Electric Field Poling in Polymeric Nonlinear Optical Materials. Relaxation Dynamics, Model, and Experiment

Millicent A. Firestone*, Mark A. Ratner, Tobin J. Marks

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

41 Scopus citations


Simulations of the electric field poling process for second-order NLO-active polymeric materials containing dipolar chromophores were performed by modeling the time-dependent dynamics of a dipole interacting with an externally applied field and subsequent force-free relaxation, employing several modifications of the Smoluchowski equation. The model examines chromophore dipole alignment/relaxation processes in both two- and three-dimensional space. The 3-D model predicts that at field-on equilibrium, the ratio, R, of the second-harmonic coefficients, d33/d31, approaches 3.0, in accord with static statistical-mechanical models. In contrast, the 2-D model predicts R ~ 6.0. The dimensionality in which the rotational diffusion process is confined also determines the rate of dipolar alignment/relaxation, with a slower rate predicted in the 2-D case. Suitability of the rotational diffusion model for the alignment and relaxation dynamics of appended NLO chromophores in poled polymer films is also examined. At temperatures at or above the glass transition temperature, Tg, experimentally measured d33 relaxation kinetics of a prototypical chromophore-functionalized polymer, N-(4-nitrophenyl)-(S)-prolinoxy poly(p-hydroxystyrene), (S)-NPP-PHS, are well described by the bi-exponential expression predicted by the 3-D model. Below Tg, however, the dynamics are not well modeled as simple 3-D rotational diffusion, the apparent result of complex dynamical matrix interactions. Under all conditions examined, the experimental d31 relaxation dynamics can be described approximately using the 2-D model. The temperature dependence of the relaxation rate above Tg is well described by the Williams-Landel-Ferry (WLF) equation, while below Tg, the reorientation process is Arrhenius-like. The d33 growth kinetics are found to be accurately approximated using expressions derived from the 3-D rotational diffusion model. Below Tg the experimental activation energy determined from field-on polarization is identical within experimental error to that determined for field-off depolarization.

Original languageEnglish (US)
Pages (from-to)6296-6310
Number of pages15
Issue number18
StatePublished - Aug 1 1995

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry


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