High Critical-Current Density in the Heavily Pb-Doped Bi2Sr2CaCu2O8+delta Superconductor: Generation of Efficient Pinning Centers

Critical-current density (Jc) is a parameter of primary importance for potential applications of high-temperature copper oxide superconductors. It is limited principally by the breakdown of zero-resistive current due to thermally activated flux flow at high temperatures and high magnetic fields. One promising method to overcome this limitation is to introduce efficient pinning centers into crystals that can suppress the flux flow. A marked increase in Jc was observed in Bi2Sr2CaCu2O8+delta (Bi-2212) single crystals doped with a large amount of Pb. By electron microscopy, characteristic microstructures were revealed that probably underlie the observed enhancement in Jc: thin (10 to 50 nanometers), platelike domains having a modulation-free structure appeared with spacings of 50 to 100 nanometers along the b axis.     

Synthesis and characterization of anisometric cobalt nanoclusters

Sonication of aqueous Co(2+) and hydrazine resulted in the formation of anisometric (disk-shaped) cobalt nanoclusters that averaged about 100 nanometers in width and 15 nanometers in thickness. Electron diffraction from single particles revealed that they were oriented (001) crystals that conformed to a trigonal or hexagonal unit cell four times the size of the cell adopted by bulk alpha-cobalt. Lorentz microscopy indicated that these were single-magnetic domain particles, with the axis of magnetization located in the (101) plane, offset at some appreciable angle from the (001) axis.     

Oscillatory thermomechanical instability of an ultrathin catalyst

Because of the small thermal capacity of ultrathin ( approximately 200 nanometers) metal single crystals, it is possible to explore the coupling of catalytic and thermal action at low pressures. We analyzed a chemothermomechanical instability in this regime, in which catalytic reaction kinetics interact with heat transfer and mechanical buckling to create oscillations. These interacting components are separated and explored through experimentation, mathematical modeling, and scientific computation, and an explanation of the phenomenon emerges from their synthesis.     

Shape transition of germanium nanocrystals on a silicon (001) surface from pyramids to domes

Chemical vapor deposition of germanium onto the silicon (001) surface at atmospheric pressure and 600 degrees Celsius has previously been shown to produce distinct families of smaller (up to 6 nanometers high) and larger (all approximately 15 nanometers high) nanocrystals. Under ultrahigh-vacuum conditions, physical vapor deposition at approximately the same substrate temperature and growth rate produced a similar bimodal size distribution. In situ scanning tunneling microscopy revealed that the smaller square-based pyramids transform abruptly during growth to significantly larger multifaceted domes, and that few structures with intermediate size and shape remain. Both nanocrystal shapes have size-dependent energy minima that result from the interplay between strain relaxation at the facets and stress concentration at the edges. A thermodynamic model similar to a phase transition accounts for this abrupt morphology change.     

Electrochemistry and electrogenerated chemiluminescence from silicon nanocrystal quantum dots

Reversible electrochemical injection of discrete numbers of electrons into sterically stabilized silicon nanocrystals (NCs) (approximately 2 to 4 nanometers in diameter) was observed by differential pulse voltammetry (DPV) in N,N'-dimethylformamide and acetonitrile. The electrochemical gap between the onset of electron injection and hole injection-related to the highest occupied and lowest unoccupied molecular orbitals-grew with decreasing nanocrystal size, and the DPV peak potentials above the onset for electron injection roughly correspond to expected Coulomb blockade or quantized double-layer charging energies. Electron transfer reactions between positively and negatively charged nanocrystals (or between charged nanocrystals and molecular redox-active coreactants) occurred that led to electron and hole annihilation, producing visible light. The electrogenerated chemiluminescence spectra exhibited a peak maximum at 640 nanometers, a significant red shift from the photoluminescence maximum (420 nanometers) of the same silicon NC solution. These results demonstrate that the chemical stability of silicon NCs could enable their use as redox-active macromolecular species with the combined optical and charging properties of semiconductor quantum dots.     

