Enabling future nanomanufacturing through block copolymer self-assembly: A review

Cummins, Cian; Lundy, Ross; Walsh, James J.; Ponsinet, Virginie; Fleury, Guillaume; Morris, Michael A.

doi:10.1016/j.nantod.2020.100936

Cited by 169 publications

(129 citation statements)

References 325 publications

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“…Figure 4 a,b displays top-down SEM images of PLLA- b -PS BBCPs films after a brief oxygen plasma treatment, revealing well-defined dot and line-space patterns. The obtained porous PS film template are ideal to be used for pore-filling with a variety of ingredients such as metals or dielectrics for membranes, photonics, and catalysis applications [ 45 , 46 , 47 ].…”

Section: Resultsmentioning

confidence: 99%

Precise Synthesis and Thin Film Self-Assembly of PLLA-b-PS Bottlebrush Block Copolymers

Cummins

Fleury

2021

Molecules

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The ability of bottlebrush block copolymers (BBCPs) to self-assemble into ordered large periodic structures could greatly expand the scope of photonic and membrane technologies. In this paper, we describe a two-step synthesis of poly(l-lactide)-b-polystyrene (PLLA-b-PS) BBCPs and their rapid thin-film self-assembly. PLLA chains were grown from exo-5-norbornene-2-methanol via ring-opening polymerization (ROP) of l-lactide to produce norbornene-terminated PLLA. Norbonene-terminated PS was prepared using anionic polymerization followed by a termination reaction with exo-5-norbornene-2-carbonyl chloride. PLLA-b-PS BBCPs were prepared from these two norbornenyl macromonomers by a one-pot sequential ring opening metathesis polymerization (ROMP). PLLA-b-PS BBCPs thin-films exhibited cylindrical and lamellar morphologies depending on the relative block volume fractions, with domain sizes of 46–58 nm and periodicities of 70–102 nm. Additionally, nanoporous templates were produced by the selective etching of PLLA blocks from ordered structures. The findings described in this work provide further insight into the controlled synthesis of BBCPs leading to various possible morphologies for applications requiring large periodicities. Moreover, the rapid thin film patterning strategy demonstrated (>5 min) highlights the advantages of using PLLA-b-PS BBCP materials beyond their linear BCP analogues in terms of both dimensions achievable and reduced processing time.

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Section: Resultsmentioning

confidence: 99%

Precise Synthesis and Thin Film Self-Assembly of PLLA-b-PS Bottlebrush Block Copolymers

Cummins

Fleury

2021

Molecules

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“…However, the techno-economic model that underpins Moore’s law is beginning to fail due to the increased fabrication costs associated with transistors reaching atomic scales [ 3 ]. To address new miniaturisation challenges, developments in lithography should have sufficiently defined geometries, enable production of miniaturised features, be time efficient and have low production costs [ 4 , 5 , 6 , 7 ]. Bottom-up lithography techniques may offer an alternative fabrication route to conventional lithography that circumvents these challenges [ 7 , 8 , 9 , 10 ].…”

Section: Introductionmentioning

confidence: 99%

“…Production costs will also be reduced if the need for a photolithographic mask is circumvented [ 34 ]. It has been suggested that BCP and brush lithography provide rapid processing, scalable synthesis, and reduced production costs when compared to current lithographic techniques [ 4 , 36 ]. Currently less energy is required to power machinery for ASD and DSA deposition technologies.…”

Section: Introductionmentioning

confidence: 99%

Green Nanofabrication Opportunities in the Semiconductor Industry: A Life Cycle Perspective

Mullen

Morris

2021

Nanomaterials

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The turn of the 21st century heralded in the semiconductor age alongside the Anthropocene epoch, characterised by the ever-increasing human impact on the environment. The ecological consequences of semiconductor chip manufacturing are the most predominant within the electronics industry. This is due to current reliance upon large amounts of solvents, acids and gases that have numerous toxicological impacts. Management and assessment of hazardous chemicals is complicated by trade secrets and continual rapid change in the electronic manufacturing process. Of the many subprocesses involved in chip manufacturing, lithographic processes are of particular concern. Current developments in bottom-up lithography, such as directed self-assembly (DSA) of block copolymers (BCPs), are being considered as a next-generation technology for semiconductor chip production. These nanofabrication techniques present a novel opportunity for improving the sustainability of lithography by reducing the number of processing steps, energy and chemical waste products involved. At present, to the extent of our knowledge, there is no published life cycle assessment (LCA) evaluating the environmental impact of new bottom-up lithography versus conventional lithographic techniques. Quantification of this impact is central to verifying whether these new nanofabrication routes can replace conventional deposition techniques in industry as a more environmentally friendly option.

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“…3 The inherent ability of BCP thin films to define these nanoscale geometries has enabled the templating of materials for membrane, photonic, nanoeletronic, and biological applications amongst others. 4,5,6,7,8,9,10,11,12,13,14 Whilst BCPs typically constitute organic based blocks, an individual block can be selectively modified to produce inorganic nanofeatures through vapor, vacuum or solution based deposition processes. 15 This facet of BCP materials has led to the generation of nanofeatures including Fe3O4 nanodots for hydrogen peroxide sensing, 16 Au/Pt structures as memory devices, 17 WO3 nanowires as active device channels, 18 and TiO2 layers for perovskite solar cells.…”

Section: Introductionmentioning

confidence: 99%

Strategy for Enhancing Ultrahigh-Molecular-Weight Block Copolymer Chain Mobility to Access Large Period Sizes (>100 nm)

et al. 2020

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Assembling ultra-high molecular weight (UHMW) block copolymers (BCPs) in rapid timescales is perceived as a grand challenge in polymer science due to slow kinetics. Through surface engineering and identifying a non-volatile solvent (propylene glycol methyl ether acetate, PGMEA) we showcase the impressive ability of a series of lamellar poly(styrene)-block-poly(2-vinylpyridine) (PS-b-P2VP) BCPs to self-assemble directly after spin-coating. In particular, we show the formation of large period (≈ 111 nm) lamellar structures from a neat UHMW PS-b-P2VP BCP. The significant influence of solvent-polymer solubility parameters are explored to enhance polymer chain mobility. After optimization using solvent vapor annealing, increased feature order of ultra large period PS-b-P2VP BCP patterns in 1 hr is achieved. The methods described in this article center on industry compatible patterning schemes, solvents and deposition techniques. Isolated metallic and dielectric features are also demonstrated exemplifying the promise that large BCP periods offer for functional applications. Thus, our straightforward

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Enabling future nanomanufacturing through block copolymer self-assembly: A review

Cited by 169 publications

References 325 publications

Precise Synthesis and Thin Film Self-Assembly of PLLA-b-PS Bottlebrush Block Copolymers

Precise Synthesis and Thin Film Self-Assembly of PLLA-b-PS Bottlebrush Block Copolymers

Green Nanofabrication Opportunities in the Semiconductor Industry: A Life Cycle Perspective

Strategy for Enhancing Ultrahigh-Molecular-Weight Block Copolymer Chain Mobility to Access Large Period Sizes (>100 nm)

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