1. Observation of nonreciprocal polarization modulations induced by an intense terahertz electric-field pulse in an electronic-type molecular ferroelectric
- Author
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T. Kubo, T. Miyamoto, N. Takamura, M. Yamamoto, R. Ikeda, T. Sato, and H. Okamoto
- Subjects
Physics ,QC1-999 - Abstract
An intense terahertz pulse has the potential to control the polarization of ferroelectrics at the subpicosecond time scale. In some ferroelectrics, it has been reported that irradiation with a terahertz pulse on the order of 100 kV/cm modulates the polarization in a manner proportional to the electric field. If a stronger electric field is applied, it may be possible to alter the polarization nonlinearly or even cause it to disappear. However, such attempts have not been reported to date. In this paper, we aim to nonlinearly control ferroelectric polarization by irradiating an organic molecular compound tetrathiafulvalene-p-chloranil (TTF-CA), a typical electronic-type ferroelectric, with a terahertz pulse having an electric-field amplitude of up to 2.2 MV/cm. When the temperature is reduced, TTF-CA undergoes a neutral (N) to ionic (I) phase transition at T_{c}=81K, and the degree of charge transfer ρ from CA to TTF changes from 0.3 to 0.6. In the I phase, it shows the ferroelectricity owing to the collective intermolecular charge transfer at T_{c}. Therefore, if the I-to-N conversion is induced by a strong electric field, the ferroelectric polarization P may change significantly. To investigate the changes in ρ and P along the electric-field waveform of the terahertz pulse in the ferroelectric I phase of TTF-CA, in this paper, a terahertz pump-optical reflectivity probe and second harmonic generation (SHG) probe measurements are performed. For the terahertz electric-field amplitudes E_{THz}0.5MV/cm is applied parallel to P, the increases in ρ and P tend to become saturated. The increase in P is only ∼10% at a maximum electric-field amplitude of 2.2 MV/cm. In contrast, when E_{THz} is antiparallel to P, the decreases in ρ and P are proportional to E_{THz} up to 1.5 MV/cm. When E_{THz} is further increased to values >1.5 MV/cm, a partial I-to-N conversion occurs via quantum electron tunneling processes, and P decreases in a nonlinear manner. The decrease in P reaches ∼30% at 2.2 MV/cm. These nonreciprocal changes in ρ and P are discussed while considering the valence instability characteristic of TTF-CA. Furthermore, several coherent oscillations are observed in the changes of reflectivity and SHG, which reflect the modulations of ρ and P due to molecular vibrations (lattice modes), respectively. A detailed analysis of the amplitudes and phases of these coherent oscillations reveals that a molecular vibration with a frequency of ∼90 cm^{−1} is driven by changes in ρ induced by a terahertz electric field and modulates P significantly through the changes in the dimeric molecular displacements along the molecular stacking axis, that is, the polarization direction.
- Published
- 2025
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