Persistent opto-ferroelectric responses in molecular ferroelectrics

Persistent photoresponses require optical excitations to metastable states, which are rare of ionic origin due to the indirect photon-ion interaction. In this work, we explore the photoinduced metastable proton states in the proton-transfer type molecular ferroelectric croconic acid. We observe that, after the photoexcitation, the changes of structural and ferroelectric properties relax in ∼10^3s, indicating persistent photoresponses of ionic origin. In contrast, the photoconductivity relaxes within 1 s. The 10^3s timescale suggests that the ionic metastable states result from proton transfer both along and out of the hydrogen bonds. This discovery unveils an ionic mechanism for the phototunability, which offers persistent opto-ferroelectric control for proton-transfer type molecular ferroelectrics

Dynamic Tilting of Ferroelectric Domain Walls Caused by Optically Induced Electronic Screening

Optical excitation perturbs the balance of phenomena selecting the tilt orientation of domain walls within ferroelectric thin films. The high carrier density induced in a low-strain BaTiO3 thin film by an above-bandgap ultrafast optical pulse changes the tilt angle that 90{\deg} a/c domain walls form with respect to the substrate-film interface. The dynamics of the changes are apparent in time-resolved synchrotron x-ray scattering studies of the domain diffuse scattering. Tilting occurs at 298 K, a temperature at which the a/b and a/c domain phases coexist but is absent at 343 K in the better ordered single-phase a/c regime. Phase coexistence at 298 K leads to increased domain-wall charge density, and thus a larger screening effect than in the single-phase regime. The screening mechanism points to new directions for the manipulation of nanoscale ferroelectricity

Dynamic Tilting of Ferroelectric Domain Walls via Optically Induced Electronic Screening

Optical excitation perturbs the balance of phenomena selecting the tilt orientation of domain walls within ferroelectric thin films. The high carrier density induced in a low-strain BaTiO3 thin film by an above-bandgap ultrafast optical pulse changes the tilt angle that 90{\deg} a/c domain walls form with respect to the substrate-film interface. The dynamics of the changes are apparent in time-resolved synchrotron x-ray scattering studies of the domain diffuse scattering. Tilting occurs at 298 K, a temperature at which the a/b and a/c domain phases coexist but is absent at 343 K in the better ordered single-phase a/c regime. Phase coexistence at 298 K leads to increased domain-wall charge density, and thus a larger screening effect than in the single-phase regime. The screening mechanism points to new directions for the manipulation of nanoscale ferroelectricity

Tunable spin-state bistability in a spin crossover molecular complex

The spin crossover (SCO) transitions at both the surface and over the entire volume of the [Fe{H2B(pz)2}2(bipy)] polycrystalline films on Al2O3 substrates have been studied, where pz  =  pyrazol-1-yl and bipy  =  2,2'-bipyridine. For [Fe{H2B(pz)2}2(bipy)] films of hundreds of nm thick, magnetometry and x-ray absorption spectroscopy measurements show thermal hysteresis in the SCO transition with temperature, although the transition in bulk [Fe{H2B(pz)2}2(bipy)] occurs in a non-hysteretic fashion at 157 K. While the size of the crystallites in those films are similar, the hysteresis becomes more prominent in thinner films, indicating a significant effect of the [Fe{H2B(pz)2}2(bipy)]/Al2O3 interface. Bistability of spin states, which can be inferred from the thermal hysteresis, was directly observed using temperature-dependent x-ray diffraction; the crystallites behave as spin-state domains that coexist during the transition. The difference between the spin state of molecules at the surface of the [Fe{H2B(pz)2}2(bipy)] films and that of the molecules within the films, during the thermal cycle, indicates that both cooperative (intermolecular) effects and coordination are implicated in perturbations to the SCO transition

Laser-induced electron diffraction for probing rare gas atoms

Recently, using midinfrared laser-induced electron diffraction (LIED), snapshots of a vibrating diatomic molecule on a femtosecond time scale have been captured [C. I. Blaga et al., Nature (London) 483, 194 (2012)]. In this Letter, a comprehensive treatment for the atomic LIED response is reported, a critical step in generalizing this imaging method. Electron-ion differential cross sections (DCSs) of rare gas atoms are extracted from measured angular-resolved, high-energy electron momentum distributions generated by intense midinfrared lasers. Following strong-field ionization, the high-energy electrons result from elastic rescattering of a field-driven wave packet with the parent ion. For recollision energies 100 eV, the measured DCSs are indistinguishable for the neutral atoms and ions, illustrating the close collision nature of this interaction. The extracted DCSs are found to be independent of laser parameters, in agreement with theory. This study establishes the key ingredients for applying LIED to femtosecond molecular imaging

Effects of biaxial strain on the improper multiferroicity in \u3ci\u3eh\u3c/i\u3e-LuFeO\u3csub\u3e3\u3c/sub\u3e films studied using the restrained thermal expansion method

Elastic strain is potentially an important approach in tuning the properties of the improperly multiferroic hexagonal ferrites, the details of which, however, have been elusive due to experimental difficulties. Employing the method of restrained thermal expansion, we have studied the effect of isothermal biaxial strain in the basal plane of h-LuFeO3 (001) films. The results indicate that a compressive biaxial strain significantly enhances the K3 structural distortion (the order parameter of the improper ferroelectricity), and the effect is larger at higher temperatures. The compressive biaxial strain and the enhanced K3 structural distortion together cause an increase in the electric polarization and a reduction in the canting of the weak ferromagnetic moments in h-LuFeO3, according to our first principles calculations. These findings are important for understanding the strain effect as well as the coupling between the lattice and the improper multiferroicity in h-LuFeO3. The experimental elucidation of the strain effect in h-LuFeO3 films also suggests that the restrained thermal expansion can be a viable method to unravel the strain effect in many other thin film materials

OBSERVATION OF FEMTOSECOND, SUB-ANGSTROM MOLECULAR BOND RELAXATION USING LASER-INDUCED ELECTRON DIFFRACTION

Author Institution: Department of Physics, The Ohio State University, Columbus, OH 43210; Department of Physics, Kansas State University, Manhattan, KS 66506; Laser Spectroscopy Facility, Department of Chemistry, The Ohio State University, Columbus, OH 43210Imaging, or the determination of the atomic positions in molecules, has always occupied an essential role in physical, chemical and biological sciences. For structural determination, the well established methods of X-ray and electron diffraction easily achieve sub-Angstrom spatial resolution. However, these conventional approaches are not suitable for investigating structural transformations, such as the reaction of molecules or the function of biological systems that occur on the timescales faster than a picosecond. Over the past decade, major efforts directed at developing femtosecond pulsed sources, e.g. X-ray free-electron lasers and electron beams, have resulted in pioneering investigations on imaging large biological molecules and condensed phase dynamics. We report on a different approach, laser-induced electron diffraction (LIED), for achieving sub-femtosecond, sub-Angstrom spatio-temporal resolution for investigating gas-phase molecular dynamics. In contrast to the above mentioned techniques, the LIED method generates bursts of coherent electron wave packets directly from the molecule under interrogation. The study is performed by measuring the diffracted photoelectron momentum distribution produced by strong-field ionization of oxygen and nitrogen molecules at several mid-infrared wavelengths (1.7-2.3 $\mu$m). The bond lengths retrieved from the LIED analysis show sensitivity to a change of 0.05 \AA ~in 1 fs. This initial report provides the first direct evidence of bond relaxation following an electronic excitation and establishes the foundation of the LIED method as a general approach for ultrafast imaging of molecular dynamics