Solvent-assisted self-assembly of block copolymer thin films

Pula, Przemyslaw; Leniart, Arkadiusz; Majewski, Paweł

doi:10.1039/d2sm00439a

Cited by 17 publications

(14 citation statements)

References 288 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…A thorough understanding of solvent-induced effects on microdomain properties is crucial to control the performance of BCP-based polyelectrolytes , and separation membranes. − In addition, solvent-based treatment methods are widely employed to improve microdomain orientation in BCP films. − The solvent-induced swelling of BCP films has been investigated by monitoring their thickness using ellipsometry , and interferometry, their mass using a quartz crystal microbalance, microdomain spacing using scattering-based methods, − and their solvent content using infrared spectroscopy . Swelling-induced changes in surface morphology and solute permeability were shown using atomic force microscopy (AFM) , and fluorescence methods, ,, respectively.…”

Section: Introductionmentioning

confidence: 99%

Solvent-Induced Swelling Behaviors of Microphase-Separated Polystyrene-block-Poly(ethylene oxide) Thin Films Investigated Using In Situ Spectroscopic Ellipsometry and Single-Molecule Fluorescence Microscopy

et al. 2022

View full text Add to dashboard Cite

Block copolymers have attracted considerable interest in the fields of nanoscience and nanotechnology because these polymers afford well-defined nanostructures via self-assembly. An in-depth understanding of solvent effects on the physicochemical properties of these microdomains is crucial for their preparation and utilization. Herein, we employed in situ spectroscopic ellipsometry and single-molecule fluorescence techniques to gain detailed insights into microdomain properties in polystyrene-block-poly(ethylene oxide) (PS-b-PEO) films exposed to ethanol- and water-saturated N2. We observed a quick increase and a subsequent gradual decrease in the ellipsometric thickness of PS-b-PEO films upon exposure to ethanol-saturated N2. This observation was unexpected because ethanol-saturated N2 induced negligible thickness change for PS and PEO homopolymer films. The similarity in maximum thickness gain observed under ethanol- and water-saturated N2 implied the swelling of PEO microdomains. Ethanol vapor permeation through the PEO microdomains was supported by the redshift of the ensemble and single-molecule fluorescence emission of Nile red in PS-b-PEO films. Single-molecule tracking data showed the initial enhancement and subsequent reduction of the diffusion of hydrophilic sulforhodamine B molecules in PS-b-PEO films upon exposure to ethanol-saturated N2, consistent with the spectroscopic ellipsometry results. The higher ethanol susceptibility of the PEO microdomains was attributable to their amorphous nature, as shown by FTIR data.

show abstract

Section: Introductionmentioning

confidence: 99%

Solvent-Induced Swelling Behaviors of Microphase-Separated Polystyrene-block-Poly(ethylene oxide) Thin Films Investigated Using In Situ Spectroscopic Ellipsometry and Single-Molecule Fluorescence Microscopy

et al. 2022

View full text Add to dashboard Cite

show abstract

“…1−3 So far, the control on the orientations of phase separation in block copolymer thin films has been a critical issue. 4,5 Different approaches of alignment control and directed self-assembly have been investigated, and most studies employ prepatterned substrates to induce self-assembly. 6 For example, external electric fields have been applied to control the nanostructures of block copolymers on nanoscopic length scales.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Block copolymer self-assembly has received great interest for the potential of scalable nanopatterning and oriented structures in various applications, such as membranes, magnetic storage media, and semiconductor devices. − So far, the control on the orientations of phase separation in block copolymer thin films has been a critical issue. , Different approaches of alignment control and directed self-assembly have been investigated, and most studies employ prepatterned substrates to induce self-assembly . For example, external electric fields have been applied to control the nanostructures of block copolymers on nanoscopic length scales .…”

Section: Introductionmentioning

confidence: 99%

“…For example, external electric fields have been applied to control the nanostructures of block copolymers on nanoscopic length scales . Solvent-assisted directed self-assembly has also been studied because of the significant acceleration of ordering kinetics using solvents . E-beam lithography and optical lithography techniques have been widely used to prepare the guide templates in the directed self-assembly of block copolymer thin films .…”

Section: Introductionmentioning

confidence: 99%

“…7 Solventassisted directed self-assembly has also been studied because of the significant acceleration of ordering kinetics using solvents. 5 E-beam lithography and optical lithography techniques have been widely used to prepare the guide templates in the directed self-assembly of block copolymer thin films. 8 The additional processing of the prepatterned substrates, however, increases the complexity of the nanopatterning process, and the patterns are limited by the substrates.…”

Section: ■ Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Photoinduced Alignment under Solvent Vapor Annealing (PA-SVA): Enhanced Ordering and Patterning in Block Copolymer Films

Tseng

Fan

Chang

et al. 2022

ACS Appl. Polym. Mater.

