Shaul Aloni

Non-blinking and photostable upconverted luminescence from single lanthanide-doped nanocrystals

The development of probes for single-molecule imaging has dramatically facilitated the study of individual molecules in cells and other complex environments. Single-molecule probes ideally exhibit good brightness, uninterrupted emission, resistance to photobleaching, and minimal spectral overlap with cellular autofluorescence. However, most single-molecule probes are imperfect in several of these aspects, and none have been shown to possess all of these characteristics. Here we show that individual lanthanide-doped upconverting nanoparticles (UCNPs)—specifically, hexagonal phase NaYF4 (β-NaYF4) nanocrystals with multiple Yb3+ and Er3+ dopants—emit bright anti-Stokes visible upconverted luminescence with exceptional photostability when excited by a 980-nm continuous wave laser. Individual UCNPs exhibit no on/off emission behavior, or “blinking,” down to the millisecond timescale, and no loss of intensity following an hour of continuous excitation. Amphiphilic polymer coatings permit the transfer of hydrophobic UCNPs into water, resulting in individual water-soluble nanoparticles with undiminished photophysical characteristics. These UCNPs are endocytosed by cells and show strong upconverted luminescence, with no measurable anti-Stokes background autofluorescence, suggesting that UCNPs are ideally suited for single-molecule imaging experiments.

Monolayer behaviour in bulk ReS 2 due to electronic and vibrational decoupling

Semiconducting transition metal dichalcogenides consist of monolayers held together by weak forces where the layers are electronically and vibrationally coupled. Isolated monolayers show changes in electronic structure and lattice vibration energies, including a transition from indirect to direct bandgap. Here we present a new member of the family, rhenium disulphide (ReS2), where such variation is absent and bulk behaves as electronically and vibrationally decoupled monolayers stacked together. From bulk to monolayers, ReS2 remains direct bandgap and its Raman spectrum shows no dependence on the number of layers. Interlayer decoupling is further demonstrated by the insensitivity of the optical absorption and Raman spectrum to interlayer distance modulated by hydrostatic pressure. Theoretical calculations attribute the decoupling to Peierls distortion of the 1T structure of ReS2, which prevents ordered stacking and minimizes the interlayer overlap of wavefunctions. Such vanishing interlayer coupling enables probing of two-dimensional-like systems without the need for monolayers.

Tunable Infrared Absorption and Visible Transparency of Colloidal Aluminum-Doped Zinc Oxide Nanocrystals

Plasmonic nanocrystals have been attracting a lot of attention both for fundamental studies and different applications, from sensing to imaging and optoelectronic devices. Transparent conductive oxides represent an interesting class of plasmonic materials in addition to metals and vacancy-doped semiconductor quantum dots. Herein, we report a rational synthetic strategy of high-quality colloidal aluminum-doped zinc oxide nanocrystals. The presence of substitutional aluminum in the zinc oxide lattice accompanied by the generation of free electrons is proved for the first time by tunable surface plasmon absorption in the infrared region both in solution and in thin films.

Formation of Hollow Silica Colloids through a Spontaneous Dissolution–Regrowth Process

tence of a large number of silicate species and their rich chemical interactions makes the dissolution and growth of silica challenging to study. However, this complexity also provides enormous opportunities for the development of materials with new structures and functionalities. For example, systematic investigation of the dissolution and formation of silica nanoparticles has made it possible to control the nucleation and growth, and subsequently the crystal size and shape, of zeolite materials. [4–6] Herein, we report that amorphous silica colloids, when dispersed in an aqueous solution of NaBH4, undergo a spontaneous morphology change from solid to hollow spheres. Concurrent but separate coredissolution and shell-growth processes appear to be responsible to the formation of the hollow structures. Besides the interesting fundamental aspects of this spontaneous process, this work also provides an effective self-templated route for the preparation of hollow silica nanostructures, which may find immediate applications in fields such as catalysis and drug delivery. [7–12] Since silica can coat many nanostructures through simple sol–gel processes, our discovery also allows convenient transformation of core–shell particles into yolk– shell structures, which are promising for use as nanoscale reactors and controlled-release vehicles. Compared to widely adopted methods using polymer beads and micelle and

Direct Identification of the Conducting Channels in a Functioning Memristive Device

