Ordered arrays of metal nanotubes in semiconductor envelope

We report on fabrication of metal nanotubes in semiconductor nanotemplates possessing ordered two-dimensional hexagonal arrays of pores grown in n-InP crystalline substrates using anodic etching in neutral electrolyte. Electrochemical pulsed deposition of arrays of Pt nanotubes with diameters of 70 and 140 nm is demonstrated. The produced metallo-semiconductor tubular structure behaves like a layered nanomaterial allowing one to easily cleave thin films consisting of rows of Pt nanotubes in semiconductor envelope.     

Discovery of surfactants for metal/semiconductor separation of single-wall carbon nanotubes via high-throughput screening

We report novel surfactants that can be used for the separation of metallic (M) and semiconducting (S) single-wall carbon nanotubes (SWCNTs). Among the M/S separation methods using surfactants in an aqueous solution, sodium dodecyl sulfate plays a key role in density gradient ultracentrifugation (DGU) and agarose gel separations. In this study, we screened 100 surfactants for M/S separation using a high-throughput screening system. We identified five surfactants, which could be used for both DGU and agarose gel separations, suggesting that the basic principle of these separations is common. These surfactants have relatively low dispersibilities, which is likely due to their common structural features, i.e., straight alkyl tails and charged head groups, and appeared to enable M- and S-SWCNTs to be distinguished and separated. These surfactants should stimulate research in this field and extend the application of electrically homogeneous SWCNTs not only for electronics but also for biology and medicine.     

Synthesis and optical properties of nanorattles and multiple-walled nanoshells/nanotubes made of metal alloys

The galvanic replacement reaction between silver and chloroauric acid has been exploited as a powerful means for preparing metal nanostructures with hollow interiors. Here, the utility of this approach is further extended to produce complex core/shell nanostructures made of metals by combining the replacement reaction with electroless deposition of silver. We have fabricated nanorattles consisting of Au/Ag alloy cores and Au/Ag alloy shells by starting with Au/Ag alloy colloids as the initial template. We have also prepared multiple-walled nanoshells/nanotubes (or nanoscale Matrioshka) with a variety of shapes, compositions, and structures by controlling the morphology of the template and the precursor salt used in each step of the replacement reaction. There are a number of interesting optical features associated with these new core/shell metal nanostructures. For example, nanorattles made of Au/Ag alloys displayed two well-separated extinction peaks, a feature similar to that of gold or silver nanorods. The peak at approximately 510 nm could be attributed to the Au/Ag alloy cores, while the other peak was associated with the Au/Ag alloy shells and could be continuously tuned in the spectral range from red to near-infrared.     

Electronic structures and excitonic transitions in nanocrystalline iron-doped tin dioxide diluted magnetic semiconductor films: an optical spectroscopic study

Nanocrystalline iron-doped tin dioxide (Sn(1-x)Fe(x)O(2)) films with x from 0 to 0.2 were prepared on c-sapphire substrates by pulsed laser deposition. X-ray diffraction and Raman scattering analysis show that the films are of the rutile structure at low compositions and an impurity phase related to Fe(2)O(3) appears until the x is up to 0.2, suggesting the general change of lattice structure due to the Fe ion substitution. The dielectric functions are successfully determined from 0.0248 to 6.5 eV using the Lorentz multi-oscillator and Tauc-Lorentz dispersion models in the low and high photon energy regions, respectively. With increasing Fe composition, the highest-frequency transverse optical phonons E(u) shifts towards a lower energy side and can be well described by (608 - 178x) cm(-1). From the transmittance spectra, the fundamental absorption edge is found to be decreased with the Fe composition due to the joint contributions from SnO(2) and Fe(2)O(3). It can be observed that the doped films exhibit evident excitonic excitation features, which are strongly related to the Fe doping. Among them, the 6A(1g)→ 4T(2g) transition contributes to the onset of optical absorption. Moreover, the remarkable intensity reduction and a red-shift trend with the doping composition, except for the pure film, can be testified by the photoluminescence spectra. It can be concluded that the replacement of Sn with the Fe ion could induce the 2p-3d hybridization and result in the electronic band structure modification of the Sn(1-x)Fe(x)O(2) films.     

Charge transitions in metal adsorbates on foreign metal substrates

Narrow current peaks in the voltammogram for the adsorption of metal ions on foreign metal substrates have been interpreted as charge transitions. A simple quantum-mechanical model for electrochemical adsorption is presented; it may explain why the adsorbate charge can change discontinuously at a certain electrode potential, and why such transitions are seen for adsorption on terraces, but not on steps.     

Electron-stimulated oxidation of metal and semiconductor surfaces

The electron-stimulated adsorption of oxygen from the gas phase is studied. The basic laws governing the changes in the surface structure induced by electron-stimulated adsorption are determined.     

