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The ability to control, with atomic precision, heterostructures comprising two dissimilar electronic materials has provided us with an unprecedented opportunity: to tailor novel low-dimensional electronic systems.In this it has been responsible for the discovery of many novel physical phenomena and has facilitated new technologies.While tremendous success has been achieved using semiconductor heterostructures or metallic heterostructures, the same cannot be said for metal/semiconductor heterostructures, due to the fact that most metals do not wet on semiconductors.Over the last decade, however, significant progress has been made in epitaxial growth of metastable metallic thin films on semiconductor substrates.