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Summary of in situ epitaxial nucleation and growth measurements

In situ nucleation and growth measurements of Ag and Au on single-crystal PbSe thin films were made using a transmission electron microscope. Properties studied were polymorphism, crystalline perfection, and the stoichiometric composition of the initial and the autoepitaxially thickened PbSe substrates. The quantitative nucleation and cluster growth measurements were limited to low-saturation conditions. The epitaxial orientations are discussed, and evidence is presented as to the stage of deposition at which the epitaxial order for Ag is introduced. Strong substrate/overgrowth interaction manifested itself by alloying and interdiffusion.

Poppa, H.

Changes induced on the surfaces of small Pd clusters by the thermal desorption of CO

The stability and adsorption/desorption properties of supported Pd crystallites less than 5 nm in size were studied by Auger electron spectroscopy and repeated flash thermal desorption of CO. The Pd particles were grown epitaxially on heat-treated, UHV-cleaved mica at a substrate temperature of 300 C and a Pd impingement flux of 10 to the 13th atoms/sq cm s. Auger analysis allowed in situ measurement of relative particle dispersion and contamination, while FTD monitored the CO desorption properties. The results show that significant changes in the adsorption properties can be detected. Changes in the Pd Auger signal and the desorption spectrum during the first few thermal cycles are due to particle coalescence and facetting and the rate of this change is dependent on the temperature and duration of the desorption. Significant reductions in the amplitude of the desorptions peak occur during successive CO desorptions which are attributed to increases of surface carbon, induced by the desorption of CO. The contamination process could be reversed by heat treatment in oxygen or hydrogen

Doering, D. L.

Photoluminescence intensity enhancement of GaAs by vapor-deposited GaS - A rational approach to surface passivation

A two order-of-magnitude enhancement of photoluminescence intensity relative to untreated GaAs has been observed for GaAs surfaces coated with chemical vapor-deposited GaS. The increase in photoluminescence intensity can be viewed as an effective reduction in surface recombination velocity and/or band bending. The gallium cluster (/t-Bu/GaS)4 was used as a single-source precursor for the deposition of GaS thin films. The cubane core of the structurally-characterized precursor is retained in the deposited film producing a cubic phase. Furthermore, a near-epitaxial growth is observed for the GaS passivating layer. Films were characterized by transmission electron microscopy, X-ray powder diffraction, and X-ray photoelectron and Rutherford backscattering spectroscopies.

Jenkins, Phillip P.

Enhancement of photoluminescence intensity of GaAs with cubic GaS chemical vapor deposited using a structurally designed single-source precursor

A two order-of-magnitude enhancement of photoluminescence intensity relative to untreated GaAs has been observed for GaAs surfaces coated with chemical vapor-deposited GaS. The increase in photoluminescence intensity can be viewed as an effective reduction in surface recombination velocity and/or band bending. The gallium cluster /(t-Bu)GaS/4 was used as a single-source precursor for the deposition of GaS thin films. The cubane core of the structurally characterized precursor is retained in the deposited film producing a cubic phase. Furthermore, a near-epitaxial growth is observed for the GaS passivating layer. Films were characterized by transmission electron microscopy, X-ray powder diffraction, and X-ray photoelectron and Rutherford backscattering spectroscopies.

Macinnes, Andrew N.

X-Ray Photoemission Measurements of La(1-x)Ca(x)CoO3(x = 0, 0.5)

X-ray photoemission measurements of the core levels and valence electronic structure of LaCoO3 and La(0.5)Ca(0.5)CoO3 high quality epitaxial films are presented. Shifts of the core levels and main valence band features are consistent with a doping-induced change in the chemical potential. Oxygen states are found to significantly contribute to a peak in the valence band at 1 eV binding energy, verifying earlier results of cluster calculations. A Fermi level crossing of this same band upon doping is observed, yielding a high Fermi level density of states.

Vasquez, R. P.

Properties of large area ErBa2Cu3O(7-x) thin films deposited by ionized cluster beams

Ionized cluster beam (ICB) deposition is employed to produce ErBa2Cu3O(7-x) films on different substrates without post-annealing. Films with diameters of up to 70 mm are grown on SrTiO3 100 plane and exhibit Tc values of 84-87 K, Jc of about 10 exp 6 A/sq m at 77 K. These films are epitaxial with the c-axis perpendicular to the plane of the substrate surface, and they can be routinely produced by ICB with good Jc and Tc.

Levenson, L. L.