Using carbon nanotubes to detect polymer transitions

Raman spectral shifts of single‐wall carbon nanotubes embedded in polymer systems were used to measure transitions in polymers. Glass‐transition temperatures and secondary transitions were observed, and Raman spectroscopic data were compared with dynamic mechanical tests for a thermosetting and a thermoplastic polymer. The data confirm that the Raman spectral response of carbon nanotubes embedded in polymers is sensitive to polymer transitions. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1492–1495, 2001     

Computer modeling of semiconductor nanotubes for water splitting

One-dimensional nanostructures such as nanorods and nanotubes (NTs) are regarded as promising materials for photoelectrochemical water splitting. Modeling the electronic properties of oxidic NTs with diameters in the range of 3–30 nm in contact with liquid water is challenging owing to the fact that the systems are too large for direct ab initio molecular dynamics simulations. Here we summarize recent efforts to develop strained two-dimensional model systems for pristine and doped titania NTs. We have studied their structural, optical and photoelectrochemical properties by a number of different techniques attributable to quantum mechanical density functional theory.     

Computer simulations of small semiconductor and metal clusters

A brief survey is presented of recent simulations of small clusters, made with both ab-initio and classical approaches, with particular emphasis on the application of the Car-Parrinello method. The discussion mainly focusses on the structural properties of a variety of materials and on the effects of temperature.     

Supercritical fluid synthesis of metal and semiconductor nanomaterials

In the near future physical and economic constraints are expected to limit the continued miniaturisation of electronic and optical devices using current "top-down" lithography-based methods. Consequently, nonlithographic methods for synthesising and organising materials on the nanometre scale are required. In response to these technological needs a number of research groups are developing new supercritical fluids methodologies to synthesise and self-assemble "building blocks" of nanomaterials, from the "bottom-up", into structurally complex device architectures. This concept paper highlights some of the recent advances in the synthesis of metal and semiconductor nanoparticles and nanowires by using supercritical fluids. In addition, we describe an efficient supercritical fluid approach for constructing ordered arrays of metal and semiconductor nanowires within mesoporous silica templates.     

Ratiometric,filter-free optical sensor based on a complementary metal oxide semiconductor buried double junction photodiode

We report a complementary metal oxide semiconductor integrated circuit (CMOS IC) with a buried double junction (BDJ) photodiode that (i) provides a real-time output signal that is related to the intensity ratio at two emission wavelengths and (ii) simultaneously eliminates the need for an optical filter to block Rayleigh scatter. We demonstrate the BDJ platform performance for gaseous NH₃ and aqueous pH detection. We also compare the BDJ performance to parallel results obtained by using a slew scanned fluorimeter (SSF). The BDJ results are functionally equivalent to the SSF results without the need for any wavelength filtering or monochromators and the BDJ platform is not prone to errors associated with source intensity fluctuations or sensor signal drift.     

Templated synthesis of metal nanorods in silica nanotubes

We report a general method for the synthesis of noble metal nanorods, including Au, Ag, Pt, and Pd, based on their seeded growth in silica nanotube templates. The controlled growth of the metals occurs exclusively on the seeds inside the silica nanotubes, which act as hard templates to confine the one-dimensional growth of the metal nanorods and define their aspect ratios. This method affords large quantities of noble metal nanorods with well-controlled aspect ratios and high yield, which may find wide use in the fields of nanophotonics, catalysis, sensing, imaging, and biomedicine.     

Length-dependent optical effects in single-wall carbon nanotubes

Among the novel chemical and physical attributes of single-wall carbon nanotubes (SWCNTs), the optical properties are perhaps the most compelling. Although much is known about how such characteristics depend on nanotube chirality and diameter, relatively little is known about how the optical response depends on length, the next most obvious and fundamental nanotube trait. We show here that the intrinsic optical response of single-wall carbon nanotubes exhibits a strong dependence on nanotube length, and we offer a simple explanation that relates this behavior to the localization of a bound exciton along the length of a nanotube. The results presented here suggest that, for a given volume fraction, the longest nanotubes display significantly enhanced absorption, near-infrared fluorescence, and Raman scattering, which has important practical implications for potential applications that seek to exploit the unique optical characteristics of SWCNTs.     

Synthesis and optical properties of gallium phosphide nanotubes

Gallium phosphide nanotubes with zinc blende structure were synthesized for the first time. The as-prepared GaP nanotubes are polycrystalline with diameters of 30-120 nm and occasionally partially filled. The growth has been reasonably proposed to follow vapor-liquid-solid (VLS) mechanism. The integration of the nanotubular structure with the unique intrinsic semiconducting properties of GaP might bring GaP nanotubes some novel optical and electronic properties and applications.     

