Hybrid nanoscale patterning strategies combine the registration and addressability of conventional lithographic techniques with the chemical and physical functionality enabled by intermolecular, electrostatic and/or biological interactions. This review aims to highlight and to provide a comprehensive description of recent developments in hybrid nanoscale patterning strategies that enhance existing lithographic techniques or can be used to fabricate functional chemical patterns that interact with their environment. These functional structures create new capabilities, such as the fabrication of physicochemical surfaces that can recognize and capture analytes from complex liquid or gaseous mixtures. The nanolithographic techniques we describe can be classified into three general areas: traditional lithography, soft lithography and scanning-probe lithography. The strengths and limitations of each hybrid patterning technique will be discussed, along with the current and potential applications of the resulting patterned, functional surfaces.

One pathway toward nanomaterials with controllable band gaps is to assemble solids where atomic clusters serve as building blocks, since the electronic structures of clusters vary with size and composition. To study the role of organization in cluster assemblies, we synthesized multiple architectures incorporating As(7)(3-) clusters through control of the countercations. Optical measurements revealed that the band gaps vary from 1.1-2.1 eV, even though the assemblies are constructed from the identical cluster building block. Theoretical studies explain this variation as being a result of altering the lowest unoccupied molecular orbital levels by changing the countercations. Additional variations in the gap are made by covalently linking the clusters with species of varying electronegativity to alter the degree of charge transfer. These findings offer a general protocol for syntheses of nanoassemblies with tunable electronic properties.

Alkanethiol molecules in solution displace 1-adamantanethiolate self-assembled monolayers on Au{111}, ultimately leading to complete molecular exchange. Specifically, here, fast insertion of n-dodecanethiolate at defects in the original 1-adamantanethiolate monolayer nucleates an island growth phase, which is followed by slow ordering of the n-dodecanethiolate domains into a denser and more crystalline form. Langmuir-based kinetics, which describe alkanethiolate adsorption on bare Au{111}, fail to model this displacement reaction. Instead, a Johnson-Mehl-Avrami-Kolmogorov model of perimeter-dependent island growth yields good agreement with kinetic data obtained by Fourier transform infrared spectrometry over 100-fold variation in n-dodecanethiol concentration. Rescaling the growth rate at each concentration collapses all the data onto a single universal curve, suggesting that displacement is a scale-free process. The rate of displacement varies as the square-root of the n-dodecanethiol concentration across the 0.01-1.0 mM range studied.

Assembling ionic solids where clusters are arranged in different architectures is a promising strategy for developing band gap-engineered nanomaterials. We synthesized a series of cluster-assembled ionic solids composed of [As(7)-Au(2)-As(7)](4-) in zero-, one-, and two-dimensional architectures. Higher connectivity is expected to decrease the band gap energy through band broadening. However, optical measurements indicate that the band gap energy increases from 1.69 to 1.98 eV when moving from zero- to two-dimensional assemblies. This increase is a result of the local electric fields generated by the adjacent counterions, which preferentially stabilize the occupied cluster electronic states.

We have investigated the dynamics of solution-phase displacement of preformed 1-adamantanethiolate selfassembled monolayers on Au{111} by n-dodecanethiol molecules on both the ensemble (millimeter) and molecular (nanometer) scales. Employing scanning tunneling microscopy, Fourier-transform infrared spectroscopy, and cyclic voltammetry, we have observed complete displacement of the preformed 1-adamantanethiolate self-assembled monolayers by n-dodecanethiol molecules via nucleation and growth. We have established and evaluated the experimental parameters that influence 1-adamantanethiolate selfassembled monolayer displacement. With established parameters, the resolution and reproducibility of chemically patterned surfaces, applicable in areas ranging from microelectronics to biocompatible systems, have been improved to fabricate and to control structures at the supramolecular 1-100 nm scale.