Hierarchical Self-Assembled Structures from POSS-Containing Block Copolymers Synthesized by Living Anionic Polymerization

Hirai, Tomoyasu; Leolukman, Melvina; Jin, Seunghun; Goseki, Raita; Ishida, Yasuhiro; Kakimoto, Masa Aki; Hayakawa, Teruaki; Ree, Moonhor; Gopalan, Padma

doi:10.1021/ma9018944

Cited by 165 publications

(186 citation statements)

References 31 publications

Supporting

Mentioning

174

Contrasting

Unclassified

Order By: Relevance

“…In general, the SFE gap is crucial in nanofabrication, as perpendicular orientation control can be difficult, with the PDMS block exhibiting a lower SFE and tending to segregate easily to the top surface of the thin film. Other Si-containing BCPs have the potential to form sub-10 nm features [18][19][20][21], however they also exhibit drawbacks relating to orientation control.…”

Section: Introductionmentioning

confidence: 99%

Perpendicularly Oriented Cylinders of Si-containing Block Copolymers by Atmospheric Thermal Annealing

Seshimo¹,

Odashima

Maeda

et al. 2016

J. Photopol. Sci. Technol.

Self Cite

View full text Add to dashboard Cite

The directed self-assembly (DSA) of block copolymers (BCPs) can realize as one of candidates for next generation lithography. The BCPs for DSA should exhibit a high resolution, an ability to form perpendicularly oriented domains in the thin film by thermal annealing under mild condition, and a high etching selectivity. Here, we report a new Si-containing BCPs targeted to form perpendicularly oriented cylinders in thin films. The hydroxyl groups in the side chains introduced in the Si-containing block provide a good surface free energy (SFE) balance leading to the perpendicular orientation. Furthermore, this orientation can be completed in only one minute atmospheric thermal annealing at 150 °C. Oxygen plasma etching for the thin films results in the achievement of hexagonally packed cylinders.

show abstract

Section: Introductionmentioning

confidence: 99%

Perpendicularly Oriented Cylinders of Si-containing Block Copolymers by Atmospheric Thermal Annealing

Seshimo¹,

Odashima

Maeda

et al. 2016

J. Photopol. Sci. Technol.

Self Cite

View full text Add to dashboard Cite

show abstract

“…We have reported the development and study of a series of silicon-containing PMAPOSS-based BCPs. [22][23][24][25][26] These polymers can self assemble with much smaller periodic features (X10 nm) because they exhibit strongly segregating microphases. A high etch contrast can also be achieved between the polymer domains.…”

Section: Introductionmentioning

confidence: 99%

“…In our previous study, we attempted to control the phase morphology and long-range ordering of the microphase-separated nanostructures of a series of POSS-containing BCPs. [22][23][24][25][26][27] The solvent annealing strongly affected the growth and reformation of the assemblies in the as-cast thin films of PS-b-PMAPOSS and PMMA-b-PMAPOSS, resulting in long-range ordered arrays of dots and lines. However, a long duration of annealing, from several minutes to hours, was necessary.…”

Section: Introductionmentioning

confidence: 99%

Rapid and reversible morphology control in thin films of poly(ethylene oxide)-block-POSS-containing poly(methacrylate)

Goseki

Hirai

Ishida

et al. 2012

Polym J

Self Cite

View full text Add to dashboard Cite

Here we report rapid control of the morphology of a polyhedral oligomeric silsesquioxane (POSS)-containing block copolymer (PEO 143 -b-PMAPOSS 12 ), which is composed of poly(ethylene oxide) (PEO) and POSS-containing poly(methacrylate), (PMAPOSS), between ordered arrays of dots and lines for several tens of seconds by a combination of thermal annealing and solvent annealing. The PEO 143 -b-PMAPOSS 12 was synthesized by atom transfer radical polymerization of POSS methacrylate by using a macroinitiator of PEO. An ordered array of dots was obtained by thermal annealing for the as-spun cast thin film at 90 1C for 60 s. The resultant ordered dots were quickly converted to lines by solvent annealing with chloroform vapor at room temperature for 120 s. The lines were converted back to dots by thermal annealing under the same conditions (90 1C, 60 s) without any changes to the initial diameter, d-spacing or thickness. We also demonstrated the simple and rapid formation of a hexagonally packed array of dots by spin casting onto a trench-patterned silicon wafer under chloroform vapor. Under thermal and solvent annealing conditions, reversibility and a high degree of ordering in the phase morphology of PEO 143 -b-PMAPOSS 12 are distinctive properties that can be attributed to highly mobile polymer chains. Polymer Journal (2012) 44, 658-664; doi:10.1038/pj.2012.67; published online 18 April 2012Keywords: annealing; block copolymer; polyethylene oxide (PEO); polyhedral oligomeric silsesquioxane (POSS); self-assembly; thin film INTRODUCTIONThe self-assembly of thin films from block copolymers (BCPs) has attracted a considerable research interest because of the potential applications to plasmonic waveguides, magnetic logic gates, magnetic data storage and microelectronic devices. 1-7 Block copolymer lithography (BCPL) is a promising next generation lithographic technique that could be used for high-throughput and large-area nanolithography; BCPL utilizes the self-assembled nanostructures that form by microphase separation of BCP in thin films. [8][9][10][11][12] The vast majority of research on self-assembling polymers for BCPL has been devoted to polystyrene-block-poly(methyl methacrylate) because the PMMA block can be selectively removed by ultraviolet or oxygen plasma exposure. 13-15 Despite significant progress, controlling the orientation and long-range ordering of the microphase-separated nanodomains in the thin films remains a formidable technological challenge in terms of feature sizes. It is difficult to form features with a full pitch size o20 nm with most BCPs because of their small FloryHuggins interaction parameter. Silicon-containing BCPs, such as poly(styrene-block-dimethylsiloxane) (PS-b-PDMS), [16][17][18] PS-blockpoly(ferrocenylsilane) [19][20][21] and PMMA-block-polyhedral oligomeric silsesquioxane (POSS)-containing poly(methacrylate), (PMMA-b-

show abstract

“…One proposed pathway without using the prepatterned substrates to less time-consuming and simpler patterning objectives involves utilizing multifunctional block copolymer resist materials. We have recently reported a new series of silicon-containing block copolymers based on polyhedral oligomeric silsesquioxane (POSS)-containing poly(methacrylate) (PMAPOSS) [11][12][13][14][15]. PMAPOSS-based block copolymers can self assemble with small periodic features with a full pitch around 10 nm and the resulting phase morphologies can be reversibly controlled with a long-range order by solvent and/or thermal annealing.…”

Section: Introductionmentioning

confidence: 99%

Selective Area Morphology Control of Self-Assembled Patterns using Silsesquioxane-containing Block Copolymers

Ushiro

Mikami

Sato

et al. 2012

J. Photopol. Sci. Technol.

Self Cite

View full text Add to dashboard Cite

Hierarchical Self-Assembled Structures from POSS-Containing Block Copolymers Synthesized by Living Anionic Polymerization

Cited by 165 publications

References 31 publications

Perpendicularly Oriented Cylinders of Si-containing Block Copolymers by Atmospheric Thermal Annealing

Perpendicularly Oriented Cylinders of Si-containing Block Copolymers by Atmospheric Thermal Annealing

Rapid and reversible morphology control in thin films of poly(ethylene oxide)-block-POSS-containing poly(methacrylate)

Selective Area Morphology Control of Self-Assembled Patterns using Silsesquioxane-containing Block Copolymers

Contact Info

Product

Resources

About