We report the first analysis of the polarization and lattice dynamics in a metal/ferroelectric/metal nanolayer system by femtosecond x-ray diffraction. Two Bragg reflections provide information on the coupled dynamics of the two relevant phonon modes for ferroelectricity in perovskites, the tetragonal distortion and the soft mode. Optical excitation of the SrRuO(3) metal layers generates giant stress (>1 GPa) compressing the PbZr(0.2)Ti(0.8)O(3) layers by up to 2%. The resulting change of tetragonality reaches a maximum after 1.3 ps. As a result, the ferroelectric polarization P is reduced by up to 100% with a slight delay that is due to the anharmonic coupling of the two modes.
The assembly of polyelectrolytes and gold nanoparticles yields stratified multilayers with very low roughness and high structural perfection. The films are prepared by spin-assisted layer-by-layer self-assembly (LbL) and are characterized by X-ray reflectivity (XRR), UV-vis spectroscopy, atomic force microscopy (AFM), and transmission electron microscopy (TEM). Typical structures have four repeat units, each of which consists of eight double layers (DL) of poly(sodium 4-styrenesulfonate)/poly(allylamine hydrochloride), one monolayer of gold nanoparticles (10 nm diameter), and another layer of poly(allylamine hydrochloride). XRR scans show small-angle Bragg peaks up to seventh order, evidencing the highly stratified structure. Pronounced Kiessig fringes indicate a low global roughness, which is confirmed by local AFM measurements. TEM images corroborate the layered structure in the growth direction and nicely show the distinct separation of the individual particle layers. An AFM study reveals the lateral gold particle distribution within one individual particle layer. Interestingly, the spin-assisted deposition of polyelectrolytes reduces the roughness induced by the particle layers, leading to self-healing of roughness defects and a rather perfect stratification.
When gold nanoparticles are covered with nanometric layers of transparent polyelectrolytes, the plasmon absorption spectrum A(λ) increases by a factor of approximately three and shifts to the red. These modifications of dissipative experimental observables stop when the cover layer thickness approaches the particle diameter. Spectral modifications of dispersive parameters like the reflection R, however, keep changing with increasing cover layer thickness. The shift of the plasmon resonance caused by two interacting particle layers is studied as a function of the separating distance between the two layers. We discuss these observations in the context of an effective medium theory and conclude that it can only be applied for a layer thickness on the order of the particle diameter.
Strain propagation in a perovskite heterostructure grown on a SrTiO 3 ͑STO͒ substrate is studied by ultrafast x-ray diffraction. Femtosecond displacive phonon excitation in a PbZr 0.2 Ti 0.8 O 3 / SrRuO 3 ͑PZT/SRO͒ film launches acoustic strain waves propagating into the STO substrate. We demonstrate a two-step time evolution of diffracted x-ray intensity which originates from different interfering contributions to the ͑004͒ Bragg peak of the STO substrate. Analysis by dynamical x-ray diffraction theory gives the absolute strain ⌬a / a 0 in a wide range of optical pump fluences. Ultrafast transient strain as small as ⌬a / a 0 =2ϫ 10 −5 is determined in this way.
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