Fabricating Tunable Nanoparticle Density Gradients with the Contact Printing Based Approach

Recently, the generation of spatial gradient nanoparticle assemblies has attracted much attention. Such assemblies can be intriguing templates for building novel molecular architectures, and be employed as a combinatorial tool for quick determination of interaction selectivity for nanoparticles. In this communication, we report on convenient contact printing based techniques for generating lateral gradients containing nanoparticles with tunable geometry, scale and steepness. In the first method, octadecyltrichlorosilane (OTS) gradient surfaces were generated via the contact printing approach, and then spaces un-occupied by OTS molecules were back-filled with an amine-terminated silane, which allows the grafting of nanoparticles that were surface functionalized with carboxylic acid. By varying the size and geometry of the stamp, different geometrical gradients were generated. In addition, by changing the stamping procedures, either well-defined stepwise gradients or continuous gradients can be achieved. Furthermore, the contact printing based technique can be utilized in combination with diffusion of the aminosilane molecules to directly create its gradient, and consequently a nanoparticle density gradient