Observation of surface layering in a nonmetallic liquid

Oscillatory density profiles (layers) have previously been observed at the free surfaces of liquid metals, but not in other isotropic liquids. We have used x-ray reflectivity to study a molecular liquid, tetrakis(2-ethylhexoxy)silane. When cooled to T/Tc~0.25 (well above the freezing point for this liquid), density oscillations appear at the surface. Lateral order within the layers is liquid-like. Our results confirm theoretical predictions that a surface-layered state will appear even in dielectric liquids at sufficiently low temperatures, if not preempted by freezing.Comment: accepted for publication in Phys. Rev. Lett. 15 pages 4 figure

Optical and microstructural characterization of Er3+^{3+} doped epitaxial cerium oxide on silicon

Rare-earth ion dopants in solid-state hosts are ideal candidates for quantum communication technologies such as quantum memory, due to the intrinsic spin-photon interface of the rare-earth ion combined with the integration methods available in the solid-state. Erbium-doped cerium oxide (Er:CeO$_2$) is a particularly promising platform for such a quantum memory, as it combines the telecom-wavelength (~1.5 $\mu$m) 4f-4f transition of erbium, a predicted long electron spin coherence time supported by CeO$_2$, and is also near lattice-matched to silicon for heteroepitaxial growth. In this work, we report on the epitaxial growth of Er:CeO$_2$ thin films on silicon using molecular beam epitaxy (MBE), with controlled erbium concentration down to 2 parts per million (ppm). We carry out a detailed microstructural study to verify the CeO$_2$ host structure, and characterize the spin and optical properties of the embedded Er$^{3+}$ ions. In the 2-3 ppm Er regime, we identify EPR linewidths of 245(1) MHz, optical inhomogeneous linewidths of 9.5(2) GHz, optical excited state lifetimes of 3.5(1) ms, and spectral diffusion-limited homogenoeus linewidths as narrow as 4.8(3) MHz in the as-grown material. We test annealing of the Er:CeO$_2$ films up to 900 deg C, which yields modest narrowing of the inhomogeneous linewidth by 20% and extension of the excited state lifetime by 40%. We have also studied the variation of the optical properties as a function of Er doping and find that the results are consistent with the trends expected from inter-dopant charge interactions.Comment: 15 pages, 6 figures (including supplemental information

Systematic approach to electrostatically induced 2D crystallization of nanoparticles at liquid interfaces

We report an experimental demonstration of a strategy for inducing two-dimensional (2D) crystallization of charged nanoparticles on oppositely charged fluid interfaces. This strategy aims to maximize the interfacial adsorption of nanoparticles, and hence their lateral packing density, by utilizing a combination of weakly charged particles and a high surface charge density on the planar interface. In order to test this approach, we investigated the assembly of cowpea mosaic virus (CPMV) on positively charged lipid monolayers at the aqueous solution surface, by means of in situ X-ray scattering measurements at the liquid-vapor interface. The assembly was studied as a function of the solution pH, which was used to vary the charge on CPMV, and of the mole fraction of the cationic lipid in the binary lipid monolayer, which set the interface charge density. The 2D crystallization of CPMV occurred in a narrow pH range just above the particle's isoelectric point, where the particle charge was weakly negative, and only when the cationic-lipid fraction in the monolayer exceeded a threshold. The observed 2D crystals exhibited nearly the same packing density as the densest lattice plane within the known 3D crystals of CPMV. The above electrostatic approach of maximizing interfacial adsorption may provide an efficient route to the crystallization of nanoparticles at aqueous interfaces

Effects of Divalent Cations on Phase Behavior and Structure of a Zwitterionic Phospholipid (DMPC) Monolayer at the Air−Water Interface

Effects of divalent cations (Ca²⁺, Mg²⁺, Ni²⁺, and Zn²⁺) on a zwitterionic phospholipid monolayer at the air−water interface are investigated by surface pressure−area isotherms and in situ X-ray scattering. Divalent cations lower the surface pressure for the fluid (LE) to condensed (L₂) phase transition in a strongly ion-specific manner. Surprisingly, the two-dimensional lattice dimensions and the tilt of the lipids’ alkyl tails in the L₂ phase show a nearly ion-nonspecific dependence on the excess surface pressure above the transition pressure. An empirical “universal” relationship was found between the tail tilt and the excess pressure, with the tails in the L₂ phase always displaying a tilt of 29° at the transition. A practical implication of these results is that, regardless of the divalent cation present, the microscopic details of the lipid tail packing in the L₂ phase can be deduced at any surface pressure once the transition pressure is obtained from isotherms

How Ag Nanospheres Are Transformed into AgAu Nanocages

Bimetallic hollow, porous noble metal nanoparticles are of broad interest for biomedical, optical and catalytic applications. The most straightforward method for preparing such structures involves the reaction between HAuCl₄ and well-formed Ag particles, typically spheres, cubes, or triangular prisms, yet the mechanism underlying their formation is poorly understood at the atomic scale. By combining in situ nanoscopic and atomic-scale characterization techniques (XAFS, SAXS, XRF, and electron microscopy) to follow the process, we elucidate a plausible reaction pathway for the conversion of citrate-capped Ag nanospheres to AgAu nanocages; importantly, the hollowing event cannot be explained by the nanoscale Kirkendall effect, nor by Galvanic exchange alone, two processes that have been previously proposed. We propose a modification of the bulk Galvanic exchange process that takes into account considerations that can only occur with nanoscale particles. This <i>nanoscale</i> Galvanic exchange process explains the novel morphological and chemical changes associated with the typically observed hollowing process