Piezoelectricity describes interconversion between electrical charge and mechanical strain. As expected for lattice ions displaced in an electric field, the proportionality constant is positive for all piezoelectric materials. The exceptions are poly(vinylidene fluoride) (PVDF) and its copolymers with trifluoroethylene (P(VDF-TrFE)), which exhibit a negative longitudinal piezoelectric coefficient. Reported explanations exclusively consider contraction with applied electric field of either the crystalline or the amorphous part of these semi-crystalline polymers. To distinguish between these conflicting interpretations, we have performed in situ dynamic X-ray diffraction measurements on P(VDF-TrFE) capacitors. We find that the piezoelectric effect is dominated by the change in lattice constant but, surprisingly, it cannot be accounted for by the polarization-biased electrostrictive contribution of the crystalline part alone. Our quantitative analysis shows that an additional contribution is operative, which we argue is due to an electromechanical coupling between the intermixed crystalline lamellae and amorphous regions. Our findings tie the counterintuitive negative piezoelectric response of PVDF and its copolymers to the dynamics of their composite microstructure.

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The negative piezoelectric effect of the ferroelectric polymer poly(vinylidene fluoride)

Ferroelectrets generate an electric field large enough to modulate the conductance of the source-drain channel of a thin-film field-effect transistor. Integrating a ferroelectret with a thin-film transistor produces a ferroelectret field-effect transistor. The authors made such transistors by laminating cellular polypropylene films and amorphous silicon thin-film transistors on polyimide substrates. They show that these ferrroelectret field-effect transistors respond in a static capacitive or dynamic piezoelectric mode. A touch sensor, a pressure-activated switch, and a microphone are demonstrated. The structure can be scaled up to large-area flexible transducer arrays, such as roll-up steerable compliant sensor skin.

Flexible ferroelectret field-effect transistor for large-area sensor skins and microphones

Cellular polymers can be internally charged by "microstorms" (silent or partial discharges) within the voids of the polymer foam. The resulting material, which carries positive and negative charges on the internal void surfaces, is called a ferroelectret. Ferroelectrets behave like typical ferroelectrics, hence they provide a novel class of ferroic materials. The soft foams are strongly piezoelectric and can be used, in a wide range of applications, as transducers for interconverting mechanical and electrical signals. Herein, an overview is provided on the preparation of cellular polymers by physical foaming (extrusion, biaxial stretching, and controlled inflation by pressure treatments), on their charging by "microstorms", on their piezo- and pyroelectricity, and on analogies to ferroelectrics. Finally, a survey of selected applications is presented.

Microstorms in Cellular Polymers: A Route to Soft Piezoelectric Transducer Materials with Engineered Macroscopic Dipoles

Polymers with strong piezo-, pyro-, and ferroelectricity are attractive for a wide range of applications. In particular, semicrystalline ferroelectric polymers are suitable for a large variety of piezo- and pyroelectric transducers or sensors, while amorphous polymers containing chromophore molecules are particularly interesting for photonic devices. Recently, a new class of polymer materials has been added to this family: internally charged cellular space-charge polymer electrets (so-called “ferroelectrets”), whose piezoelectricity can be orders of magnitude higher than that of conventional ferroelectric polymers. Suitable patterning of these materials leads to improved or unusual macroscopic piezo-, pyro-, and ferroelectric or nonlinear optical properties that may be particularly useful for advanced transducer or waveguide applications. In the present paper, the piezo-, pyro-, and ferroelectricity of poled polymers is briefly introduced, an overview on the preparation of polymer electrets with patterned...

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Patterned piezo-, pyro-, and ferroelectricity of poled polymer electrets

Recent research on piezoelectric materials is predominantly devoted to enhancing the piezoelectric coefficient, but overlooks its sign, largely because almost all of them exhibit positive longitudinal piezoelectricity. The only experimentally known exception is ferroelectric polymer poly(vinylidene fluoride) and its copolymers, which condense via weak van der Waals (vdW) interaction and show negative piezoelectricity. Here we report quantitative determination of giant intrinsic negative longitudinal piezoelectricity and electrostriction in another class of vdW solids—two-dimensional (2D) layered ferroelectric CuInP2S6. With the help of single crystal x-ray crystallography and density-functional theory calculations, we unravel the atomistic origin of negative piezoelectricity in this system, which arises from the large displacive instability of Cu ions coupled with its reduced lattice dimensionality. Furthermore, the sizable piezoelectric response and negligible substrate clamping effect of the 2D vdW piezoelectric materials warrant their great potential in nanoscale, flexible electromechanical devices.

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Origin of giant negative piezoelectricity in a layered van der Waals ferroelectric

Cellular space-charge electrets have recently emerged as a new class of materials for electromechanical devices, offering chances for a wide range of applications and challenges for materials optimization. However, many fundamental and applied aspects of the physics of these novel materials are not yet explored. Here we summarize our present understanding of the (quasi)-piezo- and -pyroelectricity in such materials. In contrast to the dipole-density piezoelectricity in ferroelectric polymers, the piezoelectric-like response of cellular polymers is intrinsic, with positive d/sub 33/ and negative d/sub 31/ and d/sub 32/ piezoelectric-like coefficients. Similarities with ferroelectric materials are outlined, especially switching of "polarization" and (quasi)-piezoelectricity. First steps towards patterned charging of cellular polymers are reported, an immediate consequence of the possibility for "polarization"-switchingin cellular materials. The results on cellular space-charge electrets suggest that well-known electret devices like microphones may be seen in a new light. Examples include dielectric and electromechanical hysteresis loops obtained with a commercially available electret microphone. In view of the results, cellular polymers may henceforth be called "ferroelectrets" and their material behavior "ferroelectretic". From an applied point of view, the performance of a Fresnel zone plate for focussing ultrasound is shown. Such a device may pave the way for a simple tool in nondestructive materials inspection, and demonstrates the large potential of cellular polymers for applications.

Charged cellular polymers with "ferroelectretic" behavior

Cellular space-charge electrets have recently emerged as a new class of materials for electromechanical devices, offering chances for a wide range of applications and challenges for materials optimisation. However, many fundamental and applied aspects of the physics of these space-charge electrets are not yet fully explored. Here we summarise briefly our present understanding of the charging process and of the piezo- and pyroelectric response. In addition, wide-ranging similarities between cellular space-charge electrets and ferroelectric materials are outlined, especially switching of polarization and piezoelectricity.

Physics of electromechanically active, cellular materials

Soft, flexible and sensitive piezoelectric materials are in demand for applications, like piezoelectric phased arrays for direction sensitive acoustic wave detection and emission. Here we report on air-borne ultrasound generation with novel piezoelectric polymers: charged, cellular polypropylene foams from VTT Chemical Technology. Based on polymer foams, two focusing devices have been developed and acoustically characterised: spherical acoustical sound generators and acoustical Fresnel zone plates. Both devices may pave the way for simple tools for non-destructive materials inspection.

H. Hoislbauer

Papers

Charged cellular polymers with "ferroelectretic" behavior

Physics of electromechanically active, cellular materials

Patterned piezoelectricity in charged, cellular polymers for air-borne ultrasound devices