Search

We have examined the formation and dissolution of gels composed of intermediate volume-fraction nanoparticles with temperature-dependent short-range attractions using small-angle x-ray scattering, x-ray photon correlation spectroscopy, and rheology to obtain nanoscale and macroscale sensitivity to structure and dynamics. Gel formation after temperature quenches to the vicinity of the rheologically determined gel temperature, T_{gel}, was characterized via the slowdown of dynamics and changes in microstructure observed in the intensity autocorrelation functions and structure factor, respectively, as a function of quench depth (ΔT=T_{quench}-T_{gel}), wave vector, and formation time t_{f}. We find the wave-vector-dependent dynamics, microstructure, and rheology at a particular ΔT and t_{f} map to those at other ΔTs and t_{f}s via an effective scaling temperature, T_{s}. A single T_{s} applies to a broad range of ΔT and t_{f} but does depend on the particle size. The rate of formation implied by the scaling is a far stronger function of ΔT than expected from the attraction strength between colloids. We interpret this strong temperature dependence in terms of cooperative bonding required to form stable gels via energetically favored, local structures.

Ferroelectric-dielectric superlattices consisting of alternating layers of ferroelectric ${\mathrm{PbTiO}}_{3}$ and dielectric ${\mathrm{SrTiO}}_{3}$ exhibit a disordered striped nanodomain pattern, with characteristic length scales of 6 nm for the domain periodicity and 30 nm for the in-plane coherence of the domain pattern. Spatial disorder in the domain pattern gives rise to coherent hard $x$-ray scattering patterns exhibiting intensity speckles. We show here using variable-temperature Bragg-geometry $x$-ray photon correlation spectroscopy that $x$-ray scattering patterns from the disordered domains exhibit a continuous temporal decorrelation due to spontaneous domain fluctuations. The temporal decorrelation can be described using a compressed exponential function, consistent with what has been observed in other systems with arrested dynamics. The fluctuation speeds up at higher temperatures and the thermal activation energy estimated from the Arrhenius model is $0.35\ifmmode\pm\else\textpm\fi{}0.21\text{ }\text{ }\mathrm{eV}$. The magnitude of the energy barrier implies that the complicated energy landscape of the domain structures is induced by pinning mechanisms and domain patterns fluctuate via the generation and annihilation of topological defects similar to soft materials such as block copolymers.

The nanodomain pattern in ferroelectric-dielectric superlattices transforms to a uniform polarization state under above-band-gap optical excitation. $X$-ray scattering reveals a disappearance of domain diffuse scattering and an expansion of the lattice. The reappearance of the domain pattern occurs over a period of seconds at room temperature, suggesting a transformation mechanism in which charge carriers in long-lived trap states screen the depolarization field. A Landau-Ginzburg-Devonshire model predicts changes in lattice parameter and a critical carrier concentration for the transformation.

Bragg projection ptychography (BPP) is a coherent diffraction imaging technique capable of mapping the spatial distribution of the Bragg structure factor in nanostructured thin films. Here, we show that, because these images are projections, the structural sensitivity of the resulting images depends on the film thickness and the aspect ratio and orientation of the features of interest and that image interpretation depends on these factors. We model changes in contrast in the BPP reconstructions of simulated ${\mathrm{PbTiO}}_{3}$ ferroelectric thin films with meandering ${180}^{\ensuremath{\circ}}$ stripe domains as a function of film thickness, discuss their origin, and comment on the implication of these factors on the design of BPP experiments of general nanostructured films.

Ferroelectric-dielectric superlattices consisting of alternating layers of ferroelectric PbTiO_{3} and dielectric SrTiO_{3} exhibit a disordered striped nanodomain pattern, with characteristic length scales of 6 nm for the domain periodicity and 30 nm for the in-plane coherence of the domain pattern. Spatial disorder in the domain pattern gives rise to coherent hard x-ray scattering patterns exhibiting intensity speckles. We show here using variable-temperature Bragg-geometry x-ray photon correlation spectroscopy that x-ray scattering patterns from the disordered domains exhibit a continuous temporal decorrelation due to spontaneous domain fluctuations. The temporal decorrelation can be described using a compressed exponential function, consistent with what has been observed in other systems with arrested dynamics. The fluctuation speeds up at higher temperatures and the thermal activation energy estimated from the Arrhenius model is 0.35±0.21 eV. The magnitude of the energy barrier implies that the complicated energy landscape of the domain structures is induced by pinning mechanisms and domain patterns fluctuate via the generation and annihilation of topological defects similar to soft materials such as block copolymers.

We demonstrate delayed-frame X-ray Photon Correlation Spectroscopy with 120 microsecond time resolution, limited only by sample scattering rates, with a prototype Pixel-array detector capable of taking two image frames separated by 153 ns or less. Although the overall frame rate is currently limited to about 4 frame pairs per second, we easily measured millisecond correlation functions. This technology, coupled to the use of brighter synchrotrons such as Petra III or the NSLS-II should enable X-ray Photon Correlation Spectroscopy on microsecond time scales on a wider variety of materials.

Dynamical phase separation during a solid-solid phase transition poses a challenge for understanding the fundamental processes in correlated materials. Critical information underlying a phase transition, such as localized phase competition, is difficult to reveal by measurements that are spatially averaged over many phase separated regions. The ability to simultaneously track the spatial and temporal evolution of such systems is essential to understanding mesoscopic processes during a phase transition. Using state-of-the-art time-resolved hard x-ray diffraction microscopy, we directly visualize the structural phase progression in a VO2 film upon photoexcitation. Following a homogenous in-plane optical excitation, the phase transformation is initiated at discrete sites and completed by the growth of one lattice structure into the other, instead of a simultaneous isotropic lattice symmetry change. The time-dependent x-ray diffraction spatial maps show that the in-plane phase progression in laser-superheated VO2 is via a displacive lattice transformation as a result of relaxation from an excited monoclinic phase into a rutile phase. The speed of the phase front progression is quantitatively measured, and is faster than the process driven by in-plane thermal diffusion but slower than the sound speed in VO2. The direct visualization of localized structural changes in the time domain opens a new avenue to study mesoscopic processes in driven systems.

