Rapid Self-Assembly and Sequential Infiltration Synthesis of High χ Fluorine-Containing Block Copolymers

Cian Cummins; Daniele Mantione; Federico Cruciani; Guillaume Pino; Nils Demazy; Yulin Shi; Giuseppe Portale; Georges Hadziioannou; Guillaume Fleury

doi:10.1021/acs.macromol.0c01148

Rapid Self-Assembly and Sequential Infiltration Synthesis of High χ Fluorine-Containing Block Copolymers

Cian Cummins
, Daniele Mantione^*
, Federico Cruciani
, Guillaume Pino
, Nils Demazy
, Yulin Shi
, Giuseppe Portale
, Georges Hadziioannou
, Guillaume Fleury^*

^*Corresponding author for this work

Macromolecular Chemistry and New Polymeric Materials

Research output: Contribution to journal › Article › Academic › peer-review

18 Citations (Scopus)

280 Downloads (Pure)

Abstract

We leverage the attractive properties of a high χ-low N BCP, i.e., poly(styrene)-block-poly(2-fluoroethylmethyl acrylate) (PS-b-P2FEMA), and illustrate its utility for next-generation nanomanufacturing. The synthesis, physical characterization, and thin film self-assembly of a series of lamellar and cylindrical PS-b-P2FEMA BCPs are delineated. PS-b-P2FEMA BCPs with total molecular weights ranging from 7 to 22 kg mol-1 were synthesized by using reversible addition-fragmentation chain-transfer (RAFT) polymerization. Temperature-resolved small-angle X-ray scattering (SAXS) measurements revealed a large χ value (0.13 at 150 °C) for PS-b-P2FEMA. Solvothermal vapor annealing of PS-b-P2FEMA films produced highly oriented fingerprint patterns in as short as 60 s. Lamellar period sizes ranged from 25.9 down to 14.2 nm with feature sizes as small as 7 nm observed. We also demonstrate the integration feasibility of PS-b-P2FEMA BCPs through alumina hardmask formation using sequential infiltration synthesis. The highly favorable characteristics of the P2FEMA-based BCPs detailed here provide a versatile material option to the current library of available BCPs for sub-10 nm nanolithography.

Original language	English
Pages (from-to)	6246-6254
Number of pages	9
Journal	Macromolecules
Volume	53
Issue number	15
DOIs	https://doi.org/10.1021/acs.macromol.0c01148
Publication status	Published - 11-Aug-2020

Keywords

SUB-10 NM FEATURES
PATTERN TRANSFER
THIN-FILMS
METHACRYLATE)
ORIENTATION
STRATEGIES
POLYMERS
NANOFINS
DOMAINS

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Rapid Self-Assembly and Sequential Infiltration Synthesis of HighχFluorine-Containing Block CopolymersFinal publisher's version, 10.5 MBLicence: Taverne

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@article{edd66475185a4cd483d821670acbd236,

title = "Rapid Self-Assembly and Sequential Infiltration Synthesis of High χ Fluorine-Containing Block Copolymers",

abstract = "We leverage the attractive properties of a high χ-low N BCP, i.e., poly(styrene)-block-poly(2-fluoroethylmethyl acrylate) (PS-b-P2FEMA), and illustrate its utility for next-generation nanomanufacturing. The synthesis, physical characterization, and thin film self-assembly of a series of lamellar and cylindrical PS-b-P2FEMA BCPs are delineated. PS-b-P2FEMA BCPs with total molecular weights ranging from 7 to 22 kg mol-1 were synthesized by using reversible addition-fragmentation chain-transfer (RAFT) polymerization. Temperature-resolved small-angle X-ray scattering (SAXS) measurements revealed a large χ value (0.13 at 150 °C) for PS-b-P2FEMA. Solvothermal vapor annealing of PS-b-P2FEMA films produced highly oriented fingerprint patterns in as short as 60 s. Lamellar period sizes ranged from 25.9 down to 14.2 nm with feature sizes as small as 7 nm observed. We also demonstrate the integration feasibility of PS-b-P2FEMA BCPs through alumina hardmask formation using sequential infiltration synthesis. The highly favorable characteristics of the P2FEMA-based BCPs detailed here provide a versatile material option to the current library of available BCPs for sub-10 nm nanolithography. ",

keywords = "SUB-10 NM FEATURES, PATTERN TRANSFER, THIN-FILMS, METHACRYLATE), ORIENTATION, STRATEGIES, POLYMERS, NANOFINS, DOMAINS",

author = "Cian Cummins and Daniele Mantione and Federico Cruciani and Guillaume Pino and Nils Demazy and Yulin Shi and Giuseppe Portale and Georges Hadziioannou and Guillaume Fleury",

