Comparative investigation of the structure and properties of ferroelectric poly(vinylidene fluoride) and poly(vinylidene fluoride–trifluoroethylene) thin films crystallized on substrates

Poly(vinylidene fluoride) (PVDF) and copolymers of vinylidene fluoride and trifluoroethylene [P(VDF/TrFE)s] were deposited on silicon substrates, and their structure and properties were comparatively investigated. Compared to P(VDF/TrFE), which is the polymer material currently most dominant for ferroelectric thin-film devices applications, our β-phase PVDF homopolymer thin film demonstrated several advantages, such as higher dielectric breakdown strength, improved polarization fatigue endurance, and larger ferroelectric polarization at elevated temperatures with improved thermal stability. The reasons for the observed different characteristics between the PVDF and P(VDF/TrFE) thin films were analyzed on the basis of their different structures and morphologies. The results indicate that the low-cost β-phase PVDF homopolymer thin films have great potential as an alternative to P(VDF/TrFE) for ferroelectric and piezoelectric thin-film-device applications. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

[1]  Kui Yao,et al.  Phase transition and properties of a ferroelectric poly(vinylidene fluoride-hexafluoropropylene) copolymer , 2005 .

[2]  T. Furukawa,et al.  Factors governing ferroelectric switching characteristics of thin VDF/TrFE copolymer films , 2006, IEEE Transactions on Dielectrics and Electrical Insulation.

[3]  K. Burke,et al.  Probing surface lattice dynamics with hyperthermal ion scattering , 1994 .

[4]  K. Kim,et al.  Molecular and Crystalline Microstructure of Ferroelectric Poly(vinylidene fluoride-co-trifluoroethylene) Ultrathin Films on Bare and Self-Assembled Monolayer-Modified Au Substrates , 2008 .

[5]  T. Mukai,et al.  Piezoelectric properties of vinylidene fluoride oligomer for use in medical tactile sensor applications , 2008 .

[6]  K. Matsushige,et al.  Structural analysis of the P(VDF/TrFE) copolymer film , 2003 .

[7]  K. Kim,et al.  Metal Salt‐Induced Ferroelectric Crystalline Phase in Poly(vinylidene fluoride) Films , 2008 .

[8]  Guodong Zhu,et al.  Polarization fatigue in ferroelectric vinylidene fluoride and trifluoroethylene copolymer films , 2006 .

[9]  K. Yao,et al.  Crystallization mechanism and piezoelectric properties of solution-derived ferroelectric poly(vinylidene fluoride) thin films , 2006 .

[10]  S. Fedosov,et al.  Conductivity-induced polarization buildup in poly(vinylidene fluoride) , 2002 .

[11]  Masamichi Kobayashi,et al.  Phase transition at a temperature immediately below the melting point of poly(vinylidene fluoride) from I: A proposition for the ferroelectric Curie point , 1983 .

[12]  M. Nardelli,et al.  Collective polarization effects in β-polyvinylidene fluoride and its copolymers with tri- and tetrafluoroethylene , 2005 .

[13]  A. Hopfinger,et al.  Polymorphism of poly(vinylidene fluoride): potential energy calculations of the effects of head‐to‐head units on the chain conformation and packing of poly(vinylidene fluoride) , 1972 .

[14]  F. Fang,et al.  Deformation and fracture behavior of poly(vinylidene fluoride‐trifluorethylene) ferroelectric copolymer films under uniaxial tension , 2005 .

[15]  Otto J. Gregory,et al.  The Role of Solution Phase Water on the Deposition of Thin Films of Poly(vinylidene fluoride) , 2002 .

[16]  M. Schulz,et al.  Flexible Dome and Bump Shape Piezoelectric Tactile Sensors Using PVDF-TrFE Copolymer , 2008, Journal of Microelectromechanical Systems.

[17]  H. Ohigashi,et al.  Piezoelectricity and related properties of vinylidene fluoride and trifluoroethylene copolymers , 1986 .

[18]  Robert A. Anderson,et al.  Piezoelectricity and pyroelectricity in polyvinylidene fluoride , 1978 .

[19]  K. Yao,et al.  Ferroelectric poly(vinylidene fluoride) thin films on Si substrate with the β phase promoted by hydrated magnesium nitrate , 2007 .

[20]  S. Bauer,et al.  Separate contributions to the pyroelectricity in poly(vinylidene fluoride) from the amorphous and crystalline phases, as well as from their interface , 1999 .

[21]  H. Ohigashi,et al.  Lamellar and Bulk Single Crystals Grown in Annealed Films of Vinylidene Fluoride and Trifluoroethylene Copolymers , 1988 .

[22]  S. Ducharme,et al.  Ferroelectric polymer Langmuir-Blodgett films for nonvolatile memory applications , 2005, IEEE Transactions on Device and Materials Reliability.

[23]  S. Fedosov,et al.  Back-switching of ferroelectric polarization in two-component systems , 2004 .

[24]  A. Salimi,et al.  FTIR STUDIES OF -PHASE CRYSTAL FORMATION IN STRETCHED PVDF FILMS , 2003 .

[25]  Kui Yao,et al.  Measurement of longitudinal piezoelectric coefficient of thin films by a laser-scanning vibrometer , 2003, IEEE Transactions on Ultrasonics, Ferroelectrics and Frequency Control.

[26]  Guodong Zhu,et al.  Imaging of ferroelectric vinylidene fluoride and trifluoroethylene copolymer films by scanning tunneling microscopy , 2008 .

[27]  R. Gregorio Determination of the α, β, and γ crystalline phases of poly(vinylidene fluoride) films prepared at different conditions , 2006 .