Structures composed of transition metal oxides can display a rich variety of electronic and magnetic properties including superconductivity, multiferroic behavior, and colossal magnetoresistance. [ 1 ] An additional property of technological relevance is the bipolar resistance switching phenomenon [ 2–4 ] seen in many perovskites [ 5–7 ] and binary oxides [ 8 ] when arranged in metal/insulator/metal (MIM) structures. These devices exhibit electrically driven switching of the resistance by 1000x or greater and have recently been identifi ed [ 9 ] as memristive systems, the fourth fundamental passive circuit element. [ 10 , 11 ] A full understanding of the atomic-scale mechanism and identifi cation of the material changes within the oxide remains an important goal. [ 12 ] Here, we probe within a functioning TiO 2 memristor using synchrotron-based x-ray absorption spectromicroscopy and transmission electron microscopy (TEM). We observed that electroforming of the device generated an ordered Ti 4 O 7 Magnéli phase within the initially deposited TiO 2 matrix. In a memristive system, [ 11 ] the fl ow of charge dynamically changes the material conductivity, which is “remembered” even with the removal of bias. While bipolar resistance switching of metal oxides has been observed since the 1960s, [ 2 , 4 ] only recently has the connection to the analytical theory of the memristor been made. [ 9 ] In an attempt to describe microscopically the source of the resistance change, many physical models have been put forth, including generation and dissolution of conductive channels, [ 3 , 6 ] electronic trapping and space-charge current limiting effects, [ 13 ] strongly correlated electron effects such as a metal-insulator transition, [ 14 ] and changes localized to the interface. [ 15 ] Identifying the correct model and quantifying its physical parameters has been diffi cult using primarily electrical characterization. Meanwhile, direct physical characterization [ 7 ]

In situ TEM imaging of CaCO3 nucleation reveals coexistence of direct and indirect pathways

Watching nucleation pathways in calcite The initial stage of crystallization, the formation of nuclei, is a critical process, but because of the length and time scales involved, is hard to observe. Nielsen et al. explored the crystallization of calcium carbonate, a well-studied material but one with multiple nucleation theories. Different calcium and carbonate solutions were mixed inside a fluid cell and imaged using a liquid cell inside a transmission electron microscope. Competing pathways operated during nucleation, with both the direct association of ions into nuclei from solution and the transformation of amorphous calcium carbonate into and between different crystalline polymorphs. Science, this issue p. 1158 Calcium carbonate crystal nucleation occurs via direct formation from solution and transformation from less stable phases. Mechanisms of nucleation from electrolyte solutions have been debated for more than a century. Recent discoveries of amorphous precursors and evidence for cluster aggregation and liquid-liquid separation contradict common assumptions of classical nucleation theory. Using in situ transmission electron microscopy (TEM) to explore calcium carbonate (CaCO3) nucleation in a cell that enables reagent mixing, we demonstrate that multiple nucleation pathways are simultaneously operative, including formation both directly from solution and indirectly through transformation of amorphous and crystalline precursors. However, an amorphous-to-calcite transformation is not observed. The behavior of amorphous calcium carbonate upon dissolution suggests that it encompasses a spectrum of structures, including liquids and solids. These observations of competing direct and indirect pathways are consistent with classical predictions, whereas the behavior of amorphous particles hints at an underlying commonality among recently proposed precursor-based mechanisms.

Engineering bright sub-10-nm upconverting nanocrystals for single-molecule imaging

Imaging at the single-molecule level reveals heterogeneities that are lost in ensemble imaging experiments, but an ongoing challenge is the development of luminescent probes with the photostability, brightness and continuous emission necessary for single-molecule microscopy. Lanthanide-doped upconverting nanoparticles overcome problems of photostability and continuous emission and their upconverted emission can be excited with near-infrared light at powers orders of magnitude lower than those required for conventional multiphoton probes. However, the brightness of upconverting nanoparticles has been limited by open questions about energy transfer and relaxation within individual nanocrystals and unavoidable tradeoffs between brightness and size. Here, we develop upconverting nanoparticles under 10 nm in diameter that are over an order of magnitude brighter under single-particle imaging conditions than existing compositions, allowing us to visualize single upconverting nanoparticles as small (d = 4.8 nm) as fluorescent proteins. We use advanced single-particle characterization and theoretical modelling to find that surface effects become critical at diameters under 20 nm and that the fluences used in single-molecule imaging change the dominant determinants of nanocrystal brightness. These results demonstrate that factors known to increase brightness in bulk experiments lose importance at higher excitation powers and that, paradoxically, the brightest probes under single-molecule excitation are barely luminescent at the ensemble level.

