Mechanistic investigations of nanometer-scale lithography at liquid-covered graphite surfaces

Pulse-induced nanometer-scale lithography has been performed on graphite surfaces that were in contact with pure water or other organic liquids. Very reproducible control over the pit diameter was observed in aqueous solutions, and a well-defined voltage threshold (4.0±0.2 V) was also apparent. Near the threshold voltage, 7 Å diameter×2 Å high protrusions were formed, while larger initial pulse voltages resulted in pits of diameter>~20 Å

Design of a scanning tunneling microscope for electrochemical applications

A design for a scanning tunneling microscope that is well suited for electrochemical investigations is presented. The construction of the microscope ensures that only the tunneling tip and the sample participate in electrochemical reactions. The design also allows rapid replacement of the tip or sample, and enables facile introduction of auxiliary electrodes for use in electrochemical experiments. The microscope utilizes stepper motor driven approach mechanics in order to achieve fully remote operation and to allow reproducible coarse control of tip/sample spacings for electrochemical experiments. Highly ordered pyrolytic graphite images at atomic resolution in air and aqueous solutions can be obtained with this microscope

Atomic resolution imaging of electrode surfaces in solutions containing reversible redox species

Procedures are described for insulating metal scanning tunneling microscope (STM) tips with either glass or polymer coatings. In solutions containing 0.10 M of a reversible redox couple, Fe(CN) - 3/-46 , the faradaic limiting current to polymer coated tips was 200–500 pA and that for glass coated tips was <10 pA. For polymer insulated tips, steady-state currents of 10–100 pA were observed at tip-sample displacements less than 0.3 µm. The suppression of faradaic current achieved by these coating procedures enabled the collection of the first atomic resolution STM images of highly ordered pyrolytic graphite electrodes in contact with redox-active electrolytes. Preliminary data for the in situ electrochemical characterization of these tips are also discussed

Real Time Spectroscopic Ellipsometry Analysis of First Stage CuIn1-xGaxSe2 Growth: Indium-Gallium Selenide Co-Evaporation

Real time spectroscopic ellipsometry (RTSE) has been applied for in-situ monitoring of the first stage of copper indium-gallium diselenide (CIGS) thin film deposition by the three-stage co-evaporation process used for fabrication of high efficiency thin film photovoltaic (PV) devices. The first stage entails the growth of indium-gallium selenide (In1-xGax)₂Se₃ (IGS) on a substrate of Mo-coated soda lime glass maintained at a temperature of 400 °C. This is a critical stage of CIGS deposition because a large fraction of the final film thickness is deposited, and as a result precise compositional control is desired in order to achieve the optimum performance of the resulting CIGS solar cell. RTSE is sensitive to monolayer level film growth processes and can provide accurate measurements of bulk and surface roughness layer thicknesses. These in turn enable accurate measurements of the bulk layer optical response in the form of the complex dielectric function ε = ε₁ - iε₂, spectra. Here, RTSE has been used to obtain the (ε₁, ε₂) spectra at the measurement temperature of 400 °C for IGS thin films of different Ga contents (x) deduced from different ranges of accumulated bulk layer thickness during the deposition process. Applying an analytical expression in common for each of the (ε₁, ε₂) spectra of these IGS films, oscillator parameters have been obtained in the best fits and these parameters in turn have been fitted with polynomials in x. From the resulting database of polynomial coefficients, the (ε₁, ε₂) spectra can be generated for any composition of IGS from the single parameter, x. The results have served as an RTSE fingerprint for IGS composition and have provided further structural information beyond simply thicknesses, for example information related to film density and grain size. The deduced IGS structural evolution and the (ε₁, ε₂) spectra have been interpreted as well in relation to observations from scanning electron microscopy, X-ray diffractometry and energy-dispersive X-ray spectroscopy profiling analyses. Overall the structural, optical and compositional analysis possible by RTSE has assisted in understanding the growth and properties of three stage CIGS absorbers for solar cells and shows future promise for enhancing cell performance through monitoring and control

