Growth Kinetics in Layer‐by‐Layer Assemblies of Organic Nanoparticles and Polyelectrolytes

The growth rates of layer‐by‐layer (LbL) assemblies of polyelectrolytes (PEs) with oppositely charged polystyrene (PS) nanoparticles (NPs) as a function of molecular weight (MW) of the PEs, ionic strength of the media, and NP size and charge are systematically investigated. To optimize LbL growth, the effects of suspension concentration, pH of the media, and deposition time on the growth rate of multilayers are assessed. Both linear and exponential growth behaviors are observed and, under optimal conditions, films of up to around 1 μm thick can readily be assembled after 10 or so bilayers have been deposited. For many of the cases studied, an intermediate MW of PE leads to the fastest film buildup, for both cationic poly(ethyleneimine) deposited alternately with anionic PS NPs and for anionic poly(acrylic acid) deposited alternately with cationic PS NPs. The existence of an optimal MW suggests that growth rate is determined by a balance of thermodynamic factors, including density of polymer bridges between particles, and kinetic factors, specifically the diffusivity of polymer in the film. The optimal MW, however, is very sensitive to the materials used. Moreover, depending on the MW of the PE, increasing salinity could increase or decrease the growth kinetics. Finally, the surface morphology of the films is characterized with AFM and SEM to reveal that the roughness increases less than linearly with film thickness.Growth factors: The growth rates of layer‐by‐layer (LbL) assemblies of polyelectrolytes (PEs) with oppositely charged polystyrene nanoparticles are systematically investigated. The molecular weight of a PE has a considerable effect on LbL film growth and its surface morphology (see figure).Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/135666/1/cphc201600789_am.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/135666/2/cphc201600789-sup-0001-misc_information.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/135666/3/cphc201600789.pd

Selective Binding, Self-Assembly and Nanopatterning of the Creutz-Taube Ion on Surfaces

The surface attachment properties of the Creutz-Taube ion, i.e., [(NH3)5Ru(pyrazine)Ru(NH3)5]5+, on both hydrophilic and hydrophobic types of surfaces were investigated using X-ray photoelectron spectroscopy (XPS). The results indicated that the Creutz-Taube ions only bound to hydrophilic surfaces, such as SiO2 and –OH terminated organic SAMs on gold substrates. No attachment of the ions on hydrophobic surfaces such as –CH3 terminated organic SAMs and poly(methylmethacrylate) (PMMA) thin films covered gold or SiO2 substrates was observed. Further ellipsometric, atomic force microscopy (AFM) and time-dependent XPS studies suggested that the attached cations could form an inorganic analog of the self-assembled monolayer on SiO2 substrate with a “lying-down” orientation. The strong electrostatic interaction between the highly charged cations and the anionic SiO2 surface was believed to account for these observations. Based on its selective binding property, patterning of wide (∼200 nm) and narrow (∼35 nm) lines of the Creutz-Taube ions on SiO2 surface were demonstrated through PMMA electron resist masks written by electron beam lithography (EBL)

Interfacial Behaviour of Polyelectrolyte-Nanoparticle Systems

NR 2014080