Piezoelectricity is the electric charge that accumulates in certain solid materials (such as crystals, certain ceramics, and biological matter such as bone, DNA and various proteins)^[1] in response to applied mechanical stress. The word piezoelectricity means electricity resulting from pressure and latent heat. It is derived from the Greek word πιέζειν; piezein, which means to squeeze or press, and ἤλεκτρον ēlektron, which means amber, an ancient source of electric charge.^{[2][3]/lektron)} French physicists Jacques and Pierre Curie discovered piezoelectricity in 1880.^[4]

The piezoelectric effect results from the linear electromechanical interaction between the mechanical and electrical states in crystalline materials with no inversion symmetry.^[5] The piezoelectric effect is a reversible process: materials exhibiting the piezoelectric effect (the internal generation of electrical charge resulting from an applied mechanical force) also exhibit the reverse piezoelectric effect, the internal generation of a mechanical strain resulting from an applied electrical field. For example, lead zirconate titanate crystals will generate measurable piezoelectricity when their static structure is deformed by about 0.1% of the original dimension. Conversely, those same crystals will change about 0.1% of their static dimension when an external electric field is applied to the material. The inverse piezoelectric effect is used in the production of ultrasonic sound waves.^[6]

Piezoelectricity is exploited in a number of useful applications, such as the production and detection of sound, piezoelectric inkjet printing, generation of high voltages, electronic frequency generation, microbalances, to drive an ultrasonic nozzle, and ultrafine focusing of optical assemblies. It forms the basis for a number of scientific instrumental techniques with atomic resolution, the scanning probe microscopies, such as STM, AFM, MTA, and SNOM. It also finds everyday uses such as acting as the ignition source for cigarette lighters, push-start propane barbecues, used as the time reference source in quartz watches, and in amplification pickups for some guitars.

The pyroelectric effect, by which a material generates an electric potential in response to a temperature change, was studied by Carl Linnaeus and Franz Aepinus in the mid-18th century. Drawing on this knowledge, both René Just Haüy and Antoine César Becquerel posited a relationship between mechanical stress and electric charge; however, experiments by both proved inconclusive.^[7]

The first demonstration of the direct piezoelectric effect was in 1880 by the brothers Pierre Curie and Jacques Curie.^[8] They combined their knowledge of pyroelectricity with their understanding of the underlying crystal structures that gave rise to pyroelectricity to predict crystal behavior, and demonstrated the effect using crystals of tourmaline, quartz, topaz, cane sugar, and Rochelle salt (sodium potassium tartrate tetrahydrate). Quartz and Rochelle salt exhibited the most piezoelectricity.

The Curies, however, did not predict the converse piezoelectric effect.

The converse effect was mathematically deduced from fundamental thermodynamic principles by Gabriel Lippmann in 1881.^[9] The Curies immediately confirmed the existence of the converse effect,^[10] and went on to obtain quantitative proof of the complete reversibility of electro-elasto-mechanical deformations in piezoelectric crystals.

For the next few decades, piezoelectricity remained something of a laboratory curiosity, though it was a vital tool in the discovery of polonium and radium by Pierre and Marie Curie in 1898. More work was done to explore and define the crystal structures that exhibited piezoelectricity. This culminated in 1910 with the publication of Woldemar Voigt's Lehrbuch der Kristallphysik (Textbook on Crystal Physics),^[11] which described the 20 natural crystal classes capable of piezoelectricity, and rigorously defined the piezoelectric constants using tensor analysis.

The first practical application for piezoelectric devices was sonar, first developed during World War I. In France in 1917, Paul Langevin and his coworkers developed an ultrasonic submarine detector.^[12] The detector consisted of a transducer, made of thin quartz crystals carefully glued between two steel plates, and a hydrophone to detect the returned echo. By emitting a high-frequency pulse from the transducer, and measuring the amount of time it takes to hear an echo from the sound waves bouncing off an object, one can calculate the distance to that object.

The use of piezoelectricity in sonar, and the success of that project, created intense development interest in piezoelectric devices.

Over the next few decades, new piezoelectric materials and new applications for those materials were explored and developed.

Piezoelectric devices found homes in many fields.

