Mechanism for zirconium oxide atomic layer deposition using bis(methylcyclopentadienyl)methoxymethyl zirconium

The mechanism for zirconium oxide atomic layer deposition using bis(methylcyclopentadienyl)methoxymethyl zirconium and H(2)O was examined using ab initio calculations of hydrolysis energies to predict the order of ligand loss. These predictions were tested using in situ mass spectrometric measurements which revealed that the methyl ligand, and 65% of the methylcyclopentadienyl ligands are lost during the zirconium precursor adsorption. The remaining 35% of the methylcyclopentadienyl ligands and the methoxy ligand are lost during the subsequent H(2)O exposure. These measurements agree very well with the predictions, demonstrating that thermodynamic calculations are a simple and accurate predictor for the reactivities of these compounds. (c) 2007 American Institute of Physics. (DOI: 10.1063/1.2824814

Secondary electron yield of emissive materials for large-area micro-channel plate detectors: surface composition and film thickness dependencies

The ongoing development of Atomic Layer Deposition (ALD) enables the use of relatively inexpensive and robust borosilicate micro-channel substrates for use as Micro-Channel Plates (MCPs). The surfaces of the channels in these glass plates are functionalized to control the conductivity as well as the Secondary Electron Yield (SEY). The extensive SEY data found in literature show significant variation for a given material depending on the apparatus, the measurement procedure, and the sample preparation and handling. We present systematic studies on the effects of film thickness and surface chemical composition on SEY. We have modified an existing ultra-high vacuum apparatus containing X-ray and Ultraviolet Photoelectron Spectrometers (XPS and UPS, respectively) by adding a modified Low Energy Electron Diffraction (LEED) module for SEY measurements. With these tools, we have characterized the secondary electron emissive properties for MgO, Al2O3, and multilayered MgO/TiO2 structures to serve as electron emissive layers in the channels of the MCPs

Deconvolving Instrumental and Intrinsic Broadening in Excited State X-ray Spectroscopies

Intrinsic and experimental mechanisms frequently lead to broadening of spectral features in excited-state spectroscopies. For example, intrinsic broadening occurs in x-ray absorption spectroscopy (XAS) measurements of heavy elements where the core-hole lifetime is very short. On the other hand, nonresonant x-ray Raman scattering (XRS) and other energy loss measurements are more limited by instrumental resolution. Here, we demonstrate that the Richardson-Lucy (RL) iterative algorithm provides a robust method for deconvolving instrumental and intrinsic resolutions from typical XAS and XRS data. For the K-edge XAS of Ag, we find nearly complete removal of ~9.3 eV FWHM broadening from the combined effects of the short core-hole lifetime and instrumental resolution. We are also able to remove nearly all instrumental broadening in an XRS measurement of diamond, with the resulting improved spectrum comparing favorably with prior soft x-ray XAS measurements. We present a practical methodology for implementing the RL algorithm to these problems, emphasizing the importance of testing for stability of the deconvolution process against noise amplification, perturbations in the initial spectra, and uncertainties in the core-hole lifetime.Comment: 35 pages, 13 figure

Conversion of plutonium scrap and residue to boroilicate glass using the GMODS process

Plutonium scrap and residue represent major national and international concerns because (1) significant environmental, safety, and health (ES&H) problems have been identified with their storage; (2) all plutonium recovered from the black market in Europe has been from this category; (3) storage costs are high; and (4) safeguards are difficult. It is proposed to address these problems by conversion of plutonium scrap and residue to a CRACHIP (CRiticality, Aerosol, and CHemically Inert Plutonium) glass using the Glass Material Oxidation and Dissolution System (GMODS). CRACHIP refers to a set of requirements for plutonium storage forms that minimize ES&H concerns. The concept is several decades old. Conversion of plutonium from complex chemical mixtures and variable geometries into a certified, qualified, homogeneous CRACHIP glass creates a stable chemical form that minimizes ES&H risks, simplifies safeguards and security, provides an easy-to-store form, decreases storage costs, and allows for future disposition options. GMODS is a new process to directly convert metals, ceramics, and amorphous solids to glass; oxidize organics with the residue converted to glass; and convert chlorides to borosilicate glass and a secondary sodium chloride stream. Laboratory work has demonstrated the conversion of cerium (a plutonium surrogate), uranium (a plutonium surrogate), Zircaloy, stainless steel, and other materials to glass. GMODS is an enabling technology that creates new options. Conventional glassmaking processes require conversion of feeds to oxide-like forms before final conversion to glass. Such chemical conversion and separation processes are often complex and expensive

Ultrathin Oxide Films by Atomic Layer Deposition on Graphene

In this paper, a method is presented to create and characterize mechanically robust, free standing, ultrathin, oxide films with controlled, nanometer-scale thickness using Atomic Layer Deposition (ALD) on graphene. Aluminum oxide films were deposited onto suspended graphene membranes using ALD. Subsequent etching of the graphene left pure aluminum oxide films only a few atoms in thickness. A pressurized blister test was used to determine that these ultrathin films have a Young's modulus of 154 \pm 13 GPa. This Young's modulus is comparable to much thicker alumina ALD films. This behavior indicates that these ultrathin two-dimensional films have excellent mechanical integrity. The films are also impermeable to standard gases suggesting they are pinhole-free. These continuous ultrathin films are expected to enable new applications in fields such as thin film coatings, membranes and flexible electronics.Comment: Nano Letters (just accepted