Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Letter
  • Published:

Kinetically driven self assembly of highly ordered nanoparticle monolayers

Abstract

When a drop of a colloidal solution of nanoparticles dries on a surface, it leaves behind coffee-stain-like rings of material with lace-like patterns or clumps of particles in the interior1,2,3,4,5,6. These non-uniform mass distributions are manifestations of far-from-equilibrium effects, such as fluid flows1 and solvent fluctuations during late-stage drying2. However, recently a strikingly different drying regime promising highly uniform, long-range-ordered nanocrystal monolayers has been found7,8. Here we make direct, real-time and real-space observations of nanocrystal self-assembly to reveal the mechanism. We show how the morphology of drop-deposited nanoparticle films is controlled by evaporation kinetics and particle interactions with the liquid–air interface. In the presence of an attractive particle–interface interaction, rapid early-stage evaporation dynamically produces a two-dimensional solution of nanoparticles at the liquid–air interface, from which nanoparticle islands nucleate and grow. This self-assembly mechanism produces monolayers with exceptional long-range ordering that are compact over macroscopic areas, despite the far-from-equilibrium evaporation process. This new drop-drying regime is simple, robust and scalable, is insensitive to the substrate material and topography, and has a strong preference for forming monolayer films. As such, it stands out as an excellent candidate for the fabrication of technologically important ultra thin film materials for sensors, optical devices and magnetic storage media.

This is a preview of subscription content, access via your institution

Access options

Rent or buy this article

Prices vary by article type

from$1.95

to$39.95

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Gold nanocrystal monolayer.
Figure 2: Monolayer island growth.
Figure 3: Island growth rates from individual islands tracked with video microscopy.
Figure 4: Phase diagram for drop casting.

Similar content being viewed by others

References

  1. Deegan, R. D. et al. Capillary flow as the cause of ring stains from dried liquid drops. Nature 389, 827–829 (1997).

    Article  Google Scholar 

  2. Rabani, E., Reichman, D. R., Geissler, P. L. & Brus, L. E. Drying-mediated self-assembly of nanoparticles. Nature 426, 271–274 (2003).

    Article  Google Scholar 

  3. Tang, J., Ge, G. L. & Brus, L. E. Gas-liquid-solid phase transition model for two-dimensional nanocrystal self-assembly on graphite. J. Phys. Chem. B 106, 5653–5658 (2002).

    Article  Google Scholar 

  4. Pileni, M. P. Nanocrystal self-assemblies: Fabrication and collective properties. J. Phys. Chem. B 105, 3358–3371 (2001).

    Article  Google Scholar 

  5. Wang, Z. L. Structural analysis of self-assembling nanocrystal superlattices. Adv. Mater. 10, 13–30 (1998).

    Article  Google Scholar 

  6. Ohara, P. C., Leff, D. V., Heath, J. R. & Gelbart, W. M. Crystallization of opals from polydisperse nanoparticles. Phys. Rev. Lett. 75, 3466–3469 (1995).

    Article  Google Scholar 

  7. Lin, X. M., Jaeger, H. M., Sorensen, C. M. & Klabunde, K. J. Formation of long-range-ordered nanocrystal superlattices on silicon nitride substrates. J. Phys. Chem. B 105, 3353–3357 (2001).

    Article  Google Scholar 

  8. Narayanan, S., Wang, J. & Lin, X.-M. Dynamical self-assembly of nanocrystal superlattices during colloidal droplet evaporation by in situ small angle X-ray scattering. Phys. Rev. Lett. 93, 135503 (2004).

    Article  Google Scholar 

  9. Ge, G. L. & Brus, L. Evidence for spinodal phase separation in two-dimensional nanocrystal self-assembly. J. Phys. Chem. B 104, 9573–9575 (2000).

    Article  Google Scholar 

  10. Korgel, B. A. & Fitzmaurice, D. Condensation of ordered nanocrystal thin films. Phys. Rev. Lett. 80, 3531–3534 (1998).

    Article  Google Scholar 

  11. Lin, Y., Skaff, H., Emrick, T., Dinsmore, A. D. & Russell, T. P. Nanoparticle assembly and transport at liquid-liquid interfaces. Science 299, 226–229 (2003).

    Article  Google Scholar 

  12. Dinsmore, A. D. et al. Colloidosomes: Selectively permeable capsules composed of colloidal particles. Science 298, 1006–1009 (2002).

    Article  Google Scholar 

  13. Santhanam, V., Liu, J., Agarwal, R. & Andres, R. P. Self-assembly of uniform monolayer arrays of nanoparticles. Langmuir 19, 7881–7887 (2003).

    Article  Google Scholar 

  14. Collier, C. P., Vossmeyer, T. & Heath, J. R. Nanocrystal superlattices. Ann. Rev. Phys. Chem. 49, 371–404 (1998).

    Article  Google Scholar 

  15. Murray, C. B., Kagan, C. R. & Bawendi, M. G. Self-organization of CdSe nanocrystallites into 3-dimensional quantum-dot superlattices. Science 270, 1335–1338 (1995).

    Article  Google Scholar 

  16. Lewis, B. & Campbell, D. S. Nucleation and initial-growth behavior of thin-film deposits. J. Vac. Sci. Technol. 4, 209–218 (1967).

    Article  Google Scholar 

  17. Venables, J. A. & Ball, D. J. Nucleation and growth of rare-gas crystals. Proc. R. Soc. Lond. A 322, 331 (1971).

    Article  Google Scholar 

  18. Pieranski, P. Two-dimensional interfacial colloidal crystals. Phys. Rev. Lett. 45, 569–572 (1980).

    Article  Google Scholar 

  19. Dinsmore, A. D., Warren, P. B., Poon, W. C. K. & Yodh, A. G. Fluid-solid transitions on walls in binary hard-sphere mixtures. Europhys. Lett. 40, 337–342 (1997).

    Article  Google Scholar 

  20. Deegan, R. D. et al. Contact line deposits in an evaporating drop. Phys. Rev. E 62, 756–765 (2000).

    Article  Google Scholar 

Download references

Acknowledgements

We thank M. Constantinides and R. Diamond for their help with early experiments. This work was supported by the UC-ANL Consortium for Nanoscience Research and by the NSF MRSEC program under DMR 0213745. X.-M.L. acknowledges support from the US Department of Energy, Basic Energy Sciences-Materials Sciences, under Contract W-31-109-ENG-38.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Heinrich M. Jaeger.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary figures S1 and S2 (PDF 176 kb)

Supplementary information

Supplementary movie (AVI 13721 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Bigioni, T., Lin, XM., Nguyen, T. et al. Kinetically driven self assembly of highly ordered nanoparticle monolayers. Nature Mater 5, 265–270 (2006). https://doi.org/10.1038/nmat1611

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nmat1611

This article is cited by

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing