Abstract: This invention in one aspect relates to a method of synthesizing a self-assembled mixed-dimensional heterostructure including 2D metallic borophene and 1D semiconducting armchair-oriented graphene nanoribbons (aGNRs). The method includes depositing boron on a substrate to grow borophene thereon at a substrate temperature in an ultrahigh vacuum (UHV) chamber; sequentially depositing 4,4?-dibromo-p-terphenyl on the borophene grown substrate at room temperature in the UHV chamber to form a composite structure; and controlling multi-step on-surface coupling reactions of the composite structure to self-assemble a borophene/graphene nanoribbon mixed-dimensional heterostructure. The borophene/aGNR lateral heterointerfaces are structurally and electronically abrupt, thus demonstrating atomically well-defined metal-semiconductor heterojunctions.