We reveal inhomogeneous structural phase transformation in photo-excited VO 2 thin films by time-resolved x-ray diffraction microscopy. The in-plane plane phase progression is a result of displacive lattice transformation rather than driven by thermal transport.

Through mapping of the spatiotemporal strain profile in ferroelectric BiFeO3 epitaxial thin films, we report an optically initiated dynamic enhancement of the strain gradient of 105–106 m−1 that lasts up to a few ns depending on the film thickness. Correlating with transient optical absorption measurements, the enhancement of the strain gradient is attributed to a piezoelectric effect driven by a transient screening field mediated by excitons. These findings not only demonstrate a new possible way of controlling the flexoelectric effect, but also reveal the important role of exciton dynamics in photostriction and photovoltaic effects in ferroelectrics.

The remnant polarization of weakly coupled ferroelectric-dielectric superlattices is distributed unequally between the component layers, and as a result the components respond differently to applied electric fields. The difference is apparent in both the nanometer-scale structure of striped polarization domains and in the development of piezoelectric strain and field-induced polarization. Both effects are probed with in situ time-resolved synchrotron x-ray diffraction in a PbTiO(3)/SrTiO(3) superlattice in fields up to 2.38 MV/cm. Domains are initially distorted to increase the polarization in the SrTiO(3) layer while retaining the striped motif. The subsequent transformation to a uniform polarization state at a later time leads to piezoelectric expansion dominated by the field-induced polarization of the SrTiO(3) layers. The results are consistent with theoretical predictions of the field dependence of the domain structure and electrical polarization.

A series of laser pump, x-ray probe experiments show that above band gap photoexcitation can generate a large out-of-plane strain in multiferroic BiFeO3 thin films. The strain decays in a time scale that is the same as the photo-induced carriers measured in an optical transient absorption spectroscopy experiment. We attribute the strain to the piezoelectric effect due to screening of the depolarization field by laser induced carriers. A strong film thickness dependence of strain and carrier relaxation is also observed, revealing the role of the carrier transport in determining the structural and carrier dynamics in complex oxide thin films.

The remnant polarization of weakly coupled ferroelectric-dielectric superlattices is distributed unequally between the component layers, and as a result the components respond differently to applied electric fields. The difference is apparent in both the nanometer-scale structure of striped polarization domains and in the development of piezoelectric strain and field-induced polarization. Both effects are probed with in situ time-resolved synchrotron x-ray diffraction in a PbTiO(3)/SrTiO(3) superlattice in fields up to 2.38 MV/cm. Domains are initially distorted to increase the polarization in the SrTiO(3) layer while retaining the striped motif. The subsequent transformation to a uniform polarization state at a later time leads to piezoelectric expansion dominated by the field-induced polarization of the SrTiO(3) layers. The results are consistent with theoretical predictions of the field dependence of the domain structure and electrical polarization.

The nanodynamics of ferroelectric ultrathin films made of PbTi(0.6)Zr(0.4)TiO(3) alloy is explored via the use of a first-principles-based technique. Our atomistic simulations predict that the nanostripe domains which constitute the ground state of ferroelectric ultrathin films under most electric boundary conditions oscillate under a driving ac field. Furthermore, we find that the atomically thin wall, or nanowall, that separates the nanodomains with different polarization directions behaves as an elastic object and has a mass associated with it. The nanowall mass is size-dependent and gives rise to a unique size-driven transition from resonance to relaxational dynamics in ultrathin films. A general theory of nanodynamics in such films is developed and used to explain all computational findings. In addition, we find an unusual dynamical coupling between nanodomains and mechanical deformations that could potentially be used in ultrasensitive electromechanical nanosensors.

A microscopic approach based on the first-principles effective Hamiltonian is developed to study the polarization response in temperature-graded ferroelectrics. This approach has been applied to the case of (Ba(0.75)Sr(0.25))TiO₃ alloy. A comparison of the computational results with available experimental data attests to the remarkable accuracy of the present approach. Our computations reveal a strong anisotropy in the response of polarization to the temperature gradient (TG). In particular, the polarization offset along the direction of TG is an order of magnitude lower than in the perpendicular direction. The large as well as the small TGs are considered and found to yield qualitatively different polarization field responses. Among other striking findings are (i) the coexistence of different phases in chemically homogeneous regions, (ii) formation of low-symmetry phases, and (iii) thermally controlled polarization rotation.

The combination of ultrafast optical excitation and time-resolved synchrotron x-ray nanodiffraction provides unique insight into the photoinduced dynamics of materials, with the spatial resolution required to probe individual nanostructures or small volumes within heterogeneous materials. Optically excited x-ray nanobeam experiments are challenging because the high total optical power required for experimentally relevant optical fluences leads to mechanical instability due to heating. For a given fluence, tightly focusing the optical excitation reduces the average optical power by more than three orders of magnitude and thus ensures sufficient thermal stability for x-ray nanobeam studies. Delivering optical pulses via a scannable fiber-coupled optical objective provides a well-defined excitation geometry during rotation and translation of the sample and allows the selective excitation of isolated areas within the sample. Experimental studies of the photoinduced lattice dynamics of a 35 nm BiFeO3 thin film on a SrTiO3 substrate demonstrate the potential to excite and probe nanoscale volumes.

International audience