by the initial band edge wavelength before tuning) of 19%. The tunability reported here exceeds
that of stretchable substrates, which have exhibited
wavelength tuning of up to 11% in the longer-wavelength infrared region (30) and is comparable
to that achieved recently using temperature-responsive polymers (31). Importantly, all structural changes, and the changes they induce in
optical properties, were reversible for at least
five cycles between large and small gaps, with
no appreciable changes to absorption spectra
observed (Fig. 4H).
The ability to control the arrangement, spacing,
and sequence of NPs within each architecture is
critical to the realization of tunable broadband
absorption. Indeed, superlattices with other se-
quences of disk, cube, and sphere Au NP archi-
tectures are predicted to exhibit very different
optical responses with considerably reduced tun-
ability (fig. S22). Beyond tunable absorption, the
ability to make responsive plasmonic nanoarchi-
tectures not yet achievable via other techniques
should dramatically increase the diversity of
structures and compositions that can now be
explored by theorists and experimentalists to
access new and useful optical properties. It should
be possible to synthesize even more sophisticated
architectures through the use of more intricate
pore designs, and new DNA sequence designs
should enable responsiveness to be extended to
light and biological signals, in addition to chem-
ical ones. Additionally, although we have only
synthesized three-layer architectures here, the
number of NP layers could in principle be in-
creased by using deeper PMMA pores.
REFERENCES AND NOTES
1. C. A. Mirkin, R. L. Letsinger, R. C. Mucic, J. J. Storhoff, Nature
382, 607–609 (1996).
2. D. Nykypanchuk, M. M. Maye, D. van der Lelie, O. Gang, Nature
451, 549–552 (2008).
3. M. R. Jones, N. C. Seeman, C. A. Mirkin, Science 347, 1260901
4. Y. Wang et al., Nature 491, 51–55 (2012).
5. W. Liu et al., Science 351, 582–586 (2016).
6. W. B. Rogers, W. M. Shih, V. N. Manoharan, Nat. Rev. Mater. 1,
7. M. N. O’Brien, H.-X. Lin, M. Girard, M. Olvera de la Cruz,
C. A. Mirkin, J. Am. Chem. Soc. 138, 14562–14565 (2016).
8. M. N. O’Brien, B. Radha, K. A. Brown, M. R. Jones, C. A. Mirkin,
Angew. Chem. Int. Ed. 53, 9532–9538 (2014).
9. Q.-Y. Lin et al., Nano Lett. 15, 4699–4703 (2015).
10. M. X. Wang et al., ACS Nano 11, 180–185 (2017).
11. J. Henzie, S. C. Andrews, X. Y. Ling, Z. Li, P. Yang, Proc. Natl.
Acad. Sci. U.S.A. 110, 6640–6645 (2013).
12. X. Liu et al., Adv. Mater. 27, 7314–7319 (2015).
13. V. Flauraud et al., Nat. Nanotechnol. 12, 73–80 (2017).
14. R. A. Hughes, E. Menumerov, S. Neretina, Nanotechnology 28,
15. Materials and methods are available as supplementary
16. R. J. Macfarlane et al., Science 334, 204–208 (2011).
17. V. A. Bloomfield, D. M. Crothers, I. Tinoco, Nucleic Acids:
Structures, Properties, and Functions (University Science
Books, Sausalito, CA, 2000).
18. A. A. Koshkin et al., Tetrahedron 54, 3607–3630 (1998).
19. R. Owczarzy, Y. You, C. L. Groth, A. V. Tataurov, Biochemistry
50, 9352–9367 (2011).
20. J. Valentine et al., Nature 455, 376–379 (2008).
21. N. Liu et al., Nat. Mater. 7, 31–37 (2008).
22. M. A. Boles, M. Engel, D. V. Talapin, Chem. Rev. 116,
23. J. A. Mason et al., J. Am. Chem. Soc. 138, 8722–8725
24. N. J. Halas, S. Lal, W.-S. Chang, S. Link, P. Nordlander, Chem. Rev.
111, 3913–3961 (2011).
