Facile and Fast Interfacial Engineering Using a Frustrated Interfacial Self‐Assembly of Block Copolymers for Sub‐10‐nm Block Copolymer Nanopatterning

Abstract

A requisite for successful nanopatterning is a precise interface control to meet the adequate surface energies. In block copolymer (BCP) nanopatterning, the interfaces need to be neutralized, promoting both blocks to wet the substrate, and thus realizing the perpendicular orientation of BCPs. However, conventional methods for surface neutralization are expensive and require complex multi‐step processes, which hinders the application of BCP to continuous lithography processes. In this study, the simplest method for controlling the out‐of‐plane domain orientation using frustrated interfacial self‐assembly (FISA) of BCPs is introduced. The FISA layer is a randomly segregated structure that is readily created from the air/water interface. The FISA layer can be transferred to any target substrate, neutralizing both free and substrate interfaces. Employing FISA, the highly aligned and perpendicularly oriented sub‐10‐nm BCP patterns are produced with exceptional simplicity.

Scaling Laws for Block Copolymer Surface Micelles

“…The absence of the scaling relation for BCP surface micelles impedes advances toward potential applications, such as biomedical applications, 10 lithographic masks, 11 templates for nanomaterials, 12−15 functional polymer brushes, 16 and modifiers for interfacial energy. 17,18 Therefore, it is urgent to establish a scaling relation for BCP surface micelles.…”

“…While the scaling relation is considered as a principle governing the structure and dynamics of polymers, the scaling relation toward the BCP surface micelles has not been realized despite three decades of research progress on the surface micelle. The absence of the scaling relation for BCP surface micelles impedes advances toward potential applications, such as biomedical applications, lithographic masks, templates for nanomaterials, − functional polymer brushes, and modifiers for interfacial energy. , Therefore, it is urgent to establish a scaling relation for BCP surface micelles.…”

Constructing a Comprehensive Nanopattern Library through Morphological Transitions of Block Copolymer Surface Micelles via Direct Solvent Immersion

“…Au ions selectively adsorb to pyridyl units in the P2VP blocks when immersed in an Au ion solution. [64,65] When the Au ion-infiltrated surface micelles are etched by O 2 plasma, Au nanorings can be formed as BCPs are etched and the infiltrated ions are reduced. The morphology of the fabricated Au nanorings was observed by AFM in Figure 6b.…”

Modular Synthesis of Functional Block Copolymers by Thiol–Maleimide “Click” Chemistry for Porous Membrane Formation

“…9,10 Today, functional BCPs are produced in smaller quantities compared to typical commodities 11 but are gaining increasing interest, as they provide access to versatile properties by varying architecture and monomer composition. Possible applications range from high-end applications in the field of (electro)magnetic storage 12 to photonic materials, 13−16 lithography, 17 solar cells, 18,19 drug delivery, 20 membranes, 21,22 and many more. 5,23−26 Over the past two decades, more complex polymer architectures such as multiblock copolymers 27,28 and star or brush polymers 29,30 have been synthesized, and phase separation behavior of simple BCP architectures can easily be predicted due to a fundamental knowledge of the influence of various parameters, such as the degree of polymerization (DP n ), the block volume fraction ( f i ), and the monomer−monomer interaction characterized by the Flory−Huggins interaction parameter (χ i ) on the BCP self-assembly.…”

“…Since the advent of thermoplastic elastomer (TPE) applications in the 1960s, block copolymers (BCPs), which are composed of two or more polymer segments covalently bound to one another, have garnered increasing interest. − The unique capability of BCPs to undergo microphase separation − enables the access to an abundance of nanostructures including spheres, cylinders, lamellae, and co-continuous as well as porous structures. , Today, functional BCPs are produced in smaller quantities compared to typical commodities but are gaining increasing interest, as they provide access to versatile properties by varying architecture and monomer composition. Possible applications range from high-end applications in the field of (electro)­magnetic storage to photonic materials, − lithography, solar cells, , drug delivery, membranes, , and many more. ,− Over the past two decades, more complex polymer architectures such as multiblock copolymers , and star or brush polymers , have been synthesized, and phase separation behavior of simple BCP architectures can easily be predicted due to a fundamental knowledge of the influence of various parameters, such as the degree of polymerization (DP n ), the block volume fraction ( f i ), and the monomer–monomer interaction characterized by the Flory–Huggins interaction parameter (χ i ) on the BCP self-assembly. , The linear design is the simplest BCP architecture, and synthetic strategies to obtain them can be separated into chain growth polymerization, which is the most prevalent, and polycondensation. Harth et al described four methodologies for linear BCP synthesis .…”