Dataset Information

Segregation of Maghemite Nanoparticles within Symmetric Diblock Copolymer and Triblock Terpolymer Patterns under Solvent Vapor Annealing.

ABSTRACT: Block copolymers (BCPs), through their self-assembly, provide an excellent guiding platform for precise controlled localization of maghemite nanoparticles (MNPs). Diblock copolymers (di/BCP) represent the most applied matrix to host filler components due to their morphological simplicity. A series of nanocomposites based on diblock copolymer or triblock terpolymer matrices and magnetic nanoparticles were prepared to study and compare the influence of an additional block into the BCP matrix. MNPs were grafted with low molecular weight polystyrene (PS) chains in order to be segregated in a specific phase of the matrix to induce selective localization. After the mixing of the BCPs with 10% w/v PS-g-MNPs, nanocomposite thin films were formed by spin coating. Solvent vapor annealing (SVA) enabled the PS-g-MNPs selective placement within the PS domains of the BCPs, as revealed by atomic force microscopy (AFM). The recorded images have proven that high amounts of functionalized MNPs can be controllably localized within the same block (PS), despite the architecture of the BCPs (AB vs. ABC). The adopted lamellar structure of the "neat" BCP thin films was maintained for MNPs loading approximately up to 10% w/v, while, for higher content, the BCP adopted lamellar morphology is partially disrupted, or even disappears for both AB and ABC architectures.

SUBMITTER: Zapsas G

PROVIDER: S-EPMC7142801 | biostudies-literature | 2020 Mar

REPOSITORIES: biostudies-literature

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Publications

Segregation of Maghemite Nanoparticles within Symmetric Diblock Copolymer and Triblock Terpolymer Patterns under Solvent Vapor Annealing.

Zapsas George G Moschovas Dimitrios D Ntetsikas Konstantinos K Karydis-Messinis Andreas A Chalmpes Nikolaos N Kouloumpis Antonios A Gournis Dimitrios D Zafeiropoulos Nikolaos E NE Avgeropoulos Apostolos A

Materials (Basel, Switzerland) 20200312 6

Block copolymers (BCPs), through their self-assembly, provide an excellent guiding platform for precise controlled localization of maghemite nanoparticles (MNPs). Diblock copolymers (di/BCP) represent the most applied matrix to host filler components due to their morphological simplicity. A series of nanocomposites based on diblock copolymer or triblock terpolymer matrices and magnetic nanoparticles were prepared to study and compare the influence of an additional block into the BCP matrix. MNPs ...[more]

PMID: 32178427

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Project description:The self-assembly of ultra-high molecular weight (UHMW) block copolymers (BCPs) remains a complex and time-consuming endeavor owing to the high kinetic penalties associated with long polymer chain entanglement. In this work, we report a unique strategy of overcoming these kinetic barriers through precision solvent annealing of an UHMW polystyrene-block-poly(2-vinylpyridine) BCP system (M w: ∼800 kg/mol) by fast swelling to very high levels of solvent concentration (ϕs). Phase separation on timescales of ∼10 min is demonstrated once a thickness-dependent threshold ϕs value of ∼0.80-0.86 is achieved, resulting in lamellar feature spacings of over 190 nm. The threshold ϕs value was found to be greater for films with higher dry thickness (D 0) values. Tunability of the domain morphology is achieved through controlled variation of both D 0 and ϕs, with the kinetically unstable hexagonal perforated lamellar (HPL) phase observed at ϕs values of ∼0.67 and D 0 values of 59-110 nm. This HPL phase can be controllably induced into an order-order transition to a lamellar morphology upon further increase of ϕs to 0.80 or above. As confirmed by grazing-incidence small-angle X-ray scattering, the lateral ordering of the lamellar domains is shown to improve with increasing ϕs up to a maximum value at which the films transition to a disordered state. Thicker films are shown to possess a higher maximum ϕs value before transitioning to a disordered state. The swelling rate is shown to moderately influence the lateral ordering of the phase-separated structures, while the amount of hold time at a particular value of ϕs does not notably enhance the phase separation process. These large period self-assembled lamellar domains are then employed to facilitate pattern transfer using a liquid-phase infiltration method, followed by plasma etching, generating ordered, high aspect ratio Si nanowall structures with spacings of ∼190 nm and heights of up to ∼500 nm. This work underpins the feasibility of a room-temperature, solvent-based annealing approach for the reliable and scalable fabrication of sub-wavelength nanostructures via BCP lithography.

Dataset Information

Segregation of Maghemite Nanoparticles within Symmetric Diblock Copolymer and Triblock Terpolymer Patterns under Solvent Vapor Annealing.

Publications

Segregation of Maghemite Nanoparticles within Symmetric Diblock Copolymer and Triblock Terpolymer Patterns under Solvent Vapor Annealing.

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