelectric properties of kp = 41.7%, d33 =
ment of cations such as Ca2+ at the A-position and Sn4+/Zr4+ at 469 pC N1 and d33 
¼ 1335 pm V1 were achieved for the x =
the B-position, and its performance might be comparable with 0.05 BS content and an electric field of 10 kV cm1 under
the soft PZT materials.152–157 Substitution of the Ca2+ cation ambient conditions near the orthorhombic–tetragonal (T–O)
in the BaTiO3 system creates the Ba1xCaxTiO3 (BCT) structure, phase transition.169 Similarly, Chen et al. proposed higher

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Fig. 10 Application of lead-free NaNbO3, BCT–BZT, BaTiO3–TiO2, Bi4Ti3O12–PDMS, BTO–PVDF and BCZTO piezoelectric nanogenerators (PENGs) in
various areas. (A) schematic of NaNbO3-based PENG: (a) image of NaNbO3 nanowires; (b) schematic of a NaNbO3–PDMS fabricated PENG; (c) optical
microscope and SEM images; and (d) dipole alignments of the ferroelectric nanowires via the poling process; reproduced with permission from ref. 139.
Copyright 2011, ACS Publications. (B) Lead-free flexible BCT-BZT fabrication and its real-time applications: (a) schematic of fabricated BCT–BZT PENG;
(b) SEM image of the composite nanofiber mat; and (c)–(e) demonstration of the output voltage using finger (c), wrist (d) and elbow (e) movements;
reproduced with permission from ref. 140. Copyright 2020, Elsevier. (C) Lead-free flexible and transparent BaTiO3–Ti-mesh PENG as an energy
harvester: (a)–(c) device-fabrication process of BTO on a Ti substrate; (d) and (e) device output voltage (d) and current (e) during bending and relaxing
conditions; and (f) optical images of the LCD in connection with the PENG, which is turned on and off with the bending and releasing mode, respectively;
adapted with permission from ref. 141. Copyright 2016, Royal Society of Chemistry. (D) (a) Optical images of the Bi4Ti3O12–PDMS composite PENG
sensing application tested using finger (left), palm (middle), and foot (right) movements; and (b) and (c) output voltage (b) and current (c) measurements
with respect to these motions; reproduced with permission from ref. 142. Copyright 2019, Elsevier. (E) Testing of the BTO-PVDF PENG using (a) a coin-
dropping method, (b) attached to a fan, and (c) and (d) the obtained output voltage (c) and current (d) generated via a finger-tapping method;
(e) connection of two PENG10 devices with a capacitor (10 mF), and (f) functioning of a calculator powered by the PENG; reproduced with permission
from ref. 143. Copyright 2021, MDPI. (F) Self-poled and bio-sustainable (BCZT-based polydopamine-embedded) BF-PNG showing an open-circuit
voltage of 14.4 V and a short-circuit current of 0.55 mA under general finger tapping; reproduced with permission from ref. 144. Copyright 2021, Elsevier.

d33 = 650 pC N1, kP = 59.6%, and Pr = 10.2 mC cm2, which were determine whether or not the device will be suitable for a
attained by doping Y3+ (x = 0.03) in the BCTS ceramic near the particular application.147 As discussed before, piezoelectric
morphological phase boundary with poling conditions of coefficient values are highly influenced by the poling condi-
35 kV cm1 at room temperature for 15 min.170 Recently, tions, and Table 2 shows the reported d33 or d33 
values that are
d’Ambrogio et al. fabricated a BaTiO3–PDMS based piezoelec- dependent on the poling effect. Based on data in Table 2 a
tric sensor for the diagnosis of coronary stenosis by adopting graph was plotted (Fig. 11), which illustrates the impact of the
the novel technique dielectrophoresis, and showed that the poling conditions on the piezoelectric coefficient of BT-based
BaTiO3–PDMS bio-sensor exhibited higher piezoelectric proper- piezoelectric materials.
ties for a high-temperature range and with a lower poling field 7.2.2 Bismuth sodium titanate (BNT)-based materials.
of 25 V mm1 compared with PVDF-based polymers (60 V mm1) Bi0.5Na0.5TiO3 (BNT) has been acknowledged as a successful
at 80 1C for 30 min.171 substitute for PZT. However, undoped BNT does not have as
Highly advanced instruments such as scanning tunnelling large a piezoelectricity coefficient compared with the Pb-
microscopy (STM) and atomic force microscopy (AFM) employ substituted materials. Rhombohedral bismuth titanate (Bi4Ti3O12,
piezoelectric devices because of their good electro-mechanical BIT)-based materials also have a significant piezoelectric activity
performance. A piezoelectric device that has a higher transduc- and the d33 value of 40 pm V1. This value is lower in comparison
tion mechanism will show a maximum output response. This with the d33 value of PT or BT, and indicates medium piezoelectric
type of activity contributes to higher values of the longitudinal strength. As a result, it was anticipated that it would be used in
d33.146,172 In addition to d33, other parameters, such as the piezoelectric and ferroelectric equipment.154 Several chemicals,
dielectric constant, electromechanical coupling factor, leakage such as Sr, Na, Nd, K, etc., were added to BNT to boost the d33
current, dielectric loss, and quality factor, are necessary and value even higher. Using the desired orientation of the domain

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Table 2 BT-based materials with d33 or d33 values with respect to their optimized poling conditions

