Pathways to Mesoporous Resin/Carbon Thin Films with Alternating Gyroid Morphology

Zhang, Qi; Matsuoka, Fumiaki; Suh, Hyo Seon; Beaucage, Peter A.; Xiong, Shenglin; Smilgies, Detlef‐M.; Tan, Kwan Wee; Werner, Jörg G.; Nealey, Paul F.; Wiesner, Ulrich

doi:10.1021/acsnano.7b06436

Cited by 39 publications

(69 citation statements)

References 56 publications

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“…In this work, we used grazing‐incidence small‐angle X‐ray scattering (GISAXS) to study the kinetics and thermodynamics of a linear, alternating gyroid‐forming ISO triblock terpolymer during SVA. GISAXS is the most direct means to study block copolymer morphologies in situ during SVA, allowing the simultaneous characterization of both in‐ and out‐of‐plane electron density correlations over macroscopically large areas in real time . We annealed ISO terpolymer films in the mixed vapors of tetrahydrofuran (THF) and methanol of various compositions, and identified the degree of in‐ and out‐of‐plane order of the resulting gyroid morphology upon varying the maximum solvent concentration and solvent removal rate.…”

Section: Introductionmentioning

confidence: 99%

Controlling Self‐Assembly in Gyroid Terpolymer Films By Solvent Vapor Annealing

Dolan

Korzeb

Dehmel

et al. 2018

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The efficacy with which solvent vapor annealing (SVA) can control block copolymer self-assembly has so far been demonstrated primarily for the simplest class of copolymer, the linear diblock copolymer. Adding a third distinct block-thereby creating a triblock terpolymer-not only provides convenient access to complex continuous network morphologies, particularly the gyroid phases, but also opens up a route toward the fabrication of novel nanoscale devices such as optical metamaterials. Such applications, however, require the generation of well-ordered 3D continuous networks, which in turn requires a detailed understanding of the SVA process in terpolymer network morphologies. Here, in situ grazing-incidence small-angle X-ray scattering (GISAXS) is employed to study the self-assembly of a gyroid-forming triblock terpolymer during SVA, revealing the effects of several key SVA parameters on the morphology, lateral order, and, in particular, its preservation in the dried film. The robustness of the terpolymer gyroid morphology is a key requirement for successful SVA, allowing the exploration of annealing parameters which may enable the generation of films with long-range order, e.g., for optical metamaterial applications.

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Section: Introductionmentioning

confidence: 99%

Controlling Self‐Assembly in Gyroid Terpolymer Films By Solvent Vapor Annealing

Dolan

Korzeb

Dehmel

et al. 2018

Small

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“…Previous attempts to produce asingle gyroid structure were based on replication from butterflyw ings, [9] lithography [10] and templating. [11] The alternatingd ouble network gyroid wasf ound in narrow compositionr anges of multiblock copolymer blends, [11, 12] leading to structures in the > 100 nm range in allc ases.T he new concept reportedh erein providesat ailoredw ay to fabricate chiral structures withm uch smaller sub-10 nm periodicities, which are of great potential in nano-templating and as enantiospecific membranes for use in enantiomer separation.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.org/10.…”

mentioning

confidence: 99%

Chirality Induction through Nano‐Phase Separation: Alternating Network Gyroid Phase by Thermotropic Self‐Assembly of X‐Shaped Bolapolyphiles

et al. 2020

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The single gyroid phase as well as the alternating double network gyroid, composed of two alternating single gyroid networks,hold asignificant place in ordered nanoscale morphologies for their potential applications as photonic crystals,m etamaterials and templates for porous ceramics and metals.Here,wereport the first alternating network cubic liquid crystals.T hey form through self-assembly of X-shaped polyphiles,w here glycerol-capped terphenyl rods lie on the gyroid surface while semiperfluorinated and aliphatic sidechains fill their respective separate channel networks.This new self-assembly mode can be considered as at wo-color symmetry-broken double gyroid morphology,p roviding at ailored way to fabricate novel chiral structures with sub-10 nm periodicities using achiral compounds.New routes to chirality from initially achiral systems are of particular contemporary interest for obtaining chiral templates in asymmetric synthesis and catalysis. [1] This is important for the use in different fields of material-and nanoscience [2] as well as for the understanding of fundamental principles of the emergence of biological homochirality. [3] Creating chirality in liquids and liquid crystals (LCs), having no fixed positions of individual molecules,i se specially challenging. [4,5] Nevertheless,i tw as recently achieved by mirror symmetry breaking through synchronization and locking-in of transient chiral conformations and configuration. [6] Here we report anew approach to spontaneous generation of chirality based on nano-phase segregation. In the reported case,b reaking the inherent mirror symmetry of the double gyroid cubic phase (Ia " 3d,Q230), known from lyotropic [7] and thermotropic liquid crystals (LCs) [8] (Figure 1a), is achieved by self-assembly of X-shaped polyphilic molecules with two different chains at opposite sides of ar od-like molecular core. [8b] Thecores organize along the gyroid minimal surface, forming aw all that separates the two enantiomeric infinite networks involving these chains.N ano-phase separation of the two poorly compatible semiperfluorinated and aliphatic side-chains,i nto their own networks (blue and red in Figure 1b), gives rise to agyroid cubic phase with two chemically non-equal networks (the "single gyroid" I4 1 32, Q214). This structure has broken mirror symmetry and represents the first alternating network gyroid cubic LC,a nd the first LC with chirality solely based on phase separation. Previous attempts to produce asingle gyroid structure were based on replication from butterflyw ings, [9] lithography [10] and templating. [11] The alternatingd ouble network gyroid wasf ound in narrow compositionr anges of multiblock copolymer blends, [11, 12] leading to structures in the > 100 nm range in allc ases.T he new concept reportedh erein providesat ailoredw ay to fabricate chiral structures withm uch smaller sub-10 nm periodicities, which are of great potential in nano-templating and as enantiospecific membranes for use in enantiomer separation.Supportinginformation and the O...

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“…This structure has broken mirror symmetry and represents the first alternating network gyroid cubic LC, and the first LC with chirality solely based on phase separation. Previous attempts to produce a single gyroid structure were based on replication from butterfly wings, lithography and templating . The alternating double network gyroid was found in narrow composition ranges of multiblock copolymer blends, leading to structures in the >100 nm range in all cases.…”

Section: Figurementioning

confidence: 99%

“…Previous attempts to produce a single gyroid structure were based on replication from butterfly wings, lithography and templating . The alternating double network gyroid was found in narrow composition ranges of multiblock copolymer blends, leading to structures in the >100 nm range in all cases. The new concept reported herein provides a tailored way to fabricate chiral structures with much smaller sub‐10 nm periodicities, which are of great potential in nano‐templating and as enantiospecific membranes for use in enantiomer separation.…”

Section: Figurementioning

confidence: 99%