Strategy for Enhancing Ultrahigh-Molecular-Weight Block Copolymer Chain Mobility to Access Large Period Sizes (>100 nm)

Abstract

Assembling ultra-high molecular weight (UHMW) block copolymers (BCPs) in rapid timescales is perceived as a grand challenge in polymer science due to slow kinetics. Through surface engineering and identifying a non-volatile solvent (propylene glycol methyl ether acetate, PGMEA) we showcase the impressive ability of a series of lamellar poly(styrene)-block-poly(2-vinylpyridine) (PS-b-P2VP) BCPs to self-assemble directly after spin-coating. In particular, we show the formation of large period (≈ 111 nm) lamellar structures from a neat UHMW PS-b-P2VP BCP. The significant influence of solvent-polymer solubility parameters are explored to enhance polymer chain mobility. After optimization using solvent vapor annealing, increased feature order of ultra large period PS-b-P2VP BCP patterns in 1 hr is achieved. The methods described in this article center on industry compatible patterning schemes, solvents and deposition techniques. Isolated metallic and dielectric features are also demonstrated exemplifying the promise that large BCP periods offer for functional applications. Thus, our straightforward

Block Copolymer Directed Metamaterials and Metasurfaces for Novel Optical Devices

“…Moreover, this is a multifaceted concern requiring attention to BCP synthesis, film development and postinfiltration of metals/dielectrics. However, in the past 5 years, several encouraging reports have detailed BCP processes that move the field forward and ever closer to meeting fab grade compatibility, e.g., solvent vapor annealing, [294][295][296] selective material infiltration, [297,298] and defect characterization. [299,300]…”

Green Nanofabrication Opportunities in the Semiconductor Industry: A Life Cycle Perspective

“…Deposition of inorganic materials into polymer brush matrix or self-assembled nanodomains of BCPs can also be achieved using liquid deposition processes such as spin coating [ 11 , 18 , 130 , 131 ]. Other methods of metal inclusion are ALD and low temperature vapour phase deposition and sequential infiltration (SIS) [ 12 , 62 , 132 ].…”

“…Microphase separation produces self-assembled architectures [15]. Structural modulation by selection of molecular composition and weight [12,125]. Polymer brush's metal binning sites facilitate deposition of inorganic films [18].…”

“…This is achieved by allowing a film to be deposited in one region of a surface while simultaneously avoiding deposition in other regions to achieve ASD [ 11 ]. In the case of DSA, inorganic material infiltrates self-assembled molecular blocks forming patterns such as nanodot arrays or nanowires post-polymer removal [ 12 ]. It is the chemical incompatibility of the BCP blocks that enables self-assembly into a variety of morphologies [ 13 , 14 , 15 ].…”

Syndiospecific Polymerization of o-Methoxystyrene and Its Silyloxy or Fluorine-Substituted Derivatives by HNC-Ligated Scandium Catalysts: Synthesis of Ultrahigh-Molecular-Weight Functionalized Polymers

“…Syndiotactic poly­(polar styrene)­s, which have not only excellent properties of syndiotactic polystyrene ( s PSt) such as fast crystallization rate, chemical heat and solvent resistance, and good dielectric performance but also special properties of poly­(polar olefin)­s such as superior hydrophilicity, adhesion, printability, and compatibility with polyolefins, are much more promising semicrystalline engineering plastics having greater potential commercial application in high-durability parts, high-end medical materials, electronic and electrical appliances, auto parts, special fibers, packaging materials, coating industry, release agents, and lubricants. − Moreover, some alkoxyl, silyloxy, halogen, or amino-substituted syndiotactic poly­(polar styrene)­s might undergo postpolymerization functionalization to afford hydroxyl-substituted syndiotactic poly­(polar styrene)­s or other macromolecules with more special properties and applications. Furthermore, like proteins and nucleic acids, ultrahigh-molecular-weight syndiotactic poly­(polar styrene)­s (UHMW, number average molecular weight ( M n ≥ 10 6 )) will have more excellent chemical, biological, and mechanical properties such as high impact strength and distortion strength with wide and potential applications. − However, syndiotactic poly­(polar styrene)­s have not been prepared by traditional polymerization such as radical, cationic, or anionic polymerization for a long time. Then, half-sandwich titanium trialkyl or trichloride catalysts could promote the coordination polymerization of protected polar styrene (Scheme a).…”