Poling conditions
d33 (pC N1)
BT-based materials Field (kV cm1) Temperature (1C) Time (min) Thickness (mm) 
or d33 (pm V1) Ref.
BaTiO3 (BT-100-SPS) 30 80 30 — 416 157
BaTiO3 (BT-100-NS) 30 80 30 — 193 157
BaTiO3 (BT-500-SPS) 30 80 30 — 216 157
BaTiO3 ceramic 10 120 — 191 146
BaTiO3 and nano-akermanite, (BT/nAK) BT90 Corona poling 110 — 30 4 173
BT–x(CT-BS) 40 RTa 30 1.5 1444b and 570 174
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0.9BaTiO3–(0.1  x)CaTiO3–xBaSnO3 [BCT–xBS] 40 RTa 30 — 1335b and 469 169

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Ba(Ti0.88Sn0.12)O3–30(Ba0.7Ca0.3)TiO3 40 RTa 30 B1 530 155

Ba(Zr0.2Ti0.8)TO3–50(Ba0.7Ca0.3)TiO3 — — — B1 620
(Ba0.98Ca0.02)(Ti0.96Sn0.04)O3 40 28 20 B1 510
(Ba0.97Ca0.03)(Ti0.94Sn0.06)O3 40 RTa 20 B1 440
BT–x(CT-BS) 40 RTa 30 B1 570
(Ba0.93Ca0.07)(Ti0.95Zr0.05)O3 50 — 387 175
(Ba1xCax)(Ti0.98Zr0.02)O3 — — — — 375 176
BSTZ-BNO 180 65 75 0.8 296 177
0.94Na0.5Bi0.5TiO3–0.06BaTiO3 50 RTa 1.4 B86 178
(Ba0.85Ca0.15)(Zr0.1Ti0.9)O3 (BCZT) 40 RTa 15 — B486 179
Ba0.90Ca0.10Ti0.90Sn0.10O3–xY2O3 (BCTSY) 35 RTa 15 — 650 170
(1  x)Ba(Zr0.2Ti0.8)O3–x(Ba0.7Ca0.3)TiO3 35 30 30 1.6 464 180
(Ba0.85Ca0.15)(Zr0.10Ti0.90)O3–xLiTaO3 40 RTa — — 433 181
(Ba0.85Ca0.15)(Zr0.1Ti0.9)O3 10 RTa — 5 — 182
a b 
RT = Room temperature. Represents the d33 value.


Fig. 11 Schematic of BT and BT-doped lead-free piezoelectric material behaviour (d33 or d33 ) with optimized poling parameters.

wall183 and through doping,184 the piezoelectric properties have of 19.9 V g1 were achieved, and that these materials can be
been increased. It has been observed that texturing can improve successfully applied as energy harvesters instead of lead-based
the d33 value of BNT and BNT–6BT185 from 98 to 289 pC N1, toxic materials.186
correspondingly. In BNT materials, texturing is achieved via the reactive-
Recently Camargo et al. investigated the lead-free BNKT templated grain increment process, using particles such as
piezoceramic, and showed that higher piezoelectric properties Na0.5Bi4.5Ti4O15 (NBiT) or Bi4Ti3O12 (BiT). Current research
(d33 = 129 pC N1 and d31 = 12.8 pC N1) and an output voltage has established ways for converting plate materials such as

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Table 3 Bismuth sodium titanate doped materials with d33 or d33 values with respect to their optimized poling conditions

Poling conditions
d33 (pC N1) (or)
BNT based materials Field (kV cm1) Temperature (1C) Time (min) Thickness (mm) 
d33 (pm V1) Ref.
BNT–KBT–BT100x 45 80 5 — — 189
BNKBT–5 35 RTa 5 2.3 168 190
BNT–BKT 35 90 15 1 207 191
CeO2 doped BNaKT 40 1.5 132 192
BNT (BNT–BKT–KN100x/100y/100z) 50 80 10 1 215 15
(1  x  y) BiNaTiO3–BiKT–yBiCrO3 50 40 15 1.2 168 194
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BNKAT (x/y) 50 80 30 — 189 195

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BNT + BiO2O3x [BNT-x] 12 RTa 7 10 98 196

NBBT 30 80 30 — 133 197
NCBT conventional 60 200 30 1 13b 198
a b 
RT = Room temperature. Represents the d33 value.


Fig. 12 Variation of d33 or d33 with the poling field, temperature, time and thickness.

NBiT or BiT particles into templates of pure-phase BNT.187,188 piezoelectric response. However, although optimization of the
Some of the accumulated poling parameters with d33 values are poling conditions of KNN-based ceramics has been investigated
listed in Table 3. Based on the data in Table 3 a plot (Fig. 12) for many years, there is still debate on which poling parameters
has been prepared. will result in the best performance. According to Du et al.,8
7.2.3 Potassium-sodium niobate (KNN)-based materials. a stronger piezoelectric response can be predicted for ceramics
Potassium-sodium niobate (K0.5Na0.5NbO3) (KNN)-based textured poled towards the polymorphic phase transition (PPT) zone of
materials developed by Saito et al. are encouraging candidates as tetragonal and orthorhombic phases, which could minimize
substitutes for lead-based piezo-ceramics92,94,199,200 in the area of the potential barrier for polarisation rotation. Morozov et al.
electromechanical conversion efficiency. KNN is extensively used discovered that poling performed at high temperatures would
because of its excellent piezoelectric response, high Curie tem- be responsible for the enhanced domain-wall orientation and
perature, and biocompatibility.201 However, without the poling reduction of the coercive field strength in the tetragonal phase,
operation, NaNbO3 showed d33 E 28 pC N1.202 However, the leading to better piezoelectricity.203 Wang et al. achieved a
addition of potassium to sodium niobate (NaNbO3) sharply markedly higher d33 value of 324 pC N1 in the Li-doped KNN
increased the d33 value. Furthermore, it was demonstrated ceramic by re-poling and ageing at room temperature for
that adjusting the system conditions – notably the electrical 2 months assisted using an advanced domain-engineering
poling parameters – is an effective method for enhancing the process.204 A larger d33 value of 490 pC N1 was achieved by

