Controlled Ordering of Block Copolymer Thin Films by the Addition of Hydrophilic Nanoparticles

Park, Sung Chan; Kim, Bumjoon J.; Hawker, Craig J.; Krämer, Edward J.; Bang, Joona; Ha, Jeong Sook

doi:10.1021/ma071442z

Cited by 73 publications

(84 citation statements)

References 33 publications

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“…41 A similar conclusion can be drawn from a report of the induction of the formation of oriented PMMA cylinders of a PS-b-PMMA block copolymer perpendicular to the film plane by adding PEO-coated Au nanoparticles to a solution that was processed by directional solvent evaporation under high-humidity conditions. 42 At low humidity, or at any humidity in the absence of the PEO-coated Au nanoparticles, no orientation and poor order were observed.…”

Section: Introductionmentioning

confidence: 97%

Square Packing and Structural Arrangement of ABC Triblock Copolymer Spheres in Thin Films

et al. 2008

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Nanoporous thin films were prepared from poly(ethylene oxide)-b-poly(methyl methacrylate)-bpolystyrene (PEO-b-PMMA-b-PS) ABC triblock copolymer by solvent annealing under high relative humidity followed by UV degradation and acid washing. Ordered half-spheres at the surface that template ordering of spheres below the surface in thin films were formed as a result of the interaction between the hydrophilic PEO segments and water vapor during processing. The spherical block copolymer domains exhibit complex packing behavior on the surface and in the interior. A half-sphere "monolayer" and a half-sphere plus whole sphere "bilayer" were formed in thin films with thicknesses of 43 and 71 nm, respectively, and have hexagonal lattice symmetry. For half-sphere plus two whole sphere "trilayers" with a nominal thickness of 117 nm, coexistence of regions of hexagonal and square packing was observed by transmission electron microscopy, scanning force microscopy, scanning electron microscopy, and grazing-incidence small-angle X-ray scattering. Square packing was consistent with a surface-truncated unit cell of a body-centered cubic lattice with the (100) plane parallel to the surface.

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Section: Introductionmentioning

confidence: 97%

Square Packing and Structural Arrangement of ABC Triblock Copolymer Spheres in Thin Films

et al. 2008

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“…29 From this observation, it was suggested that the ordering mechanism in this system is similar to PEO-based copolymers where the PMMA-PEO blend mimics the behavior of the pure PEO systems. A key factor is the interaction between the hydrophilic components (PEO blocks or Au-PEO nanoparticles) and water vapor during the solvent annealing process.…”

Section: Introductionmentioning

confidence: 76%

“…29 Because of the miscibility between PEO and PMMA, the Au-PEO nanoparticles were selectively positioned within the PMMA cylindrical microdomains. During solvent annealing under high humidity conditions ($90%), the preferential interaction of the PEO nanoparticles with water vapor induces the perpendicular orientation of PMMA microdomains.…”

Section: Resultsmentioning

confidence: 99%

“…The films were transferred to a home-built glovebox chamber, and then annealed under saturated benzene environment and controlled humidity conditions, for at least 12 h. The detailed experimental set up and conditions for solvent annealing process have been described elsewhere. [29][30][31] The relative humidity (RH) within the chamber was maintained at $90%. After solvent annealing, the film morphologies were characterized by scanning electron microscope (SEM) (Hitachi S-4300 SE) operating at 15 keV.…”

Section: Thin Film Preparation/characterizationmentioning

confidence: 99%

“…A key factor is the interaction between the hydrophilic components (PEO blocks or Au-PEO nanoparticles) and water vapor during the solvent annealing process. [29][30][31] In this work, we further analyze and simplify the use of surfactant-mediated selfassembly and examine other hydrophilic PEO additives, such as linear and star PEO, to examine the effect of molecular weight and chain architecture on the ordering of PSt-b-PMMA block copolymer thin films. This approach offers important advantages over the previous systems.…”

Section: Introductionmentioning

confidence: 99%

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Highly ordered nanoporous thin films by blending of PSt‐b‐PMMA block copolymers and PEO additives as structure directing agents

Park

Jung

Fukukawa

et al. 2008

J. Polym. Sci. A Polym. Chem.

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Herein, we present a simple method for producing nanoporous templates with a high degree of lateral ordering by self-assembly of block copolymers. A key feature of this approach is control of the orientation of polymeric microdomains through the use of hydrophilic additives as structure directing agents. Incorporation of hydrophilic poly(ethylene oxide) (PEO) moieties into poly(styrene-b-methyl methacrylate) (PSt-b-PMMA) diblock copolymers gives vertical alignment of PMMA cylinders on the substrate after solvent annealing. Because of the miscibility between PEO and PMMA, PEO additives were selectively positioned within PMMA microdomains and by controlling the processing conditions, it was found that ordering of PSt-b-PMMA diblock copolymers could be achieved. The perpendicular orientation of PMMA cylinders was achieved by increasing the molecular size of the PEO additives leading to an increased hydrophilicity of the PMMA domains and consequently to control the orientation of microdomains in PSt-b-PMMA block copolymer thin films. V V C 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: [8041][8042][8043][8044][8045][8046][8047][8048] 2008

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A Comprehensive Approach to the Alignment and Ordering of Block Copolymer Morphologies

Lazzari

Rosa

2009

Advanced Nanomaterials

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Controlled Ordering of Block Copolymer Thin Films by the Addition of Hydrophilic Nanoparticles

Cited by 73 publications

References 33 publications

Square Packing and Structural Arrangement of ABC Triblock Copolymer Spheres in Thin Films

Square Packing and Structural Arrangement of ABC Triblock Copolymer Spheres in Thin Films

Highly ordered nanoporous thin films by blending of PSt‐b‐PMMA block copolymers and PEO additives as structure directing agents

A Comprehensive Approach to the Alignment and Ordering of Block Copolymer Morphologies

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