Ceramic phonograph cartridges simplified player design, were cheap and accurate, and made record players cheaper to maintain and easier to build. The development of the ultrasonic transducer allowed for easy measurement of viscosity and elasticity in fluids and solids, resulting in huge advances in materials research. Ultrasonic time-domain reflectometers (which send an ultrasonic pulse through a material and measure reflections from discontinuities) could find flaws inside cast metal and stone objects, improving structural safety.

During World War II, independent research groups in the United States, Russia, and Japan discovered a new class of synthetic materials, called ferroelectrics, which exhibited piezoelectric constants many times higher than natural materials. This led to intense research to develop barium titanate and later lead zirconate titanate materials with specific properties for particular applications.

One significant example of the use of piezoelectric crystals was developed by Bell Telephone Laboratories.

Following World War I, Frederick R. Lack, working in radio telephony in the engineering department, developed the "AT cut" crystal, a crystal that operated through a wide range of temperatures.

Lack's crystal did not need the heavy accessories previous crystal used, facilitating its use on aircraft.

This development allowed Allied air forces to engage in coordinated mass attacks through the use of aviation radio.

Development of piezoelectric devices and materials in the United States was kept within the companies doing the development, mostly due to the wartime beginnings of the field, and in the interests of securing profitable patents.

New materials were the first to be developed—quartz crystals were the first commercially exploited piezoelectric material, but scientists searched for higher-performance materials.

Despite the advances in materials and the maturation of manufacturing processes, the United States market did not grow as quickly as Japan's did.

Without many new applications, the growth of the United States' piezoelectric industry suffered.

In contrast, Japanese manufacturers shared their information, quickly overcoming technical and manufacturing challenges and creating new markets.

In Japan, a temperature stable crystal cut was developed by Issac Koga. Japanese efforts in materials research created piezoceramic materials competitive to the United States materials but free of expensive patent restrictions. Major Japanese piezoelectric developments included new designs of piezoceramic filters for radios and televisions, piezo buzzers and audio transducers that can connect directly to electronic circuits, and the piezoelectric igniter, which generates sparks for small engine ignition systems and gas-grill lighters, by compressing a ceramic disc. Ultrasonic transducers that transmit sound waves through air had existed for quite some time but first saw major commercial use in early television remote controls. These transducers now are mounted on several car models as an echolocation device, helping the driver determine the distance from the car to any objects that may be in its path.

The nature of the piezoelectric effect is closely related to the occurrence of electric dipole moments in solids. The latter may either be induced for ions on crystal lattice sites with asymmetric charge surroundings (as in BaTiO3 and PZTs) or may directly be carried by molecular groups (as in cane sugar). The dipole density or polarization (dimensionality [C·m/m3] ) may easily be calculated for crystals by summing up the dipole moments per volume of the crystallographic unit cell.^[13] As every dipole is a vector, the dipole density P is a vector field. Dipoles near each other tend to be aligned in regions called Weiss domains. The domains are usually randomly oriented, but can be aligned using the process of poling (not the same as magnetic poling), a process by which a strong electric field is applied across the material, usually at elevated temperatures. Not all piezoelectric materials can be poled.^[14]

Of decisive importance for the piezoelectric effect is the change of polarization P when applying a mechanical stress. This might either be caused by a reconfiguration of the dipole-inducing surrounding or by re-orientation of molecular dipole moments under the influence of the external stress. Piezoelectricity may then manifest in a variation of the polarization strength, its direction or both, with the details depending on: 1. the orientation of P within the crystal; 2. crystal symmetry; and 3. the applied mechanical stress. The change in P appears as a variation of surface charge density upon the crystal faces, i.e. as a variation of the electric field extending between the faces caused by a change in dipole density in the bulk. For example, a 1 cm3 cube of quartz with 2 kN (500 lbf) of correctly applied force can produce a voltage of 12500 V.^[15]

Piezoelectric materials also show the opposite effect, called the converse piezoelectric effect, where the application of an electrical field creates mechanical deformation in the crystal.

Linear piezoelectricity is the combined effect of

These may be combined into so-called coupled equations, of which the strain-charge form is:^[16]

In matrix form,

where [d] is the matrix for the direct piezoelectric effect and [dt] is the matrix for the converse piezoelectric effect. The superscript* Eindicates a zero, or constant, electric field; the superscript T* indicates a zero, or constant, stress field; and the superscript t stands for transposition of a matrix.

