Consequences of surface neutralization in diblock copolymer thin films

Sangwon Kim; Christopher M. Bates; Anthony Thio; Julia D. Cushen; Christopher J. Ellison; C. Grant Willson; Frank S. Bates

doi:10.1021/nn403616r

Consequences of surface neutralization in diblock copolymer thin films

Sangwon Kim, Christopher M. Bates, Anthony Thio, Julia D. Cushen, Christopher J. Ellison, C. Grant Willson, Frank S. Bates

Chemical Engineering and Materials Science

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56 Scopus citations

Abstract

Two high-χ block copolymers, lamella-forming poly(styrene-block- [isoprene-random-epoxyisoprene]) (PS-PEI78, with 78 mol % epoxidation) and lamella-forming poly(4-trimethylsilylstyrene-block-d,l-lactide) (PTMSS-PLA), were used to study three combinations of interfacial neutrality involving at least one neutral interface. PS-PEI78 annealed on a nonpreferential polymer mat (SMG) produced perpendicular lamellae independent of film thickness, indicating a neutral substrate and neutral free surface. In contrast, the presence of only one neutral interface results in the formation of surface topography ("islands" and "holes") with 0.5L₀ step heights. PS-PEI78 (neutral free surface) annealed on PS brush (PS block preferential) forms "half" islands and holes. The inverse experiment, PTMSS-PLA (with a PTMSS preferential free surface) annealed on a neutral (or near neutral) substrate surface, also generates 0.5L₀ topography. These "half" island and hole structures are stable to extended thermal annealing. PS-PEI78 exposes both blocks at the free surface in contrast to PTMSS-PLA, which exposes just one. All three combinations of interfacial neutrality are explained by the precise balancing of the wetting tendencies of the two blocks. Evolution of the 0.5L₀ motifs appears to be facilitated by a preference to form half-period thick nuclei in the initial stages of morphological development.

Original language	English (US)
Pages (from-to)	9905-9919
Number of pages	15
Journal	ACS Nano
Volume	7
Issue number	11
DOIs	https://doi.org/10.1021/nn403616r
State	Published - Nov 26 2013

Keywords

0.5 L
block copolymer
holes
islands
step height
thickness quantization
thin film interfaces

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title = "Consequences of surface neutralization in diblock copolymer thin films",

abstract = "Two high-χ block copolymers, lamella-forming poly(styrene-block- [isoprene-random-epoxyisoprene]) (PS-PEI78, with 78 mol % epoxidation) and lamella-forming poly(4-trimethylsilylstyrene-block-d,l-lactide) (PTMSS-PLA), were used to study three combinations of interfacial neutrality involving at least one neutral interface. PS-PEI78 annealed on a nonpreferential polymer mat (SMG) produced perpendicular lamellae independent of film thickness, indicating a neutral substrate and neutral free surface. In contrast, the presence of only one neutral interface results in the formation of surface topography ({"}islands{"} and {"}holes{"}) with 0.5L0 step heights. PS-PEI78 (neutral free surface) annealed on PS brush (PS block preferential) forms {"}half{"} islands and holes. The inverse experiment, PTMSS-PLA (with a PTMSS preferential free surface) annealed on a neutral (or near neutral) substrate surface, also generates 0.5L0 topography. These {"}half{"} island and hole structures are stable to extended thermal annealing. PS-PEI78 exposes both blocks at the free surface in contrast to PTMSS-PLA, which exposes just one. All three combinations of interfacial neutrality are explained by the precise balancing of the wetting tendencies of the two blocks. Evolution of the 0.5L0 motifs appears to be facilitated by a preference to form half-period thick nuclei in the initial stages of morphological development.",

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AU - Bates, Christopher M.

AU - Thio, Anthony

AU - Cushen, Julia D.

AU - Ellison, Christopher J.

AU - Willson, C. Grant

AU - Bates, Frank S.

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N2 - Two high-χ block copolymers, lamella-forming poly(styrene-block- [isoprene-random-epoxyisoprene]) (PS-PEI78, with 78 mol % epoxidation) and lamella-forming poly(4-trimethylsilylstyrene-block-d,l-lactide) (PTMSS-PLA), were used to study three combinations of interfacial neutrality involving at least one neutral interface. PS-PEI78 annealed on a nonpreferential polymer mat (SMG) produced perpendicular lamellae independent of film thickness, indicating a neutral substrate and neutral free surface. In contrast, the presence of only one neutral interface results in the formation of surface topography ("islands" and "holes") with 0.5L0 step heights. PS-PEI78 (neutral free surface) annealed on PS brush (PS block preferential) forms "half" islands and holes. The inverse experiment, PTMSS-PLA (with a PTMSS preferential free surface) annealed on a neutral (or near neutral) substrate surface, also generates 0.5L0 topography. These "half" island and hole structures are stable to extended thermal annealing. PS-PEI78 exposes both blocks at the free surface in contrast to PTMSS-PLA, which exposes just one. All three combinations of interfacial neutrality are explained by the precise balancing of the wetting tendencies of the two blocks. Evolution of the 0.5L0 motifs appears to be facilitated by a preference to form half-period thick nuclei in the initial stages of morphological development.

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KW - 0.5 L

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KW - islands

KW - step height

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ER -

Consequences of surface neutralization in diblock copolymer thin films

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