Tunable and rapid self-assembly of block copolymers using mixed solvent vapors

Park, Woon Ik; Tong, Sheng; Liu, Yuzi; Jung, Il Woong; Roelofs, Andreas; Hong, Seungbum

doi:10.1039/C4NR04726E

Tunable and rapid self-assembly of block copolymers using mixed solvent vapors

Journal Article · Wed Nov 05 23:00:00 EST 2014 · Nanoscale

DOI:https://doi.org/10.1039/C4NR04726E· OSTI ID:1357472

Park, Woon Ik ^[1]; Tong, Sheng ^[2]; Liu, Yuzi ^[2]; Jung, Il Woong ^[2]; Roelofs, Andreas ^[2]; Hong, Seungbum ^[1]

Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
Argonne National Lab. (ANL), Argonne, IL (United States). Nanoscience and Technology Division

Pattern generation of well-controlled block copolymers (BCPs) with a high Flory–Huggins interaction parameter (χ) is important for applications in sub-20 nm nanolithography. In this paper, we used mixed solvents of dimethylformamide (DMF) and toluene to control the morphology as well as the time to achieve the targeted morphology via self-assembly of BCPs. By precisely controlling the volume ratio of DMF and toluene, well-ordered line, honeycomb, circular hole, and lamellar nanostructures were obtained from a cylinder-forming poly(styrene-b-2-vinylpyridine) (PS-b-P2VP) BCP with high χ. Furthermore, a well-aligned 12 nm line pattern was successfully achieved in the guiding template within one minute using the mixed solvents. Finally, this practical method may also be applicable to self-assembly of other BCPs, providing more opportunities for the next-generation sub-10 nm lithography applications.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1357472

Journal Information:: Nanoscale, Journal Name: Nanoscale Journal Issue: 24 Vol. 6; ISSN 2040-3364

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (41)

