Advanced Materials - 2023 - Yuan - Piezoelectricity Pyroelectricity and Ferroelectricity in Biomaterials and Biomedical

REVIEW
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Piezoelectricity, Pyroelectricity, and Ferroelectricity in

Biomaterials and Biomedical Applications
Xue Yuan, Jiacheng Shi, Yong Kang, Jinrui Dong, Zhengcun Pei, and Xiaoyuan Ji*
recently captured much attention. These

Piezoelectric, pyroelectric, and ferroelectric materials are considered unique materials can convert mechanical, thermal,
biomedical materials due to their dielectric crystals and asymmetric centers and electrical energies into one another,
that allow them to directly convert various primary forms of energy in the making them ideal for catalysis and en-
environment, such as sunlight, mechanical energy, and thermal energy, into ergy capture. These materials have demon-
strated significant promise in biomateri-
secondary energy, such as electricity and chemical energy. These materials
als and biomedical applications due to
possess exceptional energy conversion ability and excellent catalytic their ability to interface with biological sys-
properties, which have led to their widespread usage within biomedical fields. tems and stimulate cellular responses.[3–8]
Numerous biomedical applications have demonstrated great potential with When mechanical strain or stress is ap-
these materials, including disease treatment, biosensors, and tissue plied, piezoelectric materials have the abil-
ity to produce an electric field. In bioma-
engineering. For example, piezoelectric materials are used to stimulate cell
terials, applications for piezoelectric mate-
growth in bone regeneration, while pyroelectric materials are applied in skin rials include biosensing, drug delivery, tis-
cancer detection and imaging. Ferroelectric materials have even found use in sue engineering, and wound healing. Addi-
neural implants that record and stimulate electrical activity in the brain. This tionally, they are capable of acting as energy
paper reviews the relationship between ferroelectric, piezoelectric, and harvesters by transforming mechanical en-
pyroelectric effects and the fundamental principles of different catalytic ergy from human movement into electri-
cal energy for implantable technology. Py-
reactions. It also highlights the preparation methods of these three materials
roelectric materials can generate an electric
and the significant progress made in their biomedical applications. The review field when their temperature changes. In
concludes by presenting key challenges and future prospects for efficient biomedical applications, pyroelectric mate-
catalysts based on piezoelectric, pyroelectric, and ferroelectric nanomaterials rials have been used for thermometry, in-
for biomedical applications. frared sensing, and medical imaging. En-
ergy harvesting can also be performed with
pyroelectric materials by converting body
heat into electrical energy to power im-
plantable devices. Ferroelectric materials
1. Introduction can have their spontaneous polarization switched around by us-
Noncentrosymmetric (NCS) or uncentered crystal classes ex- ing an external electric field. In biomaterials, ferroelectric ma-
hibit materials with a variety of technically important phys- terials have been used for sensory applications, such as touch
ical properties, including piezoelectricity, pyroelectricity, and sensors and pressure sensors. Other applications for ferroelectric
ferroelectricity.[1,2] Because of their particular physical fea- materials include energy harvesting and biological catalysis.[9–13]
tures, piezoelectric, pyroelectric, and ferroelectric materials have Overall, the unique electrical properties of these materials have
enabled the development of new and innovative biomedical ap-
plications with the potential for a significant impact on patient
X. Yuan, J. Shi, Y. Kang, J. Dong, Z. Pei, X. Ji health and wellbeing.
Academy of Medical Engineering and Translational Medicine Recently, Xu et al.[14] summarized the development of bio-
Medical College
Tianjin University piezoelectric platforms, while Hu et al.[15] introduced the applica-
Tianjin 300072, China tion of pyroelectric technology in medical devices. Wang et al.[16]
E-mail: jixiaoyuan@tju.edu.cn reviewed the use of pyroelectric catalysts in dynamic treatment
X. Ji and pollutant decomposition, while Zhang et al.[17] focused on
Shandong Province Key Laboratory of Detection Technology for Tumor pyroelectric and chemical coupling in ferroelectric materials. Shi
Makers
Medical College
and co-workers[7] provided a systematic overview of recent re-
Linyi University search progress of piezocatalytic medicine based on piezoelectric
Linyi 276000, China nanomaterials. Piezoelectric, pyroelectric, and ferroelectric ma-
terials are closely related and share some common characteris-
The ORCID identification number(s) for the author(s) of this article tics, but they also have distinct properties. It is worth noting that
can be found under https://doi.org/10.1002/adma.202308726
there is an overlap between these three types of materials. Many
DOI: 10.1002/adma.202308726
Adv. Mater. 2024, 36, 2308726 2308726 (1 of 28) © 2023 Wiley-VCH GmbH
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ferroelectric materials also exhibit piezoelectric and pyroelectric

