However, despite much effort over the decades in the PE field, the junctions formed at the contact between a printed electrode and a semiconductor remains a crucial challenge. Moon et al. provided the careful description of the silver (Ag)/organic semiconductor interface created by ink-jet method with Ag nanoparticle ink. They observed that ligand molecules capped on Ag nanoparticles induce an interface dipole, which causes an increase in the work function of the resulting printed electrodes. This work showed the work function of the metal electrodes made from metal nanoparticle ink could be modulated by the electronic disturbance induced when metal nanoparticle transformed into Ag electrode. Though the understanding and engineering of junctions formed at the M/S interface with the printing method open new way to modulate the SBH and then device performances, methodologies using the printing method have not been sufficiently explored. In addition, there are few researches on silicon (Si) substrates with metal electrode made by the printing method even though Si is one of the widely used semiconductors in practical. Because of deviation between theory and experiments in Si-based electrical devices which is mainly originated from surface oxidization, systematic investigations have not conducted for the electrical properties and morphological observations in the interface between metal electrode and Si substrate. Fine tuning of SBH between metal electrode and Si can provide benefits of achieving high-speed operations and low-voltage drives of thin field transistors, and/or high efficient energy conversions of solar cells.