Carbon nanotubes as nanoscale mass conveyors

The development of manipulation tools that are not too ‘fat’ or too ‘sticky’ for atomic scale assembly is an important challenge facing nanotechnology. Impressive nanofabrication capabilities have been demonstrated with scanning probe manipulation of atoms and molecules on clean surfaces. However, as fabrication tools, both scanning tunnelling and atomic force microscopes suffer from a loading deficiency: although they can manipulate atoms already present, they cannot efficiently deliver atoms to the work area. Carbon nanotubes, with their hollow cores and large aspect ratios, have been suggested as possible conduits for nanoscale amounts of material. Already much effort has been devoted to the filling of nanotubes and the application of such techniques. Furthermore, carbon nanotubes have been used as probes in scanning probe microscopy. If the atomic placement and manipulation capability already demonstrated by scanning probe microscopy could be combined with a nanotube delivery system, a formidable nanoassembly tool would result. Here we report the achievement of controllable, reversible atomic scale mass transport along carbon nanotubes, using indium metal as the prototype transport species. This transport process has similarities to conventional electromigration, a phenomenon of critical importance to the semiconductor industry.

Phase Transformation of Biphasic Cu2S−CuInS2 to Monophasic CuInS2 Nanorods

We synthesized wurtzite CuInS(2) nanorods (NRs) by colloidal solution-phase growth. We discovered that the growth process starts with nucleation of Cu(2)S nanodisks, followed by epitaxial overgrowth of CuInS(2) NRs onto only one face of Cu(2)S nanodisks, resulting in biphasic Cu(2)S-CISu heterostructured NRs. The phase transformation of biphasic Cu(2)S-CuInS(2) into monophasic CuInS(2) NRs occurred with growth progression. The observed epitaxial overgrowth and phase transformation is facile for three reasons. First, the sharing of the sulfur sublattice by the hexagonal chalcocite Cu(2)S and wurtzite CuInS(2) minimizes the lattice distortion. Second, Cu(2)S is in a superionic conducting state at the growth temperature of 250 degrees C wherein the copper ions move fluidly. Third, the size of the Cu(2)S nanodisks is small, resulting in fast phase transformation. Our results provide valuable insight into the controlled solution growth of ternary chalcogenide nanoparticles and will aid in the development of solar cells using ternary I-III-VI(2) semiconductors.

Evolution of Structure and Chemistry of Bimetallic Nanoparticle Catalysts under Reaction Conditions

Three series of bimetallic nanoparticle catalysts (Rh(x)Pd(1-x), Rh(x)Pt(1-x), and Pd(x)Pt(1-x), x = 0.2, 0.5, 0.8) were synthesized using one-step colloidal chemistry. X-ray photoelectron spectroscopy (XPS) depth profiles using different X-ray energies and scanning transmission electron microscopy showed that the as-synthesized Rh(x)Pd(1-x) and Pd(x)Pt(1-x) nanoparticles have a core-shell structure whereas the Rh(x)Pt(1-x) alloys are more homogeneous in structure. The evolution of their structures and chemistry under oxidizing and reducing conditions was studied with ambient-pressure XPS (AP-XPS) in the Torr pressure range. The Rh(x)Pd(1-x) and Rh(x)Pt(1-x) nanoparticles undergo reversible changes of surface composition and chemical state when the reactant gases change from oxidizing (NO or O(2) at 300 degrees C) to reducing (H(2) or CO at 300 degrees C) or catalytic (mixture of NO and CO at 300 degrees C). In contrast, no significant change in the distribution of the Pd and Pt atoms in the Pd(x)Pt(1-x) nanoparticles was observed. The difference in restructuring behavior under these reaction conditions in the three series of bimetallic nanoparticle catalysts is correlated with the surface free energy of the metals and the heat of formation of the metallic oxides. The observation of structural evolution of bimetallic nanoparticles under different reaction conditions suggests the importance of in situ studies of surface structures of nanoparticle catalysts.