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Wang et al. for the (1  x)(K1yNay)(Nb1zSbz)O3–xBi0.5- The d33 or d33 values and poling conditions of KNN-based
(Na1wKw)0.5ZrO3 system the near rhombohedral–tetragonal materials are listed in Table 4, from which we can conclude that
(R–T) phase boundary via DC poling using a silicone oil poling greatly affects the d33 value, although this is still
bath at 30 1C in the presence of a high electric field at small compared with the values of PZT-, BT- and BNT-based
30–40 kV cm1, which also demonstrated excellent dielectric materials. These materials (KNN based) are used frequently in
and piezoelectric properties.205 storage devices (in memory devices, and energy-storage
A surprisingly high d33 value of B570  10 pC N1 was devices), and in solar-energy-conversion applications.213 A sche-
achieved by Xu et al. in the KNNS-BZ-BKH system with poling matic (Fig. 13) has been prepared using the poling conditions
conditions of 20–40 kV cm1 at room temperature for 20 min, of KNN-based materials that are collected in Table 4.
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due to the combination of nanoscale strain domains with the 7.3.4. PVDF and composites. In the present era, the devel-
Open Access Article. Published on 05 September 2022. Downloaded on 9/10/2025 6:10:47 AM.

higher density ferroelectric domain wall.206 Similarly, Li et al. opment of cost-effective, flexible, compact-structure, wearable,
investigated the electrical and piezoelectric properties of the self-powered, environmentally friendly and more efficient
KNN–ZN, KNN–BF, and KNN–AL composites prepared via a power generators, which are made at the nanoscale, is receiving
femtosecond laser (FL) microprocessing spin-coating method huge attention. Together with the inorganic and toxic nature
with poling conditions of 35 kV cm1 at room temperature and of lead-based materials such as PZT36,222 and the growing
20 min. A higher d33 value of 128 pC N1 along with a kp of preference for flexible/wearable equipment, researchers have
0.41 were achieved in the KNN-ZN system; moreover, better been encouraged to create more sophisticated flexible energy-
knowledge the energy-band structure of the system was studied harvesting products. In this context, piezoelectric polymers
using a density functional theory (DFT) approach.207 Recently, have gained more attention compared with piezoelectric cera-
Song et al. reached temperature stability in the range of mics because of their affordable price, high flexibility, low
25–150 1C along with a higher piezoelectricity d33 = 508 pC N1 material density and bio-degradability. Polymers have a large
and a piezoelectric strain of 0.18% by adopting a facile carbon chain in their matrix, which helps to provide more
approach with doping by Li and Sb in the monoclinic KNN flexibility in comparison with single-crystal or ceramic
ceramic, which is greater compared with other KNN composites.208 materials.223–225 This flexibility helps the polymer-based device
The parallelism between electrical poling (DC loaded) and to be applicable in real-life applications (stretching, twisting
unipolar cycling together in lead-free and lead-based piezo- and bending purposes). Several piezoelectric polymers, such as
electric materials has already been demonstrated in the PVDF and PVDF-based polymers, polyurethanes (PU), cellulose
literature.209,210 The notion of space charge concentration and its derivatives, polylactic acid (PLA), and polyimides (PI),
around the grain boundaries210–212 can explain the unipolar have been researched for energy-harvesting applications.226–229
cycling behaviour, which is responsible for the appearance of The various types of polymers, polymer-composites and their
an intrinsic biased field (Eint) and gradual reduction of the power-harvesting implementations were described in 2019
piezoelectric characteristics. High-temperature poling may also by Mishra et al.228 Table 5 represents the d33 values of PVDF-
cause the formation of a significant Eint, which reduces the based materials in accordance with the poling techniques and
performance of piezoelectric elements. As a result, it is logical parameters.
to anticipate that the space charge concentration may possibly The molecular alignment and arrangement of the polymer
induce the degradation of piezoelectricity at higher poling matrix in the composition are responsible for the piezoelec-
temperatures. As the poling process of KNN-based piezo mate- tricity in the PVDF polymer and its co-polymers. In order to
rials is still controversial, and the significance of the space achieve piezoelectric properties, a bulk polymer configuration
charge density in the poling method has received less consid- must have molecular dipoles. Furthermore, the molecular
eration, it is vital to investigate the temperature dependence of dipoles should be able to reorient inside the matrix of the
poling characteristics. bulk material while maintaining their desired alignment site.

