A unique approach for nanoscale covalent functionalization of graphite surfaces employing self-assembled molecular monolayers of n-alkanes as templating masks is presented.Linearly aligned aryl groups with a lateral periodicity of 5 or 7 nm is demonstrated utilizing molecular templates of different lengths. The key feature of this approach is the use of a phase separated solution double layer consisting of a thin organic layer containing template molecules topped by an aqueous layer containing aryldiazonium molecules capable of electrochemical reduction to generate aryl radicals which bring about surface grafting. Upon sweeping of the potential, lateral displacement dynamics at the n-alkane terminal edges acts in conjunction with 2 electrochemical diffusion to result in templated covalent bond formation in a linear fashion. This protocol was demonstrated to be applicable to linear grafting of graphene. The present processing described herein opens molecular frontiers for the realization of rationally designed nanoscale materials.

A convenient covalent functionalization approach and nanopatterning method of graphite and graphene is developed. In contrast to expectations, electrochemically activated dediazotization of a mixture of two aryl diazonium compounds in aqueous media leads to a spatially inhomogeneous functionalization of graphitic surfaces, creating covalently modified surfaces with quasi-uniform spaced islands of pristine graphite or graphene, coined nanocorrals. Cyclic voltammetry (CV) and chronoamperometry (CA) approaches are compared. The average diameter (45-130 nm) and surface density (20 to 125 corrals/µm 2) of these nanocorrals are tunable. These chemically modified nanostructured graphitic (CMNG) surfaces are characterized by atomic force microscopy, scanning tunneling microscopy, Raman spectroscopy and microscopy, and x-ray photoelectron spectroscopy. Mechanisms leading to the formation of these CMNG surfaces are discussed. The potential of these surfaces to investigate supramolecular self-assembly and on-surface reactions under nanoconfinement conditions is demonstrated.

The barrier layer in Cu technology is essential to prevent Cu from diffusing into the dielectric layer at high temperatures; therefore, it must have a high stability and good adhesion to both Cu and the dielectric layer. In the past three decades, tantalum/tantalum nitride (Ta/TaN) has been widely used as an inter-layer to separate the dielectric layer and the Cu. However, to fulfill the demand for continuous down-scaling of the Cu technology node, traditional materials and technical processes are being challenged. Direct electrochemical deposition of Cu on top of Ta/TaN is not realistic, due to its high resistivity. Therefore, pre-deposition of a Cu seed layer by physical vapor deposition (PVD) or chemical vapor deposition (CVD) is necessary, but the non-uniformity of the Cu seed layer has a devastating effect on the defect-free fill of modern sub-20 or even sub-10 nm Cu technology nodes. New Cu diffusion barrier materials having ultra-thin size, high resistivity and stability are needed for the successful super-fill of trenches at the nanometer scale. In this review, we briefly summarize recent advances in the development of Cu diffusion-proof materials, including metals, metal alloys, self-assembled molecular layers (SAMs), two-dimensional (2D) materials and high-entropy alloys (HEAs). Also, challenges are highlighted and future research directions are suggested.