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Journal of Applied Physics / Volume 108 / Issue 1 / APPLIED PHYSICS REVIEWS—FOCUSED REVIEW
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J. Appl. Phys. 108, 011101 (2010); http://dx.doi.org/10.1063/1.3457141 (19 pages)

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

Xunlin Qiu

Department of Physics and Astronomy, Applied Condensed-Matter Physics, University of Potsdam, Karl-Liebknecht-Strasse 24-25, 14476 Potsdam-Golm, Germany

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(Received 29 January 2010; accepted 26 May 2010; published online 12 July 2010)

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 piezo-, pyro-, and ferroelectricity is provided and a survey of selected applications is presented.

© 2010 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. PIEZO-, PYRO-, AND FERROELECTRICITY IN POLED POLYMER ELECTRETS
    1. Polar polymers
    2. Ferroelectrets
      1. Poling
      2. Piezo- and pyroelectricity
  3. PATTERNING OF POLED PIEZO-, PYRO-, AND FERROELECTRIC POLYMERS
    1. Patterning by selective poling and/or depoling
      1. Corona poling through a mask
      2. Poling with patterned electrodes
      3. Electron-beam poling
      4. Photorelated poling
      5. Suitable combinations of poling techniques
    2. Direct patterning
      1. Direct patterning of single-layer polymer-electret films
      2. Patterned layer structures
  4. SELECTED APPLICATIONS
  5. CONCLUSION

ERRATUM

  1. Erratum: “Patterned piezo-, pyro-, and ferroelectricity of poled polymer electrets” [J. Appl. Phys. 108, 011101 (2010)]
    Xunlin Qiu
    J. Appl. Phys. 110, 059905 (2011)JAPIAU000110000005059905000001

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KEYWORDS and PACS

Keywords

electrets, ferroelectric materials, ferroelectricity, piezoelectricity, polymers, pyroelectricity

PACS

  • 81.20.-n

    Methods of materials synthesis and materials processing

  • 77.65.-j

    Piezoelectricity and electromechanical effects

  • 77.70.+a

    Pyroelectric and electrocaloric effects

  • 77.80.-e

    Ferroelectricity and antiferroelectricity

  • 77.22.-d

    Dielectric properties of solids and liquids

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.3457141

PUBLICATION DATA

ISSN

0021-8979 (print)  
1089-7550 (online)

Publisher

$abstract.society.value is a Member of CrossRef American Institute of Physics

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Figures (click on thumbnails to view enlargements)

FIG.1
Molecular compositions of piezoelectric polymers. (a) PVDF, (b) P(VDF-TrFE), (c) aliphatic polyurea, (d) aliphatic polyurea 5, (e) poly(vinylidene-cyanide-co-vinylacetate), (f) Polyamide 7 (PA-7), and (g) PLLA.

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FIG.2
Molecular compositions of polymers that are often used as matrix materials for chromophores. (a) PMMA, (b) polycarbonate, (c) PS, (d) polyimide, (e) poly (4,4′-isopropylidenediphenylene terephthalate) copolymer (U-100), (f) Polyurethane.

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FIG.3
Chemical compositions of several polymers suitable for ferroelectret preparation. (a) PP, (b) poly(ethylene terephthalate), (c) poly(ethylene naphthalene-2,6-dicarboxylate), (d) cyclo-olefin copolymer, (e) FEP copolymer.

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FIG.4
Schematic view of piezo-, pyro-, and ferroelectric polymer electrets. (a) In semicrystalline ferroelectric polymers, ferroelectric crystallites are dispersed in the amorphous matrix. Space charges trapped at the interfaces between crystallites and amorphous matrix compensate and stabilize the ferroelectric polarization (Ref. 1). (b) Amorphous polymers for photonics applications contain chromophore molecules with large hyperpolarizabilities and large dipole moments (Ref. 1). (c) A new member of the family of piezo-, pyro-, and ferroelectric polymer electrets: internally charged nonpolar cellular polymers with very high piezoelectricity. Charges of opposite sign are deposited on the internal top and bottom surfaces of the voids so that the charged voids can be considered as macroscopic dipoles.

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FIG.5
Scanning electron micrograph of the cross section of a cellular PP foam (Ref. 52).

