This disclosure provides methods, devices and systems for using a stamp to enhance selectivity between surface layers of a substrate, and to facilitate functionalizing selected layers. An array of flat stamps may be used to concurrently stamp multiple regions of a substrate to transfer one or more substances to the topmost layer or layers of the substrate. If desired, the affected regions of the substrate may be isolated from each other through the use of a reactor plate that, when clamped to the substrate's surface, forms reaction wells in the area of stamping. The stamp area can, if desired, be configured for stamping the substrate after the reactor plate has been fitted, with the individual stamps sized and arranged in a manner that permits stamping within each reaction well. If applied in a combinatorial process, a robotic process may be used to transfer multiple combinations of contact substances and processing chemicals to each reaction well to perform many concurrent processes upon a single substrate (e.g., a single coupon). The methods, devices and systems provided facilitate semiconductor design, optimization and qualification, and may be adapted to production manufacturing.