Confined Growth of DNA-Assembled Superlattice Films

Cindy Y. Zheng, Yudong Yao, Junjing Deng, Soenke Seifert, Alexa M. Wong, Byeongdu Lee, Chad A. Mirkin*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

3 Scopus citations

Abstract

We study the assembly of DNA-functionalized nanocubes under lateral confinement in microscale square trenches on a DNA-functionalized substrate. Microfocus small-angle X-ray scattering (SAXS) and scanning electron microscopy (SEM) are used to characterize the superlattices (SLs). The results indicate that nanocubes form simple-cubic SLs with square-prism morphology and a (100) out-of-plane orientation to maximize DNA bonding. In-plane, SLs align with the template, exposing their {100} side facets, and the degree of alignment depends on trench size. Interestingly, the distribution of in-plane orientations determined from SAXS and SEM do not agree, indicating that the internal and external structures of the SLs differ. To understand this discrepancy, X-ray ptychography is employed to image the internal structures of the SLs, revealing that SLs which appear to be single-crystalline in SEM may have subsurface grain boundaries, depending on trench size. SEM reveals that the SLs grow via nucleation and growth of randomly oriented domains, which then coalesce; this mechanism explains the observed dependence of alignment and defect structure on size. Interestingly, crystallization occurs via an unusual growth mode, whereby continuous SL layers grow on top of several misoriented islands. Overall, this work elucidates the effect of lateral confinement on the crystallization of DNA-functionalized nanoparticles and shows how X-ray ptychography can be used to gain insight into nanoparticle crystallization.

Original languageEnglish (US)
Pages (from-to)4813-4822
Number of pages10
JournalACS nano
Volume16
Issue number3
DOIs
StatePublished - Mar 22 2022

Keywords

  • X-ray ptychography
  • colloidal crystal
  • micro confinement
  • small-angle X-ray scattering
  • thin film

ASJC Scopus subject areas

  • Engineering(all)
  • Physics and Astronomy(all)
  • Materials Science(all)

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