properties to some extent. Fully understand the relationship be-
tween these three types of materials and the combination of these
characteristics opens up various applications in sensors, treat-
ment of disease, energy harvesting, and other areas of technology.
Recently, Li et al.[4] provided a summary of the catalytic applica-
tions of these three types of nanomaterials in environmental re-
mediation, energy regeneration, and chemical synthesis. Despite
their excellent catalytic properties, there has yet to be a compre-
hensive review of the potential biomedical applications of piezo-
electric, pyroelectric, and ferroelectric nanomaterials. Such a re-
view could provide valuable insights into current research and
identify areas where further investigation is necessary. Addition-
ally, it could facilitate the development of innovative medical de-
vices and therapies that leverage the unique capabilities of these
materials.
Nanomaterials are typically materials with dimensions of
100 nm or less and come in a variety of forms. In compari-
son to bulk materials, nanomaterials have several advantages.
Nanomaterials have a huge specific surface area, providing more
reactive active sites and improving biological interactions. This
makes nanomaterials better for drug delivery, imaging, and
biosensing.[18] Synthetic approaches can also change nanoma- Figure 1. The mechanism of piezoelectricity, pyroelectricity and ferroelec-
tricity in biomaterials and their biomedical applications.
terial sizes to match application needs and provide precise con-
trolled release and targeted delivery. Due to their chemical sta-
bility, nontoxicity, biocompatibility, and high catalytic proper-
ties, nanomaterials have been studied in biomedical fields for force of materials. Conversely, the application of a voltage results
decades, and their construction has become a major research in macroscopic strain. Piezoelectric materials are typically non-
focus.[19–23] Therefore, in our review, recent advancements in the centrosymmetric crystals that generate a pressure-induced volt-
use of piezoelectric, pyroelectric, and ferroelectric nanomateri- age between two end faces.[25] When subjected to external stress,
als for biomedical applications are discussed. Specifically, we fo- the crystal is polarized, resulting in piezoelectric charges of oppo-
cus on their potential uses in biosensing, biofilms, antimicrobial site sign and potential, known as the piezoelectric effect.[26] Un-
and wound healing, and cancer therapy. We start by introducing der mechanical vibration, piezoelectric materials can accumulate
the basic concepts and principles behind these effects and high- negative and positive charges on their opposite surface, leading to
lighting the differences and connections between them. Next, we catalytic reactions known as piezoelectric catalysis. Unlike pho-
describe three mechanisms: 1) the piezoelectric effect, which im- tocatalytic reactions, piezoelectric catalysis relies on the induced
proves catalytic activity via a piezoelectric potential created by an charge from mechanical force rather than photoexcited charge.
external mechanical action or the transfer of mechanical energy The ability of piezoelectric materials such as BaTiO3 and ZnO
into chemical energy; 2) the pyroelectric effect, which involves to catalyze water splitting into H2 and O2 in response to ultra-
converting heat to chemical energy utilizing pyroelectric mate- sound stimulation was demonstrated by Hong et al. in 2010.[27]
rials and temperature-induced polarization changes; and 3) the This process involves the deformation of the ZnO material under
ferroelectric effect, which employs the ferroelectric potential to an external force, generating a strain-induced electromotive force
drive or regulate various catalytic reactions. These mechanisms on the material’s surface, transferring charge to water molecules,
are summarized in Figures 1 and 2 and elaborated upon in the causing redox reactions, and ultimately decomposing H2 O. The
following sections. Finally, we discuss potential prospects and energy conversion efficiency of this process can reach 18%, pro-
problems for the use of piezoelectric, pyroelectric, and ferroelec- viding a simple and low-cost technology for water decomposition.
tric materials in biomedical applications in the future. This in- This discovery led to the proposal of the piezoelectric chemical ef-
cludes identifying areas where further investigation is necessary, fect, also known as the piezoelectric catalytic effect, in later stud-
as well as exploring new and innovative approaches to leverage ies.
the unique properties of these materials for medical devices and When piezoelectric materials are stressed externally, their crys-
therapies. tal structure changes, leading to the creation of nonzero dipole
moments in the crystal lattice. This sort of chemical reaction is
2. Mechanism known as a piezocatalytic reaction. Negative and positive charges
are dispersed on the opposing sides of the piezoelectric ma-
2.1. Piezoelectric Effect and Piezoelectric Catalysis terial, creating a polarizing potential as a result.[27] Noncen-
trosymmetric materials, such as piezoelectric, pyroelectric, and
Piezoelectricity, an interesting phenomenon that Jacques and ferroelectric materials, frequently exhibit piezoelectric features.
Pierre Curie first noticed in 1880,[24] is used to describe the capac- Piezoelectric materials are capable of generating chemical energy
ity to become electrically polarized in response to the mechanical from mechanical energy, allowing them to participate in redox
Figure 2. The catalytic mechanisms and their relationship of piezoelectric, pyroelectric and ferroelectric materials.
reactions. When a piezoelectric material is subjected to mechan- changes in polarization within the pyroelectric material and the
ical stress, it produces local polarized charges on its surface, consequent generation of pyroelectric charges on its surfaces.[16]
forming a piezoelectric field. This generates free electrons and The process of pyroelectric catalysis relies on certain essen-
holes that are thermally excited and separated spatially, moving tial conditions, including the sufficient thickness of pyroelectric
toward opposite surfaces of the catalyst. The buildup of these catalysts, operating temperature within TC limits, and tempera-
free charges on the crystal’s relative surface causes surface re- ture fluctuations. At thermal equilibrium, there is no catalytic ac-
dox reactions, which allow the transformation of mechanical en- tivity. However, in the presence of a heat source, the difference
ergy into chemical energy.[1,28–31] Significant advancements in in temperature between the two ends of the material leads to
this field of study have been accomplished recently, resulting in the excitation and separation of electrons and holes, which cre-
the exploitation of various piezoelectric material-based catalysts, ates a difference in the electric potential. This induces an elec-
such as ZnO,[32–34] BaTiO3 ,[32–34] NaNbO3 ,[35,36] and KNbO3 ,[37] tric field within the material that mediates electron–hole sepa-
C3 N4 ,[38] CdS,[39] and MoS2 .[40] ration, allowing electrons to move to a positive potential for re-
duction reactions and holes to move to a negative potential for
oxidation reactions. Chemical species with opposite charges are
attracted to and accumulate on the surface of catalysts. ROS, in-
2.2. Pyroelectric Effect and Pyroelectric Catalysis cluding superoxide radicals and hydroxyl radicals, are created
over time as a result of the conversion of these species. ROS pos-
Pyroelectric materials have the capacity to separate the posi- sess a robust oxidizing capability that can breakdown organics
tive and negative charges brought about by temperature varia- into smaller molecules such as CO2 and H2 O.[46] Furthermore,
tions, converting thermal energy into electrical energy.[41] Ad- reactive species that are induced by pyroelectricity can engage in
ditionally, this same process of charge separation and voltage redox reactions with many reactants, including water and bac-
generation can lead to ROS generation and catalytic activity terial cells. Additionally, the positively and negatively charged
within the pyroelectric material.[42,43] Pyroelectric materials that charges produced by the pyroelectric effect have the potential to
are able to function as catalysts are referred to as pyroelectric cat- interact directly with reactants. Depending on the specific pyro-
alysts, which have several advantages over traditional photoelec- electric catalysts and their intended applications, the intermedi-
tric/piezoelectric catalysts. Temperature changes can cause py- ate processes and final products will differ. Therefore, the ability
roelectric catalysis, which produce positive and negative charges of the catalysts to adsorb chemical species and separate charge
for redox processes.[44,45] The slight atomic movements within carriers significantly impacts the pyroelectric catalytic efficiency,
the crystal structure caused by changes in temperature lead to similar to photocatalysis. It is worth noting that thermodynamic
equilibrium is formed without temperature fluctuations, result- 3. The Difference and Connection between
ing in no change in the polarization magnitude. Thus, it becomes Piezoelectric, Pyroelectric, and Ferroelectric
impossible to facilitate pyroelectric catalytic reactions. However, Materials
by periodically altering the temperature, pyroelectric materials
can continually stimulate pyroelectric reactions, resulting in con- The piezoelectric effect is often linked to noncentrosymmetric
tinuous ROS production.[16] crystals, but similar properties can be found in other materials,
Thermoelectricity is also related to the difference in tempera- such as pyroelectric and ferroelectric substances. When these
ture to produce electricity, but it has a different underlying mech- materials are exposed to mechanical stress, they modulate their
anism than pyroelectricity. Thermoelectric materials produce an electric dipoles, which causes negative and positive charges to
electric current in the presence of a temperature gradient, an ef- branch to opposite sides of the material.[24] Spontaneous polar-
fect that occurs when there are differences in the thermoelectric ization can be found in pyroelectric materials even without an
properties of the two sides of the material. The temperature gradi- external force, with their electric polarization varying based on
ent causes electrons or holes to move from the hot side to the cold temperature.[61,62] The subgroup of pyroelectrics known as ferro-
side, creating an electric field and voltage.[43,47,48] Pyroelectric ma- electrics demonstrates spontaneous polarization, which can be
terials have applications in a variety of devices, such as infrared inverted by the use of an electric field, leading to the formation of
detectors, thermal sensors, and thermal imaging cameras.[16] a ferroelectric hysteresis loop.[63] Ferroelectrics, however, change
Thermoelectric materials are often used for power generation or from being ferroelectric to being paraelectric when their Curie
cooling, and they can convert waste heat into electricity.[15] De- temperature (Tc ) is exceeded.[4] Polarization alignment causes lo-
spite their differences, both thermoelectric and thermoelectric calized charges on both end surfaces in ferroelectrics with a sin-
are based on converting temperature differences into electrical gle domain; however, in polycrystalline ferroelectrics, arbitrarily
energy, making them valuable in various fields of technology and oriented domains may be aligned by an adequately strong exter-
research. nal electric field.[4]
In other words, ferroelectric crystals are also piezoelectric, and
they have asymmetry in their crystal structures. These crystals,
which fall under the category of piezoelectric crystals, must be
2.3. Ferroelectric Effect and Ferroelectric Catalysis ionic in nature and show spontaneous polarization. Notably, not
all ferroelectric crystals are piezoelectric crystals. Another kind of
Due to spontaneous polarization, ferroelectric materials have the piezoelectric crystal is a pyroelectric crystal, which likewise lacks
ability to modify adsorption and redox processes on charged polar a symcenter. Alterations in temperature can impact the strength
surfaces, as was discovered in the 1950s.[49] Free carriers can be of polarization, but again, not all piezoelectric crystals are py-
separated in different directions by an electric field that ferroelec- roelectric. While pyroelectric materials need crystal structures
tric materials can produce internally. When an external electric with a specific axis of polarity that are also noncentrosymmetric,
field is supplied, it is possible to vary the polarization direction piezoelectric materials need noncentrosymmetric crystal struc-
and strength, leading to more degrees of freedom to alter the local tures. Only 20 of the 32 different types of crystal formations ex-
band bending at the interface between reactive species and ferro- hibit piezoelectric characteristics. Furthermore, 10 out of these
electric materials. As a result, ferroelectric materials have special 20 types exhibit spontaneous polarization within their structures,
qualities that allow for catalytic redox reactions and dynamic sur- giving them pyroelectric qualities. The ferroelectric crystal struc-
face control.[50,51] Ferroelectric materials use iron electrode polar- ture belongs to the category of pyroelectric crystal structures, and
ization to control various catalytic redox reactions, called ferro- a sufficiently strong electric field from the outside can cause it to
electric catalysis. spontaneously polarize in the opposite direction. In conclusion,
A Ps –E hysteresis loop is formed when the spontaneous po- ferroelectric materials fall under both the pyroelectric and piezo-
larization of a ferroelectric (Ps ) is changed by an external elec- electric categories, whereas pyroelectric materials constitute a
tric field (E). Negative and positive bound polarization charges subset of piezoelectric materials. Figure 2 visually demonstrates
are generated on the appropriate polarized surfaces as a result the relationships among piezoelectric, pyroelectric, and ferroelec-
of the existence of Ps .[52] Typically, these surface charges are tric materials.[56]
balanced or compensated through external screening mecha-
nisms, which incorporate adsorbed charged species found in the 4. Preparation Method
environment.[53–55] For example, in the case of polarized ferro-
electric materials (FEMs) immersed in an aqueous solution, an- At present, the preparation technology of piezoelectric, pyroelec-
ions and negatively charged molecules will screen the positive tric, and ferroelectric materials mainly includes the hydrother-
polarization charge. However, many ferroelectric materials, such mal method, sol–gel method, coprecipitation method, and elec-
as lead-based compounds such as PZT,[56] include toxic compo- trospinning method. In the last few years, these materials have
nents that are hazardous to human health,[57,58] limiting the avail- also been fabricated by modern techniques such as electrospin-
ability of ferroelectric materials for disease treatment to date. On ning and 3D bioprinting (Table 1).
the other hand, some ferroelectric materials may undergo phase
shifts or depolarization when used for long periods of time or 4.1. Hydrothermal Synthesis
when exposed to biological environments, leading to degradation
or loss of ferroelectric properties, thus affecting the catalytic per- Hydrothermal synthesis is a reaction that occurs in a closed sys-
formance in practical applications.[56,59,60] tem at a specific temperature under the autogenous pressure of
Table 1. Preparation method of piezoelectric, pyroelectric, and ferroelectric nanomaterials..
Method Characteristic Materials Catalyst Refs.
Hydrothermal method Simple operation Piezoelectric material BaTiO3 [25,64,65,66]

Low cost Bi2 MoO6 NRs [67]
Small particle size
ZnO [68]
Uniform distribution
NSH700 NSs [69]
SDBTO [70]
T-BaTiO3 [71]
BaTiO3 @Au [72]
Au@BTO [73]
(K, Na) NbO3 [74,75,76]
Pyroelectric material BST/BTS [77]
Bi2 Te3 [78]
Bi13 S18 I2 [79]
BaTiO3 [64,80]
Stripping method High sample purity Piezoelectric material NSH700 NSs [69]
SIS [81]
Magnetron sputtering Quick film creation Piezoelectric material NPR-NNO [82]
method High film density NP-NNO [83]
Superb film uniformity
Pyroelectric material BaTiO3 [41]
Ferroelectric materials PZT [84]
Deposition method Uniform density Piezoelectric material BTO@Au [85]
Pyroelectric material Bi2 Te3 [86]
Ferroelectric materials SHRIMPs [87]
AgHgNpNf [88]
3D printing Size controllable Piezoelectric material ZPFSA [89]
Solution casting method Easy shape control Piezoelectric material 𝛽-Gly/CS [90]
Ferroelectric materials PVDF/rGO [91]
Electrospinning method High porosity Piezoelectric material PVDF [92]
Low density PVDF/DA [93]
High specific surface area
BaTiO3 /TiO2 [94]
High surface-to-volume ratio
Ferroelectric materials PVDF/HHE OPNs [95]
In situ synthesis Controlled synthesis speed Pyroelectric material M/CdS [96]
BTe-Pd-Au-R [97]
Bi2 Te3 [86]
Sol–gel method Good uniformity Piezoelectric material Ba0.75 Sr0.25 TiO3 (BST) [98]
BaTiO3 [99]
water as a solvent. This method enables the production of high- et al.[68] described the synthesis of ZnO nanowire-modified poly-
quality nanocrystals through a one-pot reaction inside a sealed dimethylsiloxane micropillar arrays using the hydrothermal tech-
autoclave at high temperatures. Reaction parameters such as nique. The resulting ZnO nanowire arrays are highly bendable,
temperature, pressure and time can be precisely controlled. This ultrafast responsive, and have low thermal expansion, making
makes it possible to synthesize materials with specific properties them ideal for use as flexible electronic skins. Compared to con-
that cannot be achieved by traditional methods. Wang et al.[64] ventional solid-phase methods that require high-temperature cal-
effectively produced BaTiO3 nanoparticles utilizing Ti(C4 H9 O)4 cination treatment, the hydrothermal method typically only re-
and Ba(OH)2 as raw materials, with a size of 130 nm and a fer- quires a temperature of ≈200 °C, which is easy to implement and
roelectric tetragonal form. These highly piezoelectric nanoparti- has high practical value. In summary, hydrothermal synthesis is
cles can generate free radicals (• OH or • O2 − ) when subjected to a promising technique for producing high-quality nanocrystals
ultrasonic vibrations, making them useful for teeth cleaning ap- with diverse morphologies, sizes, and dimensions.
plications. Hydrothermal methods offer several advantages, in- The hydrothermal method is a popular technique used to pre-
cluding simplicity of operation, low cost, application to gener- pare pyroelectric nanomaterials, which have potential applica-
ate diverse shapes and sizes, and the ability to create hierarchi- tions in cancer therapy. Ji et al. and Wang et al. successfully
cal nanostructures with specific geometries.[25] For instance, Ha synthesized thermoelectric materials using this method with
promising results. Ji et al.[77] prepared Bi0.5 Sb1.5 Te3 (BST) and After stripping, they created the previously reported perovskite
Bi2 Te2.8 Se0.2 (BTS) nanoplates consisting of Z scheme thermo- crystal structure by annealing PZT at 650 °C for 30 min.[102,103]
electric heterojunctions (BST/BTS) using a two-step hydrother- In the second photolithography step, they deposited an ITO film
mal method. In the tumor microenvironment, catalytic O2 re- (500 nm) using magnetron sputtering and patterned it by strip-
duction and H2 O2 dissociation lead to rapid electron–hole pair ping. The produced PZT nanoribbons can be employed as sen-
separation and dual nondependent ROS (• O2 − and • OH) gener- sitive extracellular sensors to find minor cellular deformations
ation and thus have potential therapeutic tumor potential. Sim- because they are biocompatible with cells. This gives electrome-
ilarly, Wang et al.[79] inserted a third biocompatible element, io- chanical biosensing a stretchable, minimally intrusive platform.
dine (I), to reconstitute N scheme Bi2 S3 to obtain the piezoelec-
tric nanocatalyst Bi13 S18 I2 . Bi13 S18 I2 NRs produced a sizable tem-
perature increase and had good photothermal conversion effi- 4.3. Electrospinning Method
ciency at high photon temperatures when exposed to 808 nm
laser irradiation. This suggests that these materials could be Electrostatic spinning is a widely used method for the preparation
used for targeted cancer therapy. Furthermore, the hydrothermal of nanofibers from a variety of materials.[104] The process involves
method is an effective technique for controlling the morphol- the continuous ejection of a polymer solution from a jet, which is
ogy of nanomaterials. Song et al.[78] synthesized polytypic Bi2 Te3 then formed into nanofibers on a receiving device by stretching
nanoplates (BT NPs) using a hydrothermal strategy assisted by it in a strong electric field.[14] Nanofiber membranes produced
ethylenediaminetetraacetic acid (EDTA). By adjusting the ratio of through electrospinning have several advantages, such as high
EDTA/Bi3+ , BT NPs of various shapes or sizes were created. The porosity, low density, and high specific surface area, which show
produced BT NPs, which had various sizes and surface architec- great application prospects in biomedical applications. Moreover,
tures, exhibited significant radio sensitizing effects and signifi- combining them with other materials can result in additional
cantly reduced cervical cancer development. Overall, these stud- functions. As a result, this technique has numerous applications
ies demonstrate the versatility and potential of the hydrothermal in several fields, including filtration, battery technology, superca-
method for synthesizing pyroelectric nanomaterials with various pacitors, catalysis, sensing, energy conversion, and biomedicine.
morphologies and applications in cancer therapy. Researchers have reported that using electrospun nanofibers has
Meanwhile, the hydrothermal method is also used to syn- led to significant improvements in catalytic performance.[105] For
thesize (K, Na) NbO3 -based piezoelectric materials. For exam- instance, Wu et al.[94] developed a core/shell BTO/TiO2 nanocom-
ple, using KNN gel powder as a precursor, Meng et al.[74] used posite using the electrospinning method. The polarization gen-
hydrothermal method to analyze the phase boundary of verti- erated by its piezoelectric phase significantly enhanced the cat-
cally aligned KNN nanoparticles at 190 and 220 °C, showing en- alyst’s catalytic activity. Under ultrasonic and ultraviolet excita-
hanced piezoelectric properties. Jiang et al.[75] synthesized KNLN tion, rhodamine B (RhB) dye degradation by polarized BTO/TiO2
nanocrystals with different Li content on Nb:SrTiO3 (Nb:STO) nanofibers was found to be 3.22 and 3.51 times more rapid than
single crystal substrate by hydrothermal method. Wang et al.[76] that of BTO/TiO2 nanofibers and TiO2 nanofibers under pure ul-
used hydrothermal method to synthesize basic niobate under dif- traviolet irradiation, respectively. Li et al.[93] created a study on the
ferent conditions and found that the extension of reaction time fabrication of nanofibers (NFs) made of polyvinylidene difluoride
was conducive to the formation of NaNbO3 . Compared with the (PVDF)/dopamine (DA) using a one-step electrospinning pro-
(K, Na) NbO3 (KNN) nanorods prepared by the traditional solid cess. The resulting PVDF/DA-NF showed remarkably improved
phase method (D33-80 pc/N), the piezoelectric properties of the piezoelectric properties, outstanding stability, and biocompatibil-
nanorods are significantly improved at 0.6 °C, 240 °C, and 4 h ity, which demonstrate its potential for various biomedical appli-
hydrothermal temperatures (D33-120 pc/N). The hydrothermal cations. The researchers attributed the arrangement of 𝛽-phase
method is an effective method to improve the piezoelectric prop- PVDF to the self-assembled core–shell structure, which also pro-
erties of niobate. moted 𝛽-nucleation. The ─NH2 group on DA and the ─CF2
group on PVDF were found to have a strong intermolecular in-
teraction that played a vital role in this process.
4.2. Magnetron Sputtering Method
Magnetron sputtering is characterized by fast film formation, 4.4. Sol–Gel Method

