Particle lithography is a practical approach to generate millions of organosilane nanostructures on various surfaces, without the need for vacuum environments or expensive instrumentation. This report describes a stepwise chemistry route to prepare organosilane nanostructures and then apply the patterns as a spatially selective foundation to attach gold nanoparticles. Sites with thiol terminal groups were sufficiently small to localize the attachment of clusters of 2-5 nanoparticles. Basic steps such as centrifuging, drying, heating, and rinsing were used to generate arrays of regular nanopatterns. Close-packed films of monodisperse latex spheres can be used as an evaporative mask to spatially direct the placement of nanoscopic amounts of water on surfaces. Vapor phase organosilanes deposit selectively at areas of the surface containing water residues to generate nanostructures with regular thickness, geometry, and periodicity as revealed in atomic force microscopy images. The area of contact underneath the mesospheres is effectively masked for later synthetic steps, providing exquisite control of surface coverage and local chemistry. By judicious selection in designing the terminal groups of organosilanes, surface sites can be engineered at the nanoscale for building more complex structures. The density of the nanopatterns and surface coverage scale predictably with the diameter of the mesoparticle masks. The examples presented definitively illustrate the capabilities of using the chemistry of molecularly thin films of organosilanes to spatially define the selectivity of surfaces at very small size scales.

SummaryParticle lithography offers generic capabilities for the high-throughput fabrication of nanopatterns from organosilane self-assembled monolayers, which offers the opportunity to study surface-based chemical reactions at the molecular level. Nanopatterns of octadecyltrichlorosilane (OTS) were prepared on surfaces of Si(111) using designed protocols of particle lithography combined with either vapor deposition, immersion, or contact printing. Changing the physical approaches for applying molecules to masked surfaces produced OTS nanostructures with different shapes and heights. Ring nanostructures, nanodots and uncovered pores of OTS were prepared using three protocols, with OTS surface coverage ranging from 10% to 85%. Thickness measurements from AFM cursor profiles were used to evaluate the orientation and density of the OTS nanostructures. Differences in the thickness and morphology of the OTS nanostructures are disclosed based on atomic force microscopy (AFM) images. Images of OTS nanostructures prepared on Si(111) that were generated by the different approaches provide insight into the self-assembly mechanism of OTS, and particularly into the role of water and solvents in hydrolysis and silanation.

The ability to control nanoscale morphology and molecular organization in organic semiconducting polymer thin films is an important prerequisite for enhancing the efficiency of organic thin-film devices including organic lightemitting and photovoltaic devices. The current "top-down" paradigm for making such devices is based on utilizing solution-based processing (e.g., spin-casting) of soluble semiconducting polymers. This approach typically provides only modest control over nanoscale molecular organization and polymer chain alignment. A promising alternative to using solutions of presynthesized semiconducting polymers pursues instead a "bottom-up" approach to prepare surface-grafted semiconducting polymer thin films by surface-initiated polymerization of small-molecule monomers. Herein, we describe the development of an efficient method to prepare polythiophene thin films utilizing surface-initiated Kumada catalyst transfer polymerization. In this study, we provided evidence that the surface-initiated polymerization occurs by the highly robust controlled (quasi-"living") chain-growth mechanism. Further optimization of this method enabled reliable preparation of polythiophene thin films with thickness up to 100 nm. Extensive structural studies of the resulting thin films using X-ray and neutron scattering methods as well as ultraviolet photoemission spectroscopy revealed detailed information on molecular organization and the bulk morphology of the films, and enabled further optimization of the polymerization protocol. One of the remarkable findings was that surface-initiated polymerization delivers polymer thin films showing complex molecular organization, where polythiophene chains assemble into lateral crystalline domains of about 3.2 nm size, with individual polymer chains folded to form in-plane aligned and densely packed oligomeric segments (7−8 thiophene units per each segment) within each domain. Achieving such a complex mesoscale organization is virtually impossible with traditional methods relying on solution processing of presynthesized polymers. Another significant advantage of surface-confined polymer thin films is their remarkable stability toward organic solvents and other processing conditions. In addition to controlled bulk morphology, uniform molecular organization, and stability, a unique feature of the surface-initiated polymerization is that it can be used for the preparation of large-area uniformly nanopatterned polymer thin films. This was demonstrated using a combination of particle lithography and surface-initiated polymerization. In general, surface-initiated polymerization is not limited to polythiophene but can be also expanded toward other classes of semiconducting polymers and copolymers.

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Surface-confined stepwise click polymerization was used to prepare surface-attached thin films of semiconducting polymers. These highly uniform films showed extended UV/vis absorption characteristics and a remarkable degree of molecular organization with a unidirectional alignment of the polymer chains normal to the surface.