Electrochemical Manipulation of Aligned Block Copolymer Templates

Abstract

Block copolymers have a wide range of functions in advanced electrochemistry because of their ability to self‐assemble into ordered nanometer‐sized structures, resulting in their extensive usage as nanoporous templates that can be electrochemically manipulated. These highly ordered nanoporous templates are used as working electrodes for electrodeposition and electropolymerization to build nanoelectrode arrays and can serve as models to study the diffusion pathway of redox‐active units with regard to chemical modification of pores. The block copolymer system allows different morphologies to be utilized, but the most exploited structures are standing cylinders of the minority block that are etched to expose highly aligned porous nanoelectrode array templates. This review starts with introducing alumina and track‐etched membranes as pioneer porous templates transitioning to the production of block copolymer films as succeeding templates, with a particular focus on both poly(styrene)‐block‐poly(methylmethacrylate) (PS‐b‐PMMA) and poly(styrene)‐block‐poly(lactide) (PS‐b‐PLA). The aim is to give fundamental insights of electrochemistry where functionality extends beyond to applications in the nanoscience field of biosensors and plastic electronics.

Multifunctional Structured Platforms: From Patterning of Polymer-Based Films to Their Subsequent Filling with Various Nanomaterials

“…Examples of etching procedures include UV ozone [ 243 ], oxygen [ 241 , 243 ], nitrogen [ 241 ], or other types [ 239 , 241 ] of plasma etching, CO 2 and Cl 2 /O 2 reactive ion etching [ 205 ], etching in alkaline solutions [ 204 ]), etc. As a result, BCP templates made from materials such as poly(cyclohexylethylene)- b -poly(lactide) [ 242 ], polystyrene- b -poly(2-vinyl pyridine) [ 233 , 245 ], polystyrene- b -polymethyl methacrylate [ 238 , 246 ], polystyrene- b -polydimethylsiloxane [ 239 , 247 , 248 ], or others [ 205 ] lead to the fabrication of a large variety of versatile surface relief patterns of different material nature. Examples include (metal) nanodots [ 240 , 249 , 250 ], bimetallic NP arrays [ 251 ], perovskite cylinders, lamellae or cylindrical mesh [ 245 ], 2D metal/silicon nanowires [ 206 , 249 ], metal oxide arrays [ 242 ] of nanorods [ 244 ] or nanorings [ 243 ], and more [ 205 , 252 ].…”

“…Once the polymer matrix is removed from the Pt-infiltrated BCP thin films by etching, various conductive Pt structures can be obtained [ 233 ] ( Figure 12 g). Of course, all patterns transferred with the above methods can further be employed in various applications in nanoengineering [ 246 , 249 , 251 , 252 ], quantum technology [ 247 ], or optoelectronics [ 237 ] in order, for example, to manufacture high-performance tribological generators [ 252 ], transistor circuitry [ 206 ], masks for lithographic purpose [ 206 , 253 ], photonic nanostructures [ 240 , 248 ], etc.…”

Photopatterning of Azobenzene‐Containing Liquid Crystalline Triblock Copolymers: Light‐Induced Anisotropy and Photostabilization

“…[8] In the PLCBCs, the result of the light action is the orientation of the block containing photochromes, which opens up interesting possibilities for tuning the optical properties of PLCBCs films for application in optics and optoelectronics. [28][29][30][31][32] It is important…”

“…[24][25][26]33] Due to the advancement of polymer synthetic strategies and techniques including controlled living polymerization with facile post-polymerization -functionalization, a variety of block copolymers with precisely controlled molecular weight and welldefined macromolecular architectures can be prepared. [32][33][34] The covalently linked triple block copolymers are now well recognized and used as an innovation strategy of molecular-based functional materials with a new molecular architecture. At the same time, a combination of covalently and hydrogen bonded fragments in the triple LC block copolymers ( Figure 1d) opens a new supramolecular approach for design and creation of new types of functional LC polymers.…”

Synthesis and Self-Assembly of Conjugated Block Copolymers

“…One of the most remarkable and fascinating features of BCPs is that they can self-assemble into different ordered micro/nano structures both in bulk and in solutions, which makes them good candidates for practical or potential applications at various areas, such as biomaterials, biomedicine, porous materials, nanolithography, organic electronics, etc. [ 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 ]. The self-assembly of BCPs in bulk has been extensively studied since 1960s, and the experimental and theoretical knowledge is well established [ 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 ].…”