期刊
ACS NANO
卷 6, 期 1, 页码 459-466出版社
AMER CHEMICAL SOC
DOI: 10.1021/nn203776c
关键词
solvent annealing; solvent removal; block copolymer; thin film; self-assembly; morphology; orientation
类别
资金
- NIST, U.S. Department of Commerce [70NANB7H6178]
- National Science Foundation (NSF) [DMR-0645586]
- Department of Defense through AFOSR-PECASE [FA95 50-09-1-0706]
- UD NSF REU [NSF EEC-0754348]
- E.I. DuPont de Nemours Co.
- Dow Chemical Company
- State of Illinois
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-AC02-06CH11357]
Nanoscale self-assembly of block copolymer thin films has garnered significant research Interest for nanotemplate design and membrane applications. To fulfill these roles, control of thin film morphology and orientation Is critical. Solvent vapor annealing (SVA) treatments can be used to kinetically trap morphologies in thin films not achievable by traditional thermal treatments, but many variables affect the outcome of SVA, including solvent choice, total solvent concentration/swollen film thickness, and solvent removal rate. In this work, we systematically examined the effect of solvent removal rate on the final thin film morphology of a cylinder-forming ABA triblock copolymer. By kinetically trapping the film morphologies at key points during the solvent removal process and then using successive ultraviolet ozone (UVO) etching steps followed by atomic force microscopy (AFM) imaging to examine the through-film morphologies of the films, we determined that the mechanism for cylinder reorientation from substrate-parallel to substrate-perpendicular involved the propagation of changes at the free surface through the film toward the substrate as a front. The degree of reorientation increased with successively slower solvent removal rates. Furthermore, the AFM/UVO etching scheme permitted facile real-space analysis of the thin film internal structure in comparison to cross-sectional transmission electron microscopy.
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