The strain-charge for a material of the 4mm (C4v) crystal class (such as a poled piezoelectric ceramic such as tetragonal PZT or BaTiO3) as well as the 6mm crystal class may also be written as (ANSI IEEE 176):

where the first equation represents the relationship for the converse piezoelectric effect and the latter for the direct piezoelectric effect.^[17]

Although the above equations are the most used form in literature, some comments about the notation are necessary.

Generally, D and E are vectors, that is, Cartesian tensors of rank 1; and permittivity ε is a Cartesian tensor of rank 2. Strain and stress are, in principle, also rank-2 tensors. But conventionally, because strain and stress are all symmetric tensors, the subscript of strain and stress can be relabeled in the following fashion: 11 → 1; 22 → 2; 33 → 3; 23 → 4; 13 → 5; 12 → 6. (Different conventions may be used by different authors in literature. For example, some use 12 → 4; 23 → 5; 31 → 6 instead.) That is why S and T appear to have the "vector form" of six components. Consequently, s appears to be a 6-by-6 matrix instead of a rank-3 tensor. Such a relabeled notation is often called Voigt notation. Whether the shear strain components S4, S5, S6 are tensor components or engineering strains is another question. In the equation above, they must be engineering strains for the 6,6 coefficient of the compliance matrix to be written as shown, i.e., 2(s**E11 −* s**E12). Engineering shear strains are double the value of the corresponding tensor shear, such as S6 = 2S12 and so on. This also means that s66 = 1/G12, where G*12 is the shear modulus.

In total, there are four piezoelectric coefficients, dij, eij, gij, and hij defined as follows:

where the first set of four terms corresponds to the direct piezoelectric effect and the second set of four terms corresponds to the converse piezoelectric effect, and the reason why the direct piezoelectric tensor is equal to the transpose of the converse piezoelectric tensor originated from the Maxwell Relations in Thermodynamics.^[18] For those piezoelectric crystals for which the polarization is of the crystal-field induced type, a formalism has been worked out that allows for the calculation of piezoelectrical coefficients dij from electrostatic lattice constants or higher-order Madelung constants.^[13]

Of the 32 crystal classes, 21 are non-centrosymmetric (not having a centre of symmetry), and of these, 20 exhibit direct piezoelectricity^[19] (the 21st is the cubic class 432). Ten of these represent the polar crystal classes,^[20] which show a spontaneous polarization without mechanical stress due to a non-vanishing electric dipole moment associated with their unit cell, and which exhibit pyroelectricity. If the dipole moment can be reversed by applying an external electric field, the material is said to be ferroelectric.

For polar crystals, for which P ≠ 0 holds without applying a mechanical load, the piezoelectric effect manifests itself by changing the magnitude or the direction of P or both.

For the nonpolar but piezoelectric crystals, on the other hand, a polarization P different from zero is only elicited by applying a mechanical load. For them the stress can be imagined to transform the material from a nonpolar crystal class (P = 0) to a polar one,^[13] having P ≠ 0.

Many materials, both natural and synthetic, exhibit piezoelectricity:

The action of piezoelectricity in Topaz can probably be attributed to ordering of the (F,OH) in its lattice, which is otherwise centrosymmetric: orthorhombic bipyramidal (mmm).

Topaz has anomalous optical properties which are attributed to such ordering.^[23]

Dry bone exhibits some piezoelectric properties. Studies of Fukada et al. showed that these are not due to the apatite crystals, which are centrosymmetric, thus non-piezoelectric, but due to collagen. Collagen exhibits the polar uniaxial orientation of molecular dipoles in its structure and can be considered as bioelectret, a sort of dielectric material exhibiting quasipermanent space charge and dipolar charge. Potentials are thought to occur when a number of collagen molecules are stressed in the same way displacing significant numbers of the charge carriers from the inside to the surface of the specimen. Piezoelectricity of single individual collagen fibrils was measured using piezoresponse force microscopy, and it was shown that collagen fibrils behave predominantly as shear piezoelectric materials.^[24]

The piezoelectric effect is generally thought to act as a biological force sensor.^[25][26] This effect was exploited by research conducted at the University of Pennsylvania in the late 1970s and early 1980s, which established that sustained application of electrical potential could stimulate both resorption and growth (depending on the polarity) of bone in vivo.^[27] Further studies in the 1990s provided the mathematical equation to confirm long bone wave propagation as to that of hexagonal (Class 6) crystals.^[28]

