Three dimensional atom probe tomography of nanoscale thin films, interfaces and particles

This dissertation demonstrates our research effort dedicating to extend the application of 3DAPT technique to various new materials including nanoscale monolayers, thin films, interfaces and particles for the first time. Novel sample designs and preparation methods are developed in order to broaden the application of the technique into fundamentally new areas such as monolayers, organic/biomaterials, polymers and nanoparticles analysis. Samples including surface oxide layers, ionic monolayers, alkanethiol monolayers, electrodeposited polymers, nanoparticles and metal-metal interfaces were successfully analyzed for the first time. A new sample configuration is proposed as using electrodeposited polymers to encapsulate nanoscale analytes and to coat conventional atom probe tips. This design enables the technique to image varieties of new materials which can not be analyzed before. Using this approach gold nanoparticles about 1.4 ~ 2 nm were observed in the three dimensional reconstruction images. The results demonstrate the ability of modern APT technique in the new areas and inspire the future discoveries

3D atom probe tomography study on segregation of yttrium in modified Al-Si alloys

Yttrium segregation behavior in Al-Si alloys has been studied using the three-dimensional atom probe tomography technique. Al-Si alloys were prepared by casting method, and yttrium was added to modify the eutectic silicon morphology in these alloys. The results indicated that yttrium is preferentially located within the Si phase, with the highest concentration at the interface between eutectic Al and eutectic Si

Three-Dimensional Atom Probe Tomography of Oxide, Anion, and Alkanethiolate Coatings on Gold

We have used three-dimensional atom probe tomography to analyze several nanometer-thick and monomolecular films on gold surfaces. High-purity gold wire was etched by electropolishing to create a sharp tip suitable for field evaporation with a radius of curvature of layer, primarily consisting of water and atmospheric gases, was observed on a fresh tip. This sample exhibited crystalline lattice spacings consistent with the interlayer spacing of {200} lattice planes of bulk gold. A thin oxide layer was created on the gold surface via plasma oxidation, and the thickness and composition of this layer was measured. Clear evidence of a nanometer-thick oxide layer was seen coating the gold tip, and the atomic composition of the oxide layer was consistent with the expected stoichiometry for gold oxide. Monomolecular anions layers of Br− and I− were created via adsorption from aqueous solutions onto the gold. Atom probe data verified the presence of the monomolecular anion layers on the gold surface, with ion density values consistent with literature values. A hexanethiolate monolayer was coated onto the gold tip, and atom probe analysis revealed a thin film whose ion fragments were consistent with the molecular composition of the monolayer and a surface coverage similar to that expected from literature. Details of the various coating compositions and structures are presented, along with discussion of the reconstruction issues associated with properly analyzing these thin-film systems

Atomic Scale Structure and Chemical Composition across Order-Disorder Interfaces

Through a combination of aberration-corrected high-resolution scanning transmission electron microscopy and three-dimensional atom probe tomography, the true atomic-scale structure and change in chemical composition across the complex order-disorder interface in a metallic alloy has been determined. The study reveals the presence of two interfacial widths, one corresponding to an order-disorder transition, and the other to the compositional transition across the interface, raising fundamental questions regarding the definition of the interfacial width in such systems

Elemental distributions within multiphase quaternary Pb chalcogenide thermoelectric materials determined through three-dimensional atom probe tomography

Nanostructured multiphase p-type lead chalcogenides have shown the highest efficiencies amongst thermoelectric materials. However, their electronic transport properties have been described assuming homogenous distribution of dopants between phases. Here, we have analyzed elemental distributions in precipitates and matrices of nanostructured multiphase quaternary Pb chalcogenides doped to levels below and above the solubility limit of the matrix, using three-dimensional atom probe tomography. We demonstrate that partitioning of sodium and selenium occur between the matrix and secondary phase in both lightly- and heavily-doped compounds and that the concentrations of sodium and selenium in precipitates are higher than those in the matrices. This can contribute to the transport properties of such multiphase compounds The sodium concentration reached ~3 at% in sulfur-rich (PbS) precipitates and no nano precipitates of Na-rich phases were observed within either phase, a result that is supported by high resolution TEM analysis, indicating that the solubility limit of sodium in PbS is much higher than previously thought. However, non-equilibrium segregation of sodium is identified at the precipitates/matrix interfaces. These findings can lead to further advances in designing and characterizing multiphase thermoelectric materials

On the process of co-deformation and phase dissolution in a hard-soft immiscible Cu Co alloy system during high-pressure torsion deformation

In this study, dual phase CuCo composites with a total immiscibility in the solid state and a very different initial phase strength are deformed by severe plastic deformation. Nanocrystalline supersaturated solid solutions are reached in all CuCo composites independent of the initial composition. The deformation and mechanical mixing process is studied thoroughly by combining scanning electron microscopy, transmission electron microscopy, three-dimensional atom probe tomography and nanoindentation. The indentation hardness of the Cu and Co phase and its evolution as a function of the applied strain is linked to deformation and mechanical mixing process to gain a better understanding how the phase strength mismatch of the Cu and Co phase effects the amount of co-deformation and deformation-induced mixing. Our results show that co-deformation is not a necessary requirement to achieve mechanical mixing

On the process of co-deformation and phase dissolution in a hard-soft immiscible CuCo alloy system during high-pressure torsion deformation

In this study, dual phase Cusingle bondCo composites with a total immiscibility in the solid state and a very different initial phase strength are deformed by severe plastic deformation. Nanocrystalline supersaturated solid solutions are reached in all Cusingle bondCo composites independent of the initial composition. The deformation and mechanical mixing process is studied thoroughly by combining scanning electron microscopy, transmission electron microscopy, three-dimensional atom probe tomography and nanoindentation. The indentation hardness of the Cu and Co phase and its evolution as a function of the applied strain is linked to deformation and mechanical mixing process to gain a better understanding how the phase strength mismatch of the Cu and Co phase effects the amount of co-deformation and deformation-induced mixing. Our results show that co-deformation is not a necessary requirement to achieve mechanical mixing