high film density, and good uniformity. Compared with other
thin film deposition techniques, magnetron sputtering offers a Sol–gel method is a chemical method for the synthesis of various
relatively high deposition rate and is a well-established thin film nanostructures, especially metal oxide nanoparticles. In the sol–
preparation technique for a wide range of materials.[100] The elec- gel method, substances with a high concentration of chemically
trons between the target and substrate are simultaneously driven active components are solidified in a solution, sol, or gel and then
by the electric field during the magnetron sputtering process and heated to produce oxides or other solid substances. Due to the low
confined by the magnetic field. This results in collision between reaction temperature, the sol–gel method allows precise control
the electrons and gas molecules, leading to higher ionization of the composition and structure of the resulting material. Since
rates of the plasma.[101] Nguyen et al. successfully synthesized the gel obtained from the hydrolysis process is wet, it should be
high-performance PZT nanoribbons using magnetron sputter- dried using an appropriate method depending on the desired
ing. They first stripped the PZT with AZ 5214 photoresist and properties and application of the gel.[106–108] Xu et al.[99] used
then deposited it epitaxially using magnetron sputtering for 5 h. the traditional sol–gel method combined with electrospinning
technology to synthesize BTO nanofibers with extremely high 5.1.1. Biosensing

piezoelectric activity. They conducted a piezoelectric catalytic ex-
periment on RhB and found that the catalytic decomposition ef- Piezoelectric sensors have the ability to identify specific
ficiency of BTO nanofibers was 97.5% under 60 min of ultra- molecules and proteins in biological samples, making them a
sonic vibration. Electron spin resonance (ESR) experiments con- valuable tool in biomedical research. [116–119] A high-speed piezo-
firmed that the active group in the catalytic process was mainly electric material is particularly ideal for this application. AIN
hydroxyl radicals. Li et al.[98] used Ba(OH)2 8H2 O, Ti(OBu)4 , and piezoelectric acoustic sensors offer immediate response and
Sr(OH)2 ·8H2 O as raw materials and then annealed them for 2 h measurable data.[120,121] In studies on pesticide residue detection,
at 500 °C using the sol–gel method to obtain Ba0.75 Sr0.25 TiO3 Chen et al.[120] developed a highly sensitive AIN sensor. Acetyl-
nanoparticles. The catalytic degradation rate of rhodamine B cholinesterase was attached to one side of the piezoelectric res-
reached 99.0% within 3 h. onator’s sensitive coating, enabling detection of trace amounts
of organic phosphorus pesticides in solution by comparing the
decrease in frequency shift with the level at which no frequency
shift occurs. AIN sensors are highly sensitive and possess low
4.5. Deposition Method detection limits while responding linearly and with good repro-
ducibility. The detection limit for typical organophosphorus pes-
Deposition methods mainly include physical vapor deposition, ticides was 4.3 × 10−11 m. These sensors are able to detect di-
chemical vapor deposition, and electrodeposition, which have verse biological processes, such as genetic hybridization, interac-
the advantages of precise control, high purity, and wide ap- tions between proteins and ligands, and antigen–antibody bind-
plicability, and are widely used in the synthesis and fabrica- ing, providing valuable insights into biological reaction kinetics.
tion of a variety of materials, including coatings, thin films, The method is also adaptable for use in other fields, such as envi-
and nanoparticles.[109–111] Electrochemical deposition is a popu- ronmental monitoring and clinical diagnostics. To conclude, the
lar method for preparing ferroelectric materials. Thin mercury development and optimization of these sensors could have sig-
films electrodeposited on glass carbon or various metals, includ- nificant implications for a variety of biomedical and scientific ap-
ing platinum, iridium, copper, or silver, are commonly used by plications.
researchers to create useful electrodes.[112] Templates or thin or- Flexible ferroelectric films formed of composites of PVDF and
ganic films made of cellulose acetate or Nafion can be used to graphene oxide (GO) have a remarkable capacity to sense and dis-
cover the surfaces of these electrodes to boost their mechani- tinguish a variety of stimuli, such as temperature, pressure, and
cal stability, it also allows regular distribution, size control, and both static and dynamic pressure, with a high degree of sensi-
uniform density of nanoparticles electrodeposited on its covered tivity. The process used to prepare the PVDF/GO film involves
glassy carbon electrode.[113–115] For example, Valera et al.[88] im- crystallizing PVDF into its 𝛽 phase at 50 °C, annealing it to in-
plemented a Nafion membrane as a template to deposit silver- crease conductivity at 160 °C, and then quenching it with liq-
mercury alloy nanoparticles onto a glass carbon-based electrode. uid nitrogen. Figure 3a displays a schematic of a sensor array,
This resulted in an AgHgNpNf/GC electrode capable of indi- where a gold electrode array is positioned on the opposite side
rectly measuring cysteine, glutathione, and metallothionein. Re- of the film (18 × 12 pixels) for simultaneous arterial pulse moni-
searchers optimized the electrode using cobalt as a catalyst based toring and temperature sensing (Figure 3b).[91] Due to their flex-
on the Brdiácka reaction to measure catalytic hydrogen precipita- ibility, stretchability, and cost-effectiveness, these wearable skins
tion signals. Hence, this approach may be employed to indirectly have tremendous potential in areas such as disease prevention
determine standard solution concentrations of cysteine and glu- and early disease prediction. Liu et al.[92] produced a self-powered
tathione, as well as metallothionein levels in serum from lead- wearable PVDF sensor that is capable of respiratory sensing and
exposed rats. medical monitoring. Figure 3c shows the structure of the piezo-
electric sensor, which is sandwiched between gold electrodes and
a silicon substrate with the aim of improving flexibility. The out-
5. Biomedical Applications put open-circuit voltage and short-circuit current generated by
the generator are as high as 1.5 V and 400 nA, respectively. This
5.1. Biomedical Applications of Piezoelectric Materials sensor has the capability of detecting subtle muscle movements
and demonstrates promising application potential in the rehabil-
The most recent advancements in microelectromechanical sys- itation of patients suffering from stroke paralysis. Additionally, it
tems, manufacturing, biotechnology, and materials have led to can be utilized for recording physiological signals such as respi-
the development of a number of thrilling biosensors. The bio- ration or detecting human gestures and vocal cord vibrations. In
compatible piezoelectric materials used in the construction of sum, the flexible and versatile nature of PVDF and GO composite
these biosensors allow them to be used in a variety of applica- films, combined with the innovative designs of wearable sensors,
tions and to be firmly incorporated into biological systems. For presents exciting opportunities for advancements in healthcare
instance, some of these devices are capable of sensing biological technology.
forces, while others stimulate tissue growth and aid in the healing Li et al.[93] recently reported a straightforward method for cre-
process. Additionally, these biosensors show potential in treating ating core/shell PVDF/DA nanofibers (NFs) using electrospin-
medical problems such as cancer. Overall, the development and ning. They were able to promote the spontaneous organization
increasing adoption of these innovative biosensors are expected of 𝛽-phase PVDF during the electrospinning process by using
to revolutionize the field of biomedical research and treatment. 1.0 wt% DA. To form a continuous DA nanoshell around the
Figure 3. a) Human palm temperature distribution detection. b) Wearable electronic skin photo for measuring the temperature and arterial pulse
rate. Reproduced with permission.[91] Copyright 2015, American Association for the Advancement of Science. c) Schematic diagram of a wearable PVDF
electrospinning sensor for health monitoring. Reproduced with permission.[92] Copyright 2017, IOP Publishing. d) Schematic of the order and orientation
of PVDF chains caused by interactions between molecules during the electrospinning of PVDF/DA core/shell nanochains. e) The implantable sensor
based on PVDF/DA NF. f) Surgical pictures of the abdominal diaphragm (upper) and femoral artery (lower) with PVDF/DA NF sensors attached. g)
Blood pulsation and diaphragm movement in mice in various physiological states produce piezoelectric voltage signals. State i: anesthesia; State ii:
excessive anesthesia; State iii: persistent hyperanesthesia. Reproduced with permission.[93] Copyright 2021, Wiley-VCH.
PVDF NF core, charged DA molecules were electrostatically at- a normal anesthesia state, the output voltage displays a rhythmic
tracted to one another, which caused self-assembly (Figure 3d). signal (green curve, Figure 3g). The VPP driven by diaphragm
The PVDF chain is aligned, and 𝛽-phase PVDF nucleation is motion is 40 ± 20 mV, with a frequency of 1.8 Hz. When the
aided by the potent intermolecular interaction between the ─CF2 mice entered an excessive anesthesia state (2.5% isoflurane), the
group on PVDF and the ─NH2 group on DA. This interaction membrane VPP decreased to 20 ± 10 mV, and the femoral artery
also helped stabilize the 𝛽 phase. PVDF/DA NFs prepared in this VPP decreased to 2.0 ± 0.03 mV (red curve, Figure 3g). The de-
way possessed exceptional piezoelectric performance, stability, crease in output voltage is mainly due to respiratory suppression
and biocompatibility. Piezoelectric sensors can be conformably and peripheral arterial wall loosening caused by anesthesia. They
affixed to body surfaces, including the wrist, neck, and chest, us- demonstrated a potent ability to detect mouse diaphragm con-
ing flexible films consisting of randomly stacked PVDF/DA NFs. traction and peripheral arterial wall changes quickly and accu-
These sensors accurately read weak mechanical stimuli from rately under different physiological conditions. These features
blood pulsation, demonstrating their potential in vivo applica- make them useful for the early diagnosis of pulmonary and
tions. Even the diaphragm and femoral arteries of mice were im- cardiovascular conditions, as well as several acute and chronic
planted with packaged PVDF/DA NF sensors (Figure 3e,f). These pressure-related disorders. Piezoelectric PVDF/DA NFs can also
sensors monitored diaphragm movement and arterial pulsation, produce beneficial electrical stimulation from biological defor-
identifying respiratory patterns and arterial stiffness under vari- mation for the treatment of diseases or tissue regeneration and
ous physiological conditions (Figure 3g). When the mouse is in repair. The development of intelligent biomedical electronics in
fields such as regenerative medicine, medication delivery, and the separation of electron–holes and enhanced SDT efficiency
medical therapy will be greatly impacted by this soft piezoelec- (Figure 4d). Au@BTO exhibited excellent SDT antibacterial ac-
tric material and device design. tivity, with 99.23% and 99.94% inhibition against Escherichia coli
Moreover, (K, Na)NbO3 (KNN) has good piezoelectric proper- and S. aureus after just 4 min of sonication (Figure 4e). Fur-
ties, and recently, Jiang et al.[75] achieved large-area controllable thermore, Au@BTO also demonstrated a good SDT effect in the
growth of Li-doped KNN single-crystal nanorod arrays, and uti- mouse S. aureus skin infected wound model. Notably, ROS gener-
lized A-site Li doping to achieve the modulation of the nanorods’ ated during the acoustic dynamic process not only have strong an-
orthorhombic-quadratic phase boundaries, to obtain KNN-based tibacterial activity but also encourage animal cell growth and mi-
lead-free piezoelectric nanorods with an ultrahigh piezoelectric gration, after 24 h of incubation, 94.76% of cell covering area were
constant of 814 pm V−1 , the D33 is calibrated from pm V−1 to 814 obtained for the Au@BTO + US treatment (Figure 4g), which in
pm V−1 . Based on the ultrahigh-voltage electrical properties of the turn accelerates wound healing (Figure 4f).
KNLN nanorods, they constructed a sandwich-structured micro- Recently, Liu et al.[72] developed a hydrogel dressing with char-
pressure sensor device, which can be used as a self-powered wear- acteristics mechanically similar to the extracellular matrix, strong
able sensor device to monitor the movement status of human fin- adhesion, good self-healing properties, and significant bacterici-
gers, elbows, and other joints, and also sense the tiny vibrations dal ability to accelerate wound repair in infected skin (Figure 5a).
in the environment generated by the human body’s walking, run- The researchers synthesized approximately cuboidal BaTiO3 (BT)
ning, or jumping, thus realizing real-time self-powered detection nanoparticles through a hydrothermal method (Figure 5b), which
of the human body’s movement conditions. It has a broad appli- were found to have excellent piezoelectric response properties us-
cation prospect in the field of intelligent sports and health mon- ing piezoelectric response force microscopy (Figure 5c,d). They
itoring. then added these BT nanoparticles to a porous hydrogel to create
an injectable BT-OHA/THM-APMH (BT-Gel) (Figure 5e). The re-
searchers verified that ultrasound triggers the generation of ROS
5.1.2. Antimicrobial and Wound Healing using ESR techniques, which resulted in a 98.5% killing rate
against E. coli within 10 min under the action of US (Figure 5f).
Exogenous ultrasound (US) is a cutting-edge technique that is Of all the groups studied, the group after receiving BT gel + US
used in sonodynamic therapy (SDT) to activate photosensitiz- for 48 h demonstrated the most successful wound repair, suggest-
ers and produce highly hazardous ROS. Sonosensitizers made ing that the bactericidal activity of ROS triggered by US piezoelec-
of piezoelectric materials exhibit special application potential in tricity could enhance wound healing (Figure 5g). Liang et al.[89]
the treatment of infectious and bacterial disorders. utilized 3D printing technology to create ZPFSA, a new piezo-
Lei et al.[70] developed an ultrasonic (US)-responsive piezoelec- electric hydrogel scaffold. This innovative scaffold was composed
tric catalyst using sulfur-doped barium titanate (SDBTO) for ef- of PVDF and sodium alginate with the incorporation of zinc ox-
fective bacterial elimination and bone regeneration (Figure 4a), ide (ZnO) nanoparticles. The resulting ZPFSA scaffold demon-
offering a remarkable 97.12% antibacterial effectiveness against strated a dual-mode piezoelectric response model that was pre-
Staphylococcus aureus. The X-ray images of tibias after 28 days dominantly driven by vertical expansion and horizontal friction.
of different processing (Figure 4b) demonstrate that the groups This model successfully mimicked and amplified endogenous
treated with VAN and SDBTO-1 NP + US exhibit minimal evi- bioelectricity to accelerate wound healing and reduce scarring.
dence of necrotic bone or bone destruction. According to these The ZPFSA 0.5 composite scaffold, which contains 0.5% ZnO
findings, vancomycin and SDBTO-1 NPs have potent antibac- nanoparticles, outperformed other composite scaffolds in terms
terial capabilities in vivo that can effectively stop localized in- of biocompatibility, antibacterial power, and stability of the piezo-
flammation and the associated damage to bone structure. In an- electric response. The tensile strength of the ZPFSA 0.5 piezo-
other study, Feng et al.[122] employed piezoelectric semiconduc- electric support can reach 1415 kPa, and the strain is ≈33%.
tor nanomaterials in SDT for osteomyelitis treatment. Through The antibacterial rates against E. coli and S. aureus were 99.8%
electrostatic interactions, they incorporated piezoelectric MoS2 and 99.93%, respectively. Researchers were able to demonstrate
nanosheets onto the surface of a porphyrin-based hollow metal– promising results in SD rat skin defect models by promoting
organic framework (HNTM). The piezoelectric polarization of wound healing with the microcurrent generated by the ZPFSA
MoS2 induced by US promoted charge transfer at the HNTM– piezoelectric scaffold, the wound healing rate can achieve 98.74
MoS2 heterointerface (Figure 4c). Methicillin-resistant S. aureus ± 0.87% on day 14.
(MRSA) treated with HNTM–MoS2 (500 μg mL−1 ) under US ir-
radiation (1.0 MHz, 1.5 W cm−2 , 50% duty cycle) for 15 min, can
achieve an antibacterial rate of 98.5%. Rat bone marrow was suc-
cessfully cleared of MRSA by increasing ROS production. This 5.1.3. Cancer Treatment
resulted in the elimination of MRSA infection within bone tis-
sue and a reduction in inflammation. In the study of piezoelectric semiconductor nanomaterials used
Piezoelectric semiconductor nanoparticles can perform better in SDT, researchers have discovered that ultrasound has mul-
in SDT antibacterial applications by creating a heterojunction. tiple effects on these materials. First, it can activate the piezo-
This was demonstrated by Wu et al.[73] through the construc- electric properties of the nanomaterials deep within tumor tis-
tion of a barium titanate piezoacoustic sensitizer Au@BaTiO3 sues through both cavitation and piezoelectric mechanisms. This
(Au@BTO) with a Schottky heterojunction structure. Under the causes the production of cytotoxic ROS, leading to irreversible
influence of US (1.5 W cm−2 , 1 MHz), this structure promoted damage to tumor cells. In addition, ultrasound can regulate the
Figure 4. a) Piezoelectric catalytic mechanism for antimicrobial and osteogenic therapy. b) Tibia X-ray images of different treatment groups. Reproduced
with permission.[70] Copyright 2022, Elsevier. c) Catalytic mechanism of HNTM–MoS2 and therapy for osteomyelitis. Reproduced with permission.[122]
Copyright 2022, American Chemical Society. d) Piezoelectric nanocomposite Au@BTO acoustodynamic catalytic mechanism. e) The antibacterial effect
of Au@BTO in vitro. f) Scratch healing of NIH-3T3 cells at different time points. g) Representative images of infected wounds taken at various stages
of the healing process. Reproduced with permission.[73] Copyright 2021, Elsevier.
REDOX capacity of piezoelectric semiconductors by tilting their ation of ROS, such as • O2 − and • OH in the band position, but
energy bands. the transmission of electrons and holes on the surface can be
Zhu et al.[71] researched the piezoelectric qualities of nanoscale aided by the internal electric field created by the Ti4+ offset dur-
barium titanate (BaTiO3 ). They found that under US stimulation, ing US activation, tilting the energy band to generate • OH and
