Microscale Metal Patterning on Any Substrate: Exploring the Potential of Poly(dopamine) Films in High Resolution, High Contrast, Conformal Lithography

We have explored the potential of poly(dopamine) (PDA) thin films as versatile, high resolution conformal photoresists, using catalytic photoreduction of silver ions to micropattern the film. The combination of photosensitivity, biocompatibilty, and straightforward deposition under mild conditions into thin (∼45 nm) conformal coatings on nearly any material makes PDA films of interest in lithographic patterning on highly nonplanar geometries as well as on soft and biological materials where standard photoresists cannot be used. PDA and poly(norepinephrine) (PNE) films deposited with a standard autoxidation process were investigated along with PDA film deposited with a fast oxidation (FO) technique. Notably, we find that nonspecific deposition of silver off the lithographic pattern is strongly suppressed in PNE and nearly absent in FO-PDA films, which makes very high contrast lithography possible. We attribute this to a lower ratio of catechol to quinone moieties in these films compared to standard PDA films. PNE and FO-PDA films also exhibit smaller silver grain sizes (<40 nm) than standard PDA films, where grains are up to 200 nm in size. We demonstrate laser-scanning lithography patterns at 1.7 μm spatial resolution near the optical resolution limit of the experiment. Continuous silver films can readily be deposited on PDA, PNE, and FO-PDA with blue (<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mi>λ</mml:mi></mml:math> = 473 nm) and UV-A (375 nm) light, but not with green (515 nm) light. The UV light at lower intensities deposits silver several times faster than the blue light but also degrades the deposited silver at high light intensities. Silver films deposited in this way reach the percolation threshold at optical doses (at <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mi>λ</mml:mi></mml:math> = 473 nm) in the range of 10-50 kJ/cm², and SEM images of the films appear nearly pinhole free at comparable doses.