Biological materials exhibiting piezoelectric properties include:

Ceramics with randomly oriented grains must be ferroelectric to exhibit piezoelectricity.^[30] The macroscopic piezoelectricity is possible in textured polycrystalline non-ferroelectric piezoelectric materials, such as AlN and ZnO. The family of ceramics with perovskite, tungsten-bronze and related structures exhibits piezoelectricity:

More recently, there is growing concern regarding the toxicity in lead-containing devices driven by the result of restriction of hazardous substances directive regulations. To address this concern, there has been a resurgence in the compositional development of lead-free piezoelectric materials.

So far, neither the environmental effect nor the stability of supplying these substances has been measured.

A piezoelectric potential can be created in any bulk or nanostructured semiconductor crystal having non central symmetry, such as the Group III–V and II–VI materials, due to polarization of ions under applied stress and strain.

This property is common to both the zincblende and wurtzite crystal structures. To first order, there is only one independent piezoelectric coefficient in zincblende, called e14, coupled to shear components of the strain. In wurtzite, there are instead three independent piezoelectric coefficients: e31, e33 and e15. The semiconductors where the strongest piezoelectricity is observed are those commonly found in the wurtzite structure, i.e. GaN, InN, AlN and ZnO. ZnO is the most used material in the recent field of piezotronics.

Since 2006, there have also been a number of reports of strong non linear piezoelectric effects in polar semiconductors.^[34] Such effects are generally recognized to be at least important if not of the same order of magnitude as the first order approximation.

The piezo-response of polymers is not as high as the response for ceramics; however, polymers hold properties that ceramics do not. Over the last few decades, non-toxic, piezoelectric polymers have been studied and applied due to their flexibility and smaller acoustical impedance.^[35] Other properties that make these materials significant include their biocompatibility, biodegradability, low cost, and low power consumption compared to other piezo-materials (ceramics, etc.).^[36] Piezoelectric polymers and non-toxic polymer composites can be used given their different physical properties.

Piezoelectric polymers can be classified by bulk polymers, voided charged polymers, and polymer composites.

A piezo-response observed by bulk polymers is mostly due to its molecular structure.

There are two types of bulk polymers: amorphous and semi-crystalline. Examples of semi-crystalline polymers are Polyvinylidene Fluoride (PVDF) and its copolymers, Polyamides, and Paralyne-C. Non-crystalline polymers, such as Polyimide and Polyvinylidene Chloride (PVDC), fall under amorphous bulk polymers. Voided charged polymers exhibit the piezoelectric effect due to charge induced by poling of a porous polymeric film. Under an electric field, charges form on the surface of the voids forming dipoles. Electric responses can be caused by any deformation of these voids. The piezoelectric effect can also be observed in polymer composites by integrating piezoelectric ceramic particles into a polymer film. A polymer does not have to be piezo-active to be an effective material for a polymer composite.^[36] In this case, a material could be made up of an inert matrix with a separate piezo-active component.

PVDF exhibits piezoelectricity several times greater than quartz.

The piezo-response observed from PVDF is about 20-30 pC/N.

That is an order of 5-50 times less than that of piezoelectric ceramic lead zirconate titanate (PZT).^[35][36] The thermal stability of the piezoelectric effect of polymers in the PVDF family (ie. vinylidene fluoride co-poly trifluoroethylene) goes up to 125 °C. Some applications of PVDF are pressure sensors, hydrophones, and shock wave sensors.^[35]

Due to their flexibility, piezoelectric composites have been proposed as energy harvesters and nanogenerators.^[37] In 2018, it was reported by Zhu et al. that a piezoelectric response of about 17 pC/N could be obtained from PDMS/PZT nanocomposite at 60% porosity.^[31] Another PDMS nanocomposite was reported in 2017, in which BaTiO3 was integrated into PDMS to make a stretchable, transparent nanogenerator for self-powered physiological monitoring.^[31] In 2016, polar molecules were introduced into a polyurethane foam in which high responses of up to 244 pC/N were reported.^[40]

In 2000, it was shown that an actuator can be made of paper.

