• Journal of the Korean Vacuum Society
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• v.19 no.2
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• pp.81-90
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• 2010

We introduce a novel and versatile approach for preparing self-assembled nanoporous multilayered films with antireflective properties. Protonated polystyrene-block-poly (4-vinylpyrine) (PS-b-P4VP) and anionic polystyrene-block-poly (acrylic acid) (PS-b-PAA) block copolymer micelles (BCM) were used as building blocks for the layer-by-layer assembly of BCM multilayer films. BCM film growth is governed by electrostatic and hydrogen-bonding interactions between the oppositely BCMs. Both film porosity and film thickness are dependent upon the charge density of the micelles, with the porosity of the film controlled by the solution pH and the molecular weight (Mw) of the constituents. PS7K-b-P4VP28K/PS2K-b-PAA8K films prepared at pH 4 (for PS7K-b-P4VP28K) and pH 6 (for PS2K-b-PAA8K) are highly nanoporous and antireflective. In contrast, PS7K-b-P4VP28K/PS2K-b-PAA8K films assembled at pH 4/4 show a relatively dense surface morphology due to the decreased charge density of PS2K-b-PAA8K. Films formed from BCMs with increased PS block and decreased hydrophilic block (P4VP or PAA) size (e.g., PS36K-b-P4VP12K/PS16K-b-PAA4K at pH 4/4) were also nanoporous. Furthermore, we demonstrate that the nanostructured electrochemical sensors based on patterning methods show the electrochemical activities. Anionic poly(styrene sulfonate) (PSS) layers were selectively and uniformly deposited onto the catalase (CAT)-coated surface using the micro-contact printing method. The pH-induced charge reversal of catalase can provide the selective deposition of consecutive PE multilayers onto patterned PSS layers by causing the electrostatic repulsion between next PE layer and catalase. Based on this patterning method, the hybrid patterned multilayers composed of platinum nanoparticles (PtNP) and catalase were prepared and then their electrochemical properties were investigated from sensing $H_2O_2$ and NO gas. This study was based on the papers reported by our group. (J. Am. Chem. Soc. 128, 9935 (2006); Adv. Mater. 19, 4364 (2007); Electro. Mater. Lett. 3, 163 (2007)).