Graphoepitaxy of Spherical Domain Block Copolymer Films Segalman, R. A.; Yokoyama, H.; Kramer, E. J. Advanced Materials, Vol. 13, Issue 15, p. 1152-1155 https://doi.org/10.1002/1521-4095(200108)13:15<1152::AID-ADMA1152>3.0.CO;2-5	journal	August 2001
Solvent-Vapor-Induced Tunability of Self-Assembled Block Copolymer Patterns Jung, Yeon Sik; Ross, Caroline A. Advanced Materials, Vol. 21, Issue 24 https://doi.org/10.1002/adma.200802855	journal	June 2009
Three-Dimensional Nanofabrication by Block Copolymer Self-Assembly Ross, Caroline A.; Berggren, Karl K.; Cheng, Joy Y. Advanced Materials, Vol. 26, Issue 25 https://doi.org/10.1002/adma.201400386	journal	April 2014
Directed Self-Assembly with Sub-100 Degrees Celsius Processing Temperature, Sub-10 Nanometer Resolution, and Sub-1 Minute Assembly Time Park, Woon Ik; Kim, Kyungho; Jang, Hyun-Ik Small, Vol. 8, Issue 24 https://doi.org/10.1002/smll.201201407	journal	September 2012
Block copolymers and conventional lithography Stoykovich, Mark P.; Nealey, Paul F. Materials Today, Vol. 9, Issue 9, p. 20-29 https://doi.org/10.1016/S1369-7021(06)71619-4	journal	September 2006
Directed self-assembly of block copolymers for next generation nanolithography Jeong, Seong-Jun; Kim, Ju Young; Kim, Bong Hoon Materials Today, Vol. 16, Issue 12 https://doi.org/10.1016/j.mattod.2013.11.002	journal	December 2013
Sub-10 nm Feature Size PS- b -PDMS Block Copolymer Structures Fabricated by a Microwave-Assisted Solvothermal Process Borah, Dipu; Shaw, Matthew T.; Holmes, Justin D. ACS Applied Materials & Interfaces, Vol. 5, Issue 6 https://doi.org/10.1021/am302830w	journal	March 2013
Defect-Free Nanoporous Thin Films from ABC Triblock Copolymers Bang, Joona; Kim, Seung Hyun; Drockenmuller, Eric Journal of the American Chemical Society, Vol. 128, Issue 23 https://doi.org/10.1021/ja0608141	journal	June 2006
Temperature Dependence of Order, Disorder, and Defects in Laterally Confined Diblock Copolymer Cylinder Monolayers Hammond, Matthew R.; Cochran, Eric; Fredrickson, Glenn H. Macromolecules, Vol. 38, Issue 15 https://doi.org/10.1021/ma050479l	journal	July 2005
Hierarchical Self-Assembled Structures from POSS-Containing Block Copolymers Synthesized by Living Anionic Polymerization Hirai, Tomoyasu; Leolukman, Melvina; Jin, Sangwoo Macromolecules, Vol. 42, Issue 22 https://doi.org/10.1021/ma9018944	journal	November 2009
Reversible Morphology Control in Block Copolymer Films via Solvent Vapor Processing: An in Situ GISAXS Study Paik, Marvin Y.; Bosworth, Joan K.; Smilges, Detlef-M. Macromolecules, Vol. 43, Issue 9 https://doi.org/10.1021/ma902646t	journal	May 2010
Origins of Complex Self-Assembly in Block Copolymers Matsen, M. W.; Bates, F. S. Macromolecules, Vol. 29, Issue 23 https://doi.org/10.1021/ma960744q	journal	January 1996
Kinetic Constraints on the Development of Surface Microstructure in SBS Thin Films Kim, Ginam; Libera, Matthew Macromolecules, Vol. 31, Issue 8 https://doi.org/10.1021/ma9714070	journal	April 1998
Orientation-Controlled Self-Assembled Nanolithography Using a Polystyrene−Polydimethylsiloxane Block Copolymer Jung, Yeon Sik; Ross, C. A. Nano Letters, Vol. 7, Issue 7 https://doi.org/10.1021/nl070924l	journal	July 2007
Gradient Solvent Vapor Annealing of Block Copolymer Thin Films Using a Microfluidic Mixing Device Albert, Julie N. L.; Bogart, Timothy D.; Lewis, Ronald L. Nano Letters, Vol. 11, Issue 3 https://doi.org/10.1021/nl104496r	journal	March 2011
Highly Tunable Self-Assembled Nanostructures from a Poly(2-vinylpyridine- b -dimethylsiloxane) Block Copolymer Jeong, Jae Won; Park, Woon Ik; Kim, Mi-Jeong Nano Letters, Vol. 11, Issue 10 https://doi.org/10.1021/nl2016224	journal	October 2011
Solvothermal Annealing of Block Copolymer Thin Films Gotrik, Kevin W.; Ross, C. A. Nano Letters, Vol. 13, Issue 11 https://doi.org/10.1021/nl4021683	journal	October 2013
Monodisperse Pattern Nanoalloying for Synergistic Intermetallic Catalysis Mun, Jeong Ho; Chang, Yun Hee; Shin, Dong Ok Nano Letters, Vol. 13, Issue 11 https://doi.org/10.1021/nl403542h	journal	October 2013
Simple and Versatile Methods To Integrate Directed Self-Assembly with Optical Lithography Using a Polarity-Switched Photoresist Cheng, Joy Y.; Sanders, Daniel P.; Truong, Hoa D. ACS Nano, Vol. 4, Issue 8 https://doi.org/10.1021/nn100686v	journal	July 2010
Fast Assembly of Ordered Block Copolymer Nanostructures through Microwave Annealing Zhang, Xiaojiang; Harris, Kenneth D.; Wu, Nathanael L. Y. ACS Nano, Vol. 4, Issue 11 https://doi.org/10.1021/nn102387c	journal	October 2010