•
they can be polarized to establish an internal electric field, lead- O2 − (Figure 6a). Based on this idea, a thermosensitive hydro-
ing to the flow of holes and electrons to various surfaces, boost- gel that can be injected was made to keep the T-BTO nanopar-
ing ROS production and piezoelectric catalytic processes. The ticles in the tumor area. After US irradiation, tumor growth
bandgap of BaTiO3 nanoparticles is not conducive to the gener- was significantly inhibited 14 days after injection of T-BTO-gel
Figure 5. a) Diagram of preparation of BT-OHA/THM-APMH hydrogel and its promotion of wound healing. b) SEM images of the BT nanoparticles. c)
Piezoelectric amplitude and d) phase plots of the BT NPs. e) SEM images of the hydrogels with different THM-APMH concentrations. f) The growth of
Staphylococcus aureus in different treatments. g) Quantitative analysis of cell migration. Reproduced with permission.[72] Copyright 2023, Elsevier.
into the tumor.[123] Dong et al.[67] proposed glutathione (GSH)- nation of electron–hole pairs on the catalyst surface was further
enhanced SDT based on the excessive presence of GSH in the tu- suppressed by the heterojunction between ZnS/ZnFe2 O4 /ZnO,
mor microenvironment. They synthesized piezoelectrically active which reassigned surface holes and electrons to particular re-
Bi2 MoO6 nanorods (BMO NRs) using the hydrothermal method, gions crucial for redox processes (Figure 6c,d). By utilizing this
which can consume endogenous GSH and disrupt cellular re- piezoelectric-optical catalytic effect, low concentrations of cata-
dox homeostasis in cancer cells. Meanwhile, BMO NRs produce lyst and excitation energy generate ROS bursts in NSH700 NSs.
oxygen vacancies on their surface, which reduces electron–hole To measure the generation of • O2 − through electron transfer, the
recombination and boosts ROS production in SDT. Figure 6b team employed dihydrorhodamine 123 (DHR 123) probes. Flow
shows that the intrinsic energy band of BMO shifts after consum- cytometric analysis showed that exposure to a 650 nm laser and
ing GSH, and under ultrasound stimulation, the negative and US induced apoptosis/necrosis in cells by 46.6%, demonstrat-
positive charges of BMO NRs migrate to different sides, while in- ing near-infrared-triggered cell toxicity (Figure 6e). Furthermore,
ternal polarization occurs, resulting in band bending, making it their observed good tumor suppression in vivo indicates poten-
easier for holes and electrons to separate and for ROS generation. tial for clinical applications (Figure 6f). To summarize, this study
In mice treated with BMO NRs (10 mg kg−1 ) and US (40 kHz; presented a promising new approach to cancer treatment via a
3 W cm−2 ; 50% duty cycle; 5 min) irradiation, the tumor inhi- piezoelectric-optical catalytic mechanism that utilizes NSH700
bition rate reached 96.6%, in vivo experiments have also proven nanoparticles to generate ROS bursts. The researchers’ innova-
excellent antitumor effects. tive nanoparticle synthesis techniques and the use of heterojunc-
Ji and co-workers[69] proposed a novel piezoelectric-optical cat- tions contribute to the efficacy of this approach. This demon-
alytic mechanism that utilizes NSH700 nanoparticles to target strates the potential for near-infrared-triggered cell toxicity and
multiple independent regions for ROS bursts, thereby effectively good tumor suppression in vivo.
treating cancer. The researchers synthesized ultrathin NSH700 It is frequently believed that the quick recombination of the
nanoparticles using calcination and liquid exfoliation techniques electron–hole pairs in inorganic photosensitizers is the cause
to create a piezoelectric-optical catalyst. When stimulated by US of their poor performance. Zhao et al.[124] designed a piezoelec-
and 650 nm laser irradiation, holes and electrons migrate to the tric heterostructure made of Cu2−x O-BaTiO3 that can function
surface following the piezoelectric field. The recombination was both as a photosensitizer and a chemical kinetic agent to in-
prevented by this migration of electron–hole pairs, a critical fac- crease ROS generation and improve cancer treatment outcomes.
tor for efficient photocatalysis. Additionally, unwanted recombi- The Cu2–x O-BTO NCs within this heterostructure exhibit band
Figure 6. a) Diagrammatic representation of the redox reaction of T-BTO nanoparticles under piezoelectric catalysis. Reproduced with permission.[71]
Copyright 2020, Wiley-VCH. b) Band structure of BMO and GBMO NMR materials and formation of • O2 − and • OH under ultrasonic excitation. Re-
produced with permission.[67] Copyright 2021, Wiley-VCH. Charge transfer in c) NSH NSs and d) NSH700 NSs. e) Apoptosis of MCF7 cells cultured
with NSH700 NSs with different excitation energies. f) Representative tumor images of different treatment groups. Reproduced with permission.[69]
bending when exposed to US radiation, causing electron–hole through in vitro adipose-derived stem cell (ADSC) culture and
pair separation and migration. This results in a shift of CB and in vivo experiments using a rabbit cartilage defect model. The
VB positions, which then catalyzes the production of superoxide results showed that under 0.08 MPa pressure, the PLLA piezo-
anion (• O2 − ) and 1 O2 through SDT. Additionally, Cu2−x O-BTO electric material could generate a stable microcurrent to promote
NCs exhibit high Fenton-like activity in the presence of Cu(I), cartilage gene expression and regeneration (Figure 7b). Under
leading to locally generated • OH from H2 O2 production, which an impact force of ≈33 N, the output voltage measured from
can directly kill cancer cells via CDT (Figure 6g). In vitro and PLLA is 3.6 V. In vivo experiments conducted by implanting
in vivo experiments supported the efficiency of this strategy for the piezoelectric scaffold into the rabbit knee joint and subject-
treating cancer with minimal systemic toxicity, the tumor inhibi- ing it to exercise-induced joint movement resulted in improved
tion rate of the 2×Cu2−x O-BTO + US group was 76% (Figure 6h– cartilage regeneration, as seen by the group that received ex-
j). As a result, the Cu2−x O-BaTiO3 piezoelectric heterostructure ercise and piezoelectric scaffolds 2 months after implantation
has enormous potential. surgery (Figure 7c).
(K, Na) NbO3 (KNN) can go directly from mechanical pres- Chen et al.[128] developed a remarkable biodegradable 3D
sure to an electrical reaction.[125] Under ultrasonic irradiation, the piezoelectric scaffold that is capable of wireless electrical stimula-
amazing piezoelectricity of KNN nanomaterials creates a huge tion (ES) with the help of US. The scaffold has shown impressive
built-in electric field that is constantly changing. This allows results in repairing spinal cord injuries in rats. Utilizing elec-
holes and electrons to be constantly separated, which starts re- trospinning technology, researchers have successfully designed
dox reactions that are catalyzed by piezoelectricity. Also, KNN is a 3D piezoelectric scaffold with multiple channels by blending
usually full of point flaws like oxygen vacancies, which makes poly(lactic acid) (PLA) nanofibers with potassium–sodium nio-
chemo-catalytic activity a good alternative way to treat tumors.[126] bate (K0.5 Na0.5 NbO3 , KNN) nanowires. The programmable ultra-
On this basis, Wang et al.[127] found that (K, Na)NbO3 (KNN) lead- sound irradiation served as a remote mechanical stimulus that
free piezoelectric material possesses both chemical catalytic ef- enables the provision of strain in vivo on demand, with tunable
fect driven by oxygen vacancies and ultrasound-triggered piezo- duration, intensity, and timeline. The 3D tissue scaffold can ex-
electric catalytic effect, and the KNN nanocrystals have obvious pedite motion recovery and bolster spinal cord injury repair un-
toxic effects on tumor cell growth inhibition under the synergis- der suitable ultrasound stimulation (Figure 7d). Immunohisto-
tic chemical-piezoelectric catalytic effect, and can effectively in- chemical fluorescence investigations demonstrated that combin-
duce apoptosis and the apoptosis rate reached 88.6%, inhibit the ing the 3D piezoelectric scaffold with ultrasound-driven in vivo
proliferation of osteosarcoma cells. ES enhances neural stem cell differentiation and in situ vasculo-
genic at the injury site. This research shows significant promise
for spinal cord injury treatment and has the potential to facili-
5.1.4. Tissue Engineering
tate the development of analogous techniques for medical appli-
cations (Figure 7e).
Numerous studies have demonstrated the influence of electric
In addition, piezoelectric materials can be used as neural scaf-
fields on tissue development and regeneration, while it has
folds to promote nerve regeneration. Piezoelectric nanomateri-
been found that stress on piezoelectric materials makes elec-
als are particularly promising in this regard. In one study, Mao
tric fields, making them highly compatible with electrophysio-
et al.[130] utilized a PCL/ZnO nanofiber composite material that
logical processes.[128] Additionally, electrical stimulation has been
was generated by electrospinning to develop a piezoelectric nerve
shown to facilitate cell proliferation and differentiation and tis-
conduit (Figure 7f), the film tensile strength of PZNF is 10.2 MPa.
sue growth. The efficiency of piezoelectric catalysis in accelerat-
In vivo experiments demonstrated that PZNF outperformed in
ing cellular regeneration has received substantial attention, lead-
situ nerve bridging using polyglycolic acid nanofibers, result-
ing to its widespread use in tissue engineering for regenerative
ing in faster recovery and superior repair of the sciatic nerve 28
purposes.[128–135]
days after implantation. By applying piezoelectric stimulation to
Recently, Liu et al.[134] prepared a biodegradable scaffold
PZNF, the expression of vascular endothelial growth factor and
composed of nanofibers made from piezoelectric poly(lactic-co-
nerve growth factor was dramatically increased, which facilitated
glycolic acid) (PLLA). This innovative scaffold serves as an elec-
rapid repair of nerves in vivo and expedited functional recovery
tric stimulator to enhance the regeneration of cartilage tissue
within a four-week period. Similarly, Yang et al.[135] designed a
under external force or joint load. Under these conditions, the
self-powered scaffold for nerve tissue engineering by incorpo-
controlled production of piezoelectric charges by the scaffold
rating soft carbon nanotube@methacrylated gelatin/poly (l-lactic
can increase the binding of extracellular proteins, encourage
acid) (CNTs@GelMA/PLLA), it exhibited an appropriate mechan-
cell movement and recruitment, and trigger the production of
ical strength of ≈10 kPa. For the growth of cells, this scaffold of-
TGF-𝛽 by the body through the calcium signaling pathway. Both
fered a conductive milieu and endogenous piezoelectric stimu-
in vivo and in vitro, this stimulation promotes chondrogenesis
lation for cell development (Figure 7g). The scaffold was applied
and cartilage regeneration. The piezoelectric PLLA films used in
to a 10 mm sciatic nerve defect in rats, and after 12 weeks of im-
the study exhibited excellent piezoelectric properties (Figure 7a).
The effectiveness of the PLLA nanofiber scaffold was confirmed
Copyright 2021, Royal Society of Chemistry. g) Schematic diagram of Cu2−x O-BTO NC for acoustic and chemodynamic synergistic therapy. h) In vitro
antitumor performance of different treatments. i) In vivo antitumor performance of different treatments. j) Tumor photos of different treatment groups
on day 14. Reproduced with permission.[124] Copyright 2022, American Chemical Society.
Figure 7. a) Biodegradable piezoelectric scaffold for cartilage regeneration. b) Staining of nuclei (blue) and type II collagen (green) of ADSCs grown on
piezoelectric scaffolds and Alcian blue staining of GAGs in ADSCs. c) Gross images of the femur after 1 month of motion (or no motion) and 2 months of
motion (or no motion) for different groups. Yellow circles indicate the location where the defect was created. Reproduced with permission.[134] Copyright
2022, American Association for the Advancement of Science. d) Biodegradable 3D piezoelectric scaffold-based wirelessly powered ES for spinal cord
injury repair. e) Spinal cord histology was performed on mice at week 8. Reproduced with permission.[128] Copyright 2022, American Chemical Society.
f) Planar experimental design of piezoelectric nerve conduits based on PCL/ZnO nanofiber (PZNF) composites. Reproduced with permission.[130]
Copyright 2022, Elsevier. g) Schematic representation of the CNT@GelMA/PLLA scaffold production process and bionic application. Reproduced with
permission.[135] Copyright 2023, Elsevier.
plantation, it was dramatically boosted axonal development and 5.2.1. Skin Cooler
Schwann cell binding and elongation.
Compared to conventional skin cooling methods, thermoelectric
coolers (TECs) offer a number of advantages. Most importantly,
TECs do not require physical attachment to the skin to achieve
5.2. Biomedical Applications of Pyroelectric Materials direct cooling. This means that they can be used for extended pe-
riods of time without risking frostbite or other skin damage.[136]
There are several uses for pyroelectric materials in the biomed- Additionally, TECs are small in size and operate silently, making
ical field, including cryosurgery, skin cooling, and cancer them well suited for use in delicate environments where noise
treatment.[136,96] As wearable biomedical sensors and portable and disruption must be minimized, such as during surgeries or
therapeutic devices continue to rapidly develop, there is a grow- car accidents.[137] In general, the distinctive benefits of TECs ren-
ing demand for pyroelectric materials that are highly reliable, op- der them a promising technology for many applications that re-
erate without noise and are easy to handle.[137] quire precision and regulated cooling.
Figure 8. a) Schematic of the water pump-cooled TEC helmet. b) The cold-side temperature of the TEC helmets varies at various currents. Reproduced
with permission.[140] Copyright 2005, Springer Nature. c) Schematic design of the thermoelectric cooler (TEC) assembly for cryotherapy. Reproduced with
permission.[141] Copyright 2018, International Islamic University Malaysia. d) Cooling effect of two TECs. Reproduced with permission.[147] Copyright
2018, Elsevier.
Cranio-cerebral hypothermia (CCH) is a widely used treatment suppress inflammation.[141] Cooling should last between 48 and
for increasing the chance of survival for traumatic brain injury pa- 72 h, depending on the severity of the injury.[141–143] By using di-
tients by reducing enzyme reactions and cellular metabolic rates rect current, TEC can raise the temperature on one side while
in brain cells, thus lowering oxygen demand and enhancing pa- decreasing it on the other.[144] The TEC may alternate between
tient survival rates.[138,139] Figure 8a shows a TEC helmet with cooling and heating modes by reversing the current.[145] Addi-
an increased cooling capacity that is coupled to a pump and wa- tionally, TEC uses less maintenance after use and uses less Freon
ter tank by cooled water flow.[140] Because of its powerful cooling than traditional compressor cooling, which gives it a significant
system, this helmet is ideal for use in hospitals, where it can per- benefit.[146]
form CCH and improve patient survival. By combining it with a Two main kinds of TEC are used for skin cooling in the realm
human brain cooling system, a microcontroller can regulate the of biomedical engineering. One method involves coupling the
helmet temperature between −5 and 46 °C.[140] TEC helmet cool- cooling device with conventional ice packs to achieve the desired
ing performance at varying currents is shown in Figure 8b. The effect. Figure 8c shows a photo of a TEC with a thermoelectric
cold side can be kept at −6.87 °C for 3 min with a 30 A current us- module capable of generating a voltage of 15.2 V and a tempera-
ing water cooling, satisfying the requirement of a −5 °C working ture difference of 70 °C.[141] By adding the TEC to an ice pack, the
temperature for CCH. By decreasing the current to 25 A, the de- coolant inside can be directly cooled. This makes the temperature
sired temperature of −5.03 °C is reached on the cold side. Thus, drop evenly at the injury site. By putting an oscillator and temper-
this TEC helmet improves the survival rate of patients.[140] TECs ature detector into the ice pack, precise temperature readings can
are versatile in that they can also cool the skin and directly tar- be made. Additionally, the device is waterproof, utilizing plastic
get fixed brain regions. For sudden damage to soft tissue, such welding and varnish for protection.[141] The maximum voltage of
as sprains and strains, ice bags should be applied promptly to the gadget is merely 15.2 V, making it suitable for ambulance
transport. During cryotherapy, rapid skin temperature reduction hexylthiophene) polymer.[164] Nevertheless, to serve as an en-
to 5 °C should be followed by rewarming during treatment to ergy source for wearable devices, these generators’ output voltage
prevent tissue frostbite.[148] needs improvement. To address this challenge, researchers have
The cooling head of another TEC used to cool the skin makes proposed different hybrid nanogenerators, such as triboelectric–
direct contact with the skin. As shown in Figure 8d, there are two thermoelectric hybrid nanogenerators,[165,166] hybrid solar cells,
different types of cooling heads: point heads and sheet heads. The and flexible hybrid batteries.[167] These hybrid solutions aim to
cold side of the thermoelectric module is connected to the alu- improve the power density, output voltage, and reliability of ther-
minum head of the cooling device in both designs. A water chiller moelectric nanogenerators.
is connected to the hot side. Interestingly, the sheet head initially Feng et al.[41] successfully developed a nanogenerator called
cools the skin faster when operating at 50 W. However, subse- the flexible and wearable thermoelectric generator (FTEG), which
quent cooling slows down. On the other hand, the point head has the capability to produce electricity for extended periods of
takes ≈50 s to start cooling, but it can quickly lower the skin tem- time under high voltage and output power density. When the
perature below 10 °C.[147] According to these results, the cooling temperature difference reaches 50 K, the output voltage of FTEG
rate is affected differently by various cooling heads. Therefore, will not be less than 520 mV, and the power density will reach
choosing a suitable cooling head based on the patient’s injury 11.14 mW cm−2 . The technology used magnetron sputtering
and physical condition may enhance the therapeutic outcomes. techniques to deposit copper conductors onto a polyethylene ter-
phenyl ester film in combination with zone melting methods
to prepare the thermoelectric material Bi2 Te3 . To guarantee the