The wood fibers, called cellulose fibers, are aligned so that there is a dipolar orientation. This allows the material to become piezoelectric. To enhance the effect, the material can be poled for further alignment.^[36] D33 responses for cellular polypropylene are around 200 pC/N. Some applications of cellular polypropylene are musical key pads, microphones, and ultrasound-based echolocation systems.^[35]

A strong shear piezoelectric activity was observed in self-assembled diphenylalanine peptide nanotubes (PNTs), indicating electric polarization directed along the tube axis.

Comparison with LiNbO3 and lateral signal calibration yields sufficiently high effective piezoelectric coefficient values of at least 60 pm/V (shear response for tubes of ≈200 nm in diameter).

PNTs demonstrate linear deformation without irreversible degradation in a broad range of driving voltages.^[41] In addition, some other aromatic dipeptides-based supramolecular architectures also show intriguing piezoelectric properties.

For example, cyclic glycine-tryptophan crystals show a high d36 coefficient of 14.1 pC N-1)^[42], while cyclic phenylalanine-tryptophan crystals were used to fabricate power generators with excellent and stable performance producing open-circuit voltage of 1.4 V, close to the capacity of a commercial AA dry cell battery (1.5 V)^[43].

Currently, industrial and manufacturing is the largest application market for piezoelectric devices, followed by the automotive industry.

Strong demand also comes from medical instruments as well as information and telecommunications.

The global demand for piezoelectric devices was valued at approximately US$14.8 billion in 2010.

The largest material group for piezoelectric devices is piezoceramics, and piezopolymer is experiencing the fastest growth due to its low weight and small size.^[44]

Piezoelectric crystals are now used in numerous ways:

Direct piezoelectricity of some substances, like quartz, can generate potential differences of thousands of volts.

The principle of operation of a piezoelectric sensor is that a physical dimension, transformed into a force, acts on two opposing faces of the sensing element. Depending on the design of a sensor, different "modes" to load the piezoelectric element can be used: longitudinal, transversal and shear.

Detection of pressure variations in the form of sound is the most common sensor application, e.g. piezoelectric microphones (sound waves bend the piezoelectric material, creating a changing voltage) and piezoelectric pickups for acoustic-electric guitars. A piezo sensor attached to the body of an instrument is known as a contact microphone.

Piezoelectric sensors especially are used with high frequency sound in ultrasonic transducers for medical imaging and also industrial nondestructive testing (NDT).

For many sensing techniques, the sensor can act as both a sensor and an actuator—often the term transducer is preferred when the device acts in this dual capacity, but most piezo devices have this property of reversibility whether it is used or not. Ultrasonic transducers, for example, can inject ultrasound waves into the body, receive the returned wave, and convert it to an electrical signal (a voltage). Most medical ultrasound transducers are piezoelectric.

In addition to those mentioned above, various sensor applications include:

As very high electric fields correspond to only tiny changes in the width of the crystal, this width can be changed with better-than-µm precision, making piezo crystals the most important tool for positioning objects with extreme accuracy—thus their use in actuators^[52]. Multilayer ceramics, using layers thinner than 100 µm, allow reaching high electric fields with voltage lower than 150 V. These ceramics are used within two kinds of actuators: direct piezo actuators and Amplified piezoelectric actuators. While direct actuator's stroke is generally lower than 100 µm, amplified piezo actuators can reach millimeter strokes.

The piezoelectrical properties of quartz are useful as a standard of frequency.

Types of piezoelectric motor include:

Aside from the stepping stick-slip motor, all these motors work on the same principle.

Driven by dual orthogonal vibration modes with a phase difference of 90°, the contact point between two surfaces vibrates in an elliptical path, producing a frictional force between the surfaces. Usually, one surface is fixed, causing the other to move. In most piezoelectric motors, the piezoelectric crystal is excited by a sine wave signal at the resonant frequency of the motor. Using the resonance effect, a much lower voltage can be used to produce a high vibration amplitude.

A stick-slip motor works using the inertia of a mass and the friction of a clamp.

Such motors can be very small.

Some are used for camera sensor displacement, thus allowing an anti-shake function.

Different teams of researchers have been investigating ways to reduce vibrations in materials by attaching piezo elements to the material.

When the material is bent by a vibration in one direction, the vibration-reduction system responds to the bend and sends electric power to the piezo element to bend in the other direction.

Future applications of this technology are expected in cars and houses to reduce noise.