Encoding electronic properties by synthesis of axial modulation-doped silicon nanowires

We describe the successful synthesis of modulation-doped silicon nanowires by achieving pure axial elongation without radial overcoating during the growth process. Scanning gate microscopy shows that the key properties of the modulated structures-including the number, size, and period of the differentially doped regions-are defined in a controllable manner during synthesis, and moreover, that feature sizes to less than 50 nanometers are possible. Electronic devices fabricated with designed modulation-doped nanowire structures demonstrate their potential for lithography-independent address decoders and tunable, coupled quantum dots in which changes in electronic properties are encoded by synthesis rather than created by conventional lithography-based techniques.     

Ordered mesoporous materials from metal nanoparticle-block copolymer self-assembly

The synthesis of ordered mesoporous metal composites and ordered mesoporous metals is a challenge because metals have high surface energies that favor low surface areas. We present results from the self-assembly of block copolymers with ligand-stabilized platinum nanoparticles, leading to lamellar CCM-Pt-4 and inverse hexagonal (CCM-Pt-6) hybrid mesostructures with high nanoparticle loadings. Pyrolysis of the CCM-Pt-6 hybrid produces an ordered mesoporous platinum-carbon nanocomposite with open and large pores (>/=10 nanometers). Removal of the carbon leads to ordered porous platinum mesostructures. The platinum-carbon nanocomposite has very high electrical conductivity (400 siemens per centimeter) for an ordered mesoporous material fabricated from block copolymer self-assembly.     

Dynamic atomic-level rearrangements in small gold particles

Small metal particles (<5 nanometers), which are widely used in catalysis, have physical and chemical properties that are markedly different from those of the bulk metal. The differences are related to crystal structure, and it is therefore significant that structral rearrangements in small particles have been observed in real time by using high-resolution electron microscopy. A detailed investigation at the atomic level has been made of the factors affecting the dynamic activity of small gold crystals that are supported on thin films of amorphous carbon, silicon, and germanium. The rate of activity depends mainly on the current density of the incident electron beam and the degree of contact of the particle with the substrate, but this rate decreases rapidly as the particle size is increased. The activity of the particles is very similar on either carbon or silicon, but it is generally less marked on germanium because of increased contact between the particle and the substrate. The electron beam effectively heats the particles, and it appears that their dynamic behavior depends on their thermal contact with the substrate.     

A Silicon Single-Electron Transistor Memory Operating at Room Temperature

A single-electron memory, in which a bit of information is stored by one electron, is demonstrated at room temperature. The memory is a floating gate metal-oxide-semiconductor transistor in silicon with a channel width ( approximately 10 nanometers) smaller than the Debye screening length of a single electron and a nanoscale polysilicon dot ( approximately 7 nanometers by 7 nanometers) as the floating gate embedded between the channel and the control gate. Storing one electron on the floating gate screens the entire channel from the potential on the control gate and leads to (i) a discrete shift in the threshold voltage, (ii) a staircase relation between the charging voltage and the shift, and (iii) a self-limiting charging process. The structure and fabrication of the memory should be compatible with future ultralarge-scale integrated circuits.     

The (Me5C5)Si+ cation: a stable derivative of HSi+

The reaction of decamethylsilicocene, (Me5C5)2Si, with the proton-transfer reagent Me5C5H2+B(C6F5)4- produces the salt (Me5C5)Si+ B(C6F5)4(2), which can be isolated as a colorless solid that is stable in the absence of air and moisture. The crystal structure reveals the presence of a cationic pi complex with an eta5-pentamethylcyclopentadienyl ligand bound to a bare silicon center. The 29Si nuclear magnetic resonance at very high field (delta = - 400.2 parts per million) is typical of a pi complex of divalent silicon. The (eta5-Me5C5)Si+ cation in 2 can be regarded as the "resting state" of a silyliumylidene-type (eta1-Me5C5)Si+ cation. The availability of 2 opens new synthetic avenues in organosilicon chemistry. For example, 2 reacted with lithium bis(trimethylsilyl)amide to give the disilene E-[(eta1-Me5C5)[N(SiMe3)2]Si]2(3).     