Metallic Powder Core Tubular Wire (PCTW) Development for Additive Manufacturing

NASA Langley Research Center (LaRC) in Hampton, VA, and the Center for Welding, Joining, and Coating Research (CWJCR) in the Department of Metallurgical and Materials Engineering at the Colorado School of Mines (CSM) in Golden, CO, have collaborated for nearly fifteen years to develop metallic powder core tubular wire (PCTW) feedstock for additive manufacturing (AM) using electron beam deposition. The motivation for this development was to offset dealloying observed during deposition of titanium and aluminum alloy solid wire feedstock in the LaRC electron beam freeform fabrication (EBF3) system and to explore novel alloy compositions by tailoring the powder fill. EBF3 is a fusion-based AM process that is performed under vacuum and is consequently prone to vaporization loss of low vapor pressure alloying elements. Research spanning four graduate student research projects succeeded in developing the basic methodology to fabricate PCTW, the mass balance equations used to define the powder fill, microstructure control through particulate inoculation, and the feasibility of producing metal matrix composite materials. Metallic PCTW is comprised of a thin foil sheath wrapped around a powder blend. Fabrication of PCTW at CSM was accomplished using a tubular wire mill system to first bend a flat strip into a u-shaped cross section, deposit a powder fill, create a lap joint to seal the wire, and draw to final diameter. Powder management systems were developed to ensure uniform mixing of powder constituents and identify feed rates for optimum fill ratios. Processing parameters were successfully developed for titanium and aluminum alloy sheaths to account for material work hardening during drawing. Mass balance equations were developed to account for compositional contributions of the sheath and powder fill. PCTW composition can be adjusted through selection of the sheath or powder materials. PCTWs were successfully developed to offset Al loss in deposits of Ti-6-4 and Mg loss in Al 6061, resulting in deposits that were within the composition limits for each material. Ti-6-4 deposits were fabricated using PCTW comprised of commercially pure (CP) titanium sheath and a fill of pre-alloyed Ti-6-4 powder with additions of elemental Al and V powders. Additions of both elements were required to account for the CP Ti from the sheath, and Al was further enhanced to offset documented losses in EBF3 deposits. For Al 6061 deposits, composition was modulated through the choice of sheath material. The PCTW was made using an Al 5052 sheath to supplement Mg content and a fill composition of pre-alloyed 6061 powder with additions of Si and Cu.The slower solidification rate of the EBF3 process compared with laser powder bed fusion processes can lead to coarse-grained microstructures and mechanical property anisotropy. EBF3deposits of Ti-6-4 exhibited large epitaxially grown β grains, which result in degraded mechanical properties in the deposition direction. Microstructure refinement was achieved through a combination of electron beam modulation and the use of a PCTW designed for Ti-6-4 deposits and modified by the addition of powder made from Fe and B. Resulting deposits exhibited reductions in β grain size, α phase colony intercept length and lath width, and an increased volume fraction of β phase. The mechanism of microstructure refinement was related to precipitation of boride particles. Hardness testing confirmed that mechanical property anisotropy was reduced and an overall increase in hardness was achieved.Metal matrix composite (MMC) materials offer strength and stiffness benefits over unreinforced materials. Two methods were investigated using PCTW technology for producing Al 6061 basedMMC materials; the direct addition of SiC reinforcing particles and the in-situ generation of reinforcements through reaction synthesis of precursor powders. Al 6061 based MMCs reinforced with SiC exhibited particle clustering and formation of aluminum carbides during deposition. The application of a Ni coating to the SiC particles prior to incorporation into the powder fill eliminated aluminum carbide formation and aided particle distribution during deposition. Modulation of beam focus and power further reduced aluminum carbide formation and aided particle distribution. In reaction synthesis, precursor additions undergo an exothermic reaction during deposition to form new ceramic products, generally of finer scale than the initial precursor components. The product phases provide reinforcement in the MMC and act as nucleation sites during solidification, resulting in grain refinement, improved mechanical properties, and reduced susceptibility to solidification cracking. Higher tensile strength and stiffness were demonstrated in Al 6061 based MMCs with 2 vol% reinforcement. These combined research efforts demonstrate the potential of PCTW technology for customizing of alloy composition and achieving microstructure control. A manufacturing process for titanium- and aluminum-based PCTWs was developed based on iterative design, theoretical calculations, and empirical data. PCTW technology successfully mitigated Al loss from Ti-6-4 and Mg loss in Al 6061, resulted in grain refinement in Ti-6-4, and demonstrated fabrication of Al based MMCs

Marcia S Domack