Synthesis and Characterization of Block Copolymers for Nanolithography Based on Thiol-Ene 'Click' Functionalized Polystyrene-Block-Polybutadiene

Hongbo Feng; Moshe Dolejsi; Ning ZhuPhilip J. GriffinGordon S. W. CraigWen ChenStuart J. RowanPaul F. Nealey

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Synthesis and Characterization of Block Copolymers for Nanolithography Based on Thiol-Ene 'Click' Functionalized Polystyrene-Block-Polybutadiene

机译：Synthesis and Characterization of Block Copolymers for Nanolithography Based on Thiol-Ene 'Click' Functionalized Polystyrene-Block-Polybutadiene

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In developing block copolymers (BCPs) for nanolithography, the preferredmaterials and processes are BCPs that can be thermally annealed with a freesurface to yield perpendicularly orientated nanodomains with specific featuresizes and morphologies. Thiol-ene “click” chemistry is used to modify asingle parent polystyrene-block-poly(1,2-butadiene) (PS-b-PB) to create bothcylinder- and lamellae-forming A-block-(B-random-C) BCPs with differentFlory–Huggins parameters (χs) while maintaining an equal surface energy(γ, Δγ = 0) between the blocks, necessary to form perpendicular nanodomainsby thermal annealing with a free surface. The use of BCPs with an A-block-(B-random-C) architecture effectively decouples the covarying properties ofχ and Δγ. The effects of the size of the thiol and degree of thiol functionalization(?) on χ, morphology, and Δγ of the blocks are investigated for fourdifferent thiols. Modification of PS-b-PB with methyl thioglycolate or 2-(Bocamino)ethanethiol creates BCPs that form cylinders, whereas modificationwith smaller thiols, mercaptoethanol or 1-thioglycerol, retains the lamellarmorphology of the parent PS-b-PB. Cross-linking of the double bonds in PB atannealing temperatures prevents directed self-assembly (DSA) of these BCPs,but by adding a radical scavenger, butylated hydroxytoluene, the cross-linkingcan be suppressed, enabling DSA.

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《Advanced functional materials》 |2022年第46期|2206836.1-2206836.11|共11页
作者
Hongbo Feng; Moshe Dolejsi; Ning ZhuPhilip J. GriffinGordon S. W. CraigWen ChenStuart J. RowanPaul F. Nealey;
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Pritzker School of Molecular EngineeringUniversity of Chicago5640 S. Ellis Avenue, Chicago, IL 60637, USA;

Pritzker School of Molecular EngineeringUniversity of Chicago5640 S. Ellis Avenue, Chicago, IL 60637, USA;

Department of ChemistryUniversity of Chicago5735 S Ellis Avenue, Chicago, IL 60637, USA;

Pritzker School of Molecular EngineeringUniversity of Chicago5640 S. Ellis Avenue, Chicago, IL 60637, USA;

College of Biotechnology and Pharmaceutical EngineeringNanjing Tech University30 S Puzhu Road, Nanjing 211800, China;

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block copolymers; click chemistry; directed self-assemblies; equal surface energy; Flory–Huggins interaction parameter; high throughput approaches;

Synthesis and Characterization of Block Copolymers for Nanolithography Based on Thiol-Ene 'Click' Functionalized Polystyrene-Block-Polybutadiene

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