Table 4 KNN-based materials with d33 values along with the optimized poling conditions

Poling conditions
KNN based materials Field (kV cm1) Temperature (1C) Time (min) Thickness (mm) d33 (pC N1) Ref.
(K0.50Na0.50)NbO3 35 120 30 1.5 125 214
KNN–xBA–BNZ 11.56 27 — 5 306 215
KNN-CT-1: 0.96(K0.5Na0.5)NbO3–0.04CaTiO3 30 80 30 1 — 216
KLN-CZ-1: 0.96(K0.5Na0.5)NbO3–0.04CaZrO3 30 80 30 1 — 216
KNN-CZ-2: 0.96(K0.5Na0.5)NbO3–0.04CaZrO3 + 0.03Zr 30 80 30 1 160 216
KNN-CZ-3: 0.98(K0.5Na0.5)NbO3–0.02CaZrO3 + 0.03ZrO2 30 80 30 1 130 216
(K0.5Na0.5)NbO3(CuO doped) 50 100 10 0.7 86 217
(K0.476Na0.524)NbO3 (Cuo doped) 30 120 10 5 146 218
K0.5Na0.5Nb0.97Sb0.03O3 (KNNS1) 30 120 10 1 218 219
(Ag0.75Li0.1Na0.1K0.05)NbO3(ALNKN–xCuO, x = 1 mol%) 50 100 20 1 47 220
(KNL–NTS) 40 — 30 0.7 270 221

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Fig. 13 Poling behaviour of KNN-based piezoelectric materials based on the data in Table 4.


Table 5 PVDF-based materials with d33 or d33 values with respect to their optimized poling conditions

Poling conditions
Field strength Temperature Time Thickness/needle d33 (pC N1)
PVDF nanoparticles with filler (kV cm1) (1C) (min) distance (mm) 
(or) d33 (pm V1) Ref.
P(VDF-HFP) 100 100 1200 — 180 267
PVDF–BaTiO3 nanoparticles 1000 120 30 13 25 268
PVDF–BaTiO3 fibers 350 100 120 0.33 11.4b 147
P(VDF-TrFE) 500 — — 0.060 35.3 269
PVDF–ZnO nanoparticles 50 120 0.010 900 270
P(VDF-TrFE)/ZnO Corona poling 5 0.35, grid to sample 5 22 271
PVDF–ZnO nanowires 1200 — — B0.004 — 272
PVDF–PZT powders 100 80 — 0.030 84 274
PVDF–CoFe2O4 nanoparticles Corona poling 80 30 — 33 275
PVDF–Fe3O4 nanoparticles 350 60 60 0.035 37 276
PVDF-micro-CaCO3 and Mt particles Corona poling at 900 — 10 0.100 30.6 298
PVDF-MWCNTs 1500 100 30 — 23 277
PVDF-MWCNTs Electrospinning 120 — — Needle distance 0.5–1 mm 57.6 278,279
MWCNTs coated with TiO2 1200 70 80 0.02 41 280
PVDF-C60 and SWCNTs 4000 80 20 0.05 65 281
PVDF-graphite nanosheets 500 130 30 — 6.7 283
PVDF-reduced graphene oxide (PVDF-rGO) Corona poling at o50 60 30 0.050 16.66b 284
PVDF-MnO2/graphene/MWCNT hybrid 800 — — 0.012 17–33 286
PVDF 6010 Corona poling of o30 RTa 30 B1.5 B264 287
PVDF composite 700 — — 0.035 140 288
PVDF composite 20 — 120 — 5 285
a b 
RT = Room temperature. Represents the d33 value.

Adjustment of the dipoles in the matrix is accomplished using which influences the electroactive characteristics of the polymer.
the poling technique. PVDF has four phases, which are a, b, g, After obtaining the b phase, poling is carried out and the dipoles
and d, among which the b phase shows the highest piezo- are aligned in the presence of a high E, boosting the material’s
electricity behaviour. b-PVDF films are generally attained via piezoelectric response.232,233 The stretching proportion and the
elongating a-phase films.230,231 The temperature and stretching temperature at which the phase transition occurs from the a to
proportion will decide the b-phase percentage and crystallinity, the b phase also affect the switching mechanism.234,235