25. A. M. Urbas et al., J. Opt. 18, 093005 (2016).
26. N. I. Zheludev, E. Plum, Nat. Nanotechnol. 11, 16–22
27. Z. Qian, D. S. Ginger, J. Am. Chem. Soc. 139, 5266–5276
28. A. Moreau et al., Nature 492, 86–89 (2012).
29. G. M. Akselrod et al., Adv. Mater. 27, 8028–8034 (2015).
30. I. M. Pryce, K. Aydin, Y. A. Kelaita, R. M. Briggs, H. A. Atwater,
Nano Lett. 10, 4222–4227 (2010).
31. T. Ding et al., Proc. Natl. Acad. Sci. U.S.A. 113, 5503–5507
This material is based on work supported by the Center for
Bio-Inspired Energy Science, an Energy Frontier Research
Center funded by the U.S. Department of Energy, Office of
Science, Basic Energy Sciences, under award DE-SC0000989
and the Air Force Office of Scientific Research under awards
FA9550-12-1-0280, FA9550-14-1-0274, and FA9550-17-1-0348.
Use of the Center for Nanoscale Materials, an Office of Science
user facility at Argonne National Laboratory, and GISAXS
experiments at beamline 12-ID-B at the Advanced Photon
Source at Argonne National Laboratory were supported by the
U.S. Department of Energy, Office of Science, Office of Basic
Energy Sciences, under contract DE-AC02-06CH11357. This
work made use of the Electron Probe Instrumentation Center
(EPIC) facility of the Northwestern University Atomic and
Nanoscale Characterization Experimental Center (NUANCE) at
Northwestern University, which has received support from the
Soft and Hybrid Nanotechnology Experimental (SHyNE)
Resource (NSF NNCI-1542205); the Materials Research Science
and Engineering Center program (NSF DMR-1121262)
at the Materials Research Center; the International Institute for
Nanotechnology (IIN); the Keck Foundation; and the State of
Illinois, through the IIN. Q.-Y.L., Z.L., and M.R.J. gratefully
acknowledge support from the Ryan Fellowship at Northwestern
University, and M.N.O. gratefully acknowledges the National
Science Foundation for a Graduate Research Fellowship. We
thank C. Laramy and H. Lin for assistance with some
nanoparticle syntheses. The authors declare no competing
financial interests. All data are reported in the main text and the
Materials and Methods
Figs. S1 to S37
26 September 2017; accepted 26 December 2017
Published online 18 January 2018
672 9 FEBRUARY 2018 • VOL 359 ISSUE 6376 sciencemag.org SCIENCE
Fig. 4. Reconfigurable optical properties. (A) Each unit cell of the NP superlattice consists
of a gold surface, circular disk, cube, and sphere, with experimentally matched dimensions.
(B) FDTD simulations of optical absorption spectra of the disk-cube-sphere superlattice with
16-, 10-, 8-, 6-, and 4-nm gap lengths (from blue to red). (C) FDTD simulations of electric field
distributions, |E|, for 16-nm gaps (left) and 4-nm gaps (right) at l = 690 nm. (D) Cross-sectional
SEM images of a single disk-cube-sphere architecture after immersing in 0% (left) and 80%
(right) EtOH in H2O at 0.3 M NaCl. Superlattices were encased in silica before imaging to
preserve the solution-phase structure in the solid state. Scale bar, 50 nm. (E) Experimental
optical absorption spectra at 0, 40, 50, 60, and 80% EtOH in H2O (from blue to red: increasing
EtOH leads to decreasing average gap lengths). (F) Average fraction of light absorbed from
550 to 800 nm (dark purple) and wavelength of absorption band edge, ledge (pink). (G) Optical
images of the disk-cube-sphere superlattice. Scale bar, 100 mm. (H) Optical absorption spectra
are shown for five cycles between 0% (blue) and 80% (red) EtOH in H2O.