Reconfigurable, mechanically responsive crystalline materials are central components in many sensing, soft robotic, and energy conversion and storage devices1,2,3,4. Crystalline materials can readily deform under various stimuli and the extent of recoverable deformation is highly dependent upon bond type1,2,5,6,7,8,9,10. Indeed, for structures held together via simple electrostatic interactions, minimal deformations are tolerated. By contrast, structures held together by molecular bonds can, in principle, sustain much larger deformations and more easily recover their original configurations. Here we study the deformation properties of well-faceted colloidal crystals engineered with DNA. These crystals are large in size (greater than 100 µm) and have a body-centred cubic (bcc) structure with a high viscoelastic volume fraction (of more than 97%). Therefore, they can be compressed into irregular shapes with wrinkles and creases, and, notably, these deformed crystals, upon rehydration, assume their initial well-formed crystalline morphology and internal nanoscale order within seconds. For most crystals, such compression and deformation would lead to permanent, irreversible damage. The substantial structural changes to the colloidal crystals are accompanied by notable and reversible optical property changes. For example, whereas the original and structurally recovered crystals exhibit near-perfect (over 98%) broadband absorption in the ultraviolet–visible region, the deformed crystals exhibit significantly increased reflection (up to 50% of incident light at certain wavelengths), mainly because of increases in their refractive index and inhomogeneity.
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The data that support the findings of the study are available from the corresponding author, C.A.M., upon reasonable request.
The MATLAB codes used to generate the model diffraction patterns in the Supplementary Information can be found in the Supplementary Data Files.
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This material is based upon work supported by Air Force Office of Scientific Research FA9550-17-1-0348, FA9550-16-1-0150 and FA9550-18-1-0493. It was also supported as part of the Center for Bio-Inspired Energy Science, an Energy Frontier Research Center (CBES) funded by the US Department of Energy, Office of Science, Basic Energy Sciences award DE-SC0000989. This work made use of the EPIC facility of Northwestern University’s NUANCE Center, which has received support from the SHyNE Resource (NSF grant no. ECCS-2025633), the International Institute for Nanotechnology (IIN) and Northwestern’s MRSEC program (NSF grant no. DMR-1720139); the IIN; the Keck Foundation; and the State of Illinois, through the IIN. This research used resources of the Advanced Photon Source, a US Department of Energy Office of Science User Facility operated for the US Department of Energy Office of Science by Argonne National Laboratory under contract no. DE‐AC02‐06CH11357. X-ray diffraction experiments were carried out at the Dupont–Northwestern–Dow Collaborative Access Team beamline at Sector 5, 12-ID-B, and sector 21 at the Advanced Photon Source at Argonne National Laboratory. H.A.C. acknowledges support by the National Science Foundation Graduate Research Fellowship Program grant (DGE-1842165). K.A. acknowledges partial support from the Office of Naval Research Young Investigator Program (ONR-YIP) Award (no. N00014-17-1-2425). S.L. (UM) and S.C.G. acknowledge support from CBES (grant no. DE-SC0000989). MD simulations were supported in part through computational resources and services supported by Advanced Research Computing at the University of Michigan, Ann Arbor and also used the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation grant no. ACI-1548562 and XSEDE award no. DMR 140129.
The authors declare no competing interests.
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Extended data figures and tables
Extended Data Fig. 1 Melting temperature curves for the synthesis of the crystals and their SAXS patterns.
a, Melting temperature curves for solutions of A and B-type PAEs. A cooling rate of 0.1 °C/120 min was applied over the crystallization temperature range (shaded region) that encompasses the aggregation temperatures of the PAEs. b,c, SAXS patterns of BCC crystals (b) with 5-nm PAEs and (c) with 10-nm PAEs. In case of the crystals prepared with 5-nm PAEs, a smaller fraction of the crystals that have a slightly larger unit cell parameter, 292.9 Å, were detected in the diffraction profile. The two phases are likely to occur during crystallization owing to the polydispersity of the 5-nm particle cores. Size exclusion occurs more readily during crystallization of the 5-nm PAEs compared to the 10-nm PAEs, as a result of the larger relative size difference between small and large particles in the 5-nm batch. This is a well-documented behaviour for this class of materials42.