5.2.2. Wearable Thermoelectric Generator stability of the thermoelectric material, nickel plating was ap-
plied to its surface. The thermoelectric performance factor can
In addition to TECs, thermoelectric generators (TEGs) have be maintained above 0.7, with a maximum of 1.02. Additionally,
shown great potential in the medical field. TEGs have many bene- the FTEGs flexibility was optimized by utilizing a dual-sine wave-
fits over traditional power generators, including longer lifespans, form serpentine connection. With the assistance of low-power
zero emission of harmful pollutants during operation, the ab- and low-threshold voltage boosting circuits, the FTEGs output
sence of moving parts, no operating or maintenance costs, and voltage can attain the conduction voltage of low-power CMOS de-
the ability to utilize low-grade thermal energy. This makes TEGs vices. This research has significant potential for the advancement
an ideal choice for medical applications.[149] of personalized healthcare and the development of flexible wear-
Recently, self-powered flexible electronic devices and various able physical sensors.
forms of flexible energy harvesters have been extensively studied.
Wang and co-workers reported a triboelectric generator,[150–153]
while Rogers and co-workers proposed a piezoelectric energy 5.2.3. Cancer Treatment
harvester.[154,155] Both generators convert mechanical energy
from human motion into electricity. However, as flexible elec- Pyroelectric catalysis has been found to produce ROS that can ef-
tronic devices typically rely on DC power, additional rectifi- fectively kill cancer cells. As a result, several materials have been
cation and filtering circuits are required since both genera- reported as potential candidates for pyroelectric catalysis in can-
tors produce AC power. Wang and colleagues utilized lactate cer treatment.[77–79,96,97,168,169]
oxidase to catalyze the oxidation of lactate in sweat, convert- Currently, the delivery efficiency of antitumor nanomedicines
ing chemical energy into electrical energy.[156–158] Nevertheless, to tumors is less than 1%, and the pressure barrier at the tu-
the reliability of this method primarily relies on high-intensity mor site is considered a significant limiting factor. This is be-
anaerobic exercise, which means it may not be sustainable if cause there is no lymphatic system in tumor tissue, and blood
lactate levels are insufficient. It is important to note that as that enters the tumor stroma through the highly permeable vas-
warm-blooded animals, humans naturally generate and emit cular space cannot return to the blood system. As a result, the
heat through their temperature regulation system. Thermoelec- tumor interstitial pressure (TIP) gradually increases. In an effort
tric generators can convert heat into electricity in the presence to enhance drug permeation efficiency, Gao and co-workers[96]
of a temperature gradient field, making them ideal for pow- proposed a “nanolymphatic” strategy that elucidates the mecha-
ering self-sufficient wearable sensor devices. Several research nism of intratumorally delivery of nanomedicine from the per-
groups have developed various thermoelectric nanogenerators, spective of tissue fluid, blood, and lymph. The approach provides
such as Cho and colleagues’ micro-thermoelectric generator a new perspective for enhancing drug permeation efficiency. The
printed on glass fiber,[159] Hussain and colleagues’ flexible and “nanolymphatic” strategy relies on tumor targeting mediated by
foldable nano-thermoelectric generators created by combining hyaluronic acid to enrich nanoparticles at tumor sites. Near-
Bi2 Te3 and Sb2 Te3 with paper substrates,[160] Son and colleagues’ infrared two-region (1064 nm) laser irradiation is then used to
thermocouples of different shapes and thermopiles formed us- achieve photothermal therapy, generating high heat at the tumor
ing 3D printing technology,[161] Xu and colleagues’ thermoelec- site to directly kill tumor cells and ablate the extracellular ma-
tric generators that integrate n-type Bi2 Te3 and p-type Sb2 Te3 trix to reduce the solid pressure of the tumor stroma. ROS pro-
into an SU-8 photoresist substrate through pulse electroplat- duced during this process further induce tumor cell apoptosis.
ing and micromachining processes,[162] miniature thermoelec- As the TIP continuously decreases, convective diffusion in the
tric generators of Ziouche et al. made on a silicon substrate us- tumor stroma is enhanced, enabling more “nanolymphatic” to
ing bond-wire technology,[163] and Wang and colleagues’ flexi- penetrate deeper into the tumor tissue and reach tumor cells. The
ble thermoelectric nanogenerator based on a Tenanowire/poly(3- outcomes demonstrated that “nanolymphatic” reduced TIP in
Figure 9. a) Diagram of M/CdS-HA synthesis and its mechanism in tumor therapy. Reproduced with permission.[96] Copyright 2021, American Chemical
Society. b) BST/BTS Z scheme heterojunction preparation and thermoelectric treatment (TET) mechanism schematic. c) ROS generation of TET. d)
Results of live/dead cell staining of MCF-7 cells after different treatments. e) Schematic diagram of the BST/BTS heterojunction treatment protocol in
vivo and thermal infrared imaging to monitor temperature changes in mice. f) Tumor growth curves of mice under different treatments. Reproduced
with permission.[77] Copyright 2022, Wiley-VCH.
tumor tissue to 52%, demonstrating excellent tumor permeabil- lower ionization energy, causing Z scheme heterostructures to
ity and therapeutic effect (Figure 9a). After 14 days of treatment, be formed. Electrons from the conduction band of BTS bind to
the tumor inhibition rate was 93.75%. the holes in the valence band of BST. This makes the possibility
Ji et al.[77] recently developed a thermoelectric material com- for electrons and holes in the CB of BST and the VB of BTS to
posed of Z scheme heterostructures made from nanosheets of be reduced or oxidized stronger. At moderate temperature gradi-
Bi0.5 Sb1.5 Te3 (BST) and Bi2 Te2.8 Se0.2 (BTS), which were produced ents ranging between 37 and 25 °C, a self-generated electric field
using a two-step hydrothermal method. Figure 9b shows that is created, encouraging electron and hole migration toward the
the Fermi levels of BST and BTS are 0.20 and 0.63 eV, respec- surface of thermoelectric nanomaterials. This field pushes elec-
tively. When BST and BTS come into contact, electrons migrate trons and holes to move closer to the surface of thermoelectric
from the former with higher ionization energy to the latter with nanomaterials. This stops electron–hole pairs from recombining
Figure 10. a) Schematic diagram of PAI and PTT based on pyroelectric nanorods SnSe-PVP. Reproduced with permission.[169] Copyright 2018, Royal
Society of Chemistry. b) Synthesis method of Bi13S18I2 thermoelectric nanocatalysts. c) Schematic diagram of ROS generation from Bi13 S18 I2 NRs
under 808 nm laser irradiation for PEDT-enhanced photon thermal therapy. d) Bi13 S18 I2 thermoelectric nanocatalyst for research on PEDT-enhanced
photothermal treatment in vitro and in vivo. e) In vivo therapeutic effect of the Bi13 S18 I2 thermoelectric nanocatalyst on 4T1 tumor-bearing mice. f) 4T1
synergistic antitumor effect in tumor-bearing mice in vivo. Reproduced with permission.[79] Copyright 2022, Wiley-VCH.
when it is not necessary and makes it easier to make ROS at arbutin. The combination therapy and only BST/BTS NPs ther-
low amounts, including superoxide anions (·O2 − ) and hydroxyl apy showed tumor volume inhibition rates of 34.8% and 94.4%
radicals (·OH− ) (Figure 9c). The generated ROS were confirmed in vivo, respectively, demonstrating a synergistic therapeutic
through ROS-specific probes and ESR results, while cell viabil- effect.
ity assays established the anticancer effect of the thermoelectric Furthermore, pyroelectric catalytic dynamic therapy (PEDT)
material (Figure 9d). To evaluate the anticancer impact of the utilizes the ROS generated by the pyroelectric effect to attack can-
BST/BTS heterojunction in vivo on tumor-bearing mice derived cer cells and heat shock proteins (HSPs), making it a promis-
from MCF-7 cancer cells, researchers developed a new PEGylated ing method for treating tumors. Photothermal therapy (PTT) is
BST/BTS heterostructure-based thermoelectric therapy platform another effective strategy with high efficacy, precise spatiotem-
(Figure 9e,f). By administering BST/BTS intravenously, followed poral selectivity, ease of operation, and minimal invasiveness.
by tumor temperature cooling, is mediated by a water gel. It can In a recent study, Tang et al.[169] converted PTT into pyroelec-
be seen that during the evaporation of water in the hydrogel, the tric dynamic therapy by utilizing PTT agents that have pyroelec-
temperature of the tumor gradually dropped to 25 °C within 10 tric conversion ability (Figure 10a). They synthesized SnSe-PVP
min. This platform accomplished dual independent targeting of nanorods that combine both photothermal and pyroelectric con-
ROS generation and efficient cancer cell apoptosis, and can com- version abilities, resulting in highly efficient suppression of tu-
bined treatment with the clinically used chemotherapy drug 𝛽- mor growth. While thermal therapy produced by photothermal
conversion eliminates cancer cells, ROS created by pyroelectric consistent with earlier studies indicating that higher tempera-
conversion destroy cancer cells and HSPs, producing higher ther- tures and fluctuations lead to more noticeable teeth whitening
apeutic efficacy under laser excitation at 1064 nm wavelength (Figure 11e). Notably, even heavily stained teeth at the root were
and more effectively eliminating the side effects of HSPs. Simi- completely whitened at ΔT = 25 °C. These findings prove the
larly, Wang and co-workers[79] developed pyroelectric biomaterial potential of pyroelectric materials for oral disinfection and tooth
Bi13 S18 I2 nanorods with excellent pyroelectric and photothermal whitening.[80] It is worth noting that this approach is more sus-
conversion capabilities (Figure 10b). Under 808 nm laser irra- tainable and eco-friendlier than traditional tooth whitening meth-
diation, Bi13 S18 I2 NRs exhibit high photothermal conversion ef- ods, which often involve harsh chemicals and abrasive materials.
ficiency at high photon temperatures. The temperature fluctu- In summary, the use of pyroelectric materials in dental retainers
ations from thermal and cold changes convert into pyroelectric represents a promising and noninvasive tooth whitening alterna-
charges that react with surrounding O2 molecules to form a sig- tive. The approach can be easily integrated into one’s daily oral
nificant amount of ROS, attacking HSPs and reducing the ther- hygiene routine and has the potential to significantly improve the
mal resistance of PTT (Figure 10c,d). They were able to achieve aesthetic appearance of teeth without causing damage or discom-
a tumor suppression rate of up to 97.2% by combining PTT and fort.
pyroelectric dynamic therapy (Figure 10e,f). These studies pro-
vide a promising strategy for developing multifunctional pyro-
5.3. Biomedical Applications of Ferroelectric Materials
electric nanoplatforms capable of generating NIR-triggered ROS,
consuming HSPs and overcoming traditional PTT limitations on
FEMs have many properties, including piezoelectricity, pyroelec-
tumors.
tricity, inverse piezoelectricity, nonlinear optics, and ferroelectric
photovoltaics. These materials have attracted much attention for
their prospective uses in the biomedical field because of their
5.2.4. Tooth Whitening
wide variety of features.[56] The recent research on these appli-
cations will be briefly discussed in this section.
The production of ROS is necessary for tooth whitening.[64,170,171]
Studies have shown that agents containing TiO2 particles can
be used to achieve safe and effective tooth whitening when ac- 5.3.1. Biosensing
tivated by blue light.[170] A promising and nondestructive tooth
whitening technique involves substituting conventional tooth- It has been shown that ferroelectric materials interact with bio-
paste abrasives with piezoelectric BaTiO3 particles. This innova- logical agents and react to physiological processes. This makes
tive approach has demonstrated the ability to effectively whiten them good candidates for detecting biomolecules, tracking the
teeth by generating the requisite reactive oxygen species during movement of cells, and health monitoring. Recently, Selvarajan
routine toothbrushing without necessitating additional equip- et al.[171] developed a glucose molecule detection tool using BTO
ment or time.[64] nanoparticle thin film technology. Glucose molecules attached to
Wang et al.[80] recently developed a dental retainer that uti- the ferroelectric surface can act as a gate voltage, which modi-
lizes pyroelectric materials for effective tooth whitening. This fies free charge carrier screening on the piezoelectric output. This
innovative design (Figure 11a) harnesses the natural tempera- biosensor demonstrated glucose concentration detection rates of
ture changes that occur in the oral cavity during routine activ- up to 1000 μm, with a detection threshold of 7.941 μμ and sensi-
ities, such as drinking, breathing, talking, and movement, to tivity of 23.79 μA mm−1 cm2 . While this is an impressive achieve-
achieve whitening results. Unlike other methods that require ad- ment, there is still ample opportunity for further exploration in
ditional equipment or active energy supply, such as light stim- developing molecular-level FEM-based detection.
ulation or ultrasound agitation, these retainers generate a con- To understand cellular biology and chemistry, it is important
stant flow of reactive free radicals that target and degrade surface to study how cells move when they are stimulated by electric-
stains on teeth, resulting in passive whitening effects. As illus- ity. Nguyen et al.[84] used PZT nanobelts to gauge nanoscale
trated in Figure 11b–d, the breakdown of colored macromolecule mechanical deformation with maximum electromechanical effi-
groups into colorless small molecules is the mechanism behind cacy (Figure 12a). While deforming in unison with PC12 cells,
the whitening effect. Since these retainers do not rely on an active suspended PZT nanobelts recorded distinctive output signals
energy supply, they have a prolonged lifespan. Moreover, typical prompted by an external membrane voltage stimulus. The find-
oral temperature fluctuations remain well below the Curie tem- ings showed that a 120 mV membrane voltage change could
perature of the pyroelectric material used, making them durable cause a 1.6 nN cell force on the PZT film, whereas a single PZT
and effective for daily use. belt’s cell deformation could be as minute as 0.5 nm. This re-
The researchers utilized BaTiO3 nanowires to conduct exper- sult conveyed the potential of employing PZT nanobelts to mea-
iments aimed at tooth whitening. To simulate tooth staining sure and document minuscule signals from cells. Alongside PZT
caused by food intake, they performed an experiment by immers- nanobelts, some experimental research has also explored the
ing human teeth for a week in a solution of red tea, red wine, use of pyroelectric effects for discerning molecular and cellular
and blueberry juice. Afterward, the stained teeth were subjected activity.[172] However, detecting these interactions with FEMs at
to a suspension of nanowires at 36 °C, similar to the oral tem- the molecular and cellular levels could pose challenges. Despite
perature, followed by thermal catalytic experiments under vari- the conceptually validated sensors having room for enhancement
ous temperature fluctuations (ΔT = −10, +10, +25 °C). Enamel in performance, the development of FEM-based sensors directed
whitening was observed after 2000 thermal cycles, with results toward tissue or organ levels holds immense potential.
Figure 11. a) Teeth whitening method based on the pyroelectric effect. b–d) Pyroelectric particles degrade tooth stains utilizing diet-induced oral temper-
ature variations and thermal catalysis. e) Demonstration of the tooth whitening effect based on the pyroelectric effect. Reproduced with permission.[80]
Copyright 2020, Springer Nature.
Targeted biosensors for particular organs or organizations measure both arterial blood pressure and skin temperature
have gained popularity during the past few decades, as simultaneously.[174,91] Park et al.[91] reported a PVDF and reduced
they have demonstrated significant potential in the areas graphene oxide polymer composite membrane. This membrane
of physiological monitoring, health assessment, and disease possesses an interlocked microstructure and unique finger-
diagnosis.[172,173,176–178] One notable application is the field print pattern, enhancing its ability to sense static and dynamic
of electronic skin, where sensors have been developed to mechanical stimuli through piezoelectric, pyroelectric, and
Figure 12. a) Schematic of the piezoelectric nanoribbon device for neural cell culture and cell deformation on membrane voltage. Reproduced with
permission.[84] Copyright 2012, Springer Nature. b) Sensor for monitoring micropressure changes owing to early lesions and the piezoelectric signal
produced from the implanted sensor due to cardiovascular elasticity changes in pigs. Reproduced with permission.[95] Copyright 2019, American Chem-
ical Society. c) Serum-covered BFO nanoparticles are imaged as SHG engulfed by local macrophages. Reproduced with permission.[174] Copyright 2018,
Wiley-VCH. d) Schematic of cancer cell injection in 2 dpf zebrafish embryos and fluorescence and SHG imaging at 5 dpf after injection of bioharmonic
proteins into DoC of 3 dpf zebrafish embryos. Reproduced with permission.[175] Copyright 2021, American Chemical Society.
piezoresistive sensing capabilities. Another promising use of ergy into piezoelectric impulses. Under typical circumstances,
biosensors is in disease diagnosis. Li et al.[95] successfully fab- the heart and femoral arteries of the pig’s cardiovascular sys-
ricated a soft sensor from nanofibers made of PVDF and hydrox- tem produce rhythmic piezoelectric signals with peak-to-peak val-
ylamine hydrochloride (HHE). This sensor has ultrahigh detec- ues of 1.02, 0.13 V and 0.52, 0.33 V, respectively. After injec-
tion accuracy and sensitivity, detecting micropressure changes tions of propofol and isoflurane the pig was put into a coma,
outside the cardiovascular wall in real time. When the heart the sensor’s peak-to-peak voltage dropped by 58% at the heart
and blood arteries contract and relax in rhythm with the cardiac wall and 52% at the walls of the peripheral arteries (Figure 12b).
cycle, flexible implanted sensors transform biomechanical en- By differentiating changes in cardiovascular elasticity, the sensor
Table 2. Biomedical applications of piezoelectric, pyroelectric, and ferroelectric nanomaterials..
Material Application field Catalyst Properties Refs.
Piezoelectric materials Biosensing PEAS Monitor human breathing, muscular [92]

