This thesis focuses on the application of soft materials to scanning probe-based molecular printing techniques, such as dip-pen nanolithography (DPN). The selective incorporation of soft materials in place of hard materials in traditional cantilever-based scanning probe lithography (SPL) systems not only enables the deposition of a broader range of materials, but also dramatically lowers the cost while simultaneously increasing the throughput of SPL.;Chapter 1 introduces SPL and DPN, and highlights a few recent advances in using DPN to control surface chemical functionality at the nanoscale. In addition to introducing the material deposition capabilities of DPN, Chapter 1 introduces the development of the cantilever-free architecture, a relatively recent paradigm shift in high-throughput SPL. Furthermore, an in-depth synthetic methodology for making the most widely used cantilever-free tip arrays, consisting of elastomeric nanoscale pens adhered to an elastomeric backing layer on a glass slide, is included as an appendix.;Chapter 2 discusses the synthesis of metal and metal oxide nanoparticles at specified locations by using DPN to deposit the precursors dispersed in a polymer matrix; after deposition, the precursors are annealed to form single nanoparticles. This work builds on previous soft material-based advances in DPN by utilizing the polymer as a "nanoreactor" to synthesize the desired nanoparticles, where the precursors can diffuse and coalesce into a single nanoparticle within each spot. The process of precursor aggregation and single nanoparticle formation is studied, and it is found that metal precursors follow one of three pathways based upon their reduction potential.;Chapter 3 is the first of three chapters that highlights the power of soft materials in the cantilever-free architecture. In particular, Chapter 3 examines the role of the elastomeric backing layer as a compliant spring whose stiffness (as measured by the spring constant, k) can be tuned with a simple chemical change to the composition of the elastomer. In particular, the extent of cross-linking within the elastomer is found to dictate the k the backing layer, and arrays with spring constants tuned from 7 to 150 N/m are described. Furthermore, a simple geometric model is developed that explains the low variation of k within each cantilever-free array; this stands in contrast to arrays of cantilevers, which typically show large variations of k within an array.;Chapter 4 addresses the problem of individual actuation in SPL by embedding resistive heaters directly beneath the elastomeric backing layer. This actuation scheme was chosen because the elastomer used in the cantilever-free tip arrays has extraordinary thermal expansion properties, and thorough exploration of their actuation behavior shows that the heater arrays are fast (> 100 microm/s) and powerful (> 4 microm) enough for actuation. After implementing several corrections for the tip height -- a problem that is intractable without the heaters, and has never been addressed before -- printing of alkanethiols onto Au is demonstrated with a 2D array of individually actuated probes.;Chapter 5 examines the hypothesis that elastomeric tips can absorb solvent and be used to transport materials in the absence of environmental solvent. This is evaluated by first using tip arrays soaked in a nonpolar solvent to pattern a hydrophobic block copolymer that cannot be patterned by traditional DPN, and is subsequently explored for the case of water uptake into the pen arrays. Surprisingly, despite their poor water retention ability, the tip arrays can store enough water to pattern hydrophilic polymers in dry environments for over 2 hours. The dynamics of the solvent absorption are captured by a simple calculation that accounts for the dynamical behavior of water retention and the backing layer thickness, thereby allowing these results to be generalized to other solvents. This exploration of the subtle and dynamic role of absorbed solvent in cantilever-free pen arrays shows that proper pre-treatment of the arrays can be used to obviate the need for an environmental chamber in molecular printing. (Abstract shortened by UMI.).
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