Poly(cyclohexylethylene)-block-Poly(lactide) Oligomers for Ultrasmall Nanopatterning Using Atomic Layer Deposition

Li Yao, Luis E. Oquendo, Morgan W. Schulze, Ronald M. Lewis, Wayne L. Gladfelter, Marc A. Hillmyer

Research output: Contribution to journalArticlepeer-review

20 Scopus citations


Poly(cyclohexylethylene)-block-poly(lactide) (PCHE-PLA) block polymers were synthesized through a combination of anionic polymerization, heterogeneous catalytic hydrogenation and controlled ring-opening polymerization. Ordered thin films of PCHE-PLA with ultrasmall hexagonally packed cylinders oriented perpendicularly to the substrate surface were prepared by spin-coating and subsequent solvent vapor annealing for use in two distinct templating strategies. In one approach, selective hydrolytic degradation of the PLA domains generated nanoporous PCHE templates with an average pore diameter of 5 ± 1 nm corroborated by atomic force microscopy and grazing incidence small-angle X-ray scattering. Alternatively, sequential infiltration synthesis (SIS) was employed to deposit Al2O3 selectively into the PLA domains of PCHE-PLA thin films. A combination of argon ion milling and O2 reactive ion etching (RIE) enabled the replication of the Al2O3 nanoarray from the PCHE-PLA template on diverse substrates including silicon and gold with feature diameters less than 10 nm.

Original languageEnglish (US)
Pages (from-to)7431-7439
Number of pages9
JournalACS Applied Materials and Interfaces
Issue number11
StatePublished - Mar 30 2016

Bibliographical note

Funding Information:
This work was supported by the National Science Foundation through the University of Minnesota MRSEC under Award Number DMR-1420013. Parts of this work were carried out in the University of Minnesota Characterization Facility which receives partial support from NSF through the MRSEC program and in the Minnesota Nano Center which receives partial support from NSF through the NNIN program. The Hitachi SU8320 SEM was provided by NSF MRI DMR- 1229263. GISAXS was conducted at the Cornell High Energy Synchrotron Source (CHESS) which is supported by the NSF and NIH/NIGMS via NSF award DMR-1332208. Portions of this work were performed at the 12-ID-B beamline and the DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the Advanced Photon Source (APS). DND-CAT is supported by Northwestern University, E.I. DuPont de Nemours & Co., and The Dow Chemical Company. Data from 5-ID-D was collected using an instrument funded by the National Science Foundation under Award Number 0960140. APS is a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. We thank Justin Kennemur, Arthur Bertrand, Srinivas Polisetty, Christophe Sinturel, Josh Halverson and Robin Harkins for helpful discussions.

Publisher Copyright:
© 2016 American Chemical Society.


  • atomic layer deposition
  • block polymer
  • nanolithography
  • nanopores
  • selective infiltration synthesis
  • self-assembly
  • solvent vapor annealing

How much support was provided by MRSEC?

  • Shared

PubMed: MeSH publication types

  • Journal Article
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.


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