View full text Add to dashboard Cite

In the past few decades, alignment control and directed self-assembly of block copolymer thin films have been widely investigated. Most approaches, however, require chemically or topographically prepatterned substrates, increasing the processing complexity. In this work, we present a facile strategy to form well-aligned block copolymer thin films by photoinduced alignment under solvent vapor annealing (PA-SVA) without chemically or topographically prepatterned substrates. Polystyrene-block-poly(ethylene oxide) (PS-b-PEO) consisting of two polymer blocks with distinct hydrophilicities and mechanical properties is incorporated with 4-butyl-4′-hydroxyazobenzene (4AzOH) to achieve the light-assisted self-assembly. Under solvent vapor annealing, the PS-b-PEO chains are swollen and possess mobilities. Upon polarized light irradiations, light-responsive azobenzene molecules undergo trans–cis–trans isomerization and achieve photoinduced alignment. The arrangement of the azobenzene molecules can further induce the alignment of the PS-b-PEO chains through supramolecular interactions between the phenol groups of the 4AzOH and the ether groups of the PEO chains. AFM-IR measurements are applied to characterize the selective blending of the 4AzOH molecules in the PEO segments. With different PA-SVA times, the transitions of the PS-b-PEO phase separation can be observed; the alignment of the PS-b-PEO/4AzOH films is further characterized by orientation analysis. The facile design of the PA-SVA strategy not only enables the manipulation of light-responsive molecules in block copolymer chains but also provides an alternative way for obtaining well-ordered block copolymer thin films.

show abstract

Dynamics of High Molecular Weight Cylindrical and Lamellar Block Copolymers with X‐ray Photon Correlation Spectroscopy

Taleb,

Blatt,

Signorini

et al. 2024

Macro Chemistry & Physics

View full text Add to dashboard Cite

The structure and dynamics of polystyrene‐b‐poly(ethylene oxide) (PS‐b‐PEO) block copolymers (BCPs) were studied. The BCPs exhibited microphase separated cylindrical and lamellar morphologies. Structural dynamics were measured with X‐ray photon correlation spectroscopy (XPCS) in the small‐angle regime. Morphologies and domain sizes were evaluated using small angle x‐ray scattering (SAXS), scanning electron microscopy, and atomic force microscopy. Different solvent processing conditions were investigated. Grain sizes evaluated using SAXS were found to depend on processing only for the rubbery majority BCP. The structural relaxation times were examined as a function of PS volume fraction, temperature, morphology, and structural sizes. Well above the glass transition temperature (Tg) of PS, all samples exhibited stretched autocorrelation decays and diffusive dynamics. Near Tg of PS the dynamics of all samples was anomalous with compressed autocorrelation decays and hyperdiffusive dynamics. This transition occurred at 153°C or 1.13Tg of PS. In the diffusive regime (at high temperature), structural relaxation times were dependent on the processing method. Near PS Tg (at low temperature), structural relaxation times scaled with the PS volume fraction. Structural relaxation times do not correlate with grain size, indicating that the out‐of‐equilibrium state of PS dominates structural dynamics of these strongly phase segregated BCPs.This article is protected by copyright. All rights reserved

show abstract

Solvent-assisted self-assembly of block copolymer thin films

Abstract: Solvent-assisted block copolymer self-assembly is a compelling method for processing and advancing practical applications of these materials due to the exceptional level of the control of BCP morphology and significant...

Cited by 17 publications

References 288 publications

Solvent-Induced Swelling Behaviors of Microphase-Separated Polystyrene-block-Poly(ethylene oxide) Thin Films Investigated Using In Situ Spectroscopic Ellipsometry and Single-Molecule Fluorescence Microscopy

Solvent-Induced Swelling Behaviors of Microphase-Separated Polystyrene-block-Poly(ethylene oxide) Thin Films Investigated Using In Situ Spectroscopic Ellipsometry and Single-Molecule Fluorescence Microscopy

Photoinduced Alignment under Solvent Vapor Annealing (PA-SVA): Enhanced Ordering and Patterning in Block Copolymer Films

Dynamics of High Molecular Weight Cylindrical and Lamellar Block Copolymers with X‐ray Photon Correlation Spectroscopy

Contact Info

Product

Resources

About