Reversible surface oxidation and efficient luminescence quenching in semiconductor single-wall carbon nanotubes

We have investigated reversible single-wall carbon nanotube (SWNT) oxidation by quantitative analysis of the oxide-induced absorption bleaching and luminescence quenching at low pH. These data, in combination with DFT structure calculations, suggest that the nanotube oxide is a 1,4-endoperoxide. At low pH, the endoperoxide protonates to create a hydroperoxide carbocation, introducing a hole in the SWNT valence band. Nanotube luminescence is extremely sensitive to quenching by hole-doping, while the absorption is relatively robust.     

Electrochemical sensors based on metal and semiconductor nanoparticles

Metal and semiconductor nanoparticles exhibit unique optical, electrical, thermal and catalytic properties. Therefore, they have attracted considerable interest and have been employed for construction of various electrochemical sensors. This minireview gives a general view of recent advances in electrochemical sensor development based on metal and semiconductor nanoparticles covering genosensors, protein and enzyme-based sensors, gas sensors and sensor for other organic and inorganic substances. Different assay strategies based on metal and semiconductor nanoparticles for biosensor and bioelectronic applications are presented, including electrochemical, electrical, and magnetic signal transduction techniques. Electrochemical transduction principles provide signal changes in conductance, charge, potential and current. We have paid much attention to the potential-based and current-based sensors herein. Lastly, a brief introduction is given into advances concerning the role of nanoparticles, quantum dots and nanowires for nanomedicine, such as drug delivery and discovery.     

EPR spin flip transitions in some metal dithiolenes

Small line widths (ΔB_pp ≅ 0.25–0.40 mT) in the EPR spectra of ⁶³Cu²⁺ in the matrices of some transition metal dithiolenes permit the observation of not-so-easily realizable proton spin flip transitions even at room temperature and at low microwave power. These transitions, studied in four different lattices as a function of crystal orientation, microwave power and temperature, have been found to be from the protons of the counter ions and a few ångströms away from the unpaired electron-containing metal centre. It has been possible to identify the protons and estimate their distances from the metal centre by two different methods. A temperature-dependent evaluation of the distance parameters as well as the observation of the “double” and “triple” flips are reported. The differential saturation of the “main” and “satellite” (due to spin flip) lines studied by the CW saturation method has provided information on the mechanism of spin relaxation in these systems.     

Surface-functionalization-dependent optical properties of II-VI semiconductor nanocrystals

We report a study of the surface-functionalization-dependent optical properties of II-VI zinc-blende semiconductor nanocrystals on the basis of ligand-exchange chemistry, isomaterial core/shell growth, optical spectroscopy, transmission electron microscopy, and X-ray powder diffraction. Our results show that the transition energy and extinction coefficient of the 2S(h3/2)1S(e) excitonic band of these nanocrystals can be strongly modified by their surface ligands as well as ligand associated surface atomic arrangement. The oleylamine exchange of oleate-capped zinc-blende II-VI nanocrystals narrows the energy gap between their first and second excitonic absorption bands, and this narrowing effect is size-dependent. The oleylamine exchange results in the quenching, subsequent recovery, and even enhancing of the photoluminescence emission of these II-VI semiconductor nanocrystals. In addition, the results from our X-ray powder diffraction measurements and simulations completely rule out the possibility that oleate-capped zinc-blende CdSe nanocrystals can undergo zinc-blende-to-wurtzite crystal transformation upon ligand exchange with oleylamine. Moreover, our theoretical modeling results suggest that the surface-functionalization-dependent optical properties of these semiconductor nanocrystals can be caused by a thin type II isomaterial shell that is created by the negatively charged ligands (e.g., oleate and octadecyl phosphonate). Taking all these results together, we provide the unambiguous identification that II-VI semiconductor nanocrystals exhibit surface-functionalization-dependent excitonic absorption features.     

Nonlinear optical properties of carbon nitride nanotubes

The second order polarizabilities (β) of the C(3)N(4) NT systems were investigated in this study. The β values of end groups substituted C(3)N(4) NTs were calculated to find their most favorable paradigm for nonlinear optical design. It was found that their electric dipole transitions are only allowed along the tube axis direction and the position of terminal groups has a great effect on NLO properties of substituted C(3)N(4) NTs. The obtained results provide us details to understand the relation between the structure and nonlinear optical properties. The results indicate that the second-order polarizabilities originate from charge transfer from a donor (-NH(2)) to an acceptor (-O(2)N) and the electron density redistribution in heptazine units. We employ a one-dimensional two-state model to analyze the nature of the second-order polarizabilities of studied materials. The frequency-dependent second-order polarizabilities were also calculated. The second-order polarizability of the O(2)N-C(3)N(4)-NH(2) NT is 2.51 × 10(-27) esu when the input photon energy is 2.232 eV, which is much larger (about two orders of magnitude) than static second-order polarizability (2.54 × 10(-29)).