Tribochemical Nanolithography: Selective Mechanochemical Removal of Photocleavable Nitrophenyl Protecting Groups with 23 Nm Resolution at Speeds of Up to 1 Mm S

We describe the mechanochemical regulation of a reaction that would otherwise be considered to be photochemical, a simple process that yields nm spatial resolution. An atomic force microscope (AFM) probe is used to remove photocleavable nitrophenyl protecting groups from alkylsilane films at loads too small for mechanical wear, thus enabling nanoscale differentiation of chemical reactivity. Feature sizes of 20-50 nm are achieved repeatably and controllably at writing rates up to 1 mm s. Line widths vary monotonically with the load up to 2000 nN. To demonstrate the capacity for sophisticated surface functionalisation provided by this strategy, we show that functionalization of nanolines with nitrilo triacetic acid enables site-specific immobilization of histidine-tagged green fluorescent protein. Density functional theory (DFT) calculations reveal that the key energetic barrier in the photo-deprotection reaction of the nitrophenyl protecting group is excitation of a π-π* transition (3.1 eV) an intramolecular charge-transfer mechanism. Under modest loading, compression of the adsorbate layer causes a decrease in the N-N separation, with the effect that this energy barrier can be reduced to as little as 1.2 eV. Thus, deprotection becomes possible either absorption of visible photons or phononic excitation transfer, facilitating fast nanolithography with a very small feature size.