Tunable near-infrared and visible-light transmittance in nanocrystal-in-glass composites

Abstract

Amorphous metal oxides are useful in optical1,2, electronic3,4,5 and electrochemical devices6,7. The bonding arrangement within these glasses largely determines their properties, yet it remains a challenge to manipulate their structures in a controlled manner. Recently, we developed synthetic protocols for incorporating nanocrystals that are covalently bonded into amorphous materials8,9. This ‘nanocrystal-in-glass’ approach not only combines two functional components in one material, but also the covalent link enables us to manipulate the glass structure to change its properties. Here we illustrate the power of this approach by introducing tin-doped indium oxide nanocrystals into niobium oxide glass (NbOx), and realize a new amorphous structure as a consequence of linking it to the nanocrystals. The resulting material demonstrates a previously unrealized optical switching behaviour that will enable the dynamic control of solar radiation transmittance through windows. These transparent films can block near-infrared and visible light selectively and independently by varying the applied electrochemical voltage over a range of 2.5 volts. We also show that the reconstructed NbOx glass has superior properties—its optical contrast is enhanced fivefold and it has excellent electrochemical stability, with 96 per cent of charge capacity retained after 2,000 cycles.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Figure 1: Nanocrystal-in-glass film preparation and structural characterization.
Figure 2: Raman analysis probing the reconstruction of a NbOx glass matrix when linked to nanocrystals.
Figure 3: ITO nanocrystals covalently linked to amorphous NbOx.
Figure 4: Tunable dual-band solar control and optical contrast enhancement in nanocrystal-in-glass films.

References

  1. 1

    Lines, M. E. Oxide glasses for fast photonic switching—a comparative study. J. Appl. Phys. 69, 6876–6884 (1991)

  2. 2

    Kim, S. H. & Yoko, T. Non-linear optical properties of TeO2-based glasses: MO(X)-TeO2 (M = Sc, TI, V, Nb, Mo, Ta, and W) binary glasses. J. Am. Ceram. Soc. 78, 1061–1065 (1995)

  3. 3

    Nomura, K. et al. Room-temperature fabrication of transparent flexible thin-film transistors using amorphous oxide semiconductors. Nature 432, 488–492 (2004)

  4. 4

    Arhammar, C. et al. Unveiling the complex electronic structure of amorphous metal oxides. Proc. Natl Acad. Sci. USA 108, 6355–6360 (2011)

  5. 5

    Kim, Y.-H. et al. Flexible metal-oxide devices made by room-temperature photochemical activation of sol-gel films. Nature 489, 128–132 (2012)

  6. 6

    Idota, Y., Kubota, T., Matsufuji, A., Maekawa, Y. & Miyasaka, T. Tin-based amorphous oxide: a high-capacity lithium-ion-storage material. Science 276, 1395–1397 (1997)

  7. 7

    Granqvist, C. G. Handbook of Inorganic Electrochromic Materials (Elsevier Science, 2002)

  8. 8

    Tangirala, R., Baker, J. L., Alivisatos, A. P. & Milliron, D. J. Modular inorganic nanocomposites by conversion of nanocrystal superlattices. Angew. Chem. Int. Ed. 49, 2878–2882 (2010)

  9. 9

    Llordes, A. et al. Polyoxometalates and colloidal nanocrystals as building blocks for metal oxide nanocomposite films. J. Mater. Chem. 21, 11631–11638 (2011)

  10. 10

    Rosenflanz, A. et al. Bulk glasses and ultrahard nanoceramics based on alumina and rare-earth oxides. Nature 430, 761–764 (2004)

  11. 11

    Falcão-Filho, E. L. et al. Third-order optical nonlinearity of a transparent glass ceramic containing sodium niobate nanocrystals. Phys. Rev. B 69, 134204 (2004)

  12. 12

    Mattarelli, M., Gasperi, G., Montagna, M. & Verrocchio, P. Transparency and long-ranged fluctuations: the case of glass ceramics. Phys. Rev. B 82, 094204 (2010)

  13. 13

    Schirmeisen, A. et al. Fast interfacial ionic conduction in nanostructured glass ceramics. Phys. Rev. Lett. 98, 225901 (2007)

  14. 14

    Zhou, H. S., Li, D. L., Hibino, M. & Honma, I. A self-ordered, crystalline-glass, mesoporous nanocomposite for use as a lithium-based storage device with both high power and high energy densities. Angew. Chem. Int. Ed. 44, 797–802 (2005)

  15. 15

    Dong, W. et al. Controllable and repeatable synthesis of thermally stable anatase nanocrystal-silica composites with highly ordered hexagonal mesostructures. J. Am. Chem. Soc. 129, 13894–13904 (2007)

  16. 16

    Sakamoto, A. & Yamamoto, S. Glass–ceramics: engineering principles and applications. Int. J. Appl. Glass Sci. 1, 237–247 (2010)

  17. 17

    Dong, A. et al. A generalized ligand-exchange strategy enabling sequential surface functionalization of colloidal nanocrystals. J. Am. Chem. Soc. 133, 998–1006 (2011)

