Yaron Kauffmann

Single Nanocrystals of Platinum Prepared by Partial Dissolution of Au-Pt Nanoalloys

Small metal nanoparticles that are also highly crystalline have the potential for showing enhanced catalytic activity. We describe the preparation of single nanocrystals of platinum that are 2 to 3 nanometers in diameter. These particles were generated and immobilized on spherical polyelectrolyte brushes consisting of a polystyrene core (diameter of ∼100 nanometers) onto which long chains of a cationic polyelectrolyte were affixed. In a first step, a nanoalloy of gold and platinum (a solid solution) was generated within the layer of cationic polyelectrolyte chains. In a second step, the gold was slowly and selectively dissolved by cyanide ions in the presence of oxygen. Cryogenic transmission electron microscopy, wide-angle x-ray scattering, and high-resolution transmission electron microscopy showed that the resulting platinum nanoparticles are faceted single crystals that remain embedded in the polyelectrolyte-chain layer. The composite systems of the core particles and the platinum single nanocrystals exhibit an excellent colloidal stability, as well as high catalytic activity in hydrogenation reactions in the aqueous phase.

Oscillatory Mass Transport in Vapor-Liquid-Solid Growth of Sapphire Nanowires

Growing Nanowires In vapor-liquid-solid (VLS) growth of nanowires, the liquid phase acts as a transporter to bring material from the gas phase to the growing solid. By heating a single crystal of sapphire in a high-resolution transmission microscope, Oh et al. (p. 489) monitored the growth of sapphire (α-Al2O3) nanowires out of an aluminum droplet. The liquid aluminum brings oxygen to the growing wire surface, in alternating growth and dissolution reactions at the edge of the wire. The oscillation created an optimum face at the self-catalytic site for atomic stacking and regenerated the junction between the VLS phases, allowing growth of the nanowire. High-resolution transmission electron microscopy is used to identify oscillatory growth of a sapphire nanowire. In vapor-liquid-solid (VLS) growth, the liquid phase plays a pivotal role in mediating mass transport from the vapor source to the growth front of a nanowire. Such transport often takes place through the liquid phase. However, we observed by in situ transmission electron microscopy a different behavior for self-catalytic VLS growth of sapphire nanowires. The growth occurs in a layer-by-layer fashion and is accomplished by interfacial diffusion of oxygen through the ordered liquid aluminum atoms. Oscillatory growth and dissolution reactions at the top rim of the nanowires occur and supply the oxygen required to grow a new (0006) sapphire layer. A periodic modulation of the VLS triple-junction configuration accompanies these oscillatory reactions.

Vaterite Crystals Contain Two Interspersed Crystal Structures

Double Vision Vaterite is the least stable form of anhydrous crystalline calcium carbonate. While rarely found in geological contexts, it is an important biological precursor and occurs as a minor component in the shells of some organisms. The crystal structure of vaterite has long been debated with no model able to explain all the experimentally observed diffraction spots. Kabalah-Amitai et al. (p. 454) show that vaterite contains two coexisting crystallographic structures that form a pseudo-single crystal. Electron microscopy reveals that vaterite, a calcium carbonate polymorph, comprises at least two distinct crystal structures. Calcite, aragonite, and vaterite are the three anhydrous polymorphs of calcium carbonate, in order of decreasing thermodynamic stability. Although vaterite is not commonly found in geological settings, it is an important precursor in several carbonate-forming systems and can be found in biological settings. Because of difficulties in obtaining large, pure, single crystals, the crystal structure of vaterite has been elusive for almost a century. Using aberration-corrected high-resolution transmission electron microscopy, we found that vaterite is actually composed of at least two different crystallographic structures that coexist within a pseudo–single crystal. The major structure exhibits hexagonal symmetry; the minor structure, existing as nanodomains within the major matrix, is still unknown.

An experimental method for calibration of the plasmon mean free path

Transmission electron microscopy specimens in the form of elongated, conical needles were made using a dual‐beam focused ion beam system, allowing the specimen thickness to be geometrically determined for a range of thickness values. From the same samples electron energy loss maps were acquired and the plasmon mean free path (λ) for inelastic scattering was determined experimentally from the measured values of specimen thickness. To test the method λ was determined for Ni (174 ± 17 nm), α‐Al2O3 (143 ± 14 nm), Si (199 ± 20 nm) and amorphous SiO2 (238 ± 12 nm), and compared both to experimental values of λ taken from the literature and to calculated values. The calculated values of λ significantly underestimate the true sample thickness for high accelerating voltages (300 kV) and large collection angles. A linear dependence of λ on thickness was confirmed for t/λ < 0.5–0.6, but this method also provides an approach for calibrating λ at sample thicknesses for which multiple scattering occurs, thus expanding the thickness range over which electron energy loss spectroscopy can be used to determine the absolute sample thickness (t/λ > 0.6). The experimental method proposed in this contribution offers a means to calibrate λ for any type of material or phase that can be milled using a focused ion beam system.

