Reduction of Line Edge Roughness of Polystyrene-<i>block</i>-Poly(methyl methacrylate) Copolymer Nanopatterns By Introducing Hydrogen Bonding at the Junction Point of Two Block Chains

Lee, Kyu Seong; Lee, Jae Yong; Kwak, Jongheon; Moon, Hong Chul; Kim, Jin Kon

doi:10.1021/acsami.6b15885

Cited by 25 publications

(21 citation statements)

References 52 publications

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“…The termination dependent surface resonances, however, are spread over a wider termination range. This remains true for gyroid metamaterials with levels of surface roughness on the order of typical block copolymer line edge roughnesses, [27,28] S12a of the Supporting Information.…”

Section: Resultsmentioning

confidence: 89%

Surface Structure Dependent Circular Dichroism in Single and Double Gyroid Metamaterials

Cote

Lenart

Ellison

et al. 2022

Advanced Optical Materials

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Optical properties of interest in gyroids include circular dichroism (CD), Kuhn's dissymmetry factor, [10] and polarizationselective reflection and transmission.3D, chiral metamaterials are often fabricated in complex and intensive processes such as two-photon direct laser writing or multilayer electron-beam lithography. [11,12] In contrast to these top down fabrication techniques, block copolymer self-assembly and templating holds promise for large scale gyroid fabrication, producing macroscale structures with subwavelength and tunable periodicities, typically on the order of 10 s of nanometers. [13,14] At specific composition windows, triblock copolymers self-assemble into an alternating gyroid structure, consisting of two single gyroid networks surrounded by a matrix. Plasmonic, single gyroid metamaterials can then be created through the selective removal of one of the network structures, followed by infilling with a plasmonic metal as depicted in Figure 1a. [15][16][17] The resonant behavior of these plasmonic structures can therefore be tuned by typical parameters for plasmonic structures, including the unit cell dimensions, infilling fraction, and refractive index contrast with the surrounding medium.Previous theoretical investigation into the resonant properties of single gyroid metamaterials found that they support chiral modes along the 〈100〉 and 〈111〉 families of directions. [18] Unfortunately, these modes were predicted to only support low levels of CD due to the connectivity of the screw axes within the single gyroid structure. More recently, however, there is experimental evidence that silver infilled single gyroid metamaterials exhibit strong circular dichroism in the visible and near-infrared (NIR). [19] This, combined with evidence that the linear dichroism observed in single gyroid metamaterials can be attributed to resonances on the gyroid's top surface, [20] suggests that surface resonances may also significantly contribute to a gyroid metamaterial's overall chiral optical response, in addition to the resonant interactions with the bulk that have been previously investigated. Many emerging applications of gyroid metamaterials will utilize thin films, which are naturally terminated with specific surface structures. This presents an opportunity for tuning the properties of gyroid metamaterials: as we show in this manuscript using finite-difference timedomain (FDTD) simulations, the surface orientation, thickness of the metamaterial, excitations on the front and rear surfaces, and surface defects all emerge as strategies to tune the optical Gyroid optical metamaterials consist of triply periodic chiral networks that are attractive photonic structures due to the combination of intriguing optical properties and spontaneous self-assembly-based fabrication routes using materials such as block copolymers. A previous experimental investigation found that gyroid metamaterials support strong circular dichroism, beyond what simulations only considering bulk interactions predict. In this work, simulations a...

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Section: Resultsmentioning

confidence: 89%

Surface Structure Dependent Circular Dichroism in Single and Double Gyroid Metamaterials

Cote

Lenart

Ellison

et al. 2022

Advanced Optical Materials

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“…In order to obtain inorganic nanostructure arrays at the sub‐5 nm scale, it is essential for pattern transfer processes such as plasma etching and SIS to proceed in a controlled fashion with high selectivity, and at defined positions within the self‐assembled building blocks. The key herein will be the preparation of well‐defined supramolecular architectures with a one‐to‐one registration of molecular components or reactive sites, and extremely sharp interfaces . LC materials are ideally suited to address these challenges because, besides the sub‐5 nm periodicities, control over the chemical functionality allows for site‐selective chemistry such as crosslinking, selective swelling, or complexation .…”

Section: Future Challenge Of Sub‐5 Nm Patterning Using Liquid Crystalsmentioning

confidence: 99%

Directed Self‐Assembly of Liquid‐Crystalline Molecular Building Blocks for Sub‐5 nm Nanopatterning

Nickmans

Schenning

2017

Advanced Materials

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The thin‐film directed self‐assembly of molecular building blocks into oriented nanostructure arrays enables next‐generation lithography at the sub‐5 nm scale. Currently, the fabrication of inorganic arrays from molecular building blocks is restricted by the limited long‐range order and orientation of the materials, as well as suitable methodologies for creating lithographic templates at sub‐5 nm dimensions. In recent years, higher‐order liquid crystals have emerged as functional thin films for organic electronics, nanoporous membranes, and templated synthesis, which provide opportunities for their use as lithographic templates. By choosing examples from these fields, recent progress toward the design of molecular building blocks is highlighted, with an emphasis on liquid crystals, to access sub‐5 nm features, their directed self‐assembly into oriented thin films, and, importantly, the fabrication of inorganic arrays. Finally, future challenges regarding sub‐5 nm patterning with liquid crystals are discussed.

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“…by promoting the phase separation between blocks, and by shifting the order-to-disorder transition in bulk systems to higher temperatures. [23][24][25][26][27] However, stimuli-responsive switchability of a functional moiety between blocks has not been explored in these applications.…”

Section: Introductionmentioning

confidence: 99%

Light-responsive block copolymers with a spiropyran located at the block junction

Apebende

Dubois

Bruns

2019

European Polymer Journal

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Block copolymers with a functional group between their blocks are relative little explored, even though this molecular architecture can reduce the aggregation of the functional groups, promote the phase separation in nanophase-separated materials, and have other interesting effects. Spiropyrans are wellknown for their ability to switch to their polar merocyanine form in response to light, force and other stimuli. The synthesis of stimuli-responsive AB-type block copolymers with spiropyran moieties located at the junction of the blocks is presented here. A homopolymer is synthesized from an indole-based atom transfer radical polymerization (ATRP) initiator, followed by its modification to a spiropyran endfunctionalized polymer. The spiropyran functionalized polymer is then used as a macro-initiator for the synthesis of a second polymer block by ring opening polymerization (ROP). Alternatively, spiropyran homopolymers are conjugated to other preformed polymers by esterification. The resulting block copolymers reversibly switch under UV and white light irradiation over multiple cycles, and a block copolymer reduced the tendency of the merocyanine to aggregate during switching. The stimuliresponsive block copolymer could be useful for a range of applications, e.g. for bioinspired polymersome nanoreactors, or in membranes with switchable permeability.

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Reduction of Line Edge Roughness of Polystyrene-block-Poly(methyl methacrylate) Copolymer Nanopatterns By Introducing Hydrogen Bonding at the Junction Point of Two Block Chains

Cited by 25 publications

References 52 publications

Surface Structure Dependent Circular Dichroism in Single and Double Gyroid Metamaterials

Surface Structure Dependent Circular Dichroism in Single and Double Gyroid Metamaterials

Directed Self‐Assembly of Liquid‐Crystalline Molecular Building Blocks for Sub‐5 nm Nanopatterning

Light-responsive block copolymers with a spiropyran located at the block junction

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