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An wide-ranging study has been conducted to enhance the cost-effective, and the voltage supplied throughout the synth-
b-phase percentage in PVDF through solvent casting, phase esis enables the preferred b-phase PVDF to be acquired.
transition, or the synthesis of PVDF-copolymers. Mechanical A suitable perpendicular mechanical loading or bending or
drafting/annealing in the presence of a high temperature and twisting or stress/strain need to be applied on the polarized
pressure is required to obtain the necessary ferroelectric b-PVDF film, which results in the generation of desirable
b-PVDF phase. A detailed study236,237 has been carried out on quantity of voltage.254 The method has the benefit of enhancing
the high-pressure crystallization of PVDF in both low and high the piezoelectricity in situ during the production of nanofibers.245
melting phases. In their preliminary studies, Yang et al.236 As a result, because the poling method includes characteristically
discovered that by quenching and subsequently annealing the exposing PVDF to a high E, electrospinning is a beneficial
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PVDF sheets, b-phase crystallisation is induced instantly from approach for fabricating sophisticated polymer films.
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the melt. The a-PVDF phase was extracted straight from the In addition to the popularly used electrospinning method,
melt.238–240 Then the stretching, annealing or poling the newly introduced additive manufacturing (AM) process is
procedure241 was executed for b-phase induction. used for the production of continuous printable piezoelectric
In 1969, Kawai was the first to reveal piezoelectricity in PVDF samples from polymeric PVDF filament rods in the presence of
through the application of a strong field and mechanical a strong E. This procedure is popularly known as the electric
stretching.242,243 For significant piezoelectric characteristics, poling-assisted additive manufacturing (EPAM) process of
PVDF must have a high percentage of the electroactive b-phase PVDF, which includes AM as well as the electric poling
b-phase. Mechanical stretching and traditional poling techni- technique and can consistently produce free-form shape piezo-
ques such as electro-poling or corona discharge can be used to electric equipment.255 This technique enables the homogenous
achieve the polar b-phase in the initial stage. Conventionally, alignment of electric dipoles in preferred orientation, which
the polarity of PVDF was achieved using mechanical stretching helps to manufacture large area films with the user required
and the electro-poling or corona discharge technique. Although designs. During the EPAM method, melted PVDF polymer is
b-phase PVDF is appealing for generating an adequate electrical mechanically stressed by the leading nozzle tip as well as being
performance, monomer alignment is a tedious process and poled by a strong E in a higher poling temperature bed. The
requires costly equipment with the application of high elec- EPAM technique is used efficiently for the production of piezo-
trical fields. The challenge with the traditional poling method electric devices. This procedure does not lead to dipole align-
is that E can only be supplied at the surface of the sample, ment of the PVDF polymer in the absence of an electric field.
which gives rise to various kinds of stress and strain.244 Kawai The EPAM technique is assumed to apply hugely in AM for
adapted the uniaxial drawing process for development of PVDF making a wide range of piezoelectric PVDF polymer-composite
film, but the film contains higher nonpolar a-phases due to the devices for energy harvesting, sensing and actuator purposes
weak crystallization.242,245 Moreover, the phase transformation using easy, single and cost-effective processing and fabrication
from a-phase to b-phase is rarely successful, i.e., about 20% of steps.256,257 Furthermore, the newly used self-poling method is
the a phase still retained in the PVDF material. The above- also an advantageous process for improving b-PVDF and its
described conventional process can only be used to make films composites.258
with a depth of a few millimetres. The disadvantages of Because of the diverse applications of PVDF, there are
these old methodologies are solved by the electrospinning numerous studies related to PVDF and composite-based
process, the solvent-evaporation method, and the spin-coating polymers.232,233,259 PVDF and its copolymers have d33 values
technique,246–248 and they have gained increasing interest since that vary from 12 to 33 pC N1, which is extremely small in
films of nanoscale thickness are required in numerous comparison with the d33 values of other bulk polymers.57,260–266
applications. Despite this limitation, PVDF and its co-polymers have received
To produce greater piezoelectricity, all of the approaches huge appreciation due to their inherent characteristics, such as
listed above involve extra poling or mechanical elongation of larger piezoelectric strain coefficient values, high flexibility, high
the PVDF film. Electrospinning, by contrast, is a compressive elastic compliance, excellent chemical resistance to solvents,
and reliable process that utilizes electrostatic forces for the bases and acids, greater electro-mechanical coupling capability,
production of nanofibers from a liquid polymer melt or required mechanical strength, and biocompatibility.273,282 Fig. 14
solution.249,250 The electrospinning setup comprises a higher- is plotted based on the different poling parameters presented in
power supply unit, a spinneret, a syringe pump, and a ground- Table 5.
ing collector.251 Once the power is switched on, the applied E
overwhelms from the surface tension of the droplets and a
conical-shaped polymer jet solution known as a Taylor cone is 8. Applications
ejected. The mixture evaporates after reaching the earthed
collector, generating randomly distributed thin polymer fibres, In congruence with the evolution of microelectronics indus-
where the size, and microstructure can be adjusted through tries, it has become necessary for the invention of flexible,
modifying numerous parameters.252,253 So, the production of wearable and self-powered PENGs by employing the piezoelec-
PVDF nanofiber films through electrospinning is regarded tric phenomena. The benchmark for fabricating a sophisticated
to be the most efficient method because it is easy to perform, PENG are (i) it needs to be firmly attached to the operator,

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Fig. 14 PVDF and PVDF-based composites’ d33 or d33 response in accordance with the poling parameters shown in Table 5.

