Massively Parallel Patterning of Complex 2D and 3D Functional Polymer Brushes by Polymer Pen Lithography

Abstract

We report the first demonstration of centimeter-area serial patterning of complex 2D and 3D functional polymer brushes by high-throughput polymer pen lithography. Arbitrary 2D and 3D structures of poly(glycidyl methacrylate) (PGMA) brushes are fabricated over areas as large as 2 cm × 1 cm, with a remarkable throughput being 3 orders of magnitudes higher than the state-of-the-arts. Patterned PGMA brushes are further employed as resist for fabricating Au micro/nanostructures and hard molds for the subsequent replica molding of soft stamps. On the other hand, these 2D and 3D PGMA brushes are also utilized as robust and versatile platforms for the immobilization of bioactive molecules to form 2D and 3D patterned DNA oligonucleotide and protein chips. Therefore, this low-cost, yet high-throughput "bench-top" serial fabrication method can be readily applied to a wide range of fields including micro/nanofabrication, optics and electronics, smart surfaces, and biorelated studies.

Arbitrary and Parallel Nanofabrication of 3D Metal Structures with Polymer Brush Resists

“…Subsequently, polymer brushes were grown by surface‐initiated atom transfer radical polymerization (SI‐ATRP). Due to the steric effect, polymer chains at high surface‐density areas were taller than those at low surface‐density areas, resulting in the formation of 3D polymer brushes . Finally, the 3D polymer brushes were used as resists to form 3D Au structures by cycles of alternative plasma etching of the polymer and wet etching of Au, in which the lateral geometry was defined by poly(methyl methacrylate) (PMMA) brushes and height of each step was controlled by the etching conditions.…”

“…It should be noted that polymer brushes can be patterned with many other high‐throughput tools such as photolithography, nanocontact printing, polymer pen lithography, and beam pen lithography on a wide variety of metal substrates . Therefore, in principle, the 3D fabrication strategy developed here should be applicable to different kinds of metals and can be scaled up to meet the application specifications in micro‐/nanofabrication, chemical sensors, optical and electrical devices, and biomedical fields in the future.…”

Apertureless Cantilever-Free Pen Arrays for Scanning Photochemical Printing

“…In addition, continuous lines were also made by writing dot patterns with pitches smaller than the size corresponding to an individual dot (Figure S3). These patterning results suggest that the apertureless elastomer pens can be used for a variety of micro‐ and nanofabrication tasks and combinatorial screening of functional nanomaterials, soft matter, or biological processes …”

Large‐Area Patterning of Metal Nanostructures by Dip‐Pen Nanodisplacement Lithography for Optical Applications

“…However, because fabrication relies on a scanning electron beam that operates in vacuum, EBL is very expensive and time‐consuming, even when making millimeter‐size samples. In recent years, tip‐based lithography with scanning probes, namely, scanning probe lithography (SPL), has emerged as an alternative maskless strategy to EBL for nanofabrication . SPL makes use of a scanning probe to deliver or subtract materials on a surface with sub‐100 nm resolution.…”

“…In recent years, tip-based lithography with scanning probes, namely, scanning probe lithography (SPL), has emerged as an alternative maskless strategy to EBL for nanofabrication. [12][13][14][15][16][17][18][19][20][21][22][23] SPL makes use of a scanning probe to deliver or subtract materials on a surface with sub-100 nm resolution. When performed under ambient conditions, certain SPL techniques are lower in cost than EBL, and they can be used to fabricate a wider variety of structures.…”