Surface structures of magnetic nanorings were made using electroless deposition of Ni onto patterned templates of an amine-functionalized organosilane. Samples were prepared by chemical approaches based on colloidal lithography employing a surface mask of size-sorted, monodisperse silica spheres. Surface changes were evaluated after key points of the reactions using imaging modes of atomic force microscopy (AFM). Nanopatterns of 3-aminopropyltriethoxysilane (APTES) were prepared on Si(111) by applying a heated vapor to a surface mask of silica spheres. After rinsing, the particle mask was removed to reveal ring-shaped nanopatterns presenting amine groups at the interface. Organosilane nanopatterns were then immersed in a solution of Pd catalyst followed by treatment in a Ni plating bath. Changes in surface morphology after each reaction step were characterized ex situ using tapping-mode AFM to follow the time course of nanofabrication. Images of the Ni nanorings acquired with AFM were compared with SEM micrographs to further elucidate the morphology of the metal coatings. The magnetic character of the nanostructures was investigated with magnetic sample modulation (MSM-AFM), which is a hybrid of contact mode AFM combined with magnetic actuation of samples. Surface maps of the vibration of diamagnetic Pd and magnetic Ni nanorings were obtained with MSM-AFM, providing insight on processes of electroless plating. Fine details of the surface corrugation and grain structure of the Ni coated areas of the sample detected with SEM were sensitively resolved with MSM-AFM that were not apparent in AFM topography frames. Chemistry-based steps with electroless deposition (ELD) of metal and colloidal lithography provide a practical route for reproducible nanofabrication of highly regular geometries with high-throughput.

Nanostructures of 4-(chloromethyl)phenyltrichlorosilane (CMPS) were used as a foundation to attach and grow heterostructures of porphyrins and organosilanes. A protocol was developed with particle lithography using steps of immersion in organosilane solutions to selectively passivate the surface of Si(111) with octadecyltrichlorosilane (OTS). A methyl-terminated matrix was chosen to direct the growth of CMPS nanostructures to fill the uncovered sites of Si(111) to enable spatial confinement of the surface reaction. Silica spheres with a diameter of 500 nm were used as a surface mask to prepare nanoscopic holes within the OTS matrix film. Next, the samples were immersed in solutions of CMPS dissolved in toluene or bicyclohexane. Nanostructures of CMPS formed within the nanoholes, to furnish spatially selective sites for binding porphyrins. The samples were then characterized with AFM to evaluate the height and morphology of the CMPS nanostructures that had formed within the nanoholes of OTS. The samples were then refluxed in a porphyrin solution for selective binding to produce heterostructures. The attachment of porphyrins was evidenced by increases in the height and width of the CMPS nanopatterns. The measurements of size indicate that multiple layers of porphyrins were added. Through each step of the surface reaction the surrounding matrix of OTS showed minimal areas of nonspecific adsorption. The AFM studies provide insight into the mechanism of the self-polymerization of CMPS as a platform for constructing porphyrin heterostructures.

The surface assembly of 2,3,7,8,12,13,17,18-octaethylporphyrin (OEP) using silicon tetrachloride as a coupling agent was investigated using atomic force microscopy (AFM). Nanopatterned films of Si-OEP were prepared by protocols of colloidal lithography to evaluate the morphology, thickness, and molecular orientation for samples prepared on Si(111). The natural self-stacking of porphyrins can pose a challenge for molecular patterning. When making films on surfaces, porphyrins will self-associate to form co-planar configurations of random stacks of molecules. There is a tendency for the flat molecules to orient spontaneously in a side-on arrangement that is mediated by physisorption to the substrate as well as by π–π interactions between macrocycles to form a layered arrangement of packed molecules, analogous to a stack of coins. When silicon tetrachloride is introduced to the reaction vessel, the coupling between the surface and porphyrins is mediated through covalent Si–O bonding. For these studies, surface structures of Si-OEP were formed that are connected with a Si–O–Si motif to a silicon atom coordinated to the center of the porphyrin macrocycles. Protocols of colloidal lithography were used as a tool to prepare surface structures and films of Si-OEP to facilitate surface characterizations. Conceptually, by arranging the macrocycles of porphyrins with defined orientation, local AFM surface measurements can be enabled to help address mechanistic questions about how molecules self-assemble and bind to substrates.

The self-assembly and growth of 4-(chloromethyl)-phenyltrichlorosilane (CMPS) nanostructures within nanoholes that were formed within a thin film of octadecyltrichlorosilane (OTS) was studied ex situ using atomic force microscopy (AFM). The effects of selected solvents and temperatures on the growth of the CMPS were investigated to gain insight into the mechanisms of the surface assembly and self-polymerization of CMPS. Surface platforms of nanoholes were generated within a thin film of OTS using particle lithography combined with immersion steps. The film of OTS provided a resist for preventing nonspecific adsorption of CMPS in areas surrounding the nanoholes. The uncovered areas of substrate within the nanoholes were used to direct the self-assembly of CMPS. Nanopatterns were imaged using AFM after key steps of the nanofabrication procedure. The samples were immersed in solutions of CMPS that were prepared with selected solvents that included toluene, bicyclohexyl, and dichloromethane. The size and morphology of CMPS nanostructures were influenced by the nature of the solvent, and nonpolar solvents were better suited for reproducibly growing regular nanostructures. For nanostructures of CMPS grown within nanoholes, the rate of CMPS self-assembly and growth exhibited differences at the molecular level for temperatures ranging from −4 to 20 °C. The analysis of the height and width of CMPS nanopatterns reveals that multiple layers formed with taller surface structures being formed at higher temperatures. Particle lithography provides a useful tool for studying chemical reactions at the nanometer scale since basic steps of sample preparation can used to make multiple nanopatterns for surface measurements under controlled environmental conditions.