A Route to Nanoscopic Materials via Sequential Infiltration Synthesis on Block Copolymer Templates Peng, Qing; Tseng, Yu-Chih; Darling, Seth B. ACS Nano, Vol. 5, Issue 6, p. 4600-4606 https://doi.org/10.1021/nn2003234	journal	May 2011
Multicomponent Nanopatterns by Directed Block Copolymer Self-Assembly Shin, Dong Ok; Mun, Jeong Ho; Hwang, Geon-Tae ACS Nano, Vol. 7, Issue 10 https://doi.org/10.1021/nn403379k	journal	September 2013
Directed Self-Assembly of Block Copolymers for Nanolithography: Fabrication of Isolated Features and Essential Integrated Circuit Geometries Stoykovich, Mark P.; Kang, Huiman; Daoulas, Kostas Ch. ACS Nano, Vol. 1, Issue 3 https://doi.org/10.1021/nn700164p	journal	October 2007
Epitaxial self-assembly of block copolymers on lithographically defined nanopatterned substrates Ouk Kim, Sang; Solak, Harun H.; Stoykovich, Mark P. Nature, Vol. 424, Issue 6947, p. 411-414 https://doi.org/10.1038/nature01775	journal	July 2003
Nanostructure engineering by templated self-assembly of block copolymers Cheng, Joy Y.; Mayes, Anne M.; Ross, Caroline A. Nature Materials, Vol. 3, Issue 11 https://doi.org/10.1038/nmat1211	journal	October 2004
Composite mesostructures by nano-confinement Wu, Yiying; Cheng, Guosheng; Katsov, Kirill Nature Materials, Vol. 3, Issue 11 https://doi.org/10.1038/nmat1230	journal	October 2004
Assembly of aligned linear metallic patterns on silicon Chai, Jinan; Wang, Dong; Fan, Xiangning Nature Nanotechnology, Vol. 2, Issue 8 https://doi.org/10.1038/nnano.2007.227	journal	August 2007
Complex self-assembled patterns using sparse commensurate templates with locally varying motifs Yang, Joel K. W.; Jung, Yeon Sik; Chang, Jae-Byum Nature Nanotechnology, Vol. 5, Issue 4 https://doi.org/10.1038/nnano.2010.30	journal	March 2010
Host-Guest Self-assembly in Block Copolymer Blends Park, Woon Ik; Kim, YongJoo; Jeong, Jae Won Scientific Reports, Vol. 3, Issue 1 https://doi.org/10.1038/srep03190	journal	November 2013
Effect of structural anisotropy on the coarsening kinetics of diblock copolymer striped patterns Ruiz, R.; Bosworth, J. K.; Black, C. T. Physical Review B, Vol. 77, Issue 5 https://doi.org/10.1103/PhysRevB.77.054204	journal	February 2008
Directing the Self-Assembly of Block Copolymers into A Metastable Complex Network Phase via A Deep and Rapid Quench Müller, Marcus; Sun, De-Wen Physical Review Letters, Vol. 111, Issue 26 https://doi.org/10.1103/PhysRevLett.111.267801	journal	December 2013
Mechanisms of Chain Diffusion in Lamellar Block Copolymers Lodge, T. P.; Dalvi, M. C. Physical Review Letters, Vol. 75, Issue 4 https://doi.org/10.1103/PhysRevLett.75.657	journal	July 1995
Density Multiplication and Improved Lithography by Directed Block Copolymer Assembly Ruiz, R.; Kang, H.; Detcheverry, F. A. Science, Vol. 321, Issue 5891 https://doi.org/10.1126/science.1157626	journal	August 2008
Graphoepitaxy of Self-Assembled Block Copolymers on Two-Dimensional Periodic Patterned Templates Bita, I.; Yang, J. K. W.; Jung, Y. S. Science, Vol. 321, Issue 5891 https://doi.org/10.1126/science.1159352	journal	August 2008
Macroscopic 10-Terabit-per-Square-Inch Arrays from Block Copolymers with Lateral Order Park, Soojin; Lee, Dong Hyun; Xu, Ji Science, Vol. 323, Issue 5917, p. 1030-1033 https://doi.org/10.1126/science.1168108	journal	February 2009
Templating Three-Dimensional Self-Assembled Structures in Bilayer Block Copolymer Films Tavakkoli K. G., A.; Gotrik, K. W.; Hannon, A. F. Science, Vol. 336, Issue 6086 https://doi.org/10.1126/science.1218437	journal	June 2012
Polarity-Switching Top Coats Enable Orientation of Sub-10-nm Block Copolymer Domains Bates, C. M.; Seshimo, T.; Maher, M. J. Science, Vol. 338, Issue 6108 https://doi.org/10.1126/science.1226046	journal	November 2012
Controlling Polymer-Surface Interactions with Random Copolymer Brushes Mansky, P.; Liu, Y.; Huang, E. Science, Vol. 275, Issue 5305, p. 1458-1460 https://doi.org/10.1126/science.275.5305.1458	journal	March 1997
Ultrahigh-Density Nanowire Arrays Grown in Self-Assembled Diblock Copolymer Templates Thurn-Albrecht, T.; Schotter, J.; Kastle, G. A. Science, Vol. 290, Issue 5499, p. 2126-2129 https://doi.org/10.1126/science.290.5499.2126	journal	December 2000
Polymer self assembly in semiconductor microelectronics Black, C. T.; Ruiz, R.; Breyta, G. IBM Journal of Research and Development, Vol. 51, Issue 5 https://doi.org/10.1147/rd.515.0605	journal	September 2007
Directed block copolymer self-assembly for nanoelectronics fabrication Herr, Daniel J. C. Journal of Materials Research, Vol. 26, Issue 2 https://doi.org/10.1557/jmr.2010.74	journal	January 2011

