ABSTRACT
A new method for assembling organic monolayers on gold is reported that employs hafnium ions as linkers between a phosphonate headgroup and the gold surface. Monolayers of octadecylphosphonic acid (ODPA) formed on gold substrates that had been pretreated with hafnium oxychloride are representative of this new class of organic thin films. The monolayers are dense enough to completely block assembly of alkanethiols and resist displacement by alkanethiols. The composition and structure of the monolayers were investigated by contact angle goniometry, XPS, PM-IRRAS, and TOF-SIMS. From these studies, it was determined that this assembly strategy leads to the formation of ODPA monolayers similar in quality to those typically formed on metal oxide substrates. The assembly method allows for the ready generation of patterned surfaces that can be easily prepared by first patterning hafnium on the gold surface followed by alkanephosphonate assembly. Using the bifunctional (thiol-phosphonate) 2-mercaptoethylphosphonic acid (2-MEPA), we show that this new assembly chemistry is compatible with gold-thiol chemistry and use TOF-SIMS to show that the molecule attaches through the phosphonate functionality in the patterned region and through the thiol in the bare gold regions. These results demonstrate the possibility of functionalizing metal substrates with monolayers typically formed on metal oxide surfaces and show that hafnium-gold chemistry is complementary and orthogonal to well-established gold-thiol assembly strategies.
ABSTRACT
A significant challenge in materials characterization is the determination of the structure of nanoparticle assemblies that have been deposited on solid substrates, such as SiO2. The best method for obtaining quantitative information about structure, size, and spacing on the nanometer-length scale is TEM; however, commercially available TEM grids offer a limited range of substrate materials. In addition, the compositions of these grids do not permit much chemical processing. Here we describe silicon-based grids with electron-transparent SiO2 windows suitable for use as substrates for high-resolution TEM that can be easily fabricated using standard silicon microfabrication techniques. These grids are physically and chemically robust and exhibit the same surface chemistry and chemical stability as an oxide grown on a silicon wafer. Thus, the grids make possible the concurrent investigation of chemical and structural information on the same sample. Convenient modification of the surfaces of the grids provides access to a wide range of new substrates for the direct imaging of chemically modified surfaces by TEM. We demonstrate the utility of these grids by aligning DNA on the chemically modified SiO2 surface in order to direct the assembly of linear arrays of nanoparticles. Using these grids, we are able to quantify the effects of assembly conditions on nanoparticle size, spacing, and dispersity in the arrays.