The golden gate to photocatalytic hydrogen production

We demonstrate improved efficiency for the photocatalytic water splitting reduction half reaction by employing Au–Pt bimetallic cocatalysts. We employed nanoparticle-based photocatalysts consisting of CdSe@CdS rods tipped with Au, Pt, Au–Pt core–shell or Au decorated with Pt islands. By tailoring the composition and morphology of the Au–Pt bimetallic catalysts, we achieved more than a fourfold increase in activity for hydrogen production compared to pure Pt.

Sponge-like nanoporous single crystals of gold.

Single crystals in nature often demonstrate fascinating intricate porous morphologies rather than classical faceted surfaces. We attempt to grow such crystals, drawing inspiration from biogenic porous single crystals. Here we show that nanoporous single crystals of gold can be grown with no need for any elaborate fabrication steps. These crystals are found to grow following solidification of a eutectic composition melt that forms as a result of the dewetting of nanometric thin films. We also present a kinetic model that shows how this nano-porous single-crystalline structure can be obtained, and which allows the potential size of the porous single crystal to be predicted. Retaining their single-crystalline nature is due to the fact that the full crystallization process is faster than the average period between two subsequent nucleation events. Our findings clearly demonstrate that it is possible to form single-crystalline nano porous metal crystals in a controlled manner.

Reconstructing solid state nanopore shape from electrical measurements

The dependence of nanopore biosensor conductance signal on the nanopore shape makes it important to decipher the latter with high precision. We show here that the three dimensional shape of a nanopore, extracted from electron microscopy analysis, allows for modeling the conductance of the nanopore over a wide range of ionic strengths. Furthermore, we demonstrate that the dependence of the nanopore conductance on ionic strength can be used to accurately extract the nanopore shape, eliminating the need for lengthy electron microscopy analysis. The suggested methodology can be used to monitor changes in the nanopore shape and evaluate them during electrical characterization.

Photochemical oxidation on nanorod photocatalysts

The combination of photochemical oxidation with colloidal synthesis enables us to re-think the design of photocatalysts with an eye towards overall water splitting. Here, IrO2 nanoparticle oxidative catalysts that were photodeposited on colloidal CdSe@CdS nanorod photocatalysts revealed a mediated oxidative pathway, and afforded the rods remarkable photochemical stability under prolonged illumination in pure water.

A highly sensitive broadband planar metal-oxide-semiconductor photo detector fabricated on a silicon-on-insulator substrate

A high sensitivity photo-detector operating in the 245 to 880 nm wavelength range is reported. It is based on a planar Metal-Oxide-Semiconductor (MOS) structure fabricated on an insulator on silicon substrate where the insulator layer comprises a double layer dielectric stack of SiO2-HfO2. The MOS detector undergoes a voltage stress process after which it exhibits a record high responsivity of 0.4 A/W at 500–600 nm and 0.1 A/W at the spectrum edges, 245 and 880 nm. The structure is significantly simpler to fabricate than P-N or P-I-N junction devices and offers a lower dark current than Metal-Semiconductor-Metal diodes. Oxygen vacancies induced in the HfO2 sub-layer by the voltage stress form the conduction paths of the photo generated carriers. The penetration, under reverse bias conditions, of holes originating in the Si depletion layer is improved under illumination since their potential barrier is lowered. The compatibility with complimentary MOS technology processes makes this new structure attractiv...

Unique crystallographic pattern in the macro to atomic structure of Herdmania momus vateritic spicules

Biogenic vaterite is extremely rare. The only known example of a completely vateritic mineralized structure is the spicule of the solitary ascidian, Herdmania momus. In characterizing the structure of these spicules, using state-of-the-art techniques such as synchrotron X-ray diffraction and synchrotron micro- and nanotomography, we observed a continuous structural pattern from the macro down to the micro, nano, and atomic scales. We show that the spicules demonstrate a unique architecture composed of micron-sized, hexagonally faceted thorns organized in partial spirals along the cylinder-like polycrystalline body of the spicule, and tilted from it at an angle of about 26°. This morphological orientation coincides with the crystallographic orientation relationship between each thorn and the polycrystals within the spicule. Hence the entire spicule grows along the [011] direction of vaterite while the individual thorns grow along the [001] direction. This, together with the presence of both inter- and intra-crystalline organic phases, beautifully displays the organisms ability to achieve perfect control of mineralization biologically while employing an unstable polymorph of calcium carbonate: vaterite.