movement, and voice recognition
PVDF/DA NFs Detecting weak physiological mechanical [93]
stimulation from diaphragm motions and
blood pulsation
ZnO NWs Detect facial wrinkles [180]
PCNG Diagnose the sleeping disorder in humans [116]
PETF Monitored the status of hypertension [117]
monitored in real time
Kirigami stretchable Cardiac monitoring and human body [75]
piezoelectric sensor tracking
Antimicrobial ZPFSA 98% wound healing rate [89]
and wound
healing
BT-OHA/THM-APMH 98.8% wound healing rate [72]
BaTiO3 @Au Acterial survival rate decreased to 2.86% [85]
RBC–HNTM–MoS2 98.5% antibacterial efficiency [122]
SDBTO 97.12% antibacterial performance [70]
Au@BTO High antibacterial efficiency [73]
Cancer treatment T-BTO Cancer cell viability decreased to 12.6% [71]
NSH700 NSs Completely ablated the tumors [69]
Cu2−x O-BaTiO3 76% tumor inhibition [124]
BMO NRs 96.6% tumor inhibition [67]
(K, Na)NbO3 Induce apoptosis and autophagy of OS cells [127]
Tissue Poly(l-lactic acid) Grow bone in a critical-sized calvarial [131]
engineering deficiency
BT/Ti(poled) Promotes improvements in macrophage M2 [129]
pyroelectricity polarization and bone
regeneration
CNTs@GelMA/PLLA Boosted the growth and myelination of SCs [135]
and the growth of DRG neurites
PZNF Increase nerve growth factor/vascular [130]
endothelial growth factor expression
PLA/KNN@PDA Repair injured spinal cord [128]
PLLA film Improved chondrogenesis and cartilage [134]
regeneration
Pyroelectric materials Skin cooler HBHS system Cooling and heating the brain [140]
Cooling heads Cooling the skin of febrile patient [147]
Wearable Soft-covered WTED Human skin temperature drops by 1.5 °C [87]
pyroelectric
generator
Bi2 Te3 Can create an 86.2 mV open-circuit voltage [41]
at 15 °C
Cancer treatment BST/BTS ≈94.4% tumor volume inhibition ratio [77]
Bi2 Te3 ≈49.4% ± 5.8% tumor volume inhibition [78]
ratio
M/CdS-HA 93.75% tumor inhibition rate [96]
SnSe-PVP Tumors disappeared at the 9th day [169]
postinjection
BTe-Pd-Au-R Almost complete tumor elimination [97]
Rh-PEG NDs Complete suppression of colorectal cancer [168]
without recurrence
Bi13 S18 I2 97.2% tumor inhibition rate [79]
Tooth whitening BaTiO3 Teeth completely white after 10 h of vibration [64]
(Continued)
Table 2. (Continued).
Material Application field Catalyst Properties Refs.
BaTiO3 nanowires The stain was removed from the tooth [80]
surface after 2000 cycles
Ferroelectric materials Biosensing LV-like silver nanowires Real-time monitoring breath, heartbeat [177]
pulse, and swallowing
PVDF/HHE OPNS Capture micropressure changes at the [95]
outside of cardiovascular
rGO/PVDF Monitoring arterial pulse pressure and [91]
temperature simultaneously
PZT nanoribbons Measured the mechanical deformations [84]
brought on by electrical excitations in
neuronal cells
Bioimaging and Bioharmonophores Detect single cancer cells in zebrafish [175]
phototherapy embryos
SHG nanoprobes In vivo imaging 179]
SHRIMPs Effectively image second-harmonic radiation [87]
enables early diagnosis of diseases such as atherosclerosis and zebrafish embryo, improving labeling efficiency and sensitivity
thrombosis. (Figure 12d). Despite promising results in zebrafish and mouse
models, studying these nonlinear probes in larger animal models
is crucial. Nevertheless, configuring such an imaging platform is
5.3.2. Bioimaging and Phototherapy expected to be highly challenging (Table 2).
FEMs have the potential to emit light upon physical stimula-

