Spatial control of the orientation of block copolymers (BCPs) in thin films offers enormous opportunities for practical nanolithography applications. In this study, we demonstrate the use of a substrate comprised of poly(4-acetoxystyrene) to spatially control interfacial interactions and block copolymer orientation over different length scales. Upon UV irradiation poly(4-acetoxystyrene) undergoes a photo-Fries rearrangement yielding phenolic groups available for further functionalization. The wetting behaviour of PS--PMMA deposited on the poly(4-acetoxystyrene) films could be precisely controlled through controlling the UV irradiation dose. After exposure, and a mild post-exposure treatment, the substrate switches from asymmetric, to neutral and then to symmetric wetting. Upon exposure through photomasks, a range of high fidelity micro-patterns consisting of perpendicularly oriented lamellar microdomains were generated. Furthermore, the resolution of chemically patterned poly(4-acetoxystyrene) substrate could be further narrowed to submicrometer scale using electron beam lithography. When the BCP was annealed on an e-beam modified poly(4-acetoxystyrene) surface, the interface between domains of parallel and perpendicular orientation of the BCPs was well defined, especially when compared with the substrates patterned using the photomask.
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http://dx.doi.org/10.1039/c9na00095j | DOI Listing |
Angew Chem Int Ed Engl
January 2025
Chang Chun Institute of Applied Chemistry Chinese Academy of Sciences, Key Laboratory of Polymer Ecomaterials, 5625 Renmin Street, Changchun, , 130022, Changchun, CHINA.
Living cationic polymerization (LCP) is a classical technique for precision polymer synthesis; however, due to the high sensitivity of cationic active species towards chain-transfer/termination events, it is notoriously difficult to control polymerization under mild conditions, which inhibits its progress in advanced materials engineering. Here, we unlock a practical anion-binding catalytic strategy to address the historical dilemma in LCP. Our experimental and mechanistic studies demonstrate that commercially accessible hexafluoroisopropanol (HFIP), when used in high loading, can create higher-order HFIP aggregates to tame dormant-active species equilibrium via non-covalent anion-binding principle, in turn inducing distinctive polymerization kinetics behaviors that grant efficient chain propagation while minimizing competitive side reactions.
View Article and Find Full Text PDFBiomater Sci
January 2025
Zhejiang Key Laboratory of Smart BioMaterials, and College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310058, China.
Accurate imaging of tumor hypoxia is critical for early cancer diagnosis and clinical outcomes, highlighting the great need for its detection specificity and sensitivity. In this report, we propose a probe (HTRNP) that simultaneously has hypoxia-targeting and hypoxia-responsive capabilities to enhance the tumor hypoxia imaging efficiency. HTRNP was successfully prepared through the encapsulation of Pt(II)-tetrakis(pentafluorophenyl)porphyrin (PtPFPP), which exhibits hypoxia-dependent phosphorescence, within the amphiphilic block copolymer OPDMA-PF, which has hypoxia-targeting tertiary amine -oxide moieties and hydrophobic perfluorobenzene ring structures, which highly improved the loading content and water solubility of PtPFPP.
View Article and Find Full Text PDFMacromol Rapid Commun
January 2025
Chimie ParisTech, CNRS, Institut de Recherche de Chimie Paris, PSL University, Paris, 75005, France.
The development of catalysts that are both robust and highly active at room temperature can often be seen as a major challenge in anionic polymerization. However, these properties are desirable for polymer synthesis because they allow for easy and sustainable production of interesting materials. Here, iron and magnesium complexes are used to form in situ generated metalate complexes that are shown to be highly active in the room temperature copolymerization of methyl methacrylate and lactide.
View Article and Find Full Text PDFChemistry
January 2025
Beijing Institute of Technology, Polymer Materials, 5 Zhongguancun Nandajie, 100081, Beijing, CHINA.
The self-assembly of block copolymers (BCPs) to form nanostructures of various morphologies and controllable dimensions has been a very promising research area in nanotechnology in recent decades. This review mainly summarizes the recent advances in precise and controllable self-assembly of BCPs through a tailored nucleation-growth strategy to modulate the self-assembly behavior of the BCPs. These efforts have led to a better understanding of the self-assembly mechanisms and opened new possibilities for creating novel materials with designable properties.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China.
While synthesizing circular polymers with telechelic polyolefin building blocks recently emerged as a promising strategy for addressing conventional polyethylenes' sustainability challenges, the lack of telechelic PP (PP) with sufficient difunctional purity for polycondensation has been limiting the development of circular polypropylenes with PP-like structures and properties. Here we described a combined approach of coordinative chain transfer polymerization and transition-metal-catalyzed quenching reaction with various acyl chlorides, affording PPs with a high difunctional ratio (up to ∼99%) and broad end functional group scope. The steric effect of polymeryl-Zn species and the role of Pd catalyst were revealed by DFT.
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