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Comprehensive surface structuring and interfacial chemical composition of porous honeycomb films: hierarchical self-assembly of a pH-sensitive amphiphilic block copolymer
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DOI：10.1016/j.surfin.2026.109374.png)
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Abstract
En 中文
Amphiphilic block copolymers possess the intrinsic ability to self-assemble into highly ordered honeycomb-patterned surfaces via the Breath Figure imprinting, based on water droplet condensation. In this study, we present a methodological investigation to explore the characteristics, structural arrangement, and chemical distribution of a specific block copolymer (BCP), Polystyrene-b-Poly(4-vinylpyridine) (PS-b-P4VP). We integrate various analytical and surface analysis techniques to establish a comprehensive understanding of the block copolymer's hierarchical self-assembly and interfacial chemical composition, resulting from the combination of the block copolymer's spontaneous nano-segregation with the Breath Figure process. The Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM) techniques provide information on surface morphology, including surface roughness, pore dimensions, and film thickness. The Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) technique is used to investigate the interfacial distribution of functional groups at the interface between the bulk material and the air in the pores, through high-resolution 2D and 3D imaging. The sensitivity of this technique for collecting spectral signatures from the low fraction of the P4VP block and its functional end groups is demonstrated. Indeed, the TOF-SIMS analysis reveals enhanced ion emission from honeycomb (HC) films compared to flat references, suggesting preferential interfacial localization of P4VP chains. Depth profiling confirms the vertical homogeneity of the architecture, while lateral variations in signal intensity indicate a subtle chemical or topological gradient across the pore structure. These findings suggest that the HC architecture may promote the localized enrichment or exclusion of specific functional groups, depending on their position within the microstructure. The results also demonstrate that coupling surface-sensitive imaging and depth-profiling techniques provides valuable insight into the influence of confinement on block copolymer organization, paving the way for the design of responsive or site-selective polymer-based materials, such as sensors, selective adsorbents, and nanostructured coatings.
Keywords:
Honeycomb structure
Block copolymers
Self-assembly
Surface chemistry
Breath figures imprint
Chemical imaging
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