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      Photoexcitation of a polarization-inverted domain from the charge-ordered ferroelectric ground state of (TMTTF)\(_{2}\)PF\(_{6}\)

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          Abstract

          We theoretically revealed that a weak photoexcitation achieves the electric polarization-inversion with approximately \(18\%\) of all the charges, which was interpreted as a superimposition of multi-exciton states, from the charge-ordered ferroelectric ground state of (TMTTF)\(_{2}\)PF\(_{6}\) at absolute zero temperature. Regarding a relative change of electric polarization (\(\Delta P/P\)), the photoexcitation corresponds to \(36\%\), which is much larger than \(\Delta P/P\) of other typical organic materials. The value of \(\Delta P/P\sim 36\%\) can be enlarged by a strong photoexcitation. This fact is useful not only for applications of this material and other analogous materials in optical devices but also for researches toward controlling electric polarizations by light, which is one of the recent attracting issues on photoinduced phase transition phenomena. The photoexcitation of \(\Delta P/P\sim 36\%\) corresponds to the single peak of the optical conductivity in the low-energy region, which was also observed at 10 K. Theoretical calculations are based on a quarter-filled one-dimensional effective model with appropriate parameters and 50 unit cells.

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          Novel electronic ferroelectricity in an organic charge-order insulator investigated with terahertz-pump optical-probe spectroscopy

          In electronic-type ferroelectrics, where dipole moments produced by the variations of electron configurations are aligned, the polarization is expected to be rapidly controlled by electric fields. Such a feature can be used for high-speed electric-switching and memory devices. Electronic-type ferroelectrics include charge degrees of freedom, so that they are sometimes conductive, complicating dielectric measurements. This makes difficult the exploration of electronic-type ferroelectrics and the understanding of their ferroelectric nature. Here, we show unambiguous evidence for electronic ferroelectricity in the charge-order (CO) phase of a prototypical ET-based molecular compound, α-(ET)2I3 (ET:bis(ethylenedithio)tetrathiafulvalene), using a terahertz pulse as an external electric field. Terahertz-pump second-harmonic-generation(SHG)-probe and optical-reflectivity-probe spectroscopy reveal that the ferroelectric polarization originates from intermolecular charge transfers and is inclined 27° from the horizontal CO stripe. These features are qualitatively reproduced by the density-functional-theory calculation. After sub-picosecond polarization modulation by terahertz fields, prominent oscillations appear in the reflectivity but not in the SHG-probe results, suggesting that the CO is coupled with molecular displacements, while the ferroelectricity is electronic in nature. The results presented here demonstrate that terahertz-pump optical-probe spectroscopy is a powerful tool not only for rapidly controlling polarizations, but also for clarifying the mechanisms of ferroelectricity.
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            Author and article information

            Journal
            24 January 2019
            Article
            1901.08322
            95b70198-f76e-4deb-8bb2-4d4d29aa8689

            http://creativecommons.org/licenses/by/4.0/

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            Custom metadata
            24 pages, 8 figures
            cond-mat.str-el

            Condensed matter
            Condensed matter

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