Further applications to flexible structures, such as shells and plates, have also been studied for nearly three decades.

In a demonstration at the Material Vision Fair in Frankfurt in November 2005, a team from TU Darmstadt in Germany showed several panels that were hit with a rubber mallet, and the panel with the piezo element immediately stopped swinging.

Piezoelectric ceramic fiber technology is being used as an electronic damping system on some HEAD tennis rackets.^[56]

A recent review article discusses shunted electronic devises that pump kinetic energy from a vibrating piezoelectric system and damp it in the electronic part.^[57]

In people with previous total fertilization failure, piezoelectric activation of oocytes together with intracytoplasmic sperm injection (ICSI) seems to improve fertilization outcomes.^[58]

A recent application of piezoelectric ultrasound sources is piezoelectric surgery, also known as piezosurgery.^[4] Piezosurgery is a minimally invasive technique that aims to cut a target tissue with little damage to neighboring tissues. For example, Hoigne et al. ^[59] reported its use in hand surgery for the cutting of bone, using frequencies in the range 25–29 kHz, causing microvibrations of 60–210 μm. It has the ability to cut mineralized tissue without cutting neurovascular tissue and other soft tissue, thereby maintaining a blood-free operating area, better visibility and greater precision.^[60]

In 2015, Cambridge University researchers working in conjunction with researchers from the National Physical Laboratory and Cambridge-based dielectric antenna company Antenova Ltd, using thin films of piezoelectric materials found that at a certain frequency, these materials become not only efficient resonators, but efficient radiators as well, meaning that they can potentially be used as antennas.

The researchers found that by subjecting the piezoelectric thin films to an asymmetric excitation, the symmetry of the system is similarly broken, resulting in a corresponding symmetry breaking of the electric field, and the generation of electromagnetic radiation.^[61][62]

In recent years, several attempts at the macro-scale application of the piezoelectric technology have emerged^[63][64] to harvest kinetic energy from walking pedestrians. The piezoelectric floors have been trialed since the beginning of 2007 in Tokyo Japanese train stations. The electricity generated from the foot traffic is used to measure the excitement of spectators at the Vissel Kobe football stadium. In London, a famous nightclub exploited the piezoelectric technology in its dance floor. Parts of the lighting and sound systems in the club can be powered by the energy harvesting tiles.^[65] However, the piezoelectric tile deployed on the ground usually harvests energy from low frequency strikes provided by the foot traffic. This working condition may eventually lead to low power generation efficiency.^[66]

In this case, locating high traffic areas is critical for optimization of the energy harvesting efficiency, as well as the orientation of the tile pavement significantly affects the total amount of the harvested energy.

A density flow evaluation is recommended to qualitatively evaluate the piezoelectric power harvesting potential of the considered area based on the number of pedestrian crossings per unit time.^[66] In X. Li's study, the potential application of a commercial piezoelectric energy harvester in a central hub building at Macquarie University in Sydney, Australia is examined and discussed.

Optimization of the piezoelectric tile deployment is presented according to the frequency of pedestrian mobility and a model is developed where 3.1% of the total floor area with the highest pedestrian mobility is paved with piezoelectric tiles.

The modelling results indicate that the total annual energy harvesting potential for the proposed optimized tile pavement model is estimated at 1.1 MW h/year, which would be sufficient to meet close to 0.5% of the annual energy needs of the building.^[66] In Israel, there is a company which has installed piezoelectric materials under a busy highway.

The energy generated is adequate and powers street lights, billboards and signs.

Tire company Goodyear has plans to develop an electricity generating tire which has piezoelectric material lined inside it. As the tire moves, it deforms and thus electricity is generated.^[67]

The efficiency of a hybrid photovoltaic cell that contains piezoelectric materials can be increased simply by placing it near a source of ambient noise or vibration. The effect was demonstrated with organic cells using zinc oxide nanotubes. The electricity generated by the piezoelectric effect itself is a negligible percentage of the overall output. Sound levels as low as 75 decibels improved efficiency by up to 50%. Efficiency peaked at 10 kHz, the resonant frequency of the nanotubes. The electrical field set up by the vibrating nanotubes interacts with electrons migrating from the organic polymer layer. This process decreases the likelihood of recombination, in which electrons are energized but settle back into a hole instead of migrating to the electron-accepting ZnO layer.^[68][69]