A laser ablation method for the synthesis of crystalline semiconductor nanowires

A method combining laser ablation cluster formation and vapor-liquid-solid (VLS) growth was developed for the synthesis of semiconductor nanowires. In this process, laser ablation was used to prepare nanometer-diameter catalyst clusters that define the size of wires produced by VLS growth. This approach was used to prepare bulk quantities of uniform single-crystal silicon and germanium nanowires with diameters of 6 to 20 and 3 to 9 nanometers, respectively, and lengths ranging from 1 to 30 micrometers. Studies carried out with different conditions and catalyst materials confirmed the central details of the growth mechanism and suggest that well-established phase diagrams can be used to predict rationally catalyst materials and growth conditions for the preparation of nanowires.     

Ferroelectric memories

In the past year it has become possible to fabricate ferroelectric thin-film memories onto standard silicon integrated circuits that combine very high speed (30-nanosecond read/erase/rewrite operation), 5-volt standard silicon logic levels, very high density (2 by 2 micrometer cell size), complete nonvolatility (no standby power required), and extreme radiation hardness. These ferroelectric random-access memories are expected to replace magnetic core memory, magnetic bubble memory systems, and electrically erasable read-only memory for many applications. The switching kinetics of these films, 100 to 300 nanometers thick, are now well understood, with switching times that fit an activation field dependence that scales applied field and temperature. Earlier problems of fatigue and retention failure are also now understood and have been improved to acceptable levels.     

MOSFET-Embedded microcantilevers for measuring deflection in biomolecular sensors

A promising approach for detecting biomolecules follows their binding to immobilized probe molecules on microfabricated cantilevers; binding causes surface stresses that bend the cantilever. We measured this deflection, which is on the order of tens of nanometers, by embedding a metal-oxide semiconductor field-effect transistor (MOSFET) into the base of the cantilever and recording decreases in drain current with deflections as small as 5 nanometers. The gate region of the MOSFET responds to surface stresses and thus is embedded in silicon nitride so as to avoid direct contact with the sample solution. This approach, which offers low noise, high sensitivity, and direct readout, was used to detect specific binding events with biotin and antibodies.     

Self-assembly of flat nanodiscs in salt-free catanionic surfactant solutions

Discs of finite size are a very rare form of stable surfactant self-assembly. It is shown that mixing of two oppositely charged single-chain surfactants can produce rigid nanodiscs as well as swollen lamellar liquid crystals with frozen bilayers. The crucial requirement for obtaining nanodisc self-assembly is the use of H+ and OH- as counterions. These counterions then form water and lower the conductivity to 10 microsiemens per centimeter. In the case of cationic component excess, a dilute solution of nanodiscs is in thermodynamic equilibrium with a lamellar phase. The diameter of the cationic nanodiscs is continuously adjustable from a few micrometers to 30 nanometers, with the positive charge located mainly around the edges.     

Single crystal metals encapsulated in carbon nanoparticles

Single-domain microcrystals of LaC(2) encapsulated within nanoscale polyhedral carbon particles have been synthesized in a carbon arc. Typical particle sizes are on the order of 20 to 40 nanometers. The stoichiometry and phase of the La-containing crystals have been assigned from characteristic lattice spacings observed by high-resolution transmission electron microscopy and energy dispersive spectroscopy (EDS). EDS spectra show that La and C are the only elements present. Characteristic interatomic distances of 3.39 and 2.78 angstroms identify the compound inside the nanoparticle cavities as alpha-LaC(2), the phase of LaC(2) that is stable at room temperature. Bulk alpha-LaC(2) is metallic and hydrolytic. Observation of crystals of pure encapsulated alpha-LaC(2) that were exposed to air for several days before analysis indicates that the LaC(2) is protected from degradation bythe carbon polyhedral shells of the nanoparticles. A high percentage of the carbon nanoparticles have encapsulated LaC(2) single crystals. These carbon-coated metal crystals form a new class of materials that can be protected in their pure or carbide forms and may have interesting and useful properties.     

Superlattices of iron nanocubes synthesized from Fe[N(SiMe3)2]2

The reaction of the metal-organic precursor Fe[N(SiMe3)2]2 with H2 in the presence of a long-chain acid and a long-chain amine in various proportions produces monodisperse zerovalent iron nanoparticles. These Fe particles display magnetic properties that match those of bulk iron as evidenced by magnetic and M?ssbauer measurements. The nanoparticles adopt a cubic shape with edges of 7 nanometers and are incorporated into extended crystalline superlattices containing nanocubes in close proximity and with their crystallographic axes aligned. These superlattices are formed in solution, precipitate in high yield, and may be redissolved and redeposited as two-dimensional arrays.     