Self-Assembly of Linear Arrays of Semiconductor Nanoparticles on Carbon Single-Walled Nanotubes †

Ligand-stabilized nanocrystals (NCs) were strongly bound to the nanotube surfaces by simple van der Waals forces. Linear arrays of CdSe and InP quantum dots were formed by self-assembly using the grooves in bundles of carbon single-walled nanotubes (SWNTs) as a one-dimensional template. A simple geometrical model explains the ordering in terms of the anisotropic properties of the nanotube surface. CdSe quantum rods were also observed to self-organize onto SWNTs with their long axis parallel to the nanotube axis. This approach offers a route to the formation of ordered NC/SWNT architectures that avoids problems associated with surface derivatization. Both semiconductor quantum dots (QDs) 1 and carbon singlewalled nanotubes (SWNTs) 2 possess interesting and potentially useful optical and electronic properties due to their nanoscale structures. In the case of QDs, quantum confinement in three dimensions produces a size-dependent modification of the electronic band structure, resulting in the formation of discrete electronic states. QDs exhibit unique behaviors such as efficient photoluminescence and photon up-conversion, slowed relaxation and cooling of hot carriers, enhanced lasing, and carrier multiplication via impact ionization. 3 SWNTs, however, consist of sp 2 -hybridized carbon atoms that form the walls of nanometer-wide, seamless cylinders. Past efforts to attach semiconductor nanocrystals (NCs) to nanotubes have focused on forming chemical attachments between the two different nanostructures. In this approach, defects in the nanotube lattice, i.e., any site where the sp 2 -bonded carbon network is broken, are used as sites for chemical bond formation. Such defects are typically present after acid-based purification methods or may be specifically introduced by chemical derivatization. In this paper, we report the formation of organized, onedimensional (1-D) arrays of semiconductor QDs by van der Waals (vdW) adsorption onto SWNTs. Two representative II-VI and the III-V semiconductor NCs, CdSe and InP, respectively, demonstrated linear ordering when adsorbed from nonaqueous colloidal solutions onto high-purity, low-defectdensity SWNTs. The tendency to form linear arrays was greatest when tube-tube alignment was relatively good within bundles and when the QDs were relatively large. The edge-to-edge (ee) separation distance between QDs in the 1-D arrays was ∼18 Å for both the InP and the CdSe QDs, indicating that QD-QD separation is governed by the thickness of the ligand shells, as is the case in two-and three-dimensional QD arrays

Nanomaterials for alternative energy sources Nanostructured thin solid oxide fuel cells with high power density Inorganic nanomaterials for batteries Raman spectroscopy of charge transfer interactions between single wall carbon nanotubes and [FeFe] hydrog

We report a Raman spectroscopy study of charge transfer interactions in complexes formed by single-walled carbon nanotubes (SWNTs) and [FeFe] hydrogenase I (CaHydI) from Clostridium acetobutylicum. The choice of Raman excitation wavelength and sample preparation conditions allows differences to be observed for complexes involving metallic (m) and semiconducting (s) species. Adsorbed CaHydI can reversibly inject electronic charge into the LUMOs of s-SWNTs, while charge can be injected and removed from m-SWNTs at lower potentials just above the Fermi energy. Time-dependent enzymatic assays demonstrated that the reduced and oxidized forms of CaHydI are deactivated by oxygen, but at rates that varied by an order of magnitude. The time evolution of the oxidative decay of the CaHydI activity reveals different time constants when complexed with m-SWNTs and s-SWNTs. The correlation of enzymatic assays with time-dependent Raman spectroscopy provides a novel method by which the charge transfer interactions may be investigated in the various SWNT-CaHydI complexes. Surprisingly, an oxidized form of CaHydI is apparently more resistant to oxygen deactivation when complexed to m-SWNTs rather than s-SWNTs