note = "Funding Information: The authors are sincerely grateful for financial support from the University of Bordeaux and the LabEx AMADEus (ANR-10-LABEX-0042-AMADEUS). The authors thank Ahmed Bentaleb (CRPP, University of Bordeaux) for SAXS assistance. The authors also thank the LCPO support staff—Aude Manson, Melanie Bousquet, Ellena Karnezis, and Gilles Pecastaings—for their endless everyday help. This work was performed within the framework of the Equipex ELORPrintTec ANR-10-EQPX-28-01 with the help of the French state{\textquoteright}s Initiative d{\textquoteright}Excellence IdEx ANR-10-IDEX-003-02. Publisher Copyright: Copyright {\textcopyright} 2020 American Chemical Society.",

year = "2020",

month = aug,

day = "11",

doi = "10.1021/acs.macromol.0c01148",

language = "English",

volume = "53",

pages = "6246--6254",

journal = "Macromolecules",

issn = "0024-9297",

publisher = "AMER CHEMICAL SOC",

number = "15",

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TY - JOUR

T1 - Rapid Self-Assembly and Sequential Infiltration Synthesis of High χ Fluorine-Containing Block Copolymers

AU - Cummins, Cian

AU - Mantione, Daniele

AU - Cruciani, Federico

AU - Pino, Guillaume

AU - Demazy, Nils

AU - Shi, Yulin

AU - Portale, Giuseppe

AU - Hadziioannou, Georges

AU - Fleury, Guillaume

N1 - Funding Information: The authors are sincerely grateful for financial support from the University of Bordeaux and the LabEx AMADEus (ANR-10-LABEX-0042-AMADEUS). The authors thank Ahmed Bentaleb (CRPP, University of Bordeaux) for SAXS assistance. The authors also thank the LCPO support staff—Aude Manson, Melanie Bousquet, Ellena Karnezis, and Gilles Pecastaings—for their endless everyday help. This work was performed within the framework of the Equipex ELORPrintTec ANR-10-EQPX-28-01 with the help of the French state’s Initiative d’Excellence IdEx ANR-10-IDEX-003-02. Publisher Copyright: Copyright © 2020 American Chemical Society.

PY - 2020/8/11

Y1 - 2020/8/11

N2 - We leverage the attractive properties of a high χ-low N BCP, i.e., poly(styrene)-block-poly(2-fluoroethylmethyl acrylate) (PS-b-P2FEMA), and illustrate its utility for next-generation nanomanufacturing. The synthesis, physical characterization, and thin film self-assembly of a series of lamellar and cylindrical PS-b-P2FEMA BCPs are delineated. PS-b-P2FEMA BCPs with total molecular weights ranging from 7 to 22 kg mol-1 were synthesized by using reversible addition-fragmentation chain-transfer (RAFT) polymerization. Temperature-resolved small-angle X-ray scattering (SAXS) measurements revealed a large χ value (0.13 at 150 °C) for PS-b-P2FEMA. Solvothermal vapor annealing of PS-b-P2FEMA films produced highly oriented fingerprint patterns in as short as 60 s. Lamellar period sizes ranged from 25.9 down to 14.2 nm with feature sizes as small as 7 nm observed. We also demonstrate the integration feasibility of PS-b-P2FEMA BCPs through alumina hardmask formation using sequential infiltration synthesis. The highly favorable characteristics of the P2FEMA-based BCPs detailed here provide a versatile material option to the current library of available BCPs for sub-10 nm nanolithography.

AB - We leverage the attractive properties of a high χ-low N BCP, i.e., poly(styrene)-block-poly(2-fluoroethylmethyl acrylate) (PS-b-P2FEMA), and illustrate its utility for next-generation nanomanufacturing. The synthesis, physical characterization, and thin film self-assembly of a series of lamellar and cylindrical PS-b-P2FEMA BCPs are delineated. PS-b-P2FEMA BCPs with total molecular weights ranging from 7 to 22 kg mol-1 were synthesized by using reversible addition-fragmentation chain-transfer (RAFT) polymerization. Temperature-resolved small-angle X-ray scattering (SAXS) measurements revealed a large χ value (0.13 at 150 °C) for PS-b-P2FEMA. Solvothermal vapor annealing of PS-b-P2FEMA films produced highly oriented fingerprint patterns in as short as 60 s. Lamellar period sizes ranged from 25.9 down to 14.2 nm with feature sizes as small as 7 nm observed. We also demonstrate the integration feasibility of PS-b-P2FEMA BCPs through alumina hardmask formation using sequential infiltration synthesis. The highly favorable characteristics of the P2FEMA-based BCPs detailed here provide a versatile material option to the current library of available BCPs for sub-10 nm nanolithography.

KW - SUB-10 NM FEATURES

KW - PATTERN TRANSFER

KW - THIN-FILMS

KW - METHACRYLATE)

KW - ORIENTATION

KW - STRATEGIES

KW - POLYMERS

KW - NANOFINS

KW - DOMAINS

U2 - 10.1021/acs.macromol.0c01148

DO - 10.1021/acs.macromol.0c01148

M3 - Article

SN - 0024-9297

VL - 53

SP - 6246

EP - 6254

JO - Macromolecules

JF - Macromolecules

IS - 15

ER -

Rapid Self-Assembly and Sequential Infiltration Synthesis of High χ Fluorine-Containing Block Copolymers

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Keywords

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