tion and can be used as a tool for biological imaging. Ramos-
6. Conclusions and Prospects
Gomes et al. monitored lung macrophages in mice with allergic With the increasing interest in nanomaterials in biomedical
airway inflammation (AAI) using BFO nanoparticles. The BFO fields, piezoelectric, pyroelectric, and ferroelectric materials,
signal was strong and had a good signal-to-noise ratio under two- which are dielectric crystalline biomedical materials with asym-
photon laser scanning microscopy, which allowed for the detec- metric centers, have attracted new attention. They are able to
tion and tracking of macrophages in thick lung tissue while re- gather natural energy from their environment (including vibra-
ducing background fluorescence.[174] By stitching together im- tion, sun energy, mechanical energy, and temperature gradients),
ages of AAI lung slices, the researchers were able to observe convert it into chemical energy, and perform catalytic reactions.
that the number of ECF-L+ cells harboring BFO was found to This paper reviews the connection between noncentrosymmet-
have significantly increased surrounding bronchi and blood ar- ric crystalline piezoelectric, pyroelectric, and ferroelectric mate-
teries compared to the control group, with fewer cells dispersed rials, the catalytic mechanism, and their preparation methods.
throughout the tissue in the control group (Figure 12c). This ex We review the most recent developments in catalytic reactions
vivo SHG imaging approach reveals macrophage–ECM–lung dis- using these three different kinds of nanomaterials. They can be
ease cell interactions. This study labeled cells via macrophage used for diverse applications based on pyroelectric, piezoelectric,
phagocytosis rather than SHG marker-target cell identification. and piezoelectric effects. We summarize their biomedical uses
FEM-based nonlinear probes should target different cell types in for wound healing, biosensing, and tumor therapy, which are
future research. anticipated to be instructive for future catalytic research on the
To date, only a limited number of studies have utilized FEM piezoelectric series of materials.
real-time imaging with harmonic nanoparticles within living Extensive research efforts and impressive advantages have
organisms. In 2010, Pantazis and co-workers[179] injected cy5- been conducted recently. Overall, research on pyroelectric, ferro-
conjugated secondary antibody-modified BTO nanoparticles into electric, and piezoelectric materials for biomedical applications
zebrafish embryos during fertilization. The embryos were pho- is still in its initial stages and has many unresolved issues and
tographed a few days after the injection. Grange et al.[87] demon- exciting opportunities.
strated that 100 and 300 nm BTO nanoparticles can penetrate
up to 120 μm in live mouse tail tissue. Ideally, biomedical 1) Clinical applications are the ultimate goal of therapy. Despite
imaging probes used in vivo should be biodegradable without the initial success of these materials in the biomedical field.
any long-term toxic effects from byproducts. Recently, Sonay To date, most of the pyroelectric, piezoelectric, and ferroelec-
et al.[175] created a biodegradable SHG nanoprobe from FFF pep- tric materials developed for biomedical applications remain
tide nanoprobes. Researchers have found an increase in the ac- at the cellular and animal levels. Their long-term toxicity, tar-
cumulation of p32 peptide targeting biologically harmless car- geting, biosafety, and biodegradability still need to be further
riers within a single cancer cell at the tumor site of the entire evaluated. Achieving their superior performance in humans
requires more exploration and practice. The development of Keywords