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FIG.6
Schematic view of the poling process in a single polymer void. When the poling voltage reaches the threshold value Vthr, Paschen breakdown is initiated (a). At higher voltages, a second series of discharges may occur (b). During ramping down the voltage, the reverse electric field from the trapped space charge may lead to back discharges (c) (Ref. 29).

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FIG.7
Simplified layer model for ferroelectrets with alternating polymer and air layers (Refs. 59 , 60). Charges of opposite polarity are generated during the DBDs and deposited on the top and bottom air-polymer interfaces, respectively.

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FIG.8
Schematic illustration of the techniques for patterning piezo-, pyro-, and ferroelectric polymers.

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FIG.9
High-resolution 3D polarization map of a P(VDF-TrFE) sample poled with an electrode grating. Details of the electrode grating are very well reproduced (Ref. 74).

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FIG.10
Geometry of a periodically poled NLO polymer waveguide fabricated by electron-beam irradiation. The sample, spin-coated on a glass slide with a transparent ITO electrode, is irradiated by means of an electron-beam lithography system. The electron-beam irradiation is used to erase the microscopic hyperpolarizability of the chromophores within the exposed area. It may also be used to depolymerize the host polymer or to modify its Tg within the exposed area, allowing the fabrication of ridge-type optical channel waveguides of high quality in a corona or a two-step poling process (Ref. 80).

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FIG.11
Poling-field dependence (under a sinusoidal electric field at a frequency of 3 mHz) of the current density during poling of a depolarized PVDF film (left axis) in comparison to a β-phase PVDF film. The depolarization was achieved by controlled scanning of the top sample electrode with a focused laser beam (Ref. 87).

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FIG.12
(a) Schematic view of the relationship between the probe bias and the dipole polarization/bound charges resulting from local poling with a negatively biased probe. (b) Selective PIO/PID during illumination with a laser source from the rear side (Ref. 93).

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FIG.13
Selective poling schemes for polar semicrystalline ferroelectric polymers. The resultant polarization of the amorphous phase is in antiparallel with that of the crystalline phase (Ref. 117).

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FIG.14
A schematic view of the fabrication of micropatterned PVDF ferroelectrics. The localized pressure applied in microimprinting lithography leads to a polymorphic transition from the nonpolar α phase to the ferroelectric γ phase (Ref. 126).

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FIG.15
AFM surface profile of a grating on a urethane-urea copolymer developed by laser interferometry. After fabrication, the grating was heat-treated for 60 min at 150 °C, i.e., above the Tg (141 °C) of the copolymer (Ref. 155).

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FIG.16
Schematic view of the setup for preparation of thermoformed bubble structures between two polymer films (Ref. 176).

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FIG.17
(a) Schematic view of the preparation process for tubular-channel ferroelectrets. A sandwich consisting of two solid FEP films with a well-designed PTFE template between them is laminated at 300 °C. After lamination, the stack is cooled down to RT. An FEP system with open channels is obtained after removing the non-sticking PTFE template from the stack. (b) Optical micrograph of the cross section of a sample together with one of its surfaces (which is seen because of a small angle between sample surface and illuminating light (Ref. 178).

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FIG.18
SHG image of the sample after PID recording of a pattern. Top: 3D tomography over an area of 40×40 μm2. Bottom: SHG profile along a line from A to B across the sample, showing the change in SHG contrast at a constant mean power of 30 mW and for increments of 30 ms in irradiation time. The full width at half maximum of the holes is about 2.8 μm (Ref. 185).

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FIG.19
Schematic view of a FZP for focusing ultrasound (Ref. 31).

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FIG.20
Frequency response of cellular-PP piezoelectret microphones with a single film and with a stack of five films, determined by means of a comparison method in an acoustic coupler (Ref. 191)

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FIG.21
Schematic view of a new mold-transfer technique to pattern P(VDF-TrFE) films and of the new dome- and bump-shaped tactile-sensor modules for smart microcatheters which can detect forces as small as 25 mN and 40 mN, respectively (Ref. 192).

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FIG.22
(a) Schematic view of a bifunctional sensor array where the flexible polymer-ceramic sensor frontplane is laminated onto a flexible transistor backplane. The piezoelectric subcell has an antiparallel orientation of the polarizations in the ceramic nanoparticles and the ferroelectric polymer matrix, while the pyroelectric subcell has a parallel orientation of the two polarizations. (b) The equivalent circuit for the subcells. (c) A digital photograph of the sensor prototype (Ref. 121).

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