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

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

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

Adsorbate-induced structural changes in 1-3 nm platinum nanoparticles

We investigated changes in the Pt–Pt bond distance, particle size, crystallinity, and coordination of Pt nanoparticles as a function of particle size (1–3 nm) and adsorbate (H2, CO) using synchrotron radiation pair distribution function (PDF) and X-ray absorption spectroscopy (XAS) measurements. The ∼1 nm Pt nanoparticles showed a Pt–Pt bond distance contraction of ∼1.4%. The adsorption of H2 and CO at room temperature relaxed the Pt–Pt bond distance contraction to a value close to that of bulk fcc Pt. The adsorption of H2 improved the crystallinity of the small Pt nanoparticles. However, CO adsorption generated a more disordered fcc structure for the 1–3 nm Pt nanoparticles compared to the H2 adsorption Pt nanoparticles. In situ XANES measurements revealed that this disorder results from the electron back-donation of the Pt nanoparticles to CO, leading to a higher degree of rehybridization of the metal orbitals in the Pt-adsorbate system

Measuring roughness of buried interfaces by sputter depth profiling

In this communication, we report results of a high resolution sputter depth profiling analysis of a stack of 16 alternating MgO and ZnO nanolayers grown by atomic layer deposition (ALD) with thickness of ~5.5 nm per layer. We used an improved dual beam approach featuring a low energy normally incident direct current sputtering ion beam (first beam). Intensities of 24Mg+ and 64Zn+ secondary ions generated by a pulsed analysis ion beam (second beam) were measured as a function of sample depth by time-of-flight secondary ion mass spectrometry (TOF SIMS). Experimental results of this dual beam TOF SIMS depth profiling processed in the framework of the mixing-roughness-information (MRI) model formalism demonstrate that such an approach is capable of providing structural information for layers just a few nm thick. Namely, it was established that the interfacial roughness of the MgO/ZnO multilayer structure equals 1.5 nm. This finding by TOF SIMS was cross-validated by independent measurements with specular X-ray reflectivity (XRR) technique. In addition, the TOF SIMS-MRI analysis suggests that the obtained 1.5 nm roughness should be attributed to the native roughness (jagged type) of the interface rather than to interdiffusion at the interface during the ALD synthesis.Comment: Brief report of 5 pages and 5 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