biomaterials with high catalytic properties to advance clinical
translation is urgently needed to minimize the required dose. biomedical application, energy conversion, ferroelectric, piezoelectric, py-
roelectric
2) Most biopiezoelectric material investigations have examined
and improved physical qualities such shape, transparency,
Received: August 27, 2023
flexibility, piezoelectricity, and mechanical strength. Chemi- Revised: October 12, 2023
cal characteristics and piezoelectricity synergy have received Published online: November 22, 2023
little attention. Biopiezoelectric materials such as molybde-
num disulfide and black phosphorus are excellent photocata-
lysts and electrocatalysts. When integrated with chemical fea-
tures, biopiezoelectric materials will be more inventive.
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Xue Yuan received her B.S. degree from Inner Mongolia University of Technology in 2021, and now is
pursuing her Ph.D. degree under the guidance of Prof. Xiaoyuan Ji in Tianjin University. Her current
research focuses on design and development of stimulation-responsive nanobiomaterials for tumor
therapy, tissue repair, biosensing, and other fields.
Jiacheng Shi is currently a Ph.D. student in Medical School of Tianjin University under the supervi-
sion of Prof. Xiaoyuan Ji. He received his M.S. degree from the College of Biomedical Engineering of
Sichuan University in 2022. His research focuses on the topics of medical and materials science and
engineering in stimulation-responsive biomaterials for tissue engineering.
Yong Kang is currently employed as an assistant researcher at Tianjin University. He obtained his
Ph.D. degree from Institute of Process Engineering, Chinese Academy of Sciences in 2021. His pri-
mary research focuses on the design, construction, and application of antitumor nanomedicine, in-
cluding heterojunction nanodrugs and biomimetic micro/nanorobotic drugs.
Xiaoyuan Ji is the full professor in Tianjin University and the deputy director of the Engineering Re-
search Center of the Ministry of Education for Intelligent Medical Engineering. He received his Ph.D.
degree at Institute of Process Engineering, Chinese Academy of Sciences and Harvard University. His
research interest is focused on biomaterials, nanomedicine, and nanobiotechnology, which involve
the design, fabrication, biomedical application, and clinical translation of versatile biomaterials, in-
cluding heterojunction nanomedicine, micro/nanorobot, drug/gene delivery, nanodynamic therapy,
nanocatalytic therapy, and localized disease therapy.

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Piezoelectricity, Pyroelectricity, and Ferroelectricity in

recently captured much attention. These

ferroelectric materials also exhibit piezoelectric and pyroelectric

Table 1. Preparation method of piezoelectric, pyroelectric, and ferroelectric nanomaterials..

Method Characteristic Materials Catalyst Refs.

Hydrothermal method Simple operation Piezoelectric material BaTiO3 [25,64,65,66]

Magnetron sputtering is characterized by fast ﬁlm formation, 4.4. Sol–Gel Method

technology to synthesize BTO nanoﬁbers with extremely high 5.1.1. Biosensing

Table 2. Biomedical applications of piezoelectric, pyroelectric, and ferroelectric nanomaterials..

Material Application ﬁeld Catalyst Properties Refs.

Piezoelectric materials Biosensing PEAS Monitor human breathing, muscular [92]

Material Application ﬁeld Catalyst Properties Refs.

FEMs have the potential to emit light upon physical stimula-

requires more exploration and practice. The development of Keywords

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