(ii) it is lightweight, (iii) it has a long life span with high Aliane et al.296 studied the dielectric, piezoelectric, ferro-
stability, (iv) it is self-executable, and (v) it is commercially electric, and pyroelectric behaviour of the P(VDF-TrFe) copoly-
viable and inexpensive. In addition to these requirements, from mer on the basis of its crystallinity and polymer chain
a practical implementation point of view, it should be suitable dimensions. For the piezo-activation purpose, the fabricated
and comfortable for the user. In particular, for achieving P(VDF-TrFe) device (2 mm thickness) was poled with voltage of
exceptional futuristic and realistic PENGs, the poling techni- 80 V for 5 min at 85 1C. The fabricated sensor maximum output
ques and conditions are necessarily tailored.28,289–291 In the voltage was analysed by varying the time and pressure with the
literature, numerous PENGs have been framed by proper para- degree of dislocation (dZ) and the d33 value on the basis of
meters resulting in an enhanced performance. This section the AC frequency. In 2017, Yaqoob et al.297 fabricated a tri-layer
outlines some of the flourishing applications of optimized flexible PENG where the polyvinylidene fluoride–barium tita-
poled devices for commercial and biomedical purposes. nate (PVDF–BTO) nanocomposite stacks act as the top and
Nilsson et al. demonstrated the effect of the PVDF-bio-fibre bottom layer and an n-type graphene film was inserted in
composite with polyethylene or carbon black as a core portion between these two layers. For an enhanced output, the PENG
under optimized poling conditions of 60–120 1C, E = was poled with a field strength of 150 kV cm1 at 100 1C for 1 h.
1000 kV cm1, and 2 min.292 The textile PENG with a polyamide The tri-layer configuration can generate maximal peak-to-peak
yarn configuration was successfully implemented as a textile voltage, current, and power values of up to 10 V, 2.5 mA, and
sensor for heartbeat monitoring, and reported a maximum 5.8 mW, respectively, in the presence of a 2 N force at 1 MO
output voltage and power of B4 V and 15 nW, respectively. load resistance. Moreover, the structure demonstrates excellent
Later Soin et al.222 constructed an energy harvester ‘3D spacer’ stability for 1000 press-and-release periods (Fig. 16). Subsequently,
PENG through the weft knitting of a PVDF monomer Jahan et al.298 studied the stretching behaviour of a hybrid PVDF-
filament with a yarn of polyester, and Polyamide 66 coated based composite (micro-CaCO3 + montmorillonite (Mt)) prepared
with Ag metal to compensate for the 2D configuration using a co-rotating twin-screw extrusion technique with various
disadvantages.222,293,294 In the 3D textile PVDF monofilament, contents of CaCO3 (30–40 wt%). The poling conditions were
the beta-phase concentration was increased up to 85% via the adjusted to a 900 kV cm1 field strength at ambient temperature
application of an electric field of 6 kV cm1 at the temperature for 10 min and stretching percentage to obtain a maximum d33
range of B80–90 1C, and the device produced a power of value of 30.6 pC N1 and the highest beta-phase in the PVDF matrix.
B5.07 mW cm2, which is five times higher compared with a Recently Liu et al. prepared the poly(vinylidene-trifluoro-
2D textile PENG (1.18 mW cm2). Fig. 15 gives the configura- ethylene)–polyhedral oligomeric silsesquioxane (P(VDF-TrFE)–
tions and output results of 2D and 3D structured textile devices. POSS) composite-based piezoelectric nanogenerator via the

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Fig. 15 Relative study of the structural, morphological and electronic characteristics of flexible fluoropolymer textile PENGs. (a) Structure of a flexible
PVDF-based 2D woven PENG; and (b) the highlighted sensing area; reproduced from ref. 295. Copyright 2013, Wiley publication. (c) Textile pattern
formed by the woven fibres and (d) signal produced from the heartbeat via the respiration process; reprinted from ref. 292. Copyright 2013, Elsevier
publication. (e)–(g) 3D configuration of a piezo-fabric energy harvester (e), with its temporal voltage (f) and current (g) outputs (obtained by applying a
pressure of 0.034 MPa with a load of 470 kO); and (h) correlating the output power of 2D and 3D woven PENGs with applied pressure; adapted with
permission from ref. 222. Copyright 2014, Royal Society of Chemistry.

Fig. 16 Electrical and mechanical characterisation of P(VDF-TrFe)- and PVDF–BTO-based PENGs. (a) and (b) voltage variation with time (a) and pressure
(b) for the piezoelectric sensors (direct method); (c) and (d) displacement and d33 fluctuation, respectively, over the AC field; reprinted with permission
from ref. 296. Copyright 2015, Elsevier. (e) Flexibility testing of the tri-layer structure by bending; (f) and (g) PVDF-BTO PENG maximum current (f) and
power (g) output result, and (h) tri-layer device stability testing over 1000 stress-and-release cycles; reproduced with permission from ref. 297. Copyright
2017, Elsevier.

minimum-temperature solvent-evaporation procedure, and displaced a quick action of 61 ms and showed excellent voltage
confirmed the mean output current density (0.5 mA cm2) and and power output values of 9.3 V and 0.122 mW cm2, respec-
voltage (3 V) using the optimum poling parameters of 100 1C, tively, with a load of 70 MO. The output characteristics of the
800 kV cm1 for 2 h at 5 Hz frequency.299 In the same year, Yang P(VDF-TrFE)–POSS PENG and the fruitful implementation of
et al.300 developed a BTO–PVDF composite with a polydiacety- the BTO–PVDF composite sensor as a wearable device for the
lene (PDA) surface modifier-based wearable-flexible pressure detection of human movement are shown in Fig. 17(A and B).
sensor via a facial solution-casting procedure and poled the Recently Wu et al. fabricated a flexible PENG made of
PENG with an E of 50 mV m1 at the poling temperature of PVDF with a PZT and HOG filler, using poling conditions of
90 1C for 4 h. With 17% PDA, the doped BTO–PVDF composite 400 kV cm1, 5 h, and 50 1C, where the device shows a

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Fig. 17 (A) Comparative study of the voltage, current, d33 and ferroelectric properties of pure P(VDF-TrFE) and doped P(VDF-TrFE)–POSS PENGs;
reprinted with permission from ref. 299. Copyright 2020, Royal Society of Chemistry. (B) Demonstration of the bending and twisting activity of the flexible
BTO–PVDF constructed PENG and the output performance of the piezoelectric sensor, fixed to a shoe, with different movement activities; reproduced
with permission from ref. 300, Copyright 2020, Elsevier.

