We investigate the applicability of the microcontact printing technique for the patterning of polymeric etch-resistant layers with thicknesses in the order of micrometers. In contrast to small molecular materials such as thiols and silane coupling agents typically used in microcontact printing, the patterning of thick layers requires tuning of the rheological properties of an ink film to prevent pattern deformation and attain high-quality transfer. By evaluating the swelling rate of a microcontact stamp material (i.e. poly(dimethylsiloxane) (PDMS)) and the evaporation rate of solvents, we find an optimal ink formulation to attain the desired semi-dried state for the printing of polymer layers. In polymer films with solid content below the optimal limit, split- or wrinkle-type deformations were found depending on the adhesion force and deformability of ink films, while overly-dried polymer films failed to be transferred. These phenomena are in qualitative agreement with deformation curves obtained from colloidal probe microscopy measurements that successfully revealed the deformability and adhesion of semi-dried polymer films. Further investigation of the effects of stamp stiffness on pattern formation reveals that a pattern region in which the thickness profile has a small curvature radius failed to be transferred when a stiffer PDMS stamp was used. This type of defect is thought to be caused by incomplete contact between the film and substrate due to a semi-circular cap structure of the polymer film and insufficient deformation of the stamp. Herein, a detailed contacting mechanism for high-quality patterning is discussed on the basis of the Hertz contact model. Using the developed etch-resistant ink and optimized printing process conditions, a finely defined etched structure for a silicon substrate is obtained.
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