Directed self-assembly of PS-b-PMMA with ionic liquid addition

Chen, Xuanxuan; Seo, Takehito; Rincon-Delgadillo, Paulina; Matsumiya, Tasuku; Kawaue, Akiya; Maehashi, Takaya; Gronheid, Roel; Nealey, Paul F.

doi:10.1117/12.2220420

Cited by 4 publications

(7 citation statements)

References 13 publications

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“…The disadvantage of BCP self-assembly stands in the formation of defects [ 210 ]. Instead, directed self-assembly [ 211 ] uses various external stimuli (e.g., thermal annealing [ 197 , 199 , 209 , 212 , 213 , 214 ], solvent annealing [ 199 , 200 , 209 , 215 ], thermal and solvent annealing [ 199 ], ultrasounds [ 216 ], microwaves [ 217 ], magnetic fields [ 218 ], photoirradiation [ 219 ], shearing [ 220 ], addition of an ionic liquid [ 221 ], controlled spreading area [ 222 ], or epitaxy [ 210 , 223 ]) in order to induce and favor the self-assembly process. This process is also favored when employing click chemistry [ 214 ], and it displays a series of advantages: high-quality hierarchical [ 195 , 224 ] nanostructures exhibiting a low number of defects can be rapidly generated [ 195 , 213 ] over a large area [ 222 ].…”

Section: Bottom–up Lithographic Methodologiesmentioning

confidence: 99%

“…Resulting BCP-based structures, mainly lamellae and vertical/horizontal cylinders (depending on the length of each polymer block in the diblock or multiblock copolymer configuration), can undergo various etching processes that will selectively remove one of the polymer blocks, leaving behind various (empty) surface relief patterns. Examples include arrays of dots [ 202 ], hole-tilings [ 200 ] ( Figure 12 c), and curved/straight grooves [ 199 , 202 , 221 , 231 ] ( Figure 12 d).…”

Section: Bottom–up Lithographic Methodologiesmentioning

confidence: 99%

“…In the past years, BCPL was widely used in nanotechnological applications [ 200 , 208 , 211 , 217 ], including opto- [ 207 ] and microelectronics [ 228 ]. This method has proven itself to be a highly promising method, especially because it relies on a multitude of ordered structures obtained by directed and self-assembly such as parallel or perpendicularly oriented lamellar structures [ 26 , 219 , 221 , 225 , 226 , 228 , 229 ], (hexagonally packed) cylinders [ 26 , 199 , 217 ], semispherical [ 197 ] or body-centered cubic spherical structures [ 26 ], nanomesh structures [ 209 ], strand structures [ 222 ], double-gyroids [ 26 ], square, rectangular, and rhombic arrays of BCPs [ 220 ], quasi-hexagonal micellar structures [ 216 ], Archimedean tilings [ 200 ], and more [ 195 , 212 , 213 , 215 , 218 , 232 ]. Moreover, other more complex 2D [ 195 ] and hierarchical [ 195 ] or non-native [ 232 ] 3D BCP structures can be obtained via multiple self-assembly (because the fabrication of ordered structures requires an extremely precise control over ordering in BCP thin films [ 229 ], the latter can be further improved [ 216 , 218 ] inclusively through the use of chemical vapor deposition [ 201 ]).…”

Section: Bottom–up Lithographic Methodologiesmentioning

confidence: 99%

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Multifunctional Structured Platforms: From Patterning of Polymer-Based Films to Their Subsequent Filling with Various Nanomaterials

Handrea-Dragan

Botiz

2021

Polymers

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There is an astonishing number of optoelectronic, photonic, biological, sensing, or storage media devices, just to name a few, that rely on a variety of extraordinary periodic surface relief miniaturized patterns fabricated on polymer-covered rigid or flexible substrates. Even more extraordinary is that these surface relief patterns can be further filled, in a more or less ordered fashion, with various functional nanomaterials and thus can lead to the realization of more complex structured architectures. These architectures can serve as multifunctional platforms for the design and the development of a multitude of novel, better performing nanotechnological applications. In this work, we aim to provide an extensive overview on how multifunctional structured platforms can be fabricated by outlining not only the main polymer patterning methodologies but also by emphasizing various deposition methods that can guide different structures of functional nanomaterials into periodic surface relief patterns. Our aim is to provide the readers with a toolbox of the most suitable patterning and deposition methodologies that could be easily identified and further combined when the fabrication of novel structured platforms exhibiting interesting properties is targeted.

