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Solid state reactions, interfaces, and stress in core-shell nanostructures

Subject Area Thermodynamics and Kinetics as well as Properties of Phases and Microstructure of Materials
Term from 2012 to 2015
Project identifier Deutsche Forschungsgemeinschaft (DFG) - Project number 222240970
 
Final Report Year 2022

Final Report Abstract

The project studied solid state reactions in core-shell nanostructures with atom probe techniques and complementary TEM and XPS. Hemispherical geometries, produced by sputter deposition of thin films on the apex of tungsten wires are the dominant model geometry, but also core-shell nanowires are considered. Investigations were concentrated on metallic triple layers Al/Cu/Al and, more extensively, on various silicide forming systems e.g. Cu/a-Si/Cu, Ni/a-Si/Ni, Cr/a-Si/Cr. Interestingly, all triple layer systems have shown a significant asymmetry in the growth rate of the reaction product at the interfaces. In the case of Al/Cu/Al, the intermetallic product Al2Cu growth was faster at the inner interface at which Cu is stacked on top of Al, while all silicide systems showed far faster growth when the metal is stacked on top of a-Si. While the origin of the first appears to be elastic stress coupled with plastic relaxation and vacancy supersaturation, the latter effect in the silicide could be shown by APT to be caused by tiny differences in the initial chemical sharpness of the Me/Si interfaces after layer deposition. While a very sharp interface requires a rather long incubation period for the nucleation of the silicide, a chemically broader interface leads to almost spontaneous instantaneous formation of the silicide. This behavior could be shown to be in perfect quantitative agreement with a polymorphic nucleation mechanism, starting from the intermixed, but disordered interface. For cylindrical core-shell nanowires, a theoretical continuum set of equations was derived to simulate the growth of the intermetallic product. The mode predicts that the growth rate of the products might be sensitively controlled by axial compressive or tensile stress. The described growth asymmetry can be controlled and increasingly suppressed with increasing tensile stress. Core/shell stainless steel/CrC nanowires were experimentally demonstrated by electroplating into trackedged membranes. By thermal reaction, the CrC shell is formed. With further annealing these wires form hollow nanotubes of CrC.

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