Cited By (5)

In Situ Tracking of Composition and Morphology of a Diblock Copolymer Film with GISAXS during Exchange of Solvent Vapors at Elevated Temperatures Berezkin, Anatoly V.; Jung, Florian; Posselt, Dorthe Advanced Functional Materials, Vol. 28, Issue 19 https://doi.org/10.1002/adfm.201706226	journal	March 2018
Individual Confinement of Block Copolymer Microdomains in Nanoscale Crossbar Templates Park, Woon Ik; Jung, Yun Kyung; Kim, YongJoo Advanced Functional Materials https://doi.org/10.1002/adfm.201805795	journal	December 2018
Pattern formation of metal–oxide hybrid nanostructures via the self-assembly of di-block copolymer blends Jung, Dae Soo; Bang, Jiwon; Park, Tae Wan Nanoscale, Vol. 11, Issue 40 https://doi.org/10.1039/c9nr04038b	journal	January 2019
Automated solvent vapor annealing with nanometer scale control of film swelling for block copolymer thin films Hulkkonen, Hanna; Salminen, Turkka; Niemi, Tapio Soft Matter, Vol. 15, Issue 39 https://doi.org/10.1039/c9sm01322a	journal	January 2019
Shear-solvo defect annihilation of diblock copolymer thin films over a large area Kim, Ye Chan; Shin, Tae Joo; Hur, Su-Mi Science Advances, Vol. 5, Issue 6 https://doi.org/10.1126/sciadv.aaw3974	journal	June 2019

Similar Records

Orientation control of high-χ triblock copolymer for sub-10 nm patterning using fluorine-containing polymeric additives

Journal Article · Thu Jul 25 00:00:00 EDT 2019 · Journal of Micro/Nanolithography, MEMS, and MOEMS · OSTI ID:1880537

Phase Behavior of Charged Star Block Copolymers at Fluids Interface

Journal Article · Wed Jan 10 23:00:00 EST 2024 · Angewandte Chemie (International Edition) · OSTI ID:2429591

Assembling Vertical Block Copolymer Nanopores via Solvent Vapor Annealing on Homopolymer-Functionalized Substrates

Journal Article · Wed Jun 26 00:00:00 EDT 2024 · ACS Applied Materials and Interfaces · OSTI ID:2382648

Related Subjects

36 MATERIALS SCIENCE
block copolymers
honeycomb
lithography
rapid self-assembly
solvent vapor annealing

Tunable and rapid self-assembly of block copolymers using mixed solvent vapors

Citation Formats

References (41)

Cited By (5)

Similar Records

Related Subjects