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Section: Bottom–up Lithographic Methodologiesmentioning

confidence: 99%

Section: Bottom–up Lithographic Methodologiesmentioning

confidence: 99%

Section: Bottom–up Lithographic Methodologiesmentioning

confidence: 99%

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Multifunctional Structured Platforms: From Patterning of Polymer-Based Films to Their Subsequent Filling with Various Nanomaterials

Handrea-Dragan

Botiz

2021

Polymers

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“…It is well known that IL is a good solvent for the PMMA domain and a poor solvent for the PS domain in PS-b-PMMA [5]. Hence IL blended into PS-b-PMMA is distributed to PMMA domain.…”

Section: Investigation Of L 0 Shrink Mechanismmentioning

confidence: 99%

“…To further enhance resolution, such as sub-10 nm features, increasing of Flory-Huggins interaction parameter (χ), which means repulsion between two blocks, are required. Many studies about ionic liquid (IL) additives into PS-b-PMMA have been reported to achieve increasing the χ parameter [3][4][5].…”

Section: Introductionmentioning

confidence: 99%

Ionic Liquid for Directed Self-Assembly of PS-<i>b</i>-PMMA

Kawaue

Matsumiya

Seo

et al. 2016

J. Photopol. Sci. Technol.

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The most widely studied block copolymer (BCP) for directed self-assembly (DSA) is poly(styrene-block-methyl methacrylate) (PS-b-PMMA). However PS-b-PMMA has a limitation of patterning size in sub-10 nm because the Flory-Huggins interaction parameter (χ) of PS-b-PMMA is approximately 0.038 at room temperature. To obtain sub-10 nm patterning size, many high χ BCPs and systems have been studied. We investigate DSA of PS-b-PMMA with blended an ionic liquid (IL) via thermal annealing with free surface under nitrogen. L0 becomes larger than pure BCP by adding ILs in this system since χ parameter becomes higher. However there is a problem that long time (>30 min) and/or high temperature (>200 °C) annealing conditions causes L 0 shrink than in mild annealing condition (200 °C /1 min). Here, we report IL design to prevent L 0 shrink. The design of IL that we found in this study achieved less than 5 % L 0 shrink at 215 °C for 30 min annealing.

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Enhanced etching resolution of self-assembled PS-b-PMMA block copolymer films by ionic liquid additives

Chen

Ren

et al. 2023

Nanotechnology

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Polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) is one of the most widely studied block copolymers for direct self-assembly because of its excellent compatibility with traditional processes. However, pattern transfer of PS-b-PMMA block copolymers (BCPs) remains a great challenge for its applications due to the insufficient etching resolution. In this study, the effect of ionic liquid (IL) 1-hexyl-3- methylimidazolium hexafluorophosphate (HMHF) additives on the line edge roughness (LER) performances of PS-b-PMMA self-assembled patterns was studied. Trace addition of HMHF kept the photolithography compatibility of PS-b-PMMA block copolymer films, but obviously increased their Flory- Huggins interaction parameter (χ) and enabled phase separation of disordered low molecular weight BCPs. LER value was effectively decreased by blending HMHF directly with PS-b-PMMA or from a supplying top layer of polyvinylpyrrolidone (PVP) containing HMHF additives. This study shows an excellent strategy to improve the deficiencies of existing block copolymers.

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Directed self-assembly of PS-b-PMMA with ionic liquid addition

Cited by 4 publications

References 13 publications

Multifunctional Structured Platforms: From Patterning of Polymer-Based Films to Their Subsequent Filling with Various Nanomaterials

Multifunctional Structured Platforms: From Patterning of Polymer-Based Films to Their Subsequent Filling with Various Nanomaterials

Ionic Liquid for Directed Self-Assembly of PS-<i>b</i>-PMMA

Enhanced etching resolution of self-assembled PS-b-PMMA block copolymer films by ionic liquid additives

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