Extended Data Fig. 2 Crystal size dependency on the cooling rate during the crystallization process.
a, b, Optical microscopy images of crystals assembled from 5-nm PAEs at the cooling rates indicated (scale bar: 50 µm), and crystal size distribution histogram. Inset, average crystal sizes as a function of the cooling rate. c, d, Optical microscopy images of crystals assembled from 10-nm PAEs at the cooling rates indicated (scale bar: 50 µm), and crystal size distribution histogram. e, Optical microscopy images of >100-µm single crystals assembled from 5-nm and 10-nm PAEs, respectively.
a,b, Crystals assembled from (a) 5- and (b) 10-nm PAEs. Scale bars: 5 µm.
a, A crystal assembled with 5-nm PAEs (a: 223 Å). b, A crystal assembled with 10-nm PAEs (a: 274 Å). In the high-angle area of both data, FCC structure powder rings from randomly oriented AuNPs in the crystals were observed. The majority of the reflections of the BCC superlattices are blocked by the beam stop owing to the typical short sample-detector distance of the instrument configuration of a wide-angle beamline.
a, A single crystal mounted on a fibre loop. b, Tilt motor to orient the crystal. c, Y-axis control motor. d, X-axis control motor. e, X-ray beam collimator.
The SXRD patterns were collected during a dehydration-rehydration cycle. High-order, weakly observable reflections obtained from intact and rehydrated crystals are highlighted with white circles in the figure insets.
Extended Data Fig. 7 Three-dimensionally reconstructed diffraction patterns of the crystals during a deformation and recovery cycle.
a,b, The unit cell parameters were determined by overlapping the simulated BCC reciprocal matrixes (grey dotted circles) with the reconstructed diffraction patterns of the crystals assembled with (a) 5-nm PAEs and (b) 10-nm PAEs, respectively. In the case of heavily deformed crystals, precise unit cell parameter determination was impossible because of the limited number of reflections. The unit cell parameters of the heavily deformed crystals were estimated by measuring the average distances between the centers of (110) reflections and the origin of the reciprocal space and converting the average distances to the direct space values.
a, MD simulation snapshot after the crystal deformation. The crystal was fractured into many domains with different sizes and orientations. b, Effective pair potential between A-type PAEs and B-type PAEs in this model (Supplementary Methods 3). c, Diffraction pattern obtained from the (111) direction of the fractured crystal.
a, Schematic view of the simulation region used in the FDTD simulation, highlighted by the bounding box. b, Bright-field optical microscope images of the crystals measured in situ and absorption spectra of the intact and rehydrated crystals assembled with 10-nm PAEs. c, Enhanced reflection of the deformed crystals. Reflections of randomly chosen dehydrated crystals are indicated in pale blue. d, Simulated effective index plot for the crystals assembled with 10-nm PAEs, considering only contraction, without distortion, of the unit cells.
Supplementary Methods 1–6, Figs. 1–16, Tables 1–11 and references.
Source MATLAB code used to generate the diffraction fringes.
Source MATLAB code used to plot the diffraction data.
Colloidal crystals composed of PAEs during dehydration-rehydration cycles. Crystals composed of 5 nm PAEs were dehydrated and rehydrated on glass slides and their response was recorded by an optical microscope. Some crystals were able to recover their initial morphology even after six dehydration–rehydration cycles.
Reflections of dehydrated crystals during single-crystal X-ray diffraction. Dehydrated crystals composed of 5 nm PAEs frequently exhibit sharp lines and streaks in their (110) reflections during single-crystal X-ray diffraction experiments.
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Lee, S., Calcaterra, H.A., Lee, S. et al. Shape memory in self-adapting colloidal crystals. Nature 610, 674–679 (2022). https://doi.org/10.1038/s41586-022-05232-9