A new type of meteoritic diamond in the enstatite chondrite abee

Diamonds with delta(13)C values of -2 per mil and less than 50 parts per million (by mass) nitrogen have been isolated from the Abee enstatite chondrite by the same procedure used for concentrating Cdelta, the putative interstellar diamond found ubiquitously in primitive meteorites and characterized by delta(13)C values of -32 to -38 per mil, nitrogen concentrations of 2,000 to 12,500 parts per million, and delta(15)N values of -340 per mil. Because the Abee diamonds have typical solar system isotopic compositions for carbon, nitrogen, and xenon, they are presumably nebular in origin rather than presolar. Their discovery in an unshocked meteorite eliminates the possibility of origins normally invoked to account for diamonds in ureilites and iron meteorites and suggests a low-pressure synthesis. The diamond crystals are approximately 100 nanometers in size, are of an unusual lath shape, and represent approximately 100 parts per million of Abee by mass.     

Limits on silicon nanoelectronics for terascale integration

Throughout the past four decades, silicon semiconductor technology has advanced at exponential rates in both performance and productivity. Concerns have been raised, however, that the limits of silicon technology may soon be reached. Analysis of fundamental, material, device, circuit, and system limits reveals that silicon technology has an enormous remaining potential to achieve terascale integration (TSI) of more than 1 trillion transistors per chip. Such massive-scale integration is feasible assuming the development and economical mass production of double-gate metal-oxide-semiconductor field effect transistors with gate oxide thickness of about 1 nanometer, silicon channel thickness of about 3 nanometers, and channel length of about 10 nanometers. The development of interconnecting wires for these transistors presents a major challenge to the achievement of nanoelectronics for TSI.     

Size-Specific Infrared Spectra of Benzene-(H2O)n Clusters (n = 1 through 7): Evidence for Noncyclic (H2O)n Structures

Resonant ion-dip infrared spectroscopy has been used to record size-specific infrared spectra of C(6)H(6)-(H(2)O)n clusters with n = 1 through 7 in the O-H stretch region. The O-H stretch spectra show a dramatic dependence on cluster size. For the n = 3 to 5 clusters, the transitions can be divided into three types-attributable to free, pi hydrogen-bonded, and single donor water-water O-H stretches-consistent with a C(6)H(6)-(H(2)O)n structure in which benzene is on the surface of a cyclic (H(2)O)n cluster. In n = 6 and 7 clusters, the spectra show distinct new transitions in the 3500 to 3600 wave number region. After comparison of these results with the predictions of ab initio calculations on (H(2)O)n clusters, these new transitions have been assigned to double donor O-H stretches associated with the formation of a more compact, noncyclic structure beginning with (H(2)O)(6). This is the same size cluster for which ab initio calculations predict that a changeover to noncyclic (H(2)O)n structures will occur.     

Small-diameter silicon nanowire surfaces

Small-diameter (1 to 7 nanometers) silicon nanowires (SiNWs) were prepared, and their surfaces were removed of oxide and terminated with hydrogen by a hydrofluoric acid dip. Scanning tunneling microscopy (STM) of these SiNWs, performed both in air and in ultrahigh vacuum, revealed atomically resolved images that can be interpreted as hydrogen-terminated Si (111)-(1 x 1) and Si (001)-(1 x 1) surfaces corresponding to SiH3 on Si (111) and SiH2 on Si (001), respectively. These hydrogen-terminated SiNW surfaces seem to be more oxidation-resistant than regular silicon wafer surfaces, because atomically resolved STM images of SiNWs were obtained in air after several days' exposure to the ambient environment. Scanning tunneling spectroscopy measurements were performed on the oxide-removed SiNWs and were used to evaluate the electronic energy gaps. The energy gaps were found to increase with decreasing SiNW diameter from 1.1 electron volts for 7 nanometers to 3.5 electron volts for 1.3 nanometers, in agreement with previous theoretical predictions.