Nucleation and Growth of PbBrF Crystals at the Liquid Mercury-Electrolyte Interface Studied by Operando X-ray Scattering.

Detailed in operando studies of electrochemically induced PbBrF deposition at the liquid mercury/liquid electrolyte interface are presented. The nucleation and growth were monitored using time-resolved X-ray diffraction and reflectivity combined with electrochemical measurements, revealing a complex potential-dependent behavior. PbBrF deposition commences at potentials above -0.7 V with the rapid formation of an ultrathin adlayer of one unit cell thickness, on top of which (001)-oriented three-dimensional crystallites are formed. Two potential regimes are identified. At low overpotentials, slow growth of a low surface density film of large crystals is observed. At high overpotentials, crossover to a potential-independent morphology occurs, consisting of a compact PbBrF deposit with a saturation thickness of 25 nm, which forms within a few minutes. This potential behavior can be rationalized by the increasing supersaturation near the interface, caused by the potential-dependent Pb2+ deamalgamation, which changes from a slow reaction-controlled process to a fast transport-controlled process in this range of overpotentials. In addition, growth on the liquid substrate is found to involve complex micromechanical effects, such as crystal reorientation and film breakup during dissolution.

X-ray reflectivity from curved liquid interfaces.

X-ray reflectivity studies of the structure of liquid-vapour and liquid-liquid interfaces at modern sources, such as free-electron lasers, are currently impeded by the lack of dedicated liquid surface diffractometers. It is shown that this obstacle can be overcome by an alternative experimental approach that uses the natural curvature of a liquid drop for variation of the angle of incidence. Two modes of operation are shown: (i) sequential reflectivity measurements by a nanometre beam and (ii) parallel acquisition of large ranges of a reflectivity curve by micrometre beams. The feasibility of the two methods is demonstrated by studies of the Hg/vapour, H2O/vapour and Hg/0.1 M NaF interface. The obtained reflectivity curves match the data obtained by conventional techniques up to 5αc in micro-beam mode and up to 35αc in nano-beam mode, allowing observation of the Hg layering peak.

In situ X-ray studies of adlayer-induced crystal nucleation at the liquid-liquid interface.

Crystal nucleation and growth at a liquid-liquid interface is studied on the atomic scale by in situ Å-resolution X-ray scattering methods for the case of liquid Hg and an electrochemical dilute electrolyte containing Pb(2+), F(-), and Br(-) ions. In the regime negative of the Pb amalgamation potential Φ(rp) = -0.70 V, no change is observed from the surface-layered structure of pure Hg. Upon potential-induced release of Pb(2+) from the Hg bulk at Φ > Φ(rp), the formation of an intriguing interface structure is observed, comprising a well-defined 7.6-Å-thick adlayer, decorated with structurally related 3D crystallites. Both are identified by their diffraction peaks as PbFBr, preferentially aligned with their axis along the interface normal. X-ray reflectivity shows the adlayer to consist of a stack of five ionic layers, forming a single-unit-cell-thick crystalline PbFBr precursor film, which acts as a template for the subsequent quasiepitaxial 3D crystal growth. This growth behavior is assigned to the combined action of electrostatic and short-range chemical interactions.

A novel X-ray diffractometer for studies of liquid-liquid interfaces.

The study of liquid-liquid interfaces with X-ray scattering methods requires special instrumental considerations. A dedicated liquid surface diffractometer employing a tilting double-crystal monochromator in Bragg geometry has been designed. This diffractometer allows reflectivity and grazing-incidence scattering measurements of an immobile mechanically completely decoupled liquid sample, providing high mechanical stability. The available energy range is from 6.4 to 29.4 keV, covering many important absorption edges. The instrument provides access in momentum space out to 2.54 Å(-1) in the surface normal and out to 14.8 Å(-1) in the in-plane direction at 29.4 keV. Owing to its modular design the diffractometer is also suitable for heavy apparatus such as vacuum chambers. The instrument performance is described and examples of X-ray reflectivity studies performed under in situ electrochemical control and on biochemical model systems are given.

Tunable Strain in Magnetoelectric ZnO Microrod Composite Interfaces.

The intrinsic strain at coupled components in magnetoelectric composites plays an important role for the properties and function of these materials. In this in situ X-ray nanodiffraction experiment, the coating-induced as well as the magnetic-field-induced strain at the coupled interface of complex magnetoelectric microcomposites were investigated. These consist of piezoelectric ZnO microrods coated with an amorphous layer of magnetostrictive (Fe90Co10)78Si12B10. While the intrinsic strain is in the range of 10-4, the magnetic-field-induced strain is within 10-5, one order of magnitude smaller. Additionally, the strain relaxation distance of around 5 µm for both kinds of strain superposes indicating a correlation. The value of both intrinsic and magnetic-field-induced strain can be manipulated by the diameter of the rodlike composite. The intrinsic interface strain within the ZnO increases exponentially by decreasing the rod diameter while the magnetic-field-induced strain increases linearly within the given range. This study shows that miniaturizing has a huge impact on magnetoelectric composite properties, resulting in a strongly enhanced strain field and magnetic response.