  18. 18

    Rosen, E. L. et al. Exceptionally mild reactive stripping of native ligands from nanocrystal surfaces by using Meerwein's salt. Angew. Chem. Int. Ed. 51, 684–689 (2012)

  19. 19

    McConnell, A. A., Anderson, J. S. & Rao, C. N. R. Raman-spectra of niobium oxides. Spectrochim. Acta 32, 1067–1076 (1976)

  20. 20

    Jehng, J. M. & Wachs, I. E. Structural chemistry and Raman-spectra of niobium oxides. Chem. Mater. 3, 100–107 (1991)

  21. 21

    Shelby, J. E. Introduction to Glass Science and Technology Ch. 2, 5 (Royal Society of Chemistry, 2005)

  22. 22

    Monk, P., Mortimer, R. & Rosseinsky, D. Electrochromism and Electrochromic Devices Ch. 2 (Cambridge Univ. Press, 2007)

  23. 23

    Li, S.-Y., Niklasson, G. A. & Granqvist, C. G. Nanothermochromics: calculations for VO2 nanoparticles in dielectric hosts show much improved luminous transmittance and solar energy transmittance modulation. J. Appl. Phys. 108, 063525 (2010)

  24. 24

    Garcia, G. et al. Dynamically modulating the surface plasmon resonance of doped semiconductor nanocrystals. Nano Lett. 11, 4415–4420 (2011)

  25. 25

    Garcia, G. et al. Near-infrared spectrally selective plasmonic electrochromic thin films. Adv. Opt. Mater. 1, 215–220 (2013)

  26. 26

    Rosario, A. V. & Pereira, E. C. Influence of the crystallinity on the Li+ intercalation process in Nb2O5 films. J. Solid State Electrochem. 9, 665–673 (2005)

  27. 27

    Wang, R. Y., Tangirala, R., Raoux, S., Jordan-Sweet, J. L. & Milliron, D. J. Ionic and electronic transport in Ag2S nanocrystal–GeS2 matrix composites with size-controlled Ag2S nanocrystals. Adv. Mater. 24, 99–103 (2012)

  28. 28

    Lehn, J. M. Supramolecular chemistry—receptors, catalysis, and carriers. Science 227, 849–856 (1985)

  29. 29

    Li, H., Eddaoudi, M., O'Keeffe, M. & Yaghi, O. M. Design and synthesis of an exceptionally stable and highly porous metal-organic framework. Nature 402, 276–279 (1999)

  30. 30

    Buonsanti, R. et al. Assembly of ligand-stripped nanocrystals into precisely controlled mesoporous architectures. Nano Lett. 12, 3872–3877 (2012)

  31. 31

    Villa, E. M. et al. Reaction dynamics of the decaniobate ion [HxNb10O28](6−x)− in water. Angew. Chem. Int. Edn 47, 4844–4846 (2008)

  32. 32

    Choi, S. I., Nam, K. M., Park, B. K., Seo, W. S. & Park, J. T. Preparation and optical properties of colloidal, monodisperse, and highly crystalline ITO nanoparticles. Chem. Mater. 20, 2609–2611 (2008)

Download references

Acknowledgements

We thank S. Raoux and J. L. Jordan-Sweet as well as S. Mannsfeld and M. Toney for assistance in synchrotron XRD measurements at the National Synchrotron Light Source (Brookhaven National Laboratory) and Stanford Synchrotron Radiation Lightsource (SSRL); and R. Zuckermann, P. J. Schuck, R. J. Mendelsberg, and especially M. Salmeron and O. Yaghi for critical reading of the manuscript. This work was performed at the Molecular Foundry, Lawrence Berkeley National Laboratory, and was supported by the Office of Science, Office of Basic Energy Sciences, of the US Department of Energy (DOE) under contract number DE-AC02—05CH11231. D.J.M. and G.G. were supported by a DOE Early Career Research Program grant under the same contract, and J.G. was supported by Consejo Superior de Investigaciones Cientificas, CSIC, JAE. Scanning transmission electron microscopy images were taken at Oak Ridge National Laboratory (ORNL), supported by DOE-BES, Materials Sciences and Engineering Division, and by ORNL’s Shared Research Equipment (ShaRE) User Program, which is also sponsored by DOE-BES. XRD data shown in the manuscript was acquired at SSRL, beamline 11-3.

Author information

Affiliations

Authors

Contributions

A.L. synthesized the materials, carried out the experiments and analysed the data, with assistance from G.G. for the electrochemical characterization. J.G. carried out scanning transmission electron microscopy imaging. A.L. and D.J.M. were responsible for experimental design and wrote the manuscript, which incorporates critical input from all authors.

Corresponding author

Correspondence to Delia J. Milliron.

Ethics declarations

Competing interests

G.G. and D.J.M. have a financial interest in Heliotrope Technologies, a company pursuing the commercial development of electrochromic devices.

Supplementary information

Supplementary Information

This file contains Supplementary Figures 1-10 and a Supplementary Discussion. (PDF 3090 kb)

PowerPoint slides

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Llordés, A., Garcia, G., Gazquez, J. et al. Tunable near-infrared and visible-light transmittance in nanocrystal-in-glass composites. Nature 500, 323–326 (2013). https://doi.org/10.1038/nature12398

Download citation

Further reading

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.