peak-to-peak voltage of 50 V and a power density of 1.4 mW cm2 poled in a silicone oil bath with a poling field of 50 kV cm1 at
upon manual bending-and-release movements and to enable 150 1C for 24 h, and showed an increased d33 value (B2500 pm V1)
the lighting of 30 white LEDs.301 Fig. 18 illustrates the voltage with a maximum voltage and current of B7.8 V and
and current output of the flexible PENG from different figure B2.29 mA, respectively. The output signal form of PZT and
movements. PMN–PT was verified using a dynamic mechanical analyzer
Chaipanich et al. reported that the PZT ceramic poled at (DMA) (Fig. 19).
130 1C with a 10 kV cm1 field strength for 45 min has a higher Recently, Liu et al. fabricated a 4D-printed PZT composite-
d33 value (28 pC N1) and can be implemented as a smart based acoustic transducer for underwater applications. With
concrete composite for civil-engineering purposes.302 Eid et al. poling conditions of 25 kV cm1, 80 1C and 30 min, the samples
investigated PZT Portland cement (PZT-POC) samples poled at showed maximum piezoelectric properties of d33 = 103 pC N1
room temperature with a poling field of 1.5 kV cm1 for 2 h, and er = 274.34, respectively.305 Fig. 20 illustrates the whole
and proposed that this composite can act as a smart shield and fabrication process and the output characteristics of the PZT
also explain the variation of the piezoelectric coefficient with composite ultrasonic transducer.
the PZT content in PZT-POC.303 Similarly, Costa et al. success- Wang et al. successfully fabricated a flexible PNN–PZT-based
fully developed a cost-effective castor-oil-based 1–3 connectivity high-performance composite device using a direct-write 3D-
polyurethane–PZT composite (PUR-PZT) having a d33 value of printing process. The 0–3 composite specimens have a greater
246 pC N1 from optimized poling conditions of 10 kV cm1 at piezoelectric voltage coefficient (g33) of 400  103 V m N1
100 1C for 60 min, which can be implemented as an acoustic after poling it in a high electric field of 100 kV cm1, at 100 1C
emission (AE) wave sensor in healthcare systems.113 Chen et al. for 10 h. The 3D-printed flexible and stretchable PENG can light
fabricated a soft PZT nanofibre–PENG with dimensions up 20 red LEDs and can be used in artificial muscles, biology
of around 60 nm and 500 mm using poling conditions of signal identification, and soft robotics. Fig. 21 demonstrates
40 kV cm1, at a poling temperature greater than 140 1C for the PENG mechanism, 3D models, simulation results and the
about 24 h. PZT fibres were positioned over fine platinum output performance of the 3D-printed PNN–PZT device.306
electrodes of the integrated structure placed on a silicon Recently, Kim et al. achieved enhanced piezoelectric properties
substrate. The voltage and power output performance of the at lower sintering temperatures through adding CuO to PNN–
fully assembled setup was 1.63 V and 0.03 W, respectively.117 PZT. CuO–PNN–PZT shows a higher d33 and transduction
For attaining the highest d33 value, a typical study was con- coefficient of 502 pC N1 and (d33  g33) 17 354  1015 m2
ducted by Xu et al.304 on a PT-doped PMN nanowire composite N1, respectively, at the low sintering temperature of 1025 1C
(a PMN–PT-based PENG) for self-power-generating sensing. For and poling of the composite in the presence of a DC electric
an improved outcome, the PMN–PT hierarchical structure was field of 30 kV cm1 for 20 min at 100 1C (Fig. 22).307

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Fig. 18 Demonstration of the output performance of a flexible HOG/PZT/P(VDF-TrFE) PENG upon different hand motions. (a) Voltage, (b) current, and
(c) glowing of 30 LEDs generated via figure bending; (d)–(g) optical images and voltage outputs from figure tapping, figure bending, pressing, and twisting
activities; adapted with permission from ref. 301. Copyright 2021, Elsevier publication.

Fig. 19 (a) and (b) PZT nanogenerator output voltage with respect to time (a) and % fiber strain(b); (c) voltage with different load frequencies in the
polymer matrix; (d) output power against load resistance; reproduced with permission from ref. 117. Copyright 2010, ACS Publication. Voltage (e) and
current (f) generation from tapping of the PMN–PT based device with a plastic screwdriver handle; and (g) and (h) mechanical response of the PENG
upon the application of cyclic stepwise strain; reprinted with permission from ref. 304. Copyright 2013, ACS Publication.

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Fig. 20 (A) (a) Optical image of the PZT device based underwater acoustic transducer setup. (b) Fabrication of composite film by printing approach along
with the suitable mixed slurry. (B) (a) Comparative study of the signal generated input and oscilloscope output, (b) variation of transducer peak-to-peak
voltage output with rod spacing, and (c) variation of d33 value and dielectric constant with respect to rod spacing; reproduced with permission from
ref. 305. Copyright 2021, IOP publication.

Fig. 21 (A) Study of the electromechanical performance of a 3D-printed PNN–PZT composite. (a)–(c) Schematic of the poling process and dipole
orientation in PNN–PZT during the on and off conditions of the poling process; (d) and (e) P–E loops at a different electric fields with and without an
Ag-coat on the ceramic–polymer composite specimen; (f) and (g) electric field distribution (100 kV cm1) of the Ag/PNN–PZT and PNN–PZT
composites, respectively, using COMSOL simulation software; (h) output voltage before and after the poling process for Ag/PNN–PZT; and (i) voltage
output of PNN–PZT after poling, measure using a digital oscilloscope. (B) (a) 3D printing process, (b) image of pure PDMS mat; (c)–(e) different structured
printed ceramic-composites; (f) and (g) printed flexible composite fixed to wooden doll before and after hand bending; (h)–(k) flexibility testing of printed
composite. (C) (a) Application of force on 3D printed composite; (b) circuit for output measurement; (c) generated open circuit voltage within 15 seconds;
and (d) glowing of 20 red LEDs, republished with permission from ref. 306. Copyright Elsevier publications.

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Fig. 22 (A) and (B) Fluctuation of the piezoelectric properties with respect to the sintering temperature and CuO dopant percentage in PNN–PZT using a
3D model, S–E loop, and 2D plot. A(a and b) 3D plots of d33 and d33  g33 with CuO content and sintering temperature. B(a) Deviation of the S–E loop
with CuO proportion in the PNN–PZT composite; and (b) variation of the voltage output, d33, d33  g33, and energy density with CuO doping; reproduced
with permission from ref. 307. Copyright Elsevier publications.

Fig. 23 Verification of PET/EVA PENG sample via (a) corona poling, and (b) d33 coefficient consistency over a six-week period; (c) stability of the
generator under high moisture conditions; (d) illumination of six LEDs by pressing the device underwater; and (e) current output of the flexible PENG at
high temperature (70 1C); reproduced with permission from ref. 309. Copyright 2017, Elsevier publication.

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Ng et al.308 analysed the PZT–P(VDF-TrFE) composite through improve energy-harvesting efficiency and will be completely
a stepwise poled technique for three different situations: ceramic reliant on the appropriate poling conditions. As a result, the
part differently at 70 1C; both the ceramic–polymer in the similar current research opens the way for further feasibility of achiev-
direction; and both phases poled in a reverse direction at 50 1C, ing these poling conditions in the form of vibration-based
E = 100 kV cm1 for 30 min. The signals produced were verified energy harvesters, sensing devices, and vibration controllers.
using the laser-induced pressure pulse (LIPP) method. In a later It should be noted that, despite the numerous advantages,
study Vineet et al.274 investigated 0–3 PZT–PVDF composite optimum poling situations for device functioning and the
structures by varying the PZT percentage in the PVDF matrix. scientific acceptance of poling parameters is a tedious job; this
Poled PZT-PVDF films (80 1C, field of 100 kV cm1 for 24 h) is because poling techniques depend upon numerous factors
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with higher PZT filler ratio enhances the electro-active b-phase such as the filler content, synthesis procedure, poling field,
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content, which results in higher piezoelectric/dielectric temperature, time, frequency, dimensions of the element,
performance. domain orientation, voids, defects, and chemical composition
In contrast to PZT and PVDF composite PENGs, Zhong et al. of the materials. So, several investigations have been adopted
prepared an advanced wearable and flexible polyethylene tere- for complete knowledge of the domain orientation at the
phthalate or ethylene-vinyl acetate (PET/EVA) based PENG, microscopic level in the poling process. The in situ monitoring
which has a higher d33 of B6300 pC N1 and can be operated of domain-configuration evolution during ACP appears to be
under adverse environmental conditions such as higher moist- effective for identifying the abnormality of domain-structure
ure and temperature (B70 1C). The device was corona poled modification and identifying the mechanism of enhancement
with a field of 20 kV for 3 min and generated a current of of the piezoelectric properties. Introducing novel and effective
B29.6 mA and a power of B0.444 mW via conventional poling methods such as self-poling, graded poling, advanced
hand tapping (Fig. 23).309 Similarly, Karlsson et al.,193 used manufacturing technology and computer simulation proce-
the periodic poling process to produce the Rubidium Titanyle dures motivates researchers to shift attention so that piezo-
Phosphate (RbTiOPO4) bulk crystal (dimension of length 3 mm electric materials can be employed in real-life applications.
and width 0.7 mm) with high quality domain grating for the The strategy of this investigation is to establish a complete
improved frequency magnification to generate blue light. Here, knowledge of different poling techniques and their impact on
the periodic poling process is depends on the electro-optic the piezoelectric strain coefficient, and specifically in the d33
technique with a high poling voltage of 2.3 kV spotted with a mode, in order to fabricate enhanced engineered material and
cyclic electrode of 50% repetition cycle, which results the d33 device attributes. The experimental outcomes reveal that the
nonlinearity of 12.8 pm V1.193 Recently Jia et al. fabricated a electromechanical performance of the material dramatically
piezoelectric PZT-epoxy fibre-based high-frequency ultrasonic changes based on the poling parameters. The above findings
transducer with a high d33 value of 670 pC N1, and a com- shed light on the ideal projection of materials and equipment
parative study of d33 and g33 with the PZT content confirmed with superior execution, greater efficiency and reduced
that the d33 value increases and the g33 value decreases with the deterioration through the application of optimized poling
PZT content.310 Energy-harvesting and self-powering techni- procedures.
ques are auspicious and significant investigations. Because of
the optimized poling conditions with a higher piezoelectric
constant (d33) there has been an incredible development for Conflicts of interest
energy-harvesting materials. In addition, integrating with var- There are no conflicts to declare.
ious advanced materials is of great benefit concerning their
translation capacity.
Acknowledgements
The authors would like to acknowledge the Department of
Conclusion and future aspects Science and Technology (DST), New Delhi, India, for a research
This report examined the latest research progress on the poling funding under the Scheme for Young Scientists & Technologists
effect of lead-based and lead-free non-toxic piezoelectric mate- (Ref. No. SP/YO/2019/1432).
rials and composites. From this, we conclude that the poling
procedure and its optimised conditions are probably the best References
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