Patterned Self-assembled Monolayers

The formation of mixed SAMs composed of two components provides unique possibilities in the control of the physical and chemical surface properties. Besides homogeneously mixed SAMs, a directed deposition of the components results in surfaces of controlled heterogeneity. One example reported by Liedberg et ah, forming SAM gradients (Fig. 9.6d) by controlled diffusion has already been mentioned [73]. 

The feature sizes that can be reahzed by pCP are typically within the range of several micrometers whereas recently, Michel et al. reported a resolution of approx. 100 nm [111]. 

For direct patterning on the nanometer scale, scanning probe microscopy (SPM) based techniques such as dip-pen-nanolithography (DPN), [112-114] nanograftingf, nanoshaving or scanning tunneling microscopy (STM) based techniques such as electron induced diffusion or evaporation have recently been developed (Fig. 9.14) [115, 116]. The SPM based methods, allows the deposition of as-sembhes into restricted areas with 15 nm linewidths and 5 nm spatial resolution. Current capabihties and future applications of DPN are discussed in Ref. [117]. 

The preparation and application of SAM systems patterned by STM and their use in catalysis was demonstrated by Wittstock and Schuhmann [123]. The patterning (local desorption) of SAMs from alkane thiols on gold was performed by scanning electrochemical microscopy (SECM), followed by the assembly of an amino-deriva-tized disulfide and coupling of glucose oxidase to form a catalytically active pattern of the enzyme. The enzymatic activity could be monitored/imaged by SECM. 

A different approach was followed by Blackledge et al. [124]. They used the catalytic activity of a palladium coated SPM